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Handbook of Research

on Nanoscience,
Nanotechnology, and
Advanced Materials
Mohamed Bououdina
University of Bahrain, Bahrain
J. Paulo Davim
University of Aveiro, Portugal

A volume in the Advances in Chemical


and Materials Engineering (ACME) Book
Series

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Handbook of research on nanoscience, nanotechnology, and advanced materials / Mohamed Bououdina and J. Paulo Davim,
editors.
pages cm
Summary: This book presents a detailed analysis of current experimental and theoretical approaches surrounding nanomaterials science and applications in fields such as biomedicine, renewable energy, and synthetic materials-Provided by publisher.
Includes bibliographical references and index.
ISBN 978-1-4666-5824-0 (hardcover) -- ISBN 978-1-4666-5825-7 (ebook) -- ISBN 978-1-4666-5827-1 (print & perpetual
access) 1. Nanotechnology. 2. Nanostructured materials. I. Bououdina, Mohamed, 1965- editor of compilation. II. Davim,
J. Paulo, editor of compilation.
T174.7.H367 2014
620.5--dc23
2013051201
This book is published in the IGI Global book series Advances in Chemical and Materials Engineering (ACME) (ISSN:
2327-5448; eISSN: 2327-5456)

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J. Paulo Davim
University of Aveiro, Portugal

ISSN: 2327-5448
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The Advances in Chemicaland Materials Engineering(ACME) Book Series provides research
on the recent advances throughout computational and statistical methods of analysis and modeling. This
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Titles in this Series

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Handbook of Research on Nanoscience, Nanotechnology, and Advanced Materials


Mohamed Bououdina (University of Bahrain, Bahrain) and J. Paulo Davim (University of Aveiro, Portugal)
Engineering Science Reference copyright 2014 375pp H/C (ISBN: 9781466658240) US $295.00 (our price)
Quantum and Optical Dynamics of Matter for Nanotechnology
Mihai V. Putz (West University of Timisoara, Romania)
Engineering Science Reference copyright 2014 527pp H/C (ISBN: 9781466646872) US $180.00 (our price)
Advanced Solar Cell Materials, Technology, Modeling, and Simulation
Laurentiu Fara (Polytechnic University of Bucharest, Romania) and Masafumi Yamaguchi (Toyota Technological
Institute, Japan)
Engineering Science Reference copyright 2013 354pp H/C (ISBN: 9781466619272) US $195.00 (our price)
Computational Gas-Solids Flows and Reacting Systems Theory, Methods and Practice
Sreekanth Pannala (Oak Ridge National Laboratory, USA) Madhava Syamlal (National Energy Technology Laboratory, USA) and Thomas J. OBrien (National Energy Technology Laboratory, USA)
Engineering Science Reference copyright 2011 500pp H/C (ISBN: 9781615206513) US $180.00 (our price)

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Editorial Advisory Board


J. L. Bobet, Universite de Boredaux I, France
R. Boukhanouf, Universit Lille 1, France
D. Fruchart, Institut Neel, France
Z. X. Guo, University College of London, UK
M. Ishaque Khan, Illinois Institute of Technology, USA
Nouar Tabet, Qatar Energy and Environment Research Institute, Qatar
G. Walker, University of Nottingham, UK
Yokoyama, Kent State University, USA

List of Reviewers
Esam H. Abdul-Hafidh, Yanbu University College, Saudi Arabia
H. A. Adnane, Yanbu University College, Saudi Arabia
Feroz Ahmad Mir, University of Kashmir, India
Iftikhar Ahmed, University of Malakand, Pakistan
Rashid Ahmed, Universiti Teknologi Malaysia, Malaysia
Cheknane Ali, Universit Amar Telidji de Laghouat, Algeria
Luc Aymard, University of Picardie Jules Verne, France
Rachid Belkada, Centre de Recherche en Technologie des Semi-Conducteurs Pour lEnergitique, Algeria
Yaakov (Kobi) Benenson, ETH Zrich, Switzerland
Samir Boulfrad, Solar and Photovoltaics Engineering Research Center, Saudi Arabia
Costas Charitidies, University of Athens, Greece
Ingram Conrad, University of West Indies, USA
Eithiraj Rajagopal Dashinamoorthy, Donostia International Physics Centre, Spain
E. Deligoz, Aksaray University, Turkey
Thierry Djenizian, Aix-Marseille Universit Equipe Chimie-Physique, France
Ayub Elahi, University of Engineering and Technology, Pakistan
Mohamed Fathi, Centre de Recherche en Technologie des Semi-Conducteurs Pour lEnergitique, Algeria
Khaldi Fouad, Universit de Batna, Algeria
Mark Franken, University of Bath, UK
Qiang Fu, University of Connecticut, USA
Mounir Gaidi, Research and Technology Centre of Energy, Tunisia
Rukan Genc, Mersin University, Turkey

Sevdalin Georgiev, Sofia University, Bulgaria


Gopukumar, Central Electro-Chemical Research Institute, India
Wolfgang Hess, Freiburg University, Germany
Tajammul Hussain, National Centre of Physics, Pakistan
Ishrat Khan, University of Florida, USA
S. S. Islam, Central University, India
Tariq-ul Islam, Central University, India
Yassin A. Jeilani, Spelman College, USA
Dinesh Jesrotia, GGM Science College Jammu, India
Anup Kale, Singapore Bioimaging Consortium, Singapore
Amal Kasry, Austrian Institute of Technology (AIT), Austria
G. Davon Kennedy, Georgia State University, USA
R. V. Krishnarao, Defence Metallurgical Research Laboratory, India
Huayang Li, Clark Atlanta University, USA
Jing Li, Eugene Applebaum College of Pharmacy and Health Sciences, USA
K. Maaz, Chinese Academy of Sciences, China
Shazim Memon, Department of Civil and Architectural Engineering, Hong Kong
Abdelkrim Merad, International Centre for Theoretical Physics (ICTP), Italy
Rahul Mitra, Indian Institute of Technology, India
Abdul Khader Mohammad, Pharmaceutics International Inc. (PII), USA
Sylvie Morin, York University, Canada
Maqbool Muhammad, Ball State University, USA
Gautam Mukherjee, Burdwan University, India
M. Nedil, Universit du Qubec, Canada
Kemal Ozdogan, Yildiz Technical University, Turkey
Liaqat Qureshi, University of Engineering and Technology, Pakistan
Michael Rajamathi, St. Josephs College, India
S. Rath, University of Delhi, India
James L. Reed, Northwestern University, USA
El Hadi Sadki, United Arab Emirates University, UAE
Patrik Schmuki, University of Erlangen Nuremberg, Germany
Muhammad Shahid, King Abdullah University of Science and Technology, Saudi Arabia
Dimtri Shtansky, National University of Science and Technology, Russia
Andrey L. Stepanov, Kazan State Technological University, Russia
N. Tabet, King Fahd King Fahd University of Petroleum and Minerals, Saudi Arabia
Bashir Tahir, Universiti Teknologi Malaysia, Malaysia
Muhammet Toprak, KTH Institute, Sweden
Jay Wadhawan, University of Hull, UK
Lon J. Wilson, Rice University, USA
Xing-Hua Xia, Nanjing University, China
Y. Yagoub, University of Ottawa, Canada
M. Zaabat, University of Oum El Bouaghi, Algeria
Zulkarnain Zainal, Universiti Putra Malaysia, Malaysia
Hadi Zareie, Gediz niversitesi, Turkey

List of Contributors

Assa, Brahim / MPB Technologies Inc., Canada . ........................................................................ 1, 108


Ali, Zahid / Sungkyunkwan University, Korea ................................................................................... 376
Al-Nashef, InasMuen / King Saud University, Saudi Arabia ............................................................ 376
Barbhuiya, Salim / Curtin University of Technology, Australia ........................................................ 164
Bayir, Ece / Ege University, Turkey .................................................................................................... 447
Benouaz, Tayeb / Tlemcen University, Algeria .................................................................................. 492
Bilgi, Eyup / Ege University, Turkey .................................................................................................. 447
Boukherroub, Rabah / Universit Lille 1, France .................................................................... 176, 196
Boumaza, Nawel / Tlemcen University, Algeria . ............................................................................... 492
Bououdina, Mohamed / University of Bahrain, Bahrain .................................................................. 312
Brimmo, Ayoola / Masdar Institute of Science and Technology, UAE .............................................. 268
Das, Manash R. / CSIR-North East Institute of Science and Technology, Jorhat, India ................... 196
Deshmukh, Ashvini B. / CSIR-National Chemical Laboratory, India .............................................. 196
Emziane, Mahieddine / Masdar Institute of Science and Technology, UAE . ........................... 226, 268
Fruchart, D. / CNRS de Grenoble, France ........................................................................................ 312
Goumri-Said, Souraya / King Abdullah University of Science and Technology (KAUST), Saudi
Arabia ................................................................................................................................... 431, 492
Guo, Z. X. / University College London, UK ..................................................................................... 312
Harruna, Issifu / Clark Atlanta University, USA . ............................................................................... 26
Hussain, Najrul / CSIR-North East Institute of Science and Technology, Jorhat, India ................... 196
Hussain, Rafaqat / Universiti Teknologi Malaysia, Malaysia ........................................................... 376
Kamaja, Chaitanya Krishna / National Chemical Laboratory (CSIR), India ................................. 176
Kang, DaeJoon / Sungkyunkwan University, Korea .......................................................................... 376
Kanoun, Mohammed Benali / King Abdullah University of Science and Technology (KAUST),
Saudi Arabia ................................................................................................................................. 431
Khayyat, Maha Mohamed / Umm al-Qura University, Saudi Arabia .......................................... 1, 108
Li, Huayang / Clark Atlanta University, USA ...................................................................................... 26
Li, Mingguang / Wayne State University, USA .................................................................................. 146
Melnyczuk, John M. / Clark Atlanta University, USA ........................................................................ 89
Nafady, Ayman / King Saud University, Saudi Arabia ...................................................................... 376
Palchoudhury, Soubantika / Yale University, USA . ........................................................................... 89
Penchovsky, Robert / Sofia University St. Kliment Ohridski, Bulgaria ........................................ 414
Rajaperumal, M. / National Chemical Laboratory (CSIR), India .................................................... 176
Rana, Usman Ali / King Saud University, Saudi Arabia ................................................................... 376
Roy, Manish / Defence Metallurgical Research Laboratory, India ..................................................... 62
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Sarfraz, Mansoor / King Saud University, Saudi Arabia .................................................................. 376


Shah, K. A. / Govt. Degree College for Women, Anantnag, India ..................................................... 131
Shah, M. A. / National Institute of Technology, Srinagar, India . ...................................................... 131
Shakir, Imran / Sungkyunkwan University, Korea & King Saud University, Saudi Arabia .............. 376
Sharma, Ponchami / CSIR-North East Institute of Science and Technology, Jorhat, India . ............ 196
Shelke, Manjusha V. / National Chemical Laboratory (CSIR), India ...................................... 176, 196
Souier, Tewfik / Masdar Institute of Science and Technology, UAE . ................................................ 343
Szunerits, Sabine / Institut de Recherche Interdisciplinaire Universit Lille 1, France .................... 196
Urkmez, Aylin Sendemir / Ege University, Turkey ........................................................................... 447
Walker, G. / University of Nottingham, UK ....................................................................................... 312
Yoosuf, Rahana / Masdar Institute of Science and Technology, UAE ............................................... 226
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Table of Contents

Preface .................................................................................................................................................. xx
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Chapter 1
Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures
Caused by Orbital Space Debris..............................................................................................................1
Brahim Assa, MPB Technologies Inc., Canada
Maha Mohamed Khayyat, Umm al-Qura University, Saudi Arabia
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Chapter 2
Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine and Terpyridine
Complex.................................................................................................................................................26
Huayang Li, Clark Atlanta University, USA
Issifu Harruna, Clark Atlanta University, USA
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Chapter 3
Nano Indentation Response of Various Thin Films Used for Tribological Applications......................62
Manish Roy, Defence Metallurgical Research Laboratory, India
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Chapter 4
Synthesis and Characterization of Iron Oxide Nanoparticles................................................................89
John M. Melnyczuk, Clark Atlanta University, USA
Soubantika Palchoudhury, Yale University, USA
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Chapter 5
Si-NWs: Major Advances in Synthesis and Applications...................................................................108
Maha Mohamed Khayyat, Umm al-Qura University, Saudi Arabia
Brahim Assa, MPB Technologies Inc., Canada
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Chapter 6
Principles of Raman Scattering in Carbon Nanotubes.........................................................................131
K. A. Shah, Govt. Degree College for Women, Anantnag, India
M. A. Shah, National Institute of Technology, Srinagar, India
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Chapter 7
Pharmacokinetics of Polymeric Nanoparticles at Whole Body, Organ, Cell, and Molecule .
Levels...................................................................................................................................................146
Mingguang Li, Wayne State University, USA
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Chapter 8
Applications of Nanomaterials in Construction Industry....................................................................164
Salim Barbhuiya, Curtin University of Technology, Australia
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Chapter 9
Silicon Nanostructures-Graphene Nanocomposites: Efficient Materials for Energy Conversion .
and Storage...........................................................................................................................................176
Chaitanya Krishna Kamaja, National Chemical Laboratory (CSIR), India
M. Rajaperumal, National Chemical Laboratory (CSIR), India
Rabah Boukherroub, Universit Lille 1, France
Manjusha V. Shelke, National Chemical Laboratory (CSIR), India
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Chapter 10
Metal Oxide-Graphene Nanocomposites: Synthesis to Applications..................................................196
Ponchami Sharma, CSIR-North East Institute of Science and Technology, Jorhat, India
Najrul Hussain, CSIR-North East Institute of Science and Technology, Jorhat, India
Manash R. Das, CSIR-North East Institute of Science and Technology, Jorhat, India
Ashvini B. Deshmukh, CSIR-National Chemical Laboratory, India
Manjusha V. Shelke, CSIR-National Chemical Laboratory, India
Sabine Szunerits, Institut de Recherche Interdisciplinaire Universit Lille 1, France
Rabah Boukherroub, Institut de Recherche Interdisciplinaire Universit Lille 1, France
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Chapter 11
In2X3 (X=S, Se, Te) Semiconductor Thin Films: Fabrication, Properties, and Applications..............226
Mahieddine Emziane, Masdar Institute of Science and Technology, UAE
Rahana Yoosuf, Masdar Institute of Science and Technology, UAE
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Chapter 12
Carbon Nanotubes for Photovoltaics....................................................................................................268
Ayoola Brimmo, Masdar Institute of Science and Technology, UAE
Mahieddine Emziane, Masdar Institute of Science and Technology, UAE
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Chapter 13
Overview on Hydrogen Absorbing Materials: Structure, Microstructure, and Physical .
Properties.............................................................................................................................................312
G. Walker, University of Nottingham, UK
Mohamed Bououdina, University of Bahrain, Bahrain
Z. X. Guo, University College London, UK
D. Fruchart, CNRS de Grenoble, France
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Chapter 14
Conductive Probe Microscopy Investigation of Electrical and Charge Transport in Advanced
Carbon Nanotubes and Nanofibers-Polymer Nanocomposites............................................................343
Tewfik Souier, Masdar Institute of Science and Technology, UAE
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Chapter 15
Nanostructured Materials for the Realization of Electrochemical Energy Storage and Conversion
Devices: Status and Prospects..............................................................................................................376
Imran Shakir, Sungkyunkwan University, Korea & King Saud University, Saudi Arabia
Zahid Ali, Sungkyunkwan University, Korea
Usman Ali Rana, King Saud University, Saudi Arabia
Ayman Nafady, King Saud University, Saudi Arabia
Mansoor Sarfraz, King Saud University, Saudi Arabia
InasMuen Al-Nashef, King Saud University, Saudi Arabia
Rafaqat Hussain, Universiti Teknologi Malaysia, Malaysia
DaeJoon Kang, Sungkyunkwan University, Korea
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Chapter 16
Nucleic Acids-Based Nanotechnology: Engineering Principals and Applications.............................414
Robert Penchovsky, Sofia University St. Kliment Ohridski, Bulgaria
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Chapter 17
Theoretical Assessment of the Mechanical, Electronic, and Vibrational Properties of the
Paramagnetic Insulating Cerium Dioxide and Investigation of Intrinsic Defects................................431
Mohammed Benali Kanoun, King Abdullah University of Science and Technology (KAUST),
Saudi Arabia
Souraya Goumri-Said, King Abdullah University of Science and Technology (KAUST), Saudi
Arabia
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Chapter 18
Implementation of Nanoparticles in Cancer Therapy..........................................................................447
Ece Bayir, Ege University, Turkey
Eyup Bilgi, Ege University, Turkey
Aylin Sendemir Urkmez, Ege University, Turkey
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Chapter 19
Understanding the Numerical Resolution of Perturbed Soliton Propagation in Single Mode
Optical Fiber........................................................................................................................................492
Nawel Boumaza, Tlemcen University, Algeria
Tayeb Benouaz, Tlemcen University, Algeria
Souraya Goumri-Said, King Abdullah University of Science and Technology (KAUST), Saudi
Arabia
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Compilation of References . .............................................................................................................. 505


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About the Contributors .................................................................................................................... 605


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Index ................................................................................................................................................... 615


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Detailed Table of Contents

Preface .................................................................................................................................................. xx
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Chapter 1
Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures
Caused by Orbital Space Debris..............................................................................................................1
Brahim Assa, MPB Technologies Inc., Canada
Maha Mohamed Khayyat, Umm al-Qura University, Saudi Arabia
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The presence in space of orbital debris, particularly in low earth orbit, presents a continuous hazard
to orbiting satellites and spacecrafts. The development of self-healing materials offers the designer an
ability to incorporate secondary functional materials capable of counteracting service degradation whilst
still achieving the primary, usually structural, requirement. This chapter reviews the various self-healing
technologies currently being developed. Self-healing systems can be made from a variety of polymers and
metallic materials. An overview of various self-healing concepts over the past two decades is presented.
Finally, a perspective on current and future self-healing approaches using this biomimetic technique is
offered. The intention is to stimulate debate and reinforce the importance of a multidisciplinary approach
in this exciting field.
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Chapter 2
Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine and Terpyridine
Complex.................................................................................................................................................26
Huayang Li, Clark Atlanta University, USA
Issifu Harruna, Clark Atlanta University, USA
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Ruthenium bipyridine or terpyridine complexes functionalized carbon-based nanocomposites have special


properties in the electromagnetic and photochemical research field. The aims of this chapter include
development of functionalized fullerene, carbon nanotubes, and graphene with ruthenium complex and
characterization of their nanostructural properties. Such nanocomposites can be accomplished using
either covalent or non-covalent functionalization methods.
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Chapter 3
Nano Indentation Response of Various Thin Films Used for Tribological Applications......................62
Manish Roy, Defence Metallurgical Research Laboratory, India
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Various thin films used for tribological applications are classified under four heads. Based on their load
vs. displacement curves, which have some characteristics features, the ratio of nanohardness to elastic
modulus and the ratio of cube of nanohardness to square of elastic modulus are evaluated in this chapter.
It is demonstrated that depending on the type of film used, these ratios vary within a certain range. For
soft self-lubricating films, these ratios are very low; whereas for hard self-lubricating film, these ratios
are quite high.
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Chapter 4
Synthesis and Characterization of Iron Oxide Nanoparticles................................................................89
John M. Melnyczuk, Clark Atlanta University, USA
Soubantika Palchoudhury, Yale University, USA
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Iron oxide nanoparticles show great promise in bio-applications like drug delivery, magnetic resonance
imaging, and hyperthermia. This is because the size of these magnetic nanoparticles is comparable to
biomolecules and the particles can be removed via normal iron metabolic pathways. These nanoparticles
are also attractive for industrial separations and catalysis because they can be magnetically recovered.
However, the size, morphology, and surface coating of the iron oxide nanoparticles greatly affect their
magnetic properties and biocompatibility. Therefore, nanoparticles with tunable characteristics are
desirable. This chapter elaborates the synthesis techniques for the formation of iron oxide nanoparticles
with good control over reproducibility, surface and magnetic properties, and morphology. The wellknown co-precipitation and thermal decomposition methods are detailed in this chapter. The surface
modification routes and characterization of these nanoparticles are also discussed. The chapter will be
particularly useful for engineering/science graduate students and/or faculty interested in synthesizing
iron oxide nanoparticles for specific research applications.
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Chapter 5
Si-NWs: Major Advances in Synthesis and Applications...................................................................108
Maha Mohamed Khayyat, Umm al-Qura University, Saudi Arabia
Brahim Assa, MPB Technologies Inc., Canada
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Surfaces and interfaces have a special significance to nanotechnology because the surface/volume
ratio of nanomaterials is larger than for the bulk ones. Therefore, interfaces of nanomaterials are more
important to the properties of the nanomaterials than for larger scale materials. Moreover, crystal growth
and more particularly Nanowires (NWs) growth occurs at the interfaces between the growing crystals
and the supply media. This chapter focuses on the silicon nanowires grown using a Vapor-Liquid-Solid
(VLS) concept. One of the key advantages of VLS is that controlled placement or templating of the
seed metal produces templated NW growth. This templating is required for integration of NWs with
other devices, which is desirable for many applications. The authors discuss issues on the discovery of
fundamentally new phenomena versus performance benchmarking for many of the Si-NW applications.
Finally, the authors attempt to look into the future and offer their personal opinions on the upcoming
trends in nanowire research.
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Chapter 6
Principles of Raman Scattering in Carbon Nanotubes.........................................................................131
K. A. Shah, Govt. Degree College for Women, Anantnag, India
M. A. Shah, National Institute of Technology, Srinagar, India
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Carbon nanotubes have attracted the scientific community throughout the world, and in the past decade, a
lot of work has been reported related with synthesis, characterization, and applications of carbon nanotubes.
This chapter is written for readers who are not familiar with the basic principles of Raman spectroscopy
in carbon nanotubes. The structure of carbon nanotubes, types of the carbon nanotubes, Brillouin zone
of carbon nanotubes, and band structure of carbon nanotubes are discussed at length, which will serve
as foundation for the study of Raman scattering in carbon nanotubes. The Density of States (DOS) of
single walled carbon nanotubes are illustrated by an example which will encourage readers to calculate
the DOS of any type of carbon nanotube. The Raman modes of vibration are discussed, and Raman
spectroscopic analysis is presented by considering the typical spectra of single-walled carbon nanotubes.
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Chapter 7
Pharmacokinetics of Polymeric Nanoparticles at Whole Body, Organ, Cell, and Molecule .
Levels...................................................................................................................................................146
Mingguang Li, Wayne State University, USA
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Polymeric nanoparticles have been increasingly studied and applied in a variety of areas, most commonly
in biomedicine. The efficiency and toxicity are two aspects that need to be considered for nanoparticles,
and both are closely related to the pharmacokinetics of nanoparticles. In this chapter, the pharmacokinetics
of polymeric nanoparticles were introduced at the whole body level (including absorption, distribution,
metabolism, and excretion), organism level (transportation within organs and pass through physiological
barriers), cell levels (binding to cell surface, endocytosis, intracellular transition, and exocytosis), and
molecule level (protein binding and ligand-receptor binding). Examples were also given to illustrate
the modeling of the pharmacokinetics of polymeric nanoparticles at different levels. A comprehensive
understanding of the pharmacokinetics of polymeric nanoparticles will facilitate the applications in
various areas such as drug delivery and disease diagnosis.
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Chapter 8
Applications of Nanomaterials in Construction Industry....................................................................164
Salim Barbhuiya, Curtin University of Technology, Australia
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The application of nanomaterials in various applied fields has gained worldwide recognition. Nanomaterials
have the ability to manipulate the structure at nano-scale. This leads to the generation of tailored and
multifunctional composites with improved mechanical and durability performance. Recognizing this, the
construction industry recently has started to use a variety of nanomaterials. The use of these materials is
found to improve various fundamental characteristics of construction materials including the strength,
durability, and lightness. In this chapter an attempt is made to review the use of various nanomaterials
in cementitous system. This is followed by a discussion of the challenges related to their use. Finally,
the strategies for using nanomaterials in construction industry for the next ten years are identified.
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Chapter 9
Silicon Nanostructures-Graphene Nanocomposites: Efficient Materials for Energy Conversion .
and Storage...........................................................................................................................................176
Chaitanya Krishna Kamaja, National Chemical Laboratory (CSIR), India
M. Rajaperumal, National Chemical Laboratory (CSIR), India
Rabah Boukherroub, Universit Lille 1, France
Manjusha V. Shelke, National Chemical Laboratory (CSIR), India
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Global demand of energy is increasing at an alarming rate, and nanotechnology is being looked at as a
potential solution to meet this challenge (Holtren, 2007). Although the efficiency of energy conversion and
storage devices depends on a variety of factors, the overall performance strongly relies on the structure
and properties of the component materials (Whitesides, 2007). Compared to conventional materials,
silicon (Si) nanostructures and graphene nanosheets possess unique properties (i.e. morphological,
electrical, optical, and mechanical) useful for enhancing the energy-conversion and storage performances.
Graphene can enhance efficiency of nano-Si based solar cells and battery due to its high electronic
conductivity, ultrahigh mobility, high transparency, and strong mechanical property. This chapter provides
a comprehensive review of recent progress and material challenges in energy conversion (solar cells)
and storage (batteries/supercapacitors) with specific focus on composites of Si nanostructures-graphene
nanosheets.
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Chapter 10
Metal Oxide-Graphene Nanocomposites: Synthesis to Applications..................................................196
Ponchami Sharma, CSIR-North East Institute of Science and Technology, Jorhat, India
Najrul Hussain, CSIR-North East Institute of Science and Technology, Jorhat, India
Manash R. Das, CSIR-North East Institute of Science and Technology, Jorhat, India
Ashvini B. Deshmukh, CSIR-National Chemical Laboratory, India
Manjusha V. Shelke, CSIR-National Chemical Laboratory, India
Sabine Szunerits, Institut de Recherche Interdisciplinaire Universit Lille 1, France
Rabah Boukherroub, Institut de Recherche Interdisciplinaire Universit Lille 1, France
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Graphene is one of the most interesting materials in the field of nanoscience and nanotechnology. Metal
oxide nanoparticles exhibit unique physical and chemical properties due to their reduced size and high
density of corner or edge surface sites. The metal oxide-graphene nanocomposites not only possess
favorable properties of graphene and metal oxide, but also greatly enhance the intrinsic properties due
to the synergistic effect between them. These composites are used for catalysis, supercapacitors, lithium
ion batteries, solar cells, sensors, removal of pollutants from water, etc. There is a very broad scope of
further research for the development of metal oxide-graphene nanocomposites with enhanced properties
for different applications. This chapter deals with a comprehensive review of the current research
activities from the viewpoint of chemistry and materials science with a special focus on the synthesis,
characterization, and applications of metal oxide-graphene nanocomposite materials.
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Chapter 11
In2X3 (X=S, Se, Te) Semiconductor Thin Films: Fabrication, Properties, and Applications..............226
Mahieddine Emziane, Masdar Institute of Science and Technology, UAE
Rahana Yoosuf, Masdar Institute of Science and Technology, UAE
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Indium chalcogenide thin film semiconductor compounds In2X3 (with X being a chalcogen atom, i.e., S,
Se, or Te) are important materials in many current technological applications such as solar cells, microbatteries, memory devices, etc. This chapter reviews the recent progress in In2X3 (X = S, Se, or Te) thin
film research and development, with a particular attention paid to their growth and processing methods and
parameters, and the effects that these have on the films microstructure. The intimate relationship between
their fabrication conditions and the resulting physico-chemical and functional properties is discussed.
Finally, results pertaining to the fabrication and characterization of these thin film materials, as well
as the main devices and applications based on them are also highlighted and discussed in this chapter.
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Chapter 12
Carbon Nanotubes for Photovoltaics....................................................................................................268
Ayoola Brimmo, Masdar Institute of Science and Technology, UAE
Mahieddine Emziane, Masdar Institute of Science and Technology, UAE
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Recent developments show that the exceptional physical, optical, and electrical properties of Carbon
Nanotubes (CNTs) have now caught the attention of the Photovoltaics (PV) industry. This chapter
provides an updated and in-depth review of some of the most exciting and important developments in the
application of CNTs in photovoltaics. The chapter begins with a discussion of the underlying properties
of CNTs that make them promising for PV applications. A review of the literature on the application
of CNTs in the photoactive layer of Silicon (Si)-based heterojunctions, as anchors for light harvesting
materials in Dye Sensitized Solar Cells (DSSCs) and as components of other organic solar cells (OPVs),
is then presented. Findings portend the promise of CNTs in bridging the gap between the two classes of
solar cells currently in the market. Since the technology is in its early stages, it is generally limited by a
general lack of understanding of CNTs and their adequate growth mechanisms.
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Chapter 13
Overview on Hydrogen Absorbing Materials: Structure, Microstructure, and Physical .
Properties.............................................................................................................................................312
G. Walker, University of Nottingham, UK
Mohamed Bououdina, University of Bahrain, Bahrain
Z. X. Guo, University College London, UK
D. Fruchart, CNRS de Grenoble, France
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Hydrogen is a promising and clean fuel for transportation and domestic applications, but is difficult to
store. Many systems have been investigated in order to improve the maximum hydrogen storage capacity
(reversibility), high kinetics, moderate equilibrium pressure and/or decomposition temperature, and better
cyclability. In this chapter, a review of studies related to stability of Zr-based Laves phase system as
well as in-situ neutron diffraction investigation, the kinetics of TiFe, surface treatment of LaNi5 system,
mechanically alloyed Mg-based hydrides, and graphite nanofibers are reported.
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Chapter 14
Conductive Probe Microscopy Investigation of Electrical and Charge Transport in Advanced
Carbon Nanotubes and Nanofibers-Polymer Nanocomposites............................................................343
Tewfik Souier, Masdar Institute of Science and Technology, UAE
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In this chapter, the main scanning probe microscopy-based methods to measure the transport properties in
advanced polymer-Carbon Nanotubes (CNT) nanocomposites are presented. The two major approaches
to investigate the electrical and charge transport (i.e., Electrostatic Force Microscopy [EFM] and CurrentSensing Atomic Force Microscopy [CS-AFM]) are illustrated, starting from their basic principles. First,
the authors show how the EFM-related techniques can be used to provide, at high spatial resolution,
a three-dimensional representation CNT networks underneath the surface. This allows the studying of
the role of nanoscopic features such as CNTs, CNT-CNT direct contact, and polymer-CNT junctions
in determining the overall composite properties. Complementary, CS-AFM can bring insight into
the transport mechanism by imaging the spatial distribution of currents percolation paths within the
nanocomposite. Finally, the authors show how the CS-AFM can be used to quantify the surface/bulk
percolation probability and the nanoscopic electrical conductivity, which allows one to predict the
macroscopic percolation model.
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Chapter 15
Nanostructured Materials for the Realization of Electrochemical Energy Storage and Conversion
Devices: Status and Prospects..............................................................................................................376
Imran Shakir, Sungkyunkwan University, Korea & King Saud University, Saudi Arabia
Zahid Ali, Sungkyunkwan University, Korea
Usman Ali Rana, King Saud University, Saudi Arabia
Ayman Nafady, King Saud University, Saudi Arabia
Mansoor Sarfraz, King Saud University, Saudi Arabia
InasMuen Al-Nashef, King Saud University, Saudi Arabia
Rafaqat Hussain, Universiti Teknologi Malaysia, Malaysia
DaeJoon Kang, Sungkyunkwan University, Korea
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One of the greatest challenges for the modern world is the ever-increasing demand of energy, which
may soon outstrip the amount of natural resources that can be obtained using currently known energy
conversion and energy storage technologies such as solar cells, fuel cells, lithium ion batteries, and
supercapacitors. It appears that the maximum output efficiencies of these devices have already reached
the intrinsic limits of almost all electrocatalyst materials. Hence, it is a high time to think about new
material architectures by controlling size, shape, and geometry, as well as composition that can potentially
make a significant improvement in the performance of these electrochemical devices. Among several
known electrocatalyst materials are nanomaterials and their composites due to their unique electrical,
mechanical, physical, chemical, and structural characteristics. These materials have opened a whole
new territory of possibilities in designing high performance energy storage and conversion devices. In
this chapter, the authors review the recent progress in energy storage and conversion devices that utilize
various nanomaterials and their composite materials and identify future directions in which the field is
likely to develop.
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Chapter 16
Nucleic Acids-Based Nanotechnology: Engineering Principals and Applications.............................414
Robert Penchovsky, Sofia University St. Kliment Ohridski, Bulgaria
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Nanobiotechnology is emerging as a valuable field that integrates research from science and technology
to create novel nanodevices and nanostructures with various applications in modern nanotechnology.
Applications of nanobiotechnology are employed in biomedical and pharmaceutical research, biosensoring,
nanofluidics, self-assembly of nanostructures, nanopharmaceutics, molecular computing, and others. It
has been proven that nucleic acids are a very suitable medium for self-assembly of diverse nanostructures
and catalytic nanodevices for various applications. In this chapter, the authors discuss various applications
of nucleic-based nanotechnology. The areas discussed here include building nanostructures using DNA
oligonucleodite, self-assembly of integrated RNA-based nanodevices for molecular computing and
diagnostics, antibacterial drug discovery, exogenous control of gene expression, and gene silencing.
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Chapter 17
Theoretical Assessment of the Mechanical, Electronic, and Vibrational Properties of the
Paramagnetic Insulating Cerium Dioxide and Investigation of Intrinsic Defects................................431
Mohammed Benali Kanoun, King Abdullah University of Science and Technology (KAUST),
Saudi Arabia
Souraya Goumri-Said, King Abdullah University of Science and Technology (KAUST), Saudi
Arabia
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First-principles calculations are performed by taking into account the strong correlation effects on ceria. To
obtain an accurate description including f electrons, the authors optimized the Coulomb U parameter for
use in Local-Density Approximation (LDA) and Generalized Gradient Approximation (GGA) calculation.
A good agreement with experimental data is obtained within the GGA+U (Wu-Cohen scheme). Elastic
stiffness constants are found in correct agreement with the available experimental results. Born effective
charge, dielectric permittivity, and the phonon-dispersion curves are computed using density functional
perturbation theory. The origin of magnetism in undoped ceria with intrinsic defects is investigated.
The authors show that both of Ce and O vacancies induce local moments and ferromagnetism without
doping ceria by magnetic impurities in this chapter.
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Chapter 18
Implementation of Nanoparticles in Cancer Therapy..........................................................................447
Ece Bayir, Ege University, Turkey
Eyup Bilgi, Ege University, Turkey
Aylin Sendemir Urkmez, Ege University, Turkey
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Cancer is a wide group of diseases and generally characterized by uncontrolled proliferation of cells
whose metabolic activities are disrupted. Conventionally, chemotherapy, radiotherapy, and surgery are
used in the treatment of cancer. However, in theory, even a single cancer cell may trigger recurrence.
Therefore, these treatments cannot provide high survival rate for deadly types. Identification of alternative
methods in treatment of cancers is inevitable because of adverse effects of conventional methods. In
the last few decades, nanotechnology developed by scientists working in different disciplinesphysics,
chemistry, and biologyoffers great opportunities. It is providing elimination of both circulating tumor
cells and solid cancer cells by targeting cancer cells. In this chapter, inadequate parts of conventional
treatment methods, nanoparticle types used in new treatment methods of cancer, and targeting methods
of nanoparticles are summarized; furthermore, recommendations of future are provided.
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Chapter 19
Understanding the Numerical Resolution of Perturbed Soliton Propagation in Single Mode
Optical Fiber........................................................................................................................................492
Nawel Boumaza, Tlemcen University, Algeria
Tayeb Benouaz, Tlemcen University, Algeria
Souraya Goumri-Said, King Abdullah University of Science and Technology (KAUST), Saudi
Arabia
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The authors solve the propagation soliton perturbation problem in a nonlinear optical system based on a
single mode optical fiber by introducing Rayleighs dissipation function in the framework of variational
approach. The adopted methodology has facilitated the variational approach to be applied on a dissipative
system where the Lagrangian and Hamiltonian are difficult to solve. The authors model the propagation
in a nonlinear medium by using a nonlinear Schrdinger equation (NLSE). This is a mathematical model
used to describe the optical fiber. The chapter is focused on the propagation of perturbed solitary waves
in single mode fiber.
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Compilation of References . .............................................................................................................. 505


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About the Contributors .................................................................................................................... 605


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Index ................................................................................................................................................... 615


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xx

Preface

Nanoscience has been defined as the manipulation of matter as the nanoscale, as well as the discovery
of new nanomaterials with fascinating properties (mechanical, electrical, optical, thermal, catalytic, etc.)
and performances due to the quantum size effect, whereas Nanotechnology deals with the manufacturing of nanodevices. Nanotechnology offers a broad range of technological applications and industries
including semiconductors, auto and aerospace, pharmaceutical and biomedical, cosmetics, biotechnology,
energy and environment, food, forensic, military, etc. Known as the 5th industrial revolution, it has and
continues to attract a large number of scientists worldwide. It is reported that by 2015, Nanotechnology
may spawn a $ 1 trillion market and the job projection is around two million with additional 5 million
jobs in support industries. Additionally, the emergence of Nanotechnology has created a new dynamism
in our scientific and academic world: (1) drastic increase of the research funds towards nanotechnology
and national nanotechnology initiatives were developed by many countries; (2) the number of conferences
and publications (papers, books, proceedings) has increased drastically due to the extensive research
work carried out by the researchers; (3) new established academic programs at all levels; (4) new courses
and disciplines emerged including nano-chemistry, nano-physics, nano-biotechnology, nano-medicine,
nano-engineering, nano-ethics, etc; (5) commercialization of new products and the establishment of
new technologies and industries based on nanotechnology leading to the creation of new and important
number of jobs, which will have great effects on the future of global economy; (6) new journals and
books which attract a wide and large audience; etc.
The handbook consists of 2 volumes with a total number of 19 chapters covering a wide range of
topics from point of view experimental, fundamental, and applications view, written by experts and
eminent scientists in each field.
This handbook will present experimental and fundamental approaches and in depth understanding
of the chemical/physical/mechanical/electrical/biological/etc. properties of nanostructured/advanced
materials followed by some potential applications in biomedical field, renewable energy, semiconductors industry, etc. In addition, it will promote the emerging field of nanotechnology in various science
and engineering disciplines.
This handbook contains various hot topics related to energy conversion and storage, biomedical
field, semiconductors, construction, telecommunication, etc., and thus will target a large audience such
as academics, scientists, post-graduates students, engineers, etc.
The first chapter Self-Healing Materials Systems as a Way for Damage Mitigation in Composites
Structures Caused by Orbital Space Debris, consists of a review on materials self-healing when subjected
to any chemical or/and mechanical or/and thermal, etc. It contains some important concepts (such as
quantification of healing efficiency which can be assessed by various tests such as Fatigue, Tear, etc.)

xxi

and presents some self-healing systems including thermoplastic and thermosetting materials then coating systems for metallic structures, etc. The new concept/property of self-healing being considered in
engineering applications is incorporated as during the design and manufacturing of materials, thus adding
new functionality of self-repair for counteracting service degradation. Additionally, it was reported that
self-healing results in increasing material lifetime, reducing replacement costs, and improving product
safety. In terms of self-healing systems, a variety of polymers and metallic material can be used.
Chapter 2 is devoted to the study of functionalisation of carbon (fullerene, carbon nanotubes, graphene)based nanocomposites by ruthenium (Ru-bipyridine and Ru-terpyridine)-based complexes. This type
of material shows some particular catalytic, electrochemical, or magnetic properties, and offers some
potential applications in energy storage, biochemical sensors, photo-induced mechanical actuation, etc.
The chapter focuses the synthesis methods of Bipyridine/Terpyridine ligands followed by Complexation
with a metal center then Polymerization. After that, it presents the design of organic terpyridine Ligand
spacer and polymerization complex for Nanohybrid; then it gives a detailed overview on the functionalization (non-covalent and covalent) of some carbon nanostructures such as fullerene, carbon nanotubes,
and graphene, with Ru bipyridine and terpyridine complexes and finally self-assembly of Ru-terpyridine
metal-connected diblock metallopolymers on graphene nanoribbons.
Chapter 3, Nano Indentation Response of Various Thin Films Used for Tribological Applications,
addresses on of the most powerful technique to investigate the mechanical properties of nanostrucred
materials. The author focused particularly on three materials, where a detailed study is presented: (1)
ZrN films showing better corrosion resistance, improved mechanical properties, and warm golden color,
thus very suitable for tribology applications; (2) amorphous carbon (a-C) known as Diamond-Like
Carbon (DLC) and hydrogenated a-C:H films show the combination of some useful properties such
as high nanohardness, good thermal conductivity, low friction coefficient, excellent wear resistance,
ultra-smoothness, and chemical inertness (applications as magnetic hard disc, MEMS, biocompatible
coating, etc.); and (3) W-S-C films with a nanocomposite structure and showing reasonable nanohardness
and low friction coefficient, offering some potential applications such as space-related technologies, in
vacuum or in aggressive environment. It was found that H/E and H3/E2 ratios are considered as important
parameters for coatings (H: nanohardness; E: elastic modulus).
Chapter 4, Synthesis and Characterization of Iron Oxide Nanoparticles, covers various aspect of
Fe oxides including: (1) crystal structure and properties; (2) synthesis of different morphologies (nanospheres, nanowhiskers, nanocubes, nanoplates, nanoflowers, etc) using various methods; (3) dispersion
and functionalisation of NPs using chemical processes such as ligand exchange, lipid encapsulation,
polymer encapsulation, etc.; and (4) characterizations. Finally, some potential applications are presented.
Chapter 5, Si-NWs: Major Advances in Synthesis and Applications, is devoted to Si nanowires due
to their potential and broad applications including the fabrication of integrated circuit, DNA sensors,
array-based electrical and electrochemical systems, vertical surround-gate field effect transistor, high
resolution Atomic Force Microscope, etc. The authors discussed some synthesis aspects of Si-NWs
(lithography, physical, or chemical vapor deposition PVD or CVD methods, etc.) where a particular
emphasis on catalyst role during Vapor-Liquid-Solid (VLS) growth mechanism. After that, Nanoscale
Chemical Templating (NCT) using oxygen reactive materials was presented in detail followed by some
potential applications of Si-NWs such as high-resolution AFM tips, photovoltaic cells, thermoelectric
devices, and sensors to end up giving directions for future research on Si-NWs.
Chapter 6, Principles of Raman Scattering in Carbon Nanotubes, presents background and in-depth
theoretical study of carbon nanostructures (nanotubes-CNTs, nanofibers-CNFs, graphene-G) properties

xxii

then focusing mainly on CNTs. It presents crystal structure and Brillouin zone, electronic band structure,
and electronic Density Of States (DOS), which represent the backbone to access vibrational properties
through Raman spectroscopy technique.
Chapter 7, Pharmacokinetics of Polymeric Nanoparticles at Whole Body, Organ, Cell, and Molecule
Levels, deals with an important and crucial aspect of using Nanoparticles (NPs) for the biomedical
field in terms of interaction at different levels. It starts by discussing the fate of NPs in the human body
including efficiency and toxicity (which are strongly dependent on NPs shape, size, surface charge
modifications, chemical composition, etc.), through ADME (Absorption, Distribution, Metabolism, and
Excretion). Both experimental and modeling of pharmacokinetic of polymeric NPs have been presented.
Then, pharmacokinetics at different levels of interaction inside the body was discussed from point of
view of: (1) organ and sub-organ (lung, physiological, and biological barriers, tumor); (2) at cellular and
sub-cellular level (cell surface binding, cellular uptake [endocytosis] kinetics, intracellular traffic and
biotransformation kinetics, exocytosis kinetics); (3) at molecular level (protein binding, ligand-targeting).
Chapter 8, Applications of Nanomaterials in Construction Industry, presents a short overview of
the potential and challenging applications of Nanotechnology in some areas of construction industry. In
recent years, some studies devoted to the construction industry report on some interesting results such
as: (1) nanoparticles (Zn, Sio2, Fe2O3, and halloysite clay) were embedded into a commercial epoxy resin
for the enhancement of mechanical and chemical properties; (2) nano-SiO2 was investigated as additive
to cementation system, as well as nano-Fe2O3 and nano-Al2O3; (3) nano-TiO2 has been reported to produce self-cleaning and depolluting concrete as well as on roadway for pollution reduction; and (4)
Carbon Nanotubes/Nanofibres (CNTs/CNFs) as potential candidates for use as nano-reinforcements in
cement-based materials. Then the author discusses the challenges related to the use of nanomaterials as
well as strategies for using then for the next ten years with some concluding remarks.
Chapter 9, Silicon Nanostructures-Graphene Nanocomposites: Efficient Materials for Energy
Conversion and Storage, starts by highlighting energy resources/demand and that renewable energies
represent only 16% (mainly solar), as well as some background about some fundamental concepts of
solar cells energy efficiency and graphene as a potential material for energy conversion/storage. Then a
particular focus on the potential use of Si-graphene for energy conversion and stirage, Si-NWs/graphene
heterojunction device for photoelectrochemical water splitting, Si-nanostructures/graphene as anode
for Li-ion batteries showing high reversible discharge capacity, and supercapcitors. Finally, the authors
presents various methods for the preparation of various Si (NPs, NWs)/Graphene nanocomposites.
Due to the importance of graphene, Chapter 10, Metal Oxide-Graphene Nanocomposites: Synthesis
to Applications, was dedicated to metal oxides / graphene composites due to their potential application.
Several oxides / methods were presented: in-situ techniques such as precipitation (Fe3O4, CuO); sol-gel
(TiO2); hydrothermal/solvothermal (ZnO); photo-assisted reduction (TiO2); microwave-assisted synthesis
(Fe3O4 and Co3O4); atomic layer deposition (TiO2); followed by ex-situ methods such as layer-by-layer
self-assembly (TiO); etc. Then, the authors presented some potential applications of MO/graphene nanocomposites including Li-ion battery, supercapacitors, water purification, photovoltaic cells, biomedicine,
and end by giving some future research directions.
Chapter 11, In2X3 (X=S, Se, Te) Semiconductor Thin Films: Fabrication, Properties, and Applications,
presents a review on the recent progress on Indium chalcogenide thin film semiconductor compounds as
potential candidates as window/buffer-layer for photovoltaic devices. The authors discuss in more detail
the evolution of structure and microstructure as well as optical/electrical properties modifications due to
the deposition method (metal-organic chemical vapor deposition, atomic layer chemical vapor deposi-

xxiii

tion, chemical bath deposition, spray pyrolysis, molecular beam epitaxy, etc.); the effect of deposition
parameters (temperature, time, pH of the solution, type of substrate, etc.); and post-deposition treatment.
Then a particular interest is devoted to the synthesis, characterizations and properties of some selected
compounds including In2Se3, In2Te3, In2S3 then ternary compounds such as In2Se3-xTex.
Chapter 12, Carbon Nanotubes for Photovoltaics, reports an in-depth review about the use of CNTs
for PV. After introducing the outstanding physical properties of CNTs, the authors present some potential
applications of CNTs in various PV/DSSS/OPV: CNT-Si hetero-junction solar cells based on aligned
CNTs and Si-NWs, as well as some PV simulations based on molecular dynamics; Dye Sensitized Solar
Cell (DSSC) where CNTs replace Pt as CNT as counter electrode; incorporating CNT networks in the
cells conducting electrode to promote charge transport in the TiO2 layer, CNT as Transparent Conducting
Oxide (TCO) layer which is usually Indium Tin Oxide (ITO) in DSSC; and CNTs in Organic PV devices
(OPV). After that, the authors discuss a very important aspect of PV, trends to improve the efficiency,
followed by a discussion and some recommendations and concluding remarks.
Chapter 13, Overview on Hydrogen Absorbing Materials: Structure, Microstructure, and Physical
Properties, presents some important aspect of hydrogen storage in materials. The authors start by giving some fundamental background on hydrogen storage, thermodynamics, and kinetics, properties, and
mechanisms. Then a particular focus is devoted to some potential materials including: binary hydrides;
intermetallics (LaNi5, FeTi, Laves phases AB2); Mg-based materials; amorphous alloys; quasicrystals;
carbon nanostcuctures (nanofibers); light complex hydrides based on alkali-metals (Li, Na, Al, B); rareearth based hydrides thin films with optical switchable properties; and zeolites.
Chapter 14, Conductive Probe Microscopy Investigation of Electrical and Charge Transport in
Advanced Carbon Nanotubes and Nanofibers-Polymer Nanocomposites, is devoted to the fundamental
and some experimental aspects to access some properties of CNTs-Polymer nanocomposites by using
some advanced probe microscopies such as Atomic Force Microscopy (AFM); Electrostatic Force Microscopy (EFM); Current-Sensing Atomic Force Microscopy (CS-AFM). After that, a particular focus
is dedicated to DC(AC)-EFM imaging of embedded CNT-polymer nanocomposites films, followed by a
CS-AFM investigation of bulk and surface percolation as well as electrical conductivity measurements.
Chapter 15, Nanostructured Materials for the Realization of Electrochemical Energy Storage and
Conversion Devices: Status and Prospects, presents an interesting overview on some nanomaterials as
potential candidates for energy conversion and storage. After a good introduction related to fundamental
aspects of electrochemical energy storage, the authors discuss each application separately: (1) nanocatalysts (Pt, Pt-M core-shell, Pt3M, graphite-C3N4, etc.) for fuel cells; (2) photoelectrochemical water
splitting (such as nanocrystalline -Fe2O3 and nano-CdSe); (3) dye-sensitized solar cells DSSCs (oxide
semiconductors like TiO2/ZnO/SnO, nanoporous film coated with oxides Al2O3/SnO2/ZrO2/SrTiO3/ZnO,
etc.); cathode for Li-ion batteries (such as LiMO2 and spinel-type LiM2O4 where M=Co, Mn, etc.); and
anode for Li-ion batteries (graphite, Li2Si5).
Chapter 16, Nucleic Acids Based Nanotechnology: Engineering Principals and Applications,
focuses on the engineering of functional systems at the molecular level offering potential applications
such as molecular sensors, actuators, drug delivery devices, etc. After a good introduction on some very
important aspects such as nanobiotechnology, nanomedicine, etc., the author presents in more detail some
applications such as: (1) passive nanostructures based on DNA using self-assembly; (2) engineering active
nanostructures based on allosteric ribozymes; (3) RNA-based nanocircuits; (4) integrated RNA-based
nanodevices with a complex logic function as a tool for molecular diagnostics; (5) allosteric ribozymes as

xxiv

designer cis-acting gene control elements; and (6) gene silencing techniques via trans-acting ribozymes
to end up with some future research work in this field.
Chapter 17, Theoretical Assessment of the Mechanical, Electronic, and Vibrational Properties of the
Paramagnetic Insulating Cerium Dioxide and Investigation of Intrinsic Defects, presents a very detailed
study of some properties (ground-state properties, elastic stiffness constants, and electronic structure with
the inclusion of on-site Coulomb interaction, dielectric properties, lattice dynamic, and thermodynamic
properties) of CeO2 by ab-initio calculations (calculations based on Density Functional Theory [DFT]
as implemented in WIEN2K and CASTEP packages). A particular focus is dedicated to investigate the
presence of intrinsic defects (oxygen or cerium vacancies) in un-doped CeO2 (cubic structure of CaF2,
pace group Fm-3m) to create ferromagnetic behavior.
Chapter 18, Implementation of Nanoparticles in Cancer Therapy, is devoted to the application of
nanotechnology in the biomedical field. The authors start by stating conventional method used for cancer therapy (surgery, radiotherapy, chemotherapy, etc.) then present how Nanoparticles (NPs) present a
potential alternative. Then some general fundamental/experimental aspects related to some selected NPs
that are used in drug delivery and targeting in cancer therapy are presented, including Polymeric NPs,
Liposomal NPs, Dendrimer NPs, Protein NPs, Polymersome NPs, Inorganic NPs, etc. Additionally, the
authors discuss NP toxicity and safety, followed by some major cancer targets for NPs systems (including
cell marker targeting via antibodies, targeting signaling pathways, niche targeting, angiogenesis-associated
targeting) as well as targeting schemes (including passive, active, and triggered targeting), and end with
nanoparticle-mediated gene therapy with future research perspectives.
Chapter 19, Understanding the Numerical Resolution of Perturbed Soliton Propagation in Single
Mode Optical Fiber, deals with an important matter related to optical fibers used for telecommunications such as terrestrial broadcasting by a fundamental approach: how to reduce the noise to acceptable
levels by acting on device parameters such as the structure of the fiber device. Then, the authors present
a detailed theoretical background to study soliton propagation in a mono-modal optical fiber followed
by frequency domain filter system, which allow one to create a model followed by simulations using
numerical models that allow one to understand the behavior of solitons.
This handbook presents the recent advances and future prospects of several nanotechnology applications. In addition, it highlights various technological applications in biomedical, renewable energy,
electronics, etc., which will improve future life by offering solutions in health, energy, etc. It contains
chapters dealing with various topics starting from experimental approaches, simulation, and modeling,
and ending with applications and future perspectives.
Mohamed Bououdina
University of Bahrain, Bahrain
J. Paulo Davim
University of Aviero, Portugal

Chapter 1

Self-Healing Materials Systems


as a Way for Damage Mitigation
in Composites Structures
Caused by Orbital Space Debris
Brahim Assa
MPB Technologies Inc., Canada
Maha Mohamed Khayyat
Umm al-Qura University, Saudi Arabia

ABSTRACT
The presence in space of orbital debris, particularly in low earth orbit, presents a continuous hazard
to orbiting satellites and spacecrafts. The development of self-healing materials offers the designer an
ability to incorporate secondary functional materials capable of counteracting service degradation
whilst still achieving the primary, usually structural, requirement. This chapter reviews the various
self-healing technologies currently being developed. Self-healing systems can be made from a variety
of polymers and metallic materials. An overview of various self-healing concepts over the past two
decades is presented. Finally, a perspective on current and future self-healing approaches using this
biomimetic technique is offered. The intention is to stimulate debate and reinforce the importance of a
multidisciplinary approach in this exciting field.

1. INTRODUCTION
Polymers and structural composites are used in a
variety of applications. However, these materials
are susceptible to damage induced by mechanical,
chemical, thermal, UV radiation, or a combination of these factors (Bucknall, Drinkwater, &
Smith, 2004). When polymer composites used as

structural materials become damaged, there are


only a few methods available to attempt to extend
their functional lifetime. Ideal repair methods are
ones that can be executed quickly and effectively
directly on damaged site, eliminating thereby the
need to remove a component for repair. However,
the mode of damage must also be taken into consideration as repair strategies that work well for

DOI: 10.4018/978-1-4666-5824-0.ch001

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

one mode might be completely useless for another.


For example, matrix cracking can be repaired by
sealing the crack with resin, where fibre breakage
would require new fibres replacement or a fabric
patch to achieve recovery of strength. One of the
earlier healing methods for fractured surfaces was
hot plate welding, where polymer pieces were
brought into contact above the glass transition
temperature of the material, and this contact was
maintained long enough for interdiffusion across
the crack face to occur and restore strength to the
material. It has been shown, however, that the
location of the weld remains the weakest point in
the material and thus the favourable site for future
damage to occur (Liu, Lee, & Lu, 1993). For laminate composites, resin injection is often employed
to repair damage in the form of delamination. This
can be problematic, however, if the crack is not
easily accessible for such an injection. For fibre
breakage in a laminate composite, a reinforcing
patch is often used to restore some of the strength
to the material. Often, a reinforcing patch is used
in conjunction with resin injection to restore the
greatest amount of strength possible (Osswald &
Menges, 2003). None of these methods of repair
is an ideal solution to damage in a structural
composite material. These methods are temporary
solutions to prolong the lifetime of the material,
and each of these repair strategies requires monitoring of the damage and manual intervention to
enact the repair. This greatly increases the cost
of the material by requiring regular maintenance
and service.
Alternative healing strategies are therefore
of great interest. Moreover, with polymers and
composites being increasingly used in structural
applications space, automobile, defence, and construction industries, several techniques have been
developed and adopted by industries for repairing
visible or detectable damages on the polymeric
structures.
However, these conventional repair methods
are not effective, for example, for healing invisible

microcracks within the structure during its service


life. In response, the concept of self-healing
polymeric materials was proposed in the 1980s
(Jud, Kausch, & Williams, 1981) as a means of
healing invisible microcracks for extending the
working life and safety of the polymeric components. The publications in the topic by Dry and
Sottos (Dry & Sottos, 1993) in 1993 and then White
et al. (2001) further inspired world interests in these
materials (Kringos et al., 2011). Examples of such
interests were demonstrated through US Air force
(Carlson & Goretta, 2006) and European Space
Agency (Semprimosching, 2006) investments in
self-healing polymers.
Conceptually, self-healing materials have the
built-in capability to substantially recover their
mechanical properties after damage. Such recovery
can occur autonomously and/or be activated after
an application of a specific stimulus (e.g., heat,
radiation, pressure, etc.). As such, these materials
are expected to contribute greatly to the safety and
durability of polymeric components without the
high costs of active monitoring or external repair.
Throughout the development of this new range
of smart materials, the mimicking of biological
systems has been used as a source of inspiration
(since most materials in nature are themselves
self-healing composite materials) (Varghese, Lele,
& Mashelkar, 2006).
The number of publications dealing with various aspects of self-healing materials has increased
markedly in recent years. Figure 1 shows how the
number of refereed various articles in the self
healing field has steadily increased since 2001,
based on data collected from the Engineering
Village Web-based information service. Along
with the increase in the number of publications
in this area comes a need for a comprehensive
review work, and the objective of this chapter is
to address this need.
In addition, the vast majority of the surveyed
articles deal with polymer composites. Due to the
large number of articles involved and the lack of


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

Figure 1. (a) Recent refereed publications related to the field of self healing materials, together with
(b) their corresponding distribution of the employed key words vocabulary. All published languages
were included. All document types, including journal and conference articles, report paper, conference
proceeding, and monograph published chapters were recorded. Statistics are available from 2000 to
August 2013 inclusively. Data were collected from Engineering Village Web-based information service

electronic access to many conference proceedings, the emphasis of this chapter is on the more
accessible refereed journal articles. It was not
practical to cover all of these articles, and, since
a lot of articles had already been covered by
previous related paper articles, an attempt was
made to select representative articles in each of
the relevant categories.
This chapter briefly describes the traditional
methods of repairing damage in the polymeric
materials during the last decade. Table 1 provides
summary of some developments and achieved performances. It can be seen that both thermoplastic
and thermosetting materials were investigated for
self healing, where the research interests have been
more shifted to thermosetting-composite-based
systems in recent years.
We start by describing the methods for evaluating self healing efficiencies. We will then describe
briefly some examples of different approaches
proposed to heal the thermoplastic systems, and we
follow by emphasising the preparation and charac-

terization of the self healing of the thermosetting


ones. We will take a short view on the self-healing
coating for metallic structures systems, and we
conclude by future research outlooks.

2. QUANTIFICATION OF
HEALING EFFICIENCY
Healing of a polymeric material can refer to the
recovery of properties such as fracture toughness,
tensile strength, and surface smoothness. Due to
the range of properties that are healed in these materials, it can be difficult to compare the extent of
healing. Wool and OConnor (Wool & OConnor,
1981) proposed a basic method for describing the
extent of healing in polymeric systems for a range
of properties. This approach has been commonly
adopted and has been used as the basis for method
of comparing healing efficiency of different self
healing polymeric systems.


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

Table 1. Non exhaustive main developments in self-healing polymer composites


Host material
Thermosetting
and/or
thermosetting
composites

Healing system
Hollow Glass
Fibre

Stimulus

Test method

Ref.

24 hours at
ambient atm.

Flexure Strength

(Trask, & Bond,


2006)

Microencapsulation approach

80-93%

48 h at 80o C
24 h at Ambient
then 24 h at
80o C

Fatigue
resistance
Fracture
toughness
Tensile strength

(Sanada, Yasuda,
& Shindo, 2006)

Micro-vascular
network

60-70%
7- 30 cycles

12 hours at
ambient atm.

Fracture
toughness

(Toohey et al.,
2007)

Thermoplastic
additives

30-100%

10 min at 120o C
1- 2 h at 130160o C

Flexure strength
Tensile strength
Impact strength

(Hayes et al.,
2007)

77%

24 hours at
ambient atm.

Fracture
toughness

(Kirkby et al.,
2008)

46%

1-20 minutes,
70-120o C

Impact strength

(Murphy et al.,
2008)

70100%

48 hours at
ambient atm.

Tear strength

(Keller, White,
& Sottos, 2007)

100%

5 min. At 60o C.

Fracture
toughness

(Lin, Lee, & Liu,


1990)

26%

10 min. At
100o C

Flexure Strength

(Chung et al.,
2004)

Electrical

Carbon fibre
Elastomeric

Silicone rubber

Thermoplastic

Molecular
diffusion
Photo-induced
healing

Mechanical

Photo

There are different methods to effect healing


that are applicable for each individual mode of
damage as well as each unique damaged material. This makes quantifying the extent of healing
within the material and comparing it to healing in
other systems rather difficult. The susceptibility
of a given material to fracture can be expressed in
terms of the plane strain fracture toughness, KIC. It
has become standard practice to assess the healing
ability of a particular material by comparing the
fracture toughness of the material both before and
after healing. The healing efficiency is ,
(%) = K1C healed/ K1C virgin X 100

(1)

where K1C virgin is the fracture toughness of the virgin


specimen and K1C healed is the fracture toughness
of the healed specimen.

Healing
condition

93%

Shape memory
alloy

Mechanical

Best efficiency
achieved

2.1. Self-Healing Efficiency


Assessed by Fracture Test
For quasistatic fracture conditions healing efficiency is defined in terms of the recovery of
fracture toughness. Healing evaluation begins
with a virgin fracture test of an undamaged tapered
double cantilever beam (TDCB) sample (Figure
2(a)). A pre-crack is introduced to sharpen the
crack-tip, and loading of the specimen is increased
until the crack propagates along the centerline of
the sample until failure. The crack is then closed
and allowed to heal at room temperature with no
external intervention. After healing, the sample
is loaded again until failure.
Crack healing efficiency, , is defined as the
ability of a healed sample to recover fracture
toughness (Wool et al., 1981):


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

Figure 2. (Left) Schematic of the TDCB-based


fracture toughness and (Right) tear protocols to
evaluate healing performance

ics, and the rest periods employed (Brown, White,


& Sottos, 2005). The investigation considered
successful healing as the recovery of stiffness lost
due to damage induced by cyclic loading rather
than changes in crack growth rate or absolute
fatigue life.

2.3. Self-Healing Efficiency


Assessed by Tear Test

=KIC healed/KIC Virgin

(2)

where, KIC Virgin and KIC healed represent the fracture toughness of the virgin and healed samples,
respectively.

2.2. Self-Healing Efficiency


Assessed by Fatigue Test
For dynamic fracture conditions, healing efficiency based on static fracture toughness recovery is no longer meaningful. Instead, the fatigue
crack propagation behaviour of the self-healing
epoxy was evaluated using the protocol outlined
by Brown et al. who defined healing in terms of
the life extension factor (Brown, Sottos, & White,
2002):
d = N healed -N control/N control

(3)

where N healed is the total number of cycles to failure


for a self-healing sample and N control is the total
number of cycles to failure for a similar sample
without healing.
Characterization of fatigue response is more
complex than monotonic fracture because it depends on a number of factors such as the applied
stress intensity range, the loading frequency, the
ratio of applied stress intensity, the healing kinet-

For elastomeric self-healing material, the TDCBbased fracture toughness protocol to evaluate
healing performance is inappropriate. Instead, the
recovery of tear strength using a tear specimen is
used to define healing efficiency, where
c =T healed/T Virgin

(4)

A tear test utilizes a rectangular coupon of


material with a large axial pre-cut that produces
two loading arms. These arms are loaded in tension until the tear propagates through the rest of
the specimen (Figure 2(b)). Healing evaluation
begins with a virgin tear test of an undamaged
sample. After failure, the sample loading arms
are reregistered and healing occurs at room
temperature with no external intervention. After
healing, the tear sample is loaded again to failure.
Using this test protocol, more than 70% recovery
of the original tear strength was achieved in the
PDMS (polydimethylsiloxane) system (Keller et
al., 2007).

3. SELF-HEALING OF THE
THERMOPLASTIC MATERIALS
Crack healing of thermoplastic polymers has been
the subject of extensive research in the 1980s. The
polymers investigated cover amorphous, semi
crystalline, block copolymers, and fibre-reinforced
composites. It has been discovered that when


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

two pieces of the same polymer are brought into


contact at a temperature above its glass transition
(Tg), the interface gradually disappears and the
mechanical strength at the polymer-polymer interface increases as the crack heals due to molecular
diffusion across the interface. For example, by using thermoplastics chain mobility with a minimal
application of heat, Lin et al. (Lin et al., 1990)
have studied crack healing in PMMA (poly (methyl
methacrylate)) by methanol treatment from 40
to 60C. The authors have found that the tensile
strength of PMMA treated by methanol can be
fully recovered to that of the virgin material. On
the other hand, another example of photo-induced
self-healing in PMMA was reported by Chung et
al. (Chung et al., 2004). Mixture of photo linkable
TCE (1,1,1-tris-(cinnamoyloxymethyl) Ethane)
with UDME- (urethane-dimethacrylate-) and
TEGDMA- (triethyleneglycol-dimethacrylate-)
based monomers, blended with visible light photoinitiator CQ (camphorquinone), was polymerized
into a hard and transparent film after its irradiation for 10min with a 280 nm light source. The
healing was shown to only occur upon exposure
to the light of the correct wavelength, proving that
the healing was light initiated. Healing efficiencies in flexural strength up to 14% and 26% were
reported using light or a combination of light and
heat (100C). However, healing was limited to
the surfaces being exposed to light, meaning that
internal cracks or thick substrates are unlikely to
heal. In summary, self-healing of thermoplastic
polymers can be achieved via a number of different mechanisms, including (i) recombination of
chain ends, (ii) self-healing via reversible bond
formation, (iii) living polymer approach, and (iv)
self-healing by nanoparticles, in addition to the (v)
molecular inter-diffusion and (vi) photo-induced
healing reported here. The processes are well
known and have been well reported. A detailed
description of these approaches can be found in
(Wu, Meure & Solomon, 2008).

4. SELF-HEALING OF
THERMOSETTING MATERIALS
The search for self-healing thermosetting materials coincides with these materials being more
and more widely used in numerous structural
applications. These applications generally require
rigid materials with a thermal stability that most
thermoplastics do not possess. The rigidity and
thermal stability of thermosetting comes from their
cross-linked molecular structure, meaning that
they do not possess the chain mobility so heavily
utilized in the self-healing of thermoplastics. As a
result of their different chemistry and molecular
structure, the development of self-healing thermosetting has followed distinctly different routes.
The most common approaches for autonomic
self healing of thermosetting-based materials involve incorporation of self-healing agents within
a brittle vessel prior to addition of the vessels into
the polymeric matrix. These vessels fracture upon
loading of the polymer, releasing the low-viscosity
self-healing agents to the damaged sites for subsequent curing and filling of the microcracks. The
exact nature of the self-healing approach depends
on (i) the nature and location of the damage, (ii)
the type of self-healing resins, and (iii) the influence of the operational environment.

4.1. Hollow Glass Fibres Systems


The development of advanced fibre-reinforced
polymers (FRPs) to achieve performance improvements in engineering structures focuses on
the exploitation of the excellent specific strength
and stiffness that they offer. However, the planar
nature of a FRPs microstructure results in relatively
poor performance under impact loading. This is an
indication of their susceptibility to damage, which
manifests mainly in the form of delamination.
Hollow glass fibres have already been shown
to improve structural performance of materials
without creating sites of weakness within the


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

composite (Trask, Williams & Bond, 2007). These


hollow fibres offer increased flexural rigidity and
allow for greater custom tailoring of performance,
by adjusting, for example, both the thickness of
the walls and degree of hollowness (Hucker et
al., 2003). By using hollow glass fibres in these
compositesalone or in conjunction with other
reinforcing fibres it would be possible to not only
gain the desired structural improvements, but to
also introduce a reservoir suitable for the containment of a healing agent (Trask et al., 2007). Upon
mechanical stimulus (damage inducing fracture
of the fibres), this agent would bleed into the
damage site to initiate repair, not unlike biological
self healing mechanisms (Pang & Bond, 2005).
The first systems that have been investigated
in 1996 and 1998 by Dry (1996) and Li et al.
(1998), respectively, have validated that the proposed architecture for releasing chemicals from
repair fibres was totally possible and then have
used cyanoacrylate, ethyl cyanoacrylate (Li et al.,
1998), and methyl methacrylate (Dry & McMillan,
1996) as healing agents to heal cracks in concrete.
This methodology was then transferred to polymer
composite materials by Motuku et al. (1999) in the
late 1999. The healing agents contained within the
glass fibres have been either a one-part adhesive,
such as cyanoacrylate, or a two-part epoxy system,
containing both a resin and a hardener, where
either both are loaded in perpendicular fibres or
one embedded into the matrix and the other inside
fibres (Bleay et al., 2001).
One of the initial challenges encountered when
creating this type of self-healing systems is the
development of a practical technique for filling
the hollow glass fibres with repair agent. When
approaching this problem, the dimensions of the
glass fibre itself must be considered, including
diameter, wall thickness, and fibre hollowness,
as well as the viscosity and healing kinetics of
the repair agent. Bleay et al. (2001) were among
the first to develop and implement a fibre filling
method involving capillary action that is assisted

by vacuum, which is now the main commonly used


process. The chosen glass fibre should be also
evaluated for its capacity to survive to the composite manufacturing process without breakage,
while still possessing its ability to rupture during
a damage event in order to release the required
healing agent.
Motuku et al. (1999) have clearly determined
that hollow glass fibres were best suited for this
kind of application, as opposed to polymer tubes or
those made of metal, which often did not provide
controlled fracture upon impact damage.
In 2003, Hucker et al. (2003) have shown that
hollow glass fibres of a larger diameter offered
an increased compressive strength, while giving
larger volume of healing agent to be stored. The
second important parameter to investigate was the
capacity of the healing agent to adequately reach
the site of damage and subsequently undergo
healing. This mechanism will obviously depend
upon the viscosity of the healing material, as well
as the kinetics of the repair process.
For example, the cyanoacrylate system studied
by Bleay et al. (2001) was shown, indeed, to restore mechanical strength to damaged specimens
but also caused significant problems by curing
upon contact with the opening of the fibre, which
prevented the healing agent from reaching the site
of damage in the sample. Various groups (Pang et
al., 2005, Motuku et al., 1999, Trask et al., 2007)
have then used liquid dyes inside the composites in
order to serve as a damage detection mechanism,
providing hence a visible indication of the damage
site, while allowing a clear evaluation of the flow
of healing agents to those sites.
Finally, the third parameter to optimize is the
concentration of healing fibres within the matrix,
their special distribution, and the final dimensions
of the specimen, which have direct effects on the
mechanical properties of the resulting composite
material. As early demonstrated by Jang et al. (Jang
et al., 1990) in 1990, the stacking sequence of the
fibres within the composite plays a role in inhibit-


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

ing plastic deformation and delamination and will


also affect the response to an impact damage event.
In order to maintain high mechanical properties,
repair fibres need to be adequately spaced within
the composite. Motuku and coworkers (Motuku
et al., 1999) have shown that thicker composites
have shown better performances in healing studies.
These parameters, however, will depend upon the
dimension choice of fibre and chemical choice of
the healing agent employed, and so optimization
will depend on the specificities of the system
being studied.
Until recently, the majority of the works done on
self healing hollow fibre composites have focused
on demonstrating the feasibility of such concept for
self-repair and have reported qualitatively on the
healing capacity of the studied systems. Recently,
numerous works have reported quantitatively on
mechanical properties associated with healing of
the materials. The inclusion of hollow glass fibres
into a composite system was shown by Jang et
al. (1990) and Trask and Bond (2006) to give an
initial reduction in the strength of the material,
either by 16% in glass fibre reinforced polymer
(GFRP) composites and by 8% in carbon-fibre
reinforced polymer (CFRP) composites. These
self-repairing composites were shown to recover 100% of the virgin strength for GFRP and
97% of the virgin strength for CFRP, but in both
cases the composite materials were subjected to
a heat treatment to aid in delivery of the resin to
the damaged area as well as in curing of the healing agent. More recently, the work of Williams
et al. (2009) has considered the development of
autonomic self-healing within a carbon fibrereinforced polymer (CFRP), and has demonstrated
the significant strength recovery (>90%), which
was possible when a resin filled hollow glass fibre
system was distributed at specific interfaces within
a laminate, minimising thereby the reduction in
mechanical properties whilst maximising the efficiency of the healing event.

4.2. Systems Based on


Microencapsulated Healing Agents
As above mentioned, and since the first report of
the self repairing composites systems in the literature (White et al., 2001), conventional strategy
was achieved by embedding a microencapsulated
liquid healing agent and solid catalytic chemical
materials within a polymer matrix. Hence, upon
damage induced cracking in the matrix, microcapsules are supposed to release their encapsulated
liquid healing agent into the crack planes (Figure
3(a)). All the involved materials must be carefully engineered. For examples, encapsulation
procedure must be chemically compatible with the
reactive healing agent, and the liquid healing agent
must not diffuse out of the capsule shell during
its potentially long shelf-life. At the same time,
the microcapsule walls must be resistant enough
to processing conditions of the host composite,
while maintaining excellent adhesion with the
cured polymer matrix to ensure that the capsules
rupture upon composite fracture. Polymeric microcapsules are most often prepared via a mini
emulsion polymerization technique, as described
in the work of Asua (2002). The procedure involves
the well known oil-in-water dispersions mechanism of the polymeric material. In the majority
of self-healing composite systems that have been
studied, the microcapsules are made by a urea
formaldehyde polymer, encapsulating DCPD as
the liquid healing agent (White et al., 2001, Brown
et al., 2006) and/or epoxy resin (Yuan et al., 2006;
Blaiszik et al., 2009). In the case of DCPD, during
the in situ polymerization process, urea and formaldehyde react in the water phase to form a lowmolecular-weight prepolymer; when the weight
of this prepolymer increased, it deposited at the
DCPD-water interface. This urea-formaldehyde
polymer becomes highly cross-linked and forms
the microcapsule shell wall. The urea formaldehyde prepolymer particles are then deposited on
the surface of the microcapsules, providing a rough


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

Figure 3. Schematic of the autonomic healing concept incorporating encapsulated healing agent and
embedded catalyst particles in a polymer matrix; (i) damage event causes crack formation in the matrix;
(ii) crack ruptures the microcapsules, releasing liquid healing agent into crack plane; (iii) healing agent
polymerizes upon contact with embedded catalyst, bonding crack closed.

surface morphology that aids in the adhesion of


the microcapsules with the polymer matrix during
composite processing (Murphy & Wudl, 2010).
Moreover, composites using DCPD-filled urea

formaldehyde microcapsules have shown concrete


healing ability in monotonic fracture and fatigue
(White et al., 2001; Brown et al., 2006).


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

4.2.1. Size and Material


Microcapsules Effects
In 2003, Williams et al. (2009) have reported
that the microcapsules made in this oil-in-water
in situ process have an average size of 101000
m in diameter, with a smooth inner shell in the
160220 nm thick range, and fill content up to
8392% liquid healing agent. The mechanical
rupture of the microcapsule is the sine qua non
condition event for the healing process.
Hence, it is obviously important, therefore, to
fabricate microcapsules with optimal mechanical
properties and wall thickness. The relationship
between the stiffness of the capsule and the one
of the polymer matrix determines how the crack
will propagate in the sample. In 2006, Keller and
Sottos (2006) have described how a capsule that
has higher elastic modulus than the one of the
polymer matrix material should create a stress
field that tends to deflect cracks away from the
capsule; a more compliant shell wall, on the other
hand, will produce a stress field that attracts the
crack towards the microcapsule.
The influence of microcapsule diameter and
crack size on the performance of self-healing
materials was also investigated in 2007 by Rule
et al. (2007). They have used an epoxy based
material containing embedded Grubbs catalyst
particles and microencapsulated DCPD. The
amount of liquid that microcapsules could deliver
to a crack face was shown to scale linearly with
microcapsule diameter (and hence to the volume
1/3), for a given weight fraction of capsules.
Moreover, the size of the microcapsule also plays
a role in the performance of the system, in terms
of the effect on toughness of the composite, and
the nature of interface between microcapsule and
polymer matrix. Based on these relationships, the
size and weight fraction of microcapsules can
be rationally chosen to give optimal healing of a
given crack size.
However, as noted by Williams et al. (2009),
the shell wall thickness is largely independent of

10

manufacturing parameters and is typically between 160 and 220nm thick; nevertheless, slight
adjustments can be made during the encapsulation
procedure to alter the resulting microcapsules.
The microcapsule size is controlled mainly via the
rate of agitation during the encapsulation process;
typical agitation rates reported by Williams et al.
(2009) range from 200 to 2000 rpm, with finer
emulsions and therefore smaller diameter capsules
being produced with increasing rates.
In 2004, Brown et al. have noted (Brown,
White, & Sottos, 2004) that smaller microcapsules
exhibit maximum toughening at lower concentrations; on the other hand, Rule et al. (2007) have
reported, in 2007, that specimens that contain
larger microcapsules perform better than those
with smaller microcapsules at the same weight
fraction, presumably due to the amount of healing
agent present in the samples. In the latter study,
the best healing achieved was on a specimen
containing 10 wt. % of 386 m capsules, which
corresponds to 4.5mg of healing agent being delivered per unit crack area (assuming all capsules
in the crack plane rupture). The amount of healing
agent available for delivery to the crack plane was
calculated based on the microcapsule size and
weight fraction incorporated into the composite
and was verified by comparing the data from
these autonomously healing samples with that
of samples, in which a known volume of healing
agent was manually injected into the crack plane
to initiate the healing process.
In the light of synthesizing smaller microcapsules that exhibit maximum toughening at
lower concentrations, Blaiszik et al. (2008) have
reported in 2008 an in situ encapsulation method
demonstrating over an order of magnitude size
reduction for the preparation of urea-formaldehyde
(UF) capsules filled with a DCPD healing agent,
where capsules with diameters down to 220nm
were successfully achieved, using sonication
techniques and an ultrahydrophobe solution to
stabilize the DCPD droplets. The capsules were
found to possess a uniform UF shell wall (77 nm


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

average thicknesses) and display good thermal


stability. However, there are drawbacks with UF
microcapsules: first, (i) the formation of agglomerated nanoparticles debris that could act as crack
initiation sites within the host matrix, second, (ii)
rough and porous wall surfaces formed by agglomerated nanoparticles that may reduce the adhesion
between the microcapsules and matrix, and, finally,
(iii) rubbery and thin capsule walls (160220 nm
(Brown et al., 2003)) that lead to the loss of core
material during storage and cause handling difficulties during processing of the composites. In
addition to UF microcapsules, melamine formaldehyde (Yan et al., 2008) and polyurethane (Yang
et al., 2008) shell wall materials were successfully
used to prepare microcapsules of various healing
materials. We note also the works of Liu et al.,
in 2009 (Liu et al., 2009), which have produced
microcapsules for self healing applications with
a melamine-urea-formaldehyde (MUF) polymer
shell containing two different healing agent
candidates, 5-ethylidene-2-norbornene (ENB)
and ENB with 10 wt.% of a norbornene-based

cross-linking agent (CL), by in situ polymerization in an oil-in-water emulsion (Figure 4). The
microcapsules were found to be thermally stable
up to 300C and exhibited a 10 to 15% weight loss
when isothermally held at 150C for 2 h. Overall,
these MUF microcapsules exhibited superior properties compared to the urea-formaldehyde (UF)
microcapsules used extensively for self-healing
composites to date, and their manufacturing process is simpler than that made from UF. On the
other hand, it is worthy reported at this level the
innovative work of Mookhoek et al. (Mookhoek
et al. 2008), where microcapsules of size around
1.4 m dibutylphthalate-(DBP-) filled urea-formaldehyde (UF) were used as pickering stabilizers
to create larger (~140 m) microcapsules containing a second liquid phase of DCPD. The binary
microcapsules were made by encapsulating the
dispersed DCPD liquid (stabilized with the UF
(DBP) microcapsules in water), via an isocyanatealcohol interfacial polymerization reaction.
Various applications have been attempted
with more or less success. Microcapsules have

Figure 4. Optical microscopic images of 5E2N- microcapsules fabricated at MPB technologies Inc

11


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

been used in the paper industry for a range of


different purposes, for example, in self-copying
carbonless copy paper (White, 1998), and in the
food and packaging industries for applications
such as control of aroma release and temperature
or humidity indicators (Wu et al., 2008). Other
possible applications might include encapsulation
of antimicrobial agents or scavengers in active
packaging. Recently, Andersson et al. (2009) have
developed microcapsules with a hydrophobic core
surrounded by a hydrophobically modified polysaccharide membrane in aqueous suspension, to
obtain capsules fulfilling both the criteria of small
capsule size and reasonably high solids content to
match the requirements set on surface treatment
of paperboard for enhancement of packaging
functionality, and they have shown a reduced
tendency for deteriorated barrier properties and
local termination of cracks formed upon creasing.

4.2.2. Fatigue Cracks Retardation


To retard the growth of fatigue cracks, shapememory alloy (SMA) wires are well suited to
this application since they exhibit a thermoelastic
martensitic phase transformation, contracting
above their transformation temperature and exerting large recovery stresses of up to 800MPa,
when constrained at both ends (Tsoi, Schrooten,
& Stalmans, 2004). Moreover, Rogers et al. (1991)
have shown that, when an SMA wire is embedded
within an epoxy matrix, the full recovery force
acts at the free edges of the component.
Therefore, an SMA wire bridging a crack
should induce a large closure force on the crack.
Indeed, Kirkby et al. (2008) have reported on
the self-healing polymers with embedded shapememory alloy (SMA) wires, where the addition
of SMA wires shows improvements of healed
peak fracture loads by up to 160% (comparatively
with specimen without SMA), approaching the
performance of the virgin material. Moreover, the
repairs can be achieved with reduced amounts of
healing agent. The improvements in performance

12

were attributed mainly to the crack closure, which


reduces the total crack volume and increases the
crack fill factor for a given amount of healing
agent and the heating of the healing agent during
polymerization, which increases the degree of cure
of the polymerized healing agent.

4.2.3. Delaminating Substrate


Because of their excellent in-plane properties and
high specific strength, fibre-reinforced composites
with polymeric matrices have found many uses
in structural applications. Despite this success,
they are particularly prone to damage from outof-plane impact events. Although fibre damage
is usually localized at the site of impact, matrix
damage in the form of delaminations and transverse
cracks can be more widespread. Delaminations, in
particular, pose a serious issue because they can
significantly reduce compressive strength (Xiong
et al., 1995) and grow in response to fatigue loading
(Baker, Jones, & Callinan, 1985). In addition to
this problem, impact damage can be subsurface or
barely visible, necessitating the use of expensive
and time-consuming non-destructive inspection
(Baker et al., 1995). Once damage is located,
there are many repair techniques that have been
proposed and/or are currently practiced (Myhre &
Labor, 1981). As we have mentioned, most solutions rely on resin infiltration of delaminations or
composite patches, to provide load transfer across
the damaged region.
In cases of severe damage, damaged regions
are removed and replaced with new composite
material that is bonded or concurred to the original one (Myhre, 1981). These repair techniques
are generally time-consuming complicated and
require unhindered access. Recently, Patel et al.
(2010) have studied the autonomic self-healing of
impact damage in composite materials by using
a microencapsulated healing agent (DCPD liquid
healing agent and paraffin wax microspheres containing 10 wt.% Grubbs catalyst), which has been
successfully incorporated in a woven S2-glass-


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

reinforced epoxy composite. Low velocity impact


tests reveal that the self healing composite panels
are able to autonomically repair impact damage.
Fluorescent labelling of damage combined with
image processing shows that total crack length
per imaged cross-section is reduced by 51% after
self-healing.
On the other hand, flexible, laminated, selfhealing bladder material was investigated to
mediate the impact of small tears and punctures.
Previous attempts at healing puncture damage have focused on ionomers (Kalista, Ward,
& Oyetunji, 2007). A self-healing response in
ionomers initiates through the transfer of energy
from a fast moving projectile, which is typically
a few millimetres in diameter. Frictional heating
of the material from the passage of the projectile
leads to a reorientation of the polymer chains
in the ionomer. This rearrangement can, under
some conditions, seal the hole generated by the
projectile.
However, this healing occurs only when the
damaged area is heated to near the melt temperature of the material (Kalista et al., 2007). In 2009,
Beiermann et al. (2009) have manufactured a
three-layer flexible self-healing materials, capable
of repairing puncture damage. The used material
consisted of three layers: a poly (dimethylsiloxane)
(PDMS) composite, embedded with a self-healing
microcapsule system, sandwiched between two
layers of poly(urethane)-coated nylon. A protocol
was established in which samples were damaged
using a hypodermic needle or a razor blade, and
a successful heal was defined as the ability to
reseal the damage to withstand a pressure differential across the laminate of 103 kPa (at 1 atm.).
Healing was shown to vary significantly with
microcapsule size, with the maximum healing success rate (100% successfully healed) occurring in
samples with 220 m in diameter microcapsules.
Additionally, healing was found to increase with
composite layer thickness, and decreases with
increasing puncture size.

Finally, fracture testing, in the form of singleedge notched bending tests, has shown a healing
efficiency of 111%, when the concentration of
microcapsules and latent hardener were optimized.
Some preliminary tests on epoxy based fabric
laminates containing this self-healing system demonstrated a 68% recovery of virgin inter-laminar
fracture toughness. Yuan et al. (Yuan et al., 2007)
have reported another promising combination of
healing agent and catalyst for self healing polymer
composites. The healing agent, consisting of a mixture of diglycidyl ether of bisphenol A (DGEBPA)
along with a catalyst made from 1-butyl glycidyl
ether (BGE), was stored in poly(urea-formaldehyde) (PUF) microcapsules, which were prepared
by the conventional oil inwater emulsion process.
This process of preparing the PUF microcapsules
has promoted long shelf-life and good chemical
stability at temperatures below 238C. This system
is still in the early developmental stages, and its
self healing efficiency within a composite material is yet to be tested.
In sum, the microencapsulation approach is
by far the most studied self-healing concept in
recent years. Table 2 summarizes the type of
self-healing systems investigated in the literature,
and it is noticed that the self-healing system based
on living ring-opening metathesis polymerization (ROMP) has attracted most of the research
attention. There are some obvious similarities
between the microencapsulation and hollow fibre
approaches, but the use of microcapsules alleviates
the manufacturing problems experienced in the
hollow fibre approach. The microencapsulation
approach is also potentially applicable to other
brittle material systems such as ceramics and
glasses (Ritchie, 1988). On the other hand, the most
successful and extensively investigated self healing
system comprises the ROMP of dicyclopentadiene
(DCPD) with Grubbs catalyst. The synthesis and
characterization of the DCPD/Grubbs catalyst
system have recently been papered (Bielawski
& Grubbs, 2007), and their use as a self-healing

13


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

Table 2. Literature summary of self-healing chemicals investigated for the microencapsulation approach
Self-healing agent

Catalyst

Self-healing reaction

Reference

Dicyclopentadiene (DCPD)

Bis(tricyclohexylphosphine)
benzylidine ruthenium (IV)
dichloride (Grubbs catalyst)

Ring-opening metathesis
polymerization

(White et al., 2001)

5-Ethylidene-2-norbornene
(ENB)

Bis(tricyclohexylphosphine)
benzylidine ruthenium (IV)
dichloride (Grubbs catalyst)

Ring-opening metathesis
polymerization

(Lee et al., 2004)

DCPD/ENB blends

Bis(tricyclohexylphosphine)
benzylidine ruthenium (IV)
dichloride (Grubbs catalyst)

Ring-opening metathesis
polymerization

(Liu et al., 2006)

Mixture of hydroxyl end


functionalised
Polydimethylsiloxane
(HOPMDS) and
Polydiethoxysiloxane (PDES)

Di-n-butyltin dilaurate

Polycondensation

(Cho et al., 2006)

Epoxy

Amine

Polycondensation

(Yuan et al., 2006)

Styrene-based system

Cobalt naphthenate,
dimethylaniline

Radical polymerization

agent has been widely reported as we mentioned


here above. This system supposedly provides a
number of advantages such as long shelf-life, low
monomer viscosity and volatility, and completion
of polymerization at ambient conditions in several
minute. Further attempts were made to improve
the performance of the self-healing system by
replacing DCPD with 5-ethylidene-2-norbornene
(ENB) (Lee et al., 2004) or blending ENB with
DCPD (Liu et al., 2006). Microencapsulation of
ENB was also achieved by in situ polymerization
of urea and formaldehyde.
This system was supposed to overcome some
of the limitations of the DCPD including the low
melting point and the need to use a large amount
of catalysts. It is recognized that DCPD is capable
of forming a cross-linked structure with high
toughness and strength (Wu et al., 2008) whilst
ENB polymerizes to a linear chain structure
and may possess inferior mechanical properties.
However, ENB is known to react faster in the
presence of a lower amount of Grubbs catalyst,
has no melting point, and produces a resin with
a higher Tg (Wu et al., 2008). Hence, a blend
of DCPD with ENB was believed to provide a

14

(Wu et al., 2008)

more reactive healing system with acceptable


mechanical properties, making it more suitable
for practical use. Cho et al. (Cho et al., 2006)
chose to develop a completely different healing
system using di-n-butyltin dilaurate (DBTL) as
the catalyst and a mixture of HOPDMS (hydroxyl
end-functionalized polydimethylsiloxane) and
PDES (polydiethoxysiloxane) as the healing agent.
The polycondensation of HOPDMS with PDES
is alleged to occur rapidly at room temperature
in the presence of the organo tin catalyst even in
open air (Shah, 1998).

4.3. Three-Dimensional
Microchannel Structure Systems
As reported by the paper of Murphy and Wudl
(2010), complex microvascular networks are
widely observed in biological systems, such as
leaf venation (Sack & Frole, 2006) and blood
vascularisation (Jain, 2005). Indeed, in the latter
case, the human circulatory system is comprised
of vessels of varying diameter and length: arteries, veins, and capillaries. These vessels function
together in a branched system to supply blood to


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

all points in the body simultaneously. However,


due to their complex architecture, replication of
these microvascular systems remains a significant
challenge for those pursuing synthetic analogs. As
outlined in 2006 by Stroock and Cabodi (2006),
these microvascular networks can be created via
soft lithographic methods (Choi et al., 2007), in
which all microchannels can be fabricated at the
same time, laser ablation (Kam & Mazumder,
2008) or direct write methods (Therriault, White,
& Lewis, 2003), which are more suited for building
three-dimensional (3D) micro-channel structures
(Figure 3(c)). One of the main advantages of those
systems comparatively to both the hollow fibre
and microcapsule systems is their ability to heal
the same location in the material more than once.
Indeed, often, a second fracture event will occur
along the plane of the initial crack. By providing
a material with a quasi continuous flow of healing
agent, numerous healing cycles can be achieved.
In 2007, Toohey et al. (2003) have published
one of the first of these types of composite materials. Authors have reported self-healing systems that are capable of autonomously repairing
repeated damage events. The reported system
which bio-inspired coating-substrate design
delivered healing agent to cracks in a polymer
coating via a three-dimensional microvascular
network (Therriault et al., 2003) that was first
embedded into the substrate. This system utilized
the healing combination of liquid DCPD as the
healing agent and solid Grubbs catalyst to initiate ROMP polymerization of the DCPD. In the
reported work, the catalyst was incorporated into
a 700 m thick epoxy coating that was applied
to the top surface of the microvascular substrate,
and the 200 m wide channels were successfully
filled with DCPD and then sealed.
This system achieved a peak healing efficiency
up to 70% with 10 wt. % catalyst in the top coating and was able to demonstrate healing for up to
seven cycles. It is important to mention that the
amount of catalyst in the top epoxy layer did not
affect the average healing efficiency per cycle,

but rather limited how many cycles of testing


and healing could be performed successfully.
Indeed, once all of the catalyst has been used,
healing ceased due to depletion of catalyst in the
crack plane, even with a continuous supply of
monomer. To overcome this limitation, in 2009,
Toohey et al. (2009) have modified their design
by photolithographically patterning four isolated
regions within the embedded microvascular network. Authors have reported the repeated healing
of crack damage in a polymeric coating through
delivery of two-part epoxy, healing chemistry via
multiple microvascular networks embedded in
isolation within a polymeric substrate. They first
have created a continuous, interconnected microvascular network using the direct-write method.
Second, they then have isolated multiple networks
by infilling the network with a photo-curable resin
and selectively photo-polymerizing thin parallel sections of these resin-filled microchannels.
Epoxy resin and amine-based curing agents were
transported to the crack plane through two sets of
independent vascular networks embedded within
a ductile polymer substrate beneath the coating.
The two reactive components remain isolated and
stable in the vascular networks until crack formation occurs in the coating under a mechanical load.
Both healing components were wicked by capillary
forces into the crack plane, where they react and
effectively bond the crack faces closed. Several
epoxy and curing agent combinations were evaluated for their suitability in microvascular-based
autonomic systems, and healing efficiencies of
over 60% for up to 16 intermittent healing events
out of 23 cycles were successfully achieved. In
a related effort, Williams et al. have published
their version of a microvascular network containing mechanically stimulated healable material,
in the form of sandwich structure composite
configurations that contain either single (Williams, Trask, & Bond, 2007) or dual (Williams,
Trask, & Bond, 2009) fluidic networks. In the
single network design, sandwich structures use
high-performing skin materials, such as glass or

15


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

carbon fibre composites, separated by a lightweight core to obtain a material with very high
specific flexural stiffness. A vascular network
incorporated into a sandwich structure would address the larger damage volume expected of these
systems, as well as allowing for multiple healing
events to occur. Samples were fabricated with
channels containing a healing agent, which had
a negligible effect on the mechanical properties
of the composite. Rupture of the vessels released
the healing fluid, filling the void that formed as
a result of impact damage on the sample. Initial
tests were run on samples containing premixed
resin and hardener, to demonstrate the healing
capability of the system. Indeed, these samples
have shown consistent and complete recovery of
compressive stress at failure after impact damage.
In their dual network design, significant recovery
was also observed when samples were infiltrated
with pressurized unmixed dual fluids (Williams
et al., 2007).

5. SELF-HEALING COATING
SYSTEMS FOR METALLIC
STRUCTURES
The large economic impact of corrosion of metallic
structures is a very important issue all over the
world. Generally, rapid field-specific testing is
done when material failure is observed. Despite
intense research and developments in corrosion
protection coatings of metals and alloys, the
real-world performance results are not always
satisfactory.
Furthermore, development of all around
coatings to protect and prolong service life of
the infrastructure is still a big challenge, owing
to wide variations in environmental conditions.
Therefore, in order to improve the equipment
service prediction capabilities of infrastructure,
it is indispensable to develop new state-of-the-art
smart/self healing coating formulations for corrosion inhibition. In this context, autonomic healing

16

materials respond without external intervention


to environmental stimuli and have great potential
for advanced engineering systems (Cordier et al.,
2008). Self-healing coatings, which autonomically
repair and prevent corrosion of the underlying
substrate, are of particular interest. Notably, the
worldwide cost of corrosion has been estimated
to be nearly $300 billion per year (Koch et al.,
2001). Recent studies on self-healing polymers
have demonstrated repair of bulk mechanical damage as well as dramatic increases in the fatigue
life. The majority of these systems, however, have
serious chemical and mechanical limitations,
preventing their use as coatings. Polymer coating
systems are classically applied on a metal surface
to provide a dense barrier against the corrosive
species. Cathodic protection is also used for many
applications, in addition to coatings, to protect the
metal structures from corrosive attack when the
coating is damaged. Hence, self-healing coatings
are considered as an alternative route for efficient
anticorrosion protection while maintaining a low
demand in cathodic protection.
Cho et al. (2009) have explored two self-healing
coating approaches, starting from the siloxanebased materials system. In the first approach, the
catalyst was microencapsulated and the siloxanes
were present as phase-separated droplets. On
the second process, the siloxanes were also encapsulated and dispersed in the coating matrix.
Encapsulation of both phases (the catalyst and
the healing agent) is advantageous in cases where
the matrix can react with the healing agent. In the
other hand, Aramaki (2003) has prepared a highly
protective and self-healing film of organosiloxane
polymer containing sodium silicate and cerium
nitrate, on a zinc electrode previously treated in
a Ce(NO3)3 solution. Self-healing mechanism of
the film was investigated after it was scratched and
immersed in the NaCl solution for several hours,
where a passive film has been found to be formed
on the scratched surface, resulting in suppression
of pitting corrosion at the scratch. More recently,
the same group (Aramaki, 2010) has prepared


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

an ultrathin 2D polymer coating, on a passivated


iron electrode, which was subsequently healed
in NaNO3. Thus done, localized corrosion was
markedly prevented by coverage with the polymer
coating and the healing treatment in 0.1 M-NaNO3.
Indeed, prominent protection of iron from
corrosion in 0.1M-NaCl was observed. The protective efficiencies were found to be extremely
high in certain cases, where more than 99.9%
before the passive film was broken down. The
development of effective corrosion inhibitor
coatings for prevention of corrosion initiation
and suppression of galvanic activity of metals and
alloys has always been a challenging problem.
Recent concerted efforts of researchers at US
Army Engineering Research and Development
Center at the Construction Engineering Research
Laboratory (ERDC-CERL) and at other facilities
(Kumar, Stephenson, & Murray, 2006) have led
to development of self-healing corrosion inhibitors, to reduce and/or prevent corrosion of metal
hardware. Previously, heavy metal-based epoxy
primer pre-treatment systems (Kachurina et al.,
2002), including quaternary ammonium saltbased and multifunctional microencapsulated
corrosion inhibitor system (Kumar et al., 2006),
have demonstrated corrosion protection performance of metals and alloys. These studies have
demonstrated that the scribe or damaged film
area on otherwise corroded panels experienced
little lifting and blisters, among others, of the
film because of the presence of microcapsules
at the scribes. Mehta and Bogere (2009) have
evaluated the smart/self-healing microencapsulated inhibitor incorporated in epoxy primer
before painting on a steel surface, for its corrosion
protection effectiveness on exposure to ASTM
(American Society for Testing and Materials) D
5894 electrolyte in laboratory and natural tropical
seashore environment. The healant inhibitor
was industrial custom made. Their results have
indicated that the active components in ruptured
embedded inhibitor microcapsules were released
into an inflicted scribe primer and topcoat film on

steel surface on exposure to inhibit development of


an electrochemical cell. Undamaged surface film
of the test and control specimens exposed in the
environments demonstrated excellent corrosioninhibition performance as reflected by both visual
inspection and electrochemical impedance spectroscopy experimental data. All of those reported
results should provide an understanding of the
fundamental material-property relationships of
smart inhibitor coatings and, thus, should facilitate
the development of optimized paint compositions
in order to extend the useful service life of steel
infrastructure applications.

6. FUTURE OUTLOOKS
In summary, we finally know that the material degradation can occur for a wide variety
of reasons, such as fatigue loadings, thermal
effects, and corrosion, or, more in general, for
environmental effects of all kinds. However, the
materials durability is probably one of the main
challenges encountered today for structural as well
as coating applications. As the materials failure
normally starts at the nanoscale level and is then
amplified to the micro- up to the macro-scale level
until catastrophic failure occurs, the ideal solution
would be to block and/or eliminate damage as
it occurs at the nano/microscale and restore the
original material properties.
We have seen that the healing process can be
initiated by means of an external source of energy
(stimuli), as it was shown in the case of a bullet
penetration (Varley & Van der Zwaag, 2008)
where the ballistic impact caused local heating
of the material allowing self-healing of ionomers,
or in the case of self-healing paintings used in
the automotive industry. In the latter case, small
scratches can be restored by solar heating (Garcia
Espallargas, Fisher, & Van der Zwaag, 2011).
Single cracks formed in PMMA specimens
at room temperature were also shown to be
completely restored above the glass transition

17


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

temperature (Kausch, 1983). The presence of


noncovalent hydrogen bonds (Sijbesma et al.,
1997) in mechano-sensitive polymers can allow
a rearrangement of principal chemical bonds so
that they can be used for self-healing. Numerical
studies have also shown that nanoscopic gel particles, which are interconnected in a macroscopic
network by means of stable and labile bonds, have
the potential to be used in self healing applications.
To date, all the employed techniques are,
however, limited by the container size. Containers should be in the nanoscale range since larger
ones could lead to large hollow cavities that could
compromise the mechanical properties of the
hosting structural material, and/or the passive
protective properties of the coating material (Zako
& Takano, 1999). Moreover, up to date, advanced
materials are designed to be either tough or self
healing, but typically not both. It would be ideal
to have a material which could be at the same
time tougher and self-repairable, and this is still
not possible with current technologies.
Carbon nanotubes (CNTs) are considered to be
an ideal filler material for mechanical reinforcement as well as ideal molecular storage devices.
This is due to the fact that CNTs are very small,

thus they have an extremely large interfacial area.


CNTs have interesting mechanical and chemical
properties and have a hollow tubular structure.
Polymer/CNTs composites (Coleman, Khan, &
Gunko, 2006) have already shown many promising results, and various materials, such as hydrogen
(H2) (Liu et al., 1999), metal and/or metal carbide
(Guerret-Plecourt et al., 1994), C60 (Xue & Chen,
2006), CH4 (Ni et al., 2002) and DNA (Gao et al.,
2003), have been successfully inserted inside CNT.
Although a great deal of work has been done
with CNTs as self-storage devices, CNTs have
not been yet investigated as nanoreservoirs for
self-healing applications. The main challenges
related with this application are how to insert molecules into the carbon nanotubes, whether crack
can form on the sidewall of a carbon nanotube
during its propagation, and if the healing agent
will come out of the carbon nanotube when the
crack forms. In this avenue, recently, Lanzara et
al. (2009) have investigated the use of CNTs as
nanoreservoirs for automatic repairing applications, through a molecular dynamics (MD) study
with particular focus on the CNTs capacity of
delivering a healing agent. Authors have shown,
interestedly, that the CNTs were not only able to

Figure 5. Concept of the self-healing process using carbon nanotubes

18


Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures

carry the catalytic healing agent for local repair


but also can simultaneously play the role of filler
material for mechanical reinforcement prior and
after the delivery of the active material (Figure 5).

7. CONCLUSION
In conclusion, we have briefly presented a series
of recent results related to the various self-healing
concepts and systems. Research into self-healing
materials is an active and exciting field, with
an increasing number of research papers being
published every year. From the studies on healing
in concrete structures via embedded glass fibres
to the more recent work on healing using shape
memory alloy wires in a polymer composite, and/
or the use of multidimensional microvascular
network for the healing applications, the different
avenues being explored to achieve the common
end goal of prolonged functional lifetimes for
composite structural materials are astounding.
Beyond a strong interest of both academic and
commercial researchers in the hollow fibre and
microencapsulation approaches to self-healing
polymer development, new types of self healing
technology have been emerging at an increasing
rate over the last decade. Indeed, in recent years,
interesting perspectives have opened for the design
of innovative self-healing nanosystems. Computer
simulations have provided useful indications for
directing the efforts of scientists toward the fabrication of repairing systems.

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KEY TERMS AND DEFINITIONS


Autonomic: Reaction that is happening without external stimuli.
Biomimetic: The faculty to imitate the nature
in the light to fix complex problems.
Carbon Nanotube: Allotrope of carbon with
cylindrical shape nanostructures.
Delaminations: A mode of failure of composite materials occurring mainly in laminated
materials.
Microencapsulation: A process that organises liquid materials inside microspheres or
microcapsules.
Self-Healing Materials: A class of materials
having the ability to repair damage over time,
based on intrinsic property or by incorporating
appropriate materials.
Space Conditions: All environmental conditions characterizing space, including vacuum,
radiation, temperature fluctuations, and debris.
Space Debris: All manmade space waste in
orbit including old satellite debris, fragments from
disintegration, erosion and collisions.
Thermosetting: A type of petrochemical
materials (also called thermoset) which cure irreversibly under heat.

25

26

Chapter 2

Functionalization of Carbon
Nanocomposites with
Ruthenium Bipyridine and
Terpyridine Complex
Huayang Li
Clark Atlanta University, USA
Issifu Harruna
Clark Atlanta University, USA

ABSTRACT
Ruthenium bipyridine or terpyridine complexes functionalized carbon-based nanocomposites have special properties in the electromagnetic and photochemical research field. The aims of this chapter include
development of functionalized fullerene, carbon nanotubes, and graphene with ruthenium complex and
characterization of their nanostructural properties. Such nanocomposites can be accomplished using
either covalent or non-covalent functionalization methods.

INTRODUCTION
Composite nanomaterials including fullerene,
carbon nanotubes and graphene are an exciting
area of current research offering a variety of applications such as energy storage (Aliev et al.,
2009), biochemical sensors (Siqueira et al., 2009)
and photo-induced mechanical actuation (Ahir &
Terentjev, 2005). Combinations of metal ions with
polymers and carbon-based nanomaterials such as
fullerene, carbon nanotubes and graphene provide
an interesting route towards supramolecular struc-

tures with well-defined catalytic, electrochemical,


or magnetic properties (Tasis, Papagelis, Prato,
Kallitsis, & Galiotis, 2007). Metalligand coordination bonding with bipyridine or terpyridine has
become a promising tool towards such structures
(Schubert & Eschbaumer, 2002). The combination
of well-established ruthenium bipyridine or terpyridine chemistry with carbon nanocomposites is,
in general, a promising approach to novel material
fabrication (Siqueira et al., 2009). In this chapter,
we will discuss functionalization of such carbon
nanomaterials with bipyridine or terpyridine com-

DOI: 10.4018/978-1-4666-5824-0.ch002

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

plexes by chemically covalent and non-covalent


methods (excluding dopant functionalization).

Figure 1. Structures of 2,2-bipyridine and


2,2:6,2-terpyridine

BACKGROUND
Since 1987, supramolecular chemistry has become
a well-known concept and a major field in todays
research community. This concept has been defined as chemistry beyond the molecule, bearing
on the organized entities of higher complexity
that result from the association of two or more
chemical species held together by intermolecular
forces (Lehn, 1995). One of the most important
interactions found in supramolecular chemistry
is metal-ligand coordination. In this arena, chelate complexes derived from N-heteroaromatic
ligands, largely based on 2, 2-bipyridine and
2,2:6,2-terpyridine (Figure 1), have become an
ever-expanding synthetic and structural frontier.
Bipyridine has been known since 1888, (Paul,
Spey, Adams, & Thomas, 2004) ruthenium bipyridine complexes contained [Ru(bipy)3]2+have very
interesting photochemical properties making them
ideal candidates for solar energy conversion. This
is due to the long lifetime of the triplet excited
state and in part due to the fact that the structure
of the molecule allows for charge separation.
Its singlet-triplet transitions are forbidden and
therefore often slow. This unusual situation arises
because the excited state can be described as a
Ru3+ complex containing a bipy- ligand. Thus,
the photochemical properties of [Ru(bipy)3]2+ are
reminiscent of the photosynthetic assembly, which
also involves separation of an electron and a hole
(Bard & Fox, 1995). Ruthenium(II) complexes
of tris(bipyridine)ruthenium [Ru(bipy)3]2+ have
received considerable attention recently. The
stability and unique photophysical properties of
these systems have been exploited for artificial
photosynthesis, in sensors, in photorefractive
materials, in studies of electron transfer in proteins
and DNA, antitumor ability, and a wide range of
other purposes.

The chemistry of 2, 2:6,2-terpyridines


(designated as simply terpyridine or tpy) is much
younger than that of 2,2-bipyridines. In the early
1930s, terpyridine was isolated for the first time
by Morgan and Burstall (Storrier, Colbran, &
Craig, 1997; Lain et al., 2002), the well-known
characteristics of terpyridine Ruthenium complexes are their special redox and photophysical
properties, which greatly depend on the electronic
influence of the substituents. Therefore, terpyridine complexes may be used in photochemistry
for the design of luminescent devices (Loiseau et
al., 2001) or as sensitizers for light-to-electricity
conversion (Constable & Lewis, 1982; Newkome,
Hager, & Kiefer, 1986). In clinical chemistry
and biochemistry, functionalized terpyridines
have found a wide range of potential applications
from colorimetric metal determination to DNA
binding agents and anti-tumor research (Cave &
Raston, 2000, 2001; Cave, Raston, & Scott, 2001;
Fallahpour, Neuburger, & Zehnder, 1999; Sasaki,
Daran, & Balavoine, 1999). Absorption, as well
as emission spectra, revealed that a metal-ligand

27


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

charge transfer, takes place in these [Ru(tpy)2]2+


complexes. As opposed to bipyridine complexes,
where a phosphorescence phenomenon can be observed over a wide temperature range, no emission
is detected at ambient temperature in the case of
terpyridines because of a non-irradiative transition
of the excited triplet metal-to-ligand charge transfer (3MLCT) state by a triplet metal-centered (3MC)
state to the ground state. Photophysical properties
can, however, be fine tuned by the introduction
of a donor, an acceptor, or both, leading to roomtemperature luminescent [Ru(tpy)2]2+ complexes.
Another method to improve the luminescence
lifetime and quantum efficiency involves the attachment of aromatic groups.
For new functional materials, metallo-supramolecular polymers, dendrimers or micelles have
been of great interest for the last few years. Also
the combination of such stable complexes with
biopolymers such as DNA/RNA, peptides and
enzymes for labeling, intercalation and inhibition purposes is promising (Bard & Fox, 1995).
Another field which is rapidly growing due to
the technical advances made, is the build-up of
ordered structures on a molecular scale on different kinds of surfaces (Lain et al., 2002). Here,
terpyridine complexes play an increasing role for
applications such as solar cell devices or electrode
catalysis. Furthermore, such easily detectable
and multi-functional entities are of great use for
gaining a more fundamental understanding of self-

organization phenomena of organic or inorganicorganic hybrid materials on surfaces. (Figure 2)


Fullerene, carbon nanotubes and graphene are
molecules composed entirely of carbon. They
have been widely used in nanomaterials research
field. Fullerene, carbon nanotubes and graphene
are allotropes of carbon,which are valuable for
nanotechnology, electronics, and other fields of
material science and technology. In particular,
owing to their extraordinary super-thermal conductivity, mechanical and electronic properties.
But they have disadvantages in applications due to
their bundles as aggregations, hard to dispersion
in the solvents and non-affinity to biochemical
environment .The chemical functionalization
those carbon nanomaterials with polymer and
organic molecules will debundle their aggregation in polymer matrix or biological system;
solubilize them in organic solution and aqueous
media; enhance biological sensor application
and change their surface electronic properties
(Bunzli, 2010; Hirsch & Brettreich, 2005; Hirsch
& Vostrowsky, 2005). Fullerenes are of special
importance in contemporary chemistry because of
their photophysical and electrochemical properties
(Hirsch, 1994; Hirsch & Brettreich, 2005), thus
leading to the development of novel molecular
electronics or light-harvesting devices. Most of
the current research into these particular kinds of
potential solar cells includes fullerenes because
of their electron-accepting properties. Therefore,
the combination of fullerenes with [Ru(tpy)2]2+

Figure 2. Molecular structures of fullerene, carbon nanotubes and graphene

28


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

complexes has a special significance. The purpose


for functionalizing the fullerenes is to increase the
solubility of the molecule in cancer cells. Cancer
cells take up these molecules at an increased rate
because of an up-regulation of transporters in
the cancer cell, Once absorbed by the cells, the
C60 derivatives would react to light radiation by
turning molecular oxygen into reactive oxygen
which triggers apoptosis in the HeLa cells and
other cancer cells that can absorb the fullerene
molecule.
Carbon nanotubes (CNT) have raised much
interest due to their inherent electronic, mechanical, and thermal properties (Harris, 1999;
Tanaka, Yamabe & Fukui, 1999; Avouris, Dresselhaus, & Dresselhaus, 2000; Reich, Thomsen, &
Maultzsch, 2004) since they were made by Iijima
(NEC laboratories, Japan) in 1991 (Iijima, 1991).
MCNTs (multiwalled carbon nanotubes) have
extraordinary promise for applications in materials, new energy, and microelectronics; however,
their realistic application has been hindered by
processing and manipulation difficulties. The
functionalization of MWNT become necessary
to facilitate the application by improving ease of
dispersion and providing chemical attachment
to surface and polymer matrices (Bahr & Tour,
2002). There are two basic methods to functionalize multiwall carbon nanotubes: noncovalent
sidewall and covalent functionalization (Hirsch
& Vostrowsky, 2005). Carbon nanotubes (CNT)
non-covalent functionalization is mainly based
on supramolecular interaction, such as van der
Waalss and -stacking adsorption forces without
disrupting the conjugate -network (J. Chen et
al., 2002; R. J. Chen, Zhang, Wang, & Dai, 2001;
Ou & Huang, 2006; Petrov, Stassin, Pagnoulle,
& Jerome, 2003; Star et al., 2003; Steuerman et
al., 2002; Yang & Pan, 2008). Compared with
noncovalent functionalization, the covalent chemical modification (Lehn, 1995) using defect site
chemistry of CNT allows functional group to be
attached to the tube end and sidewall. Among
various covalent functionalization techniques

(Tasis et al., 2007) (Schubert & Eschbaumer,


2002), such as hydrogenation, halogenation, [2+1]
cycloaddition, radical additions and electrophilic
additions, the oxidation of CNT is probably the
most widely used and studied.
Oxidation of CNT with inorganic acid mixture, such as nitric and sulfuric acids will purify
the pristine CNT to remove metallic impurities
and will introduce carboxyl functional group to
the end of CNT. The further transformation and
modification of carboxylic group give access to
a large number of organic and polymer chemistry
of functional exploitation with amidation and
esterfication of COOH groups on the end and
surface of CNTs (Bahr & Tour, 2002; Karousis,
Tagmatarchis, & Tasis, 2010; Tasis, Tagmatarchis,
Bianco, & Prato, 2006).
In addition, graphene, a two-dimensional gapless semiconductor with -conjugated network,
has demonstrated intriguing electronic, thermal,
and mechanical properties (Geim, 2009; Geim
& Novoselov, 2007; Novoselov et al., 2004).
The high aspect-ratio of graphene and graphene
nanoribbons (GNRs) offers unprecedented opportunity for nanoscale functional interfaces that
have potential applications in electronics, sensors,
spintronics, nanoelectronics, and biodiagnostics
(Bunzli, 2010; Gokus et al., 2009; Hummers &
Offeman, 1958; Liu et al., 2010; Loh, Bao, Eda,
& Chhowalla, 2010; Xie, Ling, Fang, Zhang, &
Liu, 2009). GNRs have been fabricated using
metal particle-assisted and lithographic methods,
or oxidative longitudinal unzipping of multiwall
carbon nanotubes (MWCNTs). The modification
of graphene on the molecular level with noble
metal nanostructures is an example of a bottomup fabrication route towards nanometer-scale
devices as functional building blocks in biotechnology and nanotechnology.
All of these carbon based nanomaterials can
be modified by ruthenium bipyridine and terpyridine complexes.

29


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

MAIN FOCUS OF THE CHAPTER


Bipyridine Ligand Synthesis Method
2, 2-bipyridine (bipy) is prepared by the dehydrogenation of pyridine using Raney nickel
(Figure 3). The bipyridine core offers a myriad of
possibilities in terms of modification by different
substitution patterns which led to its manifold use
as attractive building blocks in supra-, nano- and
macromolecular chemistry, as well as, in the areas
of analytical and photochemistry.
Reflecting the popularity of this ligand design,
many substituted variants of bipy have been described in references (Hapke, Brandt, & Lutzen,
2008; George R. Newkome, Patri, Holder, &
Schubert, 2004; Okamoto, 2012; Smith, Lamba,
& Fraser, 2004; Smith, Savage, Love, & Fraser,
2004). For example, Negishi crossing-coupling
and derivation functional groups of substituted
2, 2-bipyridine are two methods that are usually
used. Recently, the metal-catalyzed [2 + 2 + 2]type cycloaddition reaction of alkynes and nitriles
(Figure 4) has attracted considerable interest as a
straightforward, atom-economical route to substituted pyridines and methods have been extensively
applied to bipyridine synthesis. Developments
in the field of 2, 2-bipyridine synthesis through
alkyne/nitrile [2 + 2 + 2] cycloaddition reactions
catalyzed by transition metals are reviewed in this
article involving two types of fully intramolecular
reaction, five types of partially intramolecular
reaction and fully intermolecular reactions .
The most prominent cross-coupling reactions
include the Stille, Negishi, SuzukiMiyaura,
Kumada and Hiyama coupling reaction(Figure
5). They have all found application in the synthesis and functionalization of heteroaromatic
compounds as well as in the preparation of 2,
2-bipyridines (Hapke et al., 2008; Smith, Savage,
et al., 2004). There are two main problems associated with the synthesis of the 2,2-bipyridine core
by cross-coupling reactions: (a) the coordination
ability of the product can have adverse effects on

30

the catalytic cycle, and (b) the synthesis of the


pyridyl derivative, especially with the appropriate
transmetallating group (TMG).
For symmetrical 2, 2-bipyridines, the synthetic approaches are in the predominant number of
cases modifications of the existing bipyridine core
structures or homo-coupling reactions of suitable
pyridine precursor molecules. For non-symmetrically substituted 2, 2-bipyridines the synthetic
approach is comparatively more complicated. The
Negishi coupling can combine the tolerance of a
large number of functional groups with a higher
transmetallation activity. For example, after the
synthesis of different ethynylated, especially the
2-chloro-5-([trimethylsilyl]ethynyl)- pyridine
(Smith, Lamba, et al., 2004), Negishi crosscoupling (Figure 6) with this 2-pyridyl chloride
derivative and electron-rich trialkylphosphane
PtBu3 gave superior yields compared to the standard catalyst PdCl2(PPh3)2, chelating phosphanes
such as 1,1-Bis(diphenylphosphino)ferrocene
dppf (Okamoto, 2012), or the biphenyl backbonebased Buchwald ligand (Hapke et al., 2008).

Terpyridine Ligand
Synthesis Method
The two basic synthetic approaches to terpyridine
are by either central ring assembly or coupling
methodologies. Ring assembly (Figure 7) is the
most prevalent strategy, but because of their
multiplicity and efficiency, modern Pd-catalyzed,
cross-coupling procedures have recently become
seriously competitive and may surpass the traditional ring-closure processes.
Modern Pd(0)-catalyzed coupling reactions
combine the desired efficiency and simplicity
with controllable substitution possibilities. Suzuki, Negishi, and Stille couplings are all based
on a Pd(0)/Pd(II) catalytic cycle. Particularly, the
Stille cross-coupling has become a popular route
to terpyridine, (Figure 8) because of its universal
building block principle, multi-gram product accessibility, and well-directed functionalization at


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 3. 2, 2-Bipyridine prepared by Raney nickel

Figure 4. 2, 2-Bipyridine synthesized by metal-catalyzed [2 + 2 + 2]-type cycloaddition reaction (Copyright 2012 The Japan Institute of Heterocyclic Chemistry)

Figure 5. The cross-coupling approaches for 2,2-bipyridines synthesis (Copyright 2004 Organic
Syntheses, Inc.)

31


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 6. Initial screening experiments for the modified Negishi cross-coupling reaction (Copyright
2008 Royal Chemistry Society)

almost every desired position(Crdenas & Sauvage, 1996; Fallahpour, 2000; Heller & Schubert,
2002; Miyaura & Suzuki, 1995; Nozaki, International Union of Pure and Applied Chemistry.
Organic Chemistry Division., Nihon Gakujutsu
Kaigi., & Nihon Kagakkai., 1983; Parks, Wagner,
& Holm, 1973; Stille, 1986; Ulrich, Bedel, Picard,
& Tisns, 2001).

32

Complexation of Bipyridine
and Terpyridine Ligands
with a Metal Center
Bisterpyridine metal complexes of the type [M
(tpy) 2(X) 2] (X = e.g. Cl, ClO4, PF6) have
been known for a long time (E. C. Constable
& Thompson, 1992; Sauvage et al., 1994; Tomasik, Ratajewicz, Newkome, & Strekowski,
1985). Complexation of terpyridine ligands with
an Ru(II) center can be conducted in a simple
two-step sequence. The Ru (III) intermediate
is generally isolated but not characterized, then


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 7. Ring-assembly methods to terpyridine: (a) and (b) Kronke reaction, (c) Potts methodology,
(d) Jameson methodology. (Copyright 2004 Wiley-VCH)

simply reacted in the next step with a second


equivalent of the same or different terpyridine
under reductive conditions to afford the desired
symmetric or asymmetric Ru(II) complex, respectively. The intermediate is subsequently suspended
with the second ligand in methanol containing
N-ethylmorpholine (Maestri, Armaroli, Balzani,
Constable, & Thompson, 1995) and refluxed for
14 h. The solvent can also act as a reducing agent
for the Ru (III)Ru (II) conversion. Alternatively,
an equimolar amount of AgBF4 can be added to

the initial Ru(III) complex in DMF or acetone to


remove chloride ion. (Figure 9)
Complexing bipyridine ligands with a Ru(II)
center can be conducted in a simple sequence.
Ru(bpy)Cl2, which was first prepared by ruthenium
(III) chloride reaction with 2, 2-bipyridine, and
then was added into one portion of bipyridine
ligands solution with ethanol as reductant and
solvent,. After refluxing and filtration, NH4PF6
was added as counter anion to make the complex
soluble in organic solvent (Figure 10).

33


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 8. Stille-coupling 2-trimethylstannylpyridines and 2,6-dihalopyridines (Copyright 2004 WileyVCH)

Figure 9. Complexation of terpyridine ligands with Ruthenium center (Copyright 2004 Wiley-VCH)

Figure 10. Complexation of bipyridine ligands with Ruthenium center

34


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Polymerization Method for


Terpyridine and Bipyridine Ligand
To design different types of Terpyridine ligand and
precisely control molecular weight and molecular
distribution, several polymerization methods have
been explored and carried out to make suitable
metallo-terpydyl complex for nanohybrid. Most
synthetic approaches have involved the construction of systems with broad molecular weight distributions and lack of control over polymer architecture. To overcome these drawbacks, living and
controlled polymerization techniques have been
employed. All controlled radical polymerization
(CRP) techniques are quite complementary in the
synthesis of polymers with controlled architecture,
and they are much simpler and user friendly than
ionic polymerizations.

Reversible Addition-Fragmentation
Chain Transfer (RAFT) Polymerization
RAFT polymerization is accessible to control molecular weight and molecular weight distribution
as well as advanced architectures such as block,
comb, and star copolymers (Chiefari et al., 1998;
Cowie & Arrighi, 2008a, 2008b; Moad, Chong,
Postma, Rizzardo, & Thang, 2005; Sbastien Perrier.& Pittaya Takolpuckdee. 2005). In contrast,
the RAFT process is distinguished by its versatility with respect to both monomer choice and
polymerization conditions. The key to successful
operation of RAFT polymerization lies on the use
of a highly efficient chain transfer agent (CTA),
which is typically a thiocarbonylthio compound. In
general, the vast majority of RAFT-prepared (co)
polymer chains bear CTA fragment groups at both
ends. Our group has used this method to prepare
the terpyridine terminated macromolecules with
well-defined structures which were further used
for preparation of supramolecular diblock metallo

macromolecules (Zhou & Harruna, 2005; Zhou,


He, Harruna, & Geckeler, 2008).
Synthesis of bipyridine-functionalized RAFT
agents (Zhou & Harruna, 2004) will also be used
to prepare bipyridine-terminated polystyrene, as a
polymer bipyridine ligand chelating with Ru(bpy)2
ion to produce tris(bipyridine)ruthenium(II)-centered polystyrene metallopolymers. (Figure 11).

Design Organic Terpyridine


Ligand Spacer and Polymerization
Complex for Nanohybrid
The aim of synthesizing metallo-supramolecular
ligands is to create a novel molecular bridge that
can reveal specific and multifunctional properties
to carbon nanotube and graphene (Figure 12). The
metallo- terpydyl complexes have double functions: one is to assembly nanotubes, graphene or
fullerene into a whole functional nanostructure
with special electrochemical, optical, magnetic
properties; another is to form a communication
bridge for biofuctional target molecules (such as,
protein and DNA) and nanotubes, graphene or
fullerene, The building blocks should therefore be
carefully selected in order to engineer new materials with tunable and tailored properties. Beside the
use of low molar mass ditopic organic ligands,
telechelic polymers bearing suitable ligands at
their extremity are extremely valuable candidates
for the formation of metallo-supramolecular polymers. In this way, the properties of the designed
materials can be manipulated not only by the
careful choice of the metal ions, but also by the
polymer backbone (Figure 12). This allows the
formation of materials synergistically combining
the characteristic features of the metal ligands
complexes to carbon nanotube/gold nanoparticles.
The following are examples of design of organic
terpyridine and polymer ligands.

35


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 11. RAFT polymerization of bis terpyridine ruthenium connected diblock polymer and schematic
representation for preparation of tris(2,2-bipyridine)ruthenium(II)-centered polystyrene metallopolymers
(Copyright 2005, American Chemical Society)

36


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 12. Schematic overview of the properties of designed metallo-terpydyl complex (Copyright 2009
Wiley-VCH)

FUNCTIONALIZATION OF
FULLERENE, CARBON
NANOTUBES AND GRAPHENE
WITH RUTHENIUM BIPYRIDINE
AND TERPYRIDINE COMPLEXES
Functionalization of Fullerene with
Ruthenium Bipyridine Complexes
Incorporation of C60 molecules into macromolecular architectures provides an attractive opportunity
to combine the unique electronic and optical
properties of fullerenes with superior physicomechanical characteristics of polymers. Fullerenes
have been extensively modified with a variety
of polymers through various approaches (Dai &
Mau, 2001; Geckeler & Samal, 1999; Geckeler &
Samal, 2000; Giacalone & Martn, 2006; Wang,
Guo, Fu, Wu, & Zhu, 2004). Varieties of C60-bound
molecules have been incorporated into polymer

backbones, pendants, or the terminal groups as


components. Approaches accessible to fullerenecontaining polymers can be divided into five main
types. First, direct copolymerization with fullerene, in which C60 as comonomer reacts with some
monomers via either free-radical polymerization
or living anionic polymerization (Camp, Lary, &
Ford, 1995; Y. Chen, Zhao, Cai, Huang, & Xiao,
1998; Ford, Nishioka, McCleskey, Mourey, & Kahol, 2000). Second, homo- and copolymerization
of the fullerene-containing monomer, in which a
fullerene-functionalized monomer is first synthesized and further homo- and/or co-polymerized
by free radical polymerization, catalytic polymerization, ring-opening metathesis polymerization
(ROMP), coupling reaction and polycondensation
reaction processes (Iwamoto & Yamakoshi, 2006;
Nishimura, Takatani, Sakurai, Maeda, & Yashima,
2002; Ramos, Rispens, van Duren, Hummelen, &
Janssen, 2001; Scamporrino, Vitalini, & Mineo,

37


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

1999; Sivula, Ball, Watanabe, & Frchet, 2006;


Zhang et al., 1995). Third, the graft to method,
in which random and block copolymers with active sites along the polymer chain reacted with
C60 to produce C60-grafted polymers, It is worth
mentioning that some fullerene-bond dendrimers
were also prepared by the graft to method
(Barrau et al., 2008; Geckeler & Hirsch, 1993;
Hawker, Wooley, & Frechet, 1994; Nierengarten,
Armaroli, Accorsi, Rio, & Eckert, 2003; Stalmach,
de Boer, Videlot, van Hutten, & Hadziioannou,
2000). Fourth, chain end functionalization, in
which fullerene-functionalized initiators were first
synthesized and further initiated polymerization
of monomers to produce fullerene end-capped
polymers (Nierengarten et al., 2003). However,
in most cases, polymers with active end-groups
reacted with fullerene to form mono- and bi-C60end-capped polymers as well as C60-cored starshaped polymers and multi-armed C60-end-capped
polymers (Zhou, Chen, Li, Du, &Li, 2000; Wang,
Pramoda, & Goh, 2006; Nepal, Samal, & Geckeler, 2003, Cloutet, Gnanou, Fillaut, & Astruc,
1996; Zhou, Harruna, Zhou, Aicher, &Geckeler,
2007). Fifth, supramolecular association, in which
fullerene-containing supramolecular polymers
are formed by hydrogen bonding, charge transfer
complexation, or other noncovalent interaction
forces (Snchez, Rispens, & Hummelen, 2002;
Laiho, et al., 2006). Particularly, the synthesis
and studies of polypyridylruthenium complexes
with electron-accepting fullerene moieties that is
very interesting from the intramolecular electron
transfer between the ruthenium metal complex donor and the fullerene acceptor can be successfully
switched on/off through regulating the structure
and distance of the spacer linking them. So far,
there are no reports that such electronic communication can be regulated by external temperature.
The molecular weight and polydispersity of the
poly(N-isopropyacryamide) (PNIPAM) block
between fullerene and tris(bipyridine)ruthenium
end-groups can be controlled during the living

38

radical polymerization step. Preliminary results


show that these metallopolymers exhibit interesting self-assembly characteristics in aqueous
solutions (Figure 13).

Fuctionalization of Carbon
Nanotubes with Ruthenium
Bipyridine or Terpyridine Complexes
Non-Covalent Functionalization of
Carbon Nanotubes by Ruthenium
Bipyridine or Terpyridine Complexes
Non-covalent functionalization of carbon nanotubes (CNTs) by polymer wrapping, interaction
with DNA or peptides, and the adsorption of ionic
or non-ionic surfactants to promote their solubility
is preferred to organic functionalization because
the pristine sp2 hybrid state is preserved. Recently,
there has been considerable interest in bringing
metal complexes in close contact with SWCNTs
with applications that include catalysis, photoinduced electron transfer and information storage.
Scientists are currently exploring the photoinduced
electron transfer reactions from similar complexes
to SWCNTs and their possible applications in
energy storage and conversion. CNTs can be efficiently dispersed with a pronounced degree of
individualization by non-covalent interactions
with water soluble Ru(II) polypyridyl complexes
containing extended systems. The dispersion
of nanotubes in aqueous media can realized by
ruthenium (II) polypyridyl complexes (Jain, Saha,
&Mart, 2011). Ru(bpy)2(dppn)2(dppn = benzo[i]
dipyrido[3,2-a:2,3-c]phenazine) showed the
highest ability to disperse SWCNTs, probably due
to their more elongated p-electron system allowing a better interaction with the SWCNTs, while
at the same time minimizing the steric effect and
increasing the distance between the SWCNT and
the positive charges of the ruthenium complex.
(Figure 14)


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 13. Synthesis route for fullerene and ruthenium dual end-functionalized thermosensitive polymers
and aggregation of tris(bipyridine)ruthenium-terminated PNIPAM metallopolymers in water (Copyright
2007 Royal Society of Chemistry; Copyright 2008 Wiley-VCH)

Among many organic and inorganic electrogenerated chemiluminescence (ECL) systems, solidstate ECLs based on immobilized luminophor,
tris(2,2-bipyridyl)ruthenium(II) (Ru(bpy)32+)
and its derivatives, are always attractive for
chemical analysis, clinical testing, light emitting
devices and luminescent imaging due to their good
stability, reversible electrochemical properties,
high luminescent quantum yield and favorable
compatibility with a wide range of analyses.

SWCNTs were functionalized noncovalently


with a new tris(bipyridyl)ruthenium(II) derivative
bearing two pyrene groups though stacking
interactions (Ding, Shan, Cosnier, & Goff, 2012)
that preserve the pristine electronic structure of
SWCNTs (Figure 15). Thanks to the high conductivity and high surface area of SWCNTs, the
electrogenerated poly-/oligopyrene derivative
exhibits enhanced electrochemical behavior with
fast electron transfer and highly reversible redox

39


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 14. Non-covalent ruthenium polypyridyl


complexescarbon nanotubes composites (Copyright 2011 Royal Society of Chemistry)

the nanocomposites afford entry into the formation


of tailored molecular surfaces capable of yielding
dense electron storage and release devices as well
as components for photovoltaic devices due to the
ability of the macrocycles to act as in progress.

Covalent Functionalization of
Carbon Nanotubes by Ruthenium
Bipyridine or Terpyridine Complexes

process for Ru(III)/Ru(II). Luminophor redox


Ru(III)/Ru(II) in this novel pyrene-Ru/SWCNT
composite thus constitutes an attractive material
for solid state ECL both in organic and aqueous
solutions.
Ruthenium terpyridine complex also can be
non-colvantly attached onto CNTs surfaces by
the preparation of a water-soluble metallomacrocycle (Figures 16 and 17) possessing positive
charges that facilitate ionic coordination with the
negatively charged carboxylate moieties of OxiSWNTs thereby forming a nanotube composite
with unique electronic properties (Wang, et al.,
2007; Hwang, 2006). This self-assembly method
shows potential for use in solar cell conversion or
electronic nanodevices, since the components of

40

Ultraviolet illumination of carboxylated SWNTs


results in the filling of valence band states of the
semiconducting SWNTs. This process presumably
includes reduced dopants defective oxidized carbon sites, together with holes in the band electronic
structure, that are inevitably generated during the
purification of SWNTs by a strong acid treatment.(Itkis,etal 2003) Acid purification results
in p-doping of semiconducting SWNTs (Itkis, et
al., 2003; Kazaoui, et al., 2001; Hennrich, et al.,
2003). Therefore, changes in the SWNT valence
band population might alter SWNT conductivity,
thus making light modulation of their electrical
conductivity possible. Covalent attachment of
Ru(bpy)32+ to the SWNT surface makes the carbon
nanotubes selectively light-sensitive, and that illumination of Ru(bpy)32+-SWNT in the characteristic
Ru(bpy)32+ absorption band results in a persistent
increase in conductivity of the semiconducting
SWNT film (Khairoutdinov et al., 2004). The
observed photoconductivity of Ru(bpy)32+-SWNT
films is indicative of electron transfer from SWNT
to the photoexcited Ru(bpy)32+, and that this is the
major mechanism of luminescence quenching in
Ru(bpy)32+-modified SWNTs. (Figure 18)
The ruthenium(II) bipyridyl derivative,
[Ru(bpy)2(AMbpy)]Cl2 (AMbpy = 4,40-aminomethyl-2,20-bipyridine) (Ru(II)) covalently linked
CNTs hybrid (Li, Guo, L. Gao, W. Xia, & Zheng,
2009) shows good electrochemical activity and ca.
17 times higher luminescence quantum efficiency
than the adsorbed derivative Ru(bpy)3. The RuCNTs based solid state ECL sensor exhibits high
stability toward determination of triphenylamine


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 15. Schematic presentations of: A) pyrene-Ru, and B) pyrene-RuSWCNTs (Copyright 2012
Wiley-VCH)

Figure 16. Illustration of multi-ion pair association of Ru-hexamer 2 with Oxi-SWNT (Copyright 2007
Royal Society of Chemistry)

41


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 17. Illustration of hexamer/MWCNT nanohybrids TEM photograph. Red arrows indicate
single hexamers, and yellow arrows show the
agglomerates of several hexamers (Copyright
2006 American Chemical Society)

(TPA). The present Ru-CNTs hybrid could be used


as both electrochemical and luminescent labels for
ultrasensitive bioanalysis (Figure 19).
An inorganic metal complex, [ruthenium(4,4dicarboxy-2,2-bipyridine)(2,2-bipyridyl)2]
(PF6)2,([Ru(dcbpy)(bpy)2](PF6)2) can be covalent
attached to amino functionalized multiwall carbon
nanotubes. (Figure 20) The tubes were ball milled
in a stainless steel drum for 100 h in a NH3 atmosphere, resulting in shortened (200-300 nm) and
open-ended MWNT, functionalized with amino

42

(-NH2) groups [Ru(dcbpy)(bpy)2](PF6)2 (Figure


20) was dissolved in 15 mL of thionyl chloride.
The reaction mixture 1B was refluxed under
argon for 5 h. The thionyl chloride was removed
by vacuum distillation. The remaining solid was
partially dissolved in dichloromethane (DCM).
That MWNT are interconnected through more
than one ruthenium to form multiwall carbon
nanotube interconnects through amide linkage
with a ruthenium complex were successfully
created. Interconnects were visualized through
AMF imaging, which showed multiple T- and
Y-junctions (Frehill, et al., 2002).
Combinations of metal ions with polymers and
nanotubes provide an interesting route towards supramolecular structures with well-defined catalytic, electrochemical, or magnetic properties. Metal
ligand coordination bonding with terpyridine has
become a promising tool towards such structures
while the combination of well-established polymer
chemistry and the versatile functionality of metal
ions is, in general, a promising approach to novel
material fabrication. Surface functionalization of
CNTs (SWCNTs or MWCNTs) with dendronized
alkoxy terpyridine-Ru(II)-terpyridine complexes
has been accomplished using either the grafting
to or the grafting from approaches. Different
sets of easily processable hybrid metallo-CNTs
composites have been efficiently synthesized
bearing either monomeric or polymeric side chain
tpy-Ru(II)-tpy dicomplexes (Muller, et al., 2009;
Stefopoulos, et al., 2009).
Using the grafting from approach, SWCNTs
were decorated with polymeric side chain dendritic tpyRu(II)tpy complexes. Starting from
SWCNTs functionalized with ATRP initiator sites
we were able to polymerize a vinyl terpyridine
monomer. The free side-terpyridine groups of
SWCNT-poly(tpy) were then complexated with
the didodecyloxy-tpy-Ru(III)Cl3 monocomplex
(II) affording the finalhybrid nanotubemetallopolymeric complex SWCNT poly(tpyRu(II)
tpy2C12H25) (Figure 21). For solubility reasons
of the CNT-metallomonomers and CNT-metal-


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 18. Dynamics of resistance changes under illumination by visible light (440 nm < < 520 nm, I
=0.015 W/cm2) of the Ru(bpy)32+-SWNT film (Copyright 2004 American chemical Society)

Figure 19. Enhanced electrochemiluminescence efficiency of Ru(II) derivative covalently linked carbon
nanotubes hybrid (Copyright 2009 Royal Society of Chemistry)

43


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 20. MWNT are interconnected one ruthenium complex ([Ru(dcbpy)(bpy)2](PF6)2) (Copyright
2002 American Chemical Society)

lopolymers, long aliphatic chains were attached


on the terpyridines which effectively acted as
solubilizers of the final hybrid metallo-CNTs. As
it is well-known, such long aliphatic substituents
located on the outer sphere of dendrimers and
dendronized polymers lead to enhanced organizational features.
The ruthenium terpyridine complexes themselves have the electron donor properties with
metal ion centers; and CNTs are often utilized as
electron acceptors with their extended electron
conjugation. The functionalization of nanotubes
with ruthenium complex can potentially form an
electronic donoracceptor system. The interaction
of CNTs and ruthenium terpyridine complexes has
been demonstrated by electrochemical monitoring of the change in ruthenium redox potential or
photophysical switching of the contact between
CNTs and ruthenium complexes. MCNTs can be
efficiently functionalized with Ru(II) terpyridine
complexes using the simple and mild methodology
of directly covalent amidation (Li, Wu, Jeilani,
Ingram, & Harruna, 2012). The tpyRutpy moi-

44

eties are interconnected or attached as aggregated


structures (100200-nm range) on the surfaces of
the carbon nanotubes after functionalization. The
electrical property of RuMCNTs depicts higher
resistance than that of OX-MCNTs (Figure 22).
Base on the amidation functionalization method, oxidized-MWCNTs can directly connected
with bis(2,2:6,2-terpyridine) ruthenium(II)
connected diblock metallopolymers increase the
solubility of functionalized MWCNTs in organic
solvents and water. (Li, etal. 2012).Metallo-supramolecular polymers based on the bis(2,2:6,2terpyridine) ruthenium(II)-connected units have
reversibility upon the application of external
stimuli, such as pH, temperature, redox processes
or application of competitive ligands. The polymer
ligand of terpyridine-ended poly(N-isopropyacryamide)(TpyPNIPAM) has been synthesized with
RAFT polymerization. It has been reported that
bis(terpyridine) ruthenium connected PNIPAM
copolymer has good hydrophilic and smart
thermo-responsive nature Furthermore, once selfassembled, this thermo-responsive nature could be


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 21. CNTs functionalized with polymeric side chain dendritic tpyRu(II)tpy complexes (Copyright
2009 Wiley-VCH)

used to enable a change in morphology by shifting


the hydrophobic to hydrophilic ration of building
block. Considering above material advantages of
such metallopolymer and MWCNTs, MWCNTs
can be easily functionalized by using a kind of
metallopolymer (RuTpyPNIPAM) to design new
kind of ruthenium-CNT based nanomaterials that
combined advantages of both ruthenium metallopolymers and CNTs (Figure 23).
A novel full-conjugated 4-(2,2:6,2-terpyrid4-yl) benzenediazonium tetrafluoroborate

(diazo-tpy) was synthesized and used for surface modification of materials, such as quartz
wafers, ITO glass, silicon, and multiwall carbon
nanotubes (MWCNTs) (Pan et al., 2010). Under
UV irradiation, the diazonium group of diazotpy is decomposed and the residual terpyridine
group is covalently anchored to the surface of
substrates. The obtained tpy-modified MWCNTs
(tpy-MWCNTs) have good solubility in common
organic solvents. Multilayer films were fabricated
from tpy-MWCNTs and ruthenium ions [Ru(III)]

45


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 22. Amidation of MWCNTs with Ruthenium (II) terpyridine complex (Copyright 2009 Springer)

via the layer-by-layer self-assembled (LBL SA)


technique (Figure 24) on the tpy-modified quartz
wafer, ITO glass, or silicon. Under illumination,
the LBL SA films on ITO showed an effective
photoinduced charge transfer because of their

46

conjugated structure and the ITO current density


changed with the number of bilayers. Upon irradiation, photocurrent is generated, which indicates
that the tpy-MWCNT-Ru(III) film is an excellent
photosensitizer in the visible region.


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 23. Amidation of MWCNTs with bis(2,2:6,2-terpyridine) ruthenium(II) connected diblock


metallopolymers (copyright 2012 American Scientific Publishers, Inc.)

Self-Assembly of Bis(2,2:6,2Terpyridine) Metal-Connected


Diblock Metallopolymers on
Graphene Nanoribbons
In recent years the self-assembly of metallosupramolecular block copolymers has made significant progress toward achieving the synthesis
of novel and functional nanostructures through
versatile and facile strategies for many desirable
applications. Metal-containing polymers combine
the processability and mechanical properties of
polymers with the unique properties of metal
complexes. Metal-ligands interaction has been
widely utilized for building up supramolecular
system (Campagna, et al., 2007; Juris, et al., 1988).
A predominantly used metal complex building

block for construction is 2, 2: 6 2-terpyridine


which is capable of forming stable chelate complex
with metals. Graphene hybridized with polymer
is expected to be a good candidate for an acceptor
material because large donor/acceptor interfaces
for charge generation and a continuous pathway
for efficient electron transfer can be built by the
graphene component (Novoselov, et al., 2004;
Campagna, et al., 2007; Juris, et al., 1988). Oneatom thickness and large 2D plane of graphene can
expect a large specific surface area in a polymer
matrix, and thus very large functional interfaces
can be formed. The modification of GNR on the
molecular level with polymer nanostructures is an
example of a bottom-up fabrication route towards
nanometer-scale devices as functional building
blocks in biotechnology and nanotechnology

47


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 24. Formation of LBL SA films fabricated from transition-metal ions and tpy-MWCNTs on the
diazo-tpy-modified functional surface (Copyright 2010 American Chemical Society)

(Xie, Ling, Fang, Zhang, & Liu, 2009; Reuven,


Li, Harruna, & Wang, 2012; Jain, Saha, & Mart,
2011). The MWCNTs were unzipped and reduced
to produce graphene ribbon. A modified graphene
nanoribbon (GNR) purification procedure was
utilized, in which the product was isolated by
repeated mixing and centrifugation steps, for
the separation of exfoliated graphene ribbons
from unzipped MWCNT. The oxidation reaction
product was poured into 5 ml of liquid nitrogen
cooled 30% hydrogen peroxide, which prevented
the precipitation of potassium permanganate.
The resultant single and bilayer GNRs were spin

48

cast from an ethanol/water (50:50) solution onto


a silicon wafer with 300 nm SiO2 wafers. The
GNRs were reduced by their adsorption on the
SiO2 surface and subsequent treatment with 1 vol%
hydrazine monohydrate and 1 vol% concentrated
ammonium hydroxide. The reduced GNRs were
washed with deionized water and dried under
nitrogen gas flow.
The supramolecular self-assembly (Pocius
& Chaudhury, 2002) of bis(terpyridine) metalconnected diblock copolymer on graphene nanoribbons by the formation of donoracceptor
complexes is mediated by enhanced van der Waals


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 25. Chemical schemes and optimized molecular structures for bis (2, 2: 6 2-terpyridine)
zinc and ruthenium-connected diblock copolymers. PS, PNIPAM, and tpy refer to polystyrene, poly(Nisopropyacryamide), and terpyridine (Copyright 2012 Royal Society of Chemistry)

interactions. Our findings (Reuven, Li, Harruna,


& Wang, 2012) provide a basis for processing
a variety of metallopolymers into controllable
nanoscale arrangements. We have studied the
interaction of bis(2,2:62-terpyridine) metalconnected AA (PS/PS) and AB (PS/PNIPAM)
block copolymers with GNRs (Figure 25).
Zn-metallo-polymer forms a distinct beaded
interconnecting Web pattern when deposited onto
a random field of GNRs resting on a silicon oxide
(SiO2) surface (Figure 15a, b and d). Atomic force
microscopy AFM images reveal that the Webbed
film is composed of Zn-metallo-polymer (Figure
26), which has an estimated height of 20 nm at
the interconnect regions. The dark beaded features
have a height of 70 nm and are evidently attributed
to the self-assembly of the Zn(tpy)2 metal centers
together with layered GNRs.
The photoluminescence (PL) of the GNR/Zincmetallopolymer hybrid was studied by confocal
laser scanning microscopy (CLSM) and flores-

cence microscopy. CLSM dark Webbed-dendrite


features correspond to PSZn(tpy)2PNIPAM/
GNR as seen in AFM images[89]. The intrinsic
PL of polystyrene is closely connected to the
prospect of imaging the PS-Zn(tpy)2-PNIPAM/
GNR film. Luminescence of the composite was
detected using fluorescence modes. In contrast
to AB Zn-polymer, the AA Ru-polymer forms
a uniform film on Si/SiO2 surface, owing to the
absence of hydrophobic/hydrophobic polymer
interactions. The Ru-metallopolymer induces the
assembly of GNRs into a distinct pseudo-fractal
dendrite pattern.
CLSM reveals that PSRu(tpy)2PS polymer
orders GNRs (dark features) into a pseudo-fractal
branching pattern (Figure 27i). A higher magnification image of a branch of ordered GNRs
is shown in the inset. We attribute the observed
GNR order to self-exclusion of amphiphilic GNRs
from the hydrophobic PSRu(tpy)2PS polymer.
As to the photoluminescence of PSRu(tpy)2PS/

49


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 26. Confocal microscopy, CLSM photoluminescence, and AFM topology images of PNIPAM
Zn(tpy)2PS polymer and PNIPAMZn (tpy)2PS/GNR self-assembly on Si/SiO2 surface. (a) Confocal
microscope; (b) CLSM photoluminescence image; (c) Edge-enhanced 3D rendered AFM image of PNIPAMZn(tpy)2PS polymer spin cast onto Si/SiO2 surface from THF solution; and (d) Edge-enhanced
3D rendered AFM image of PNIPAMZn(tpy)2PS/GNR composite on Si/SiO2 surface (Copyright 2012
Royal Society of Chemistry)

GNR film, the auto-fluorescence of polystyrene


block copolymer is apparent in GFP, DAPI and
rhodamine fluorescent microscope images of
PSRu(tpy)2PS polymer. The auto-fluorescence
of the PSRu(tpy)2PS /GNR composite film is
predominantly seen at the GNR branches (Figure
27). The branched features of the composite are

50

composed of GNRs and are of higher PL than the


polymer film counterpart.
The Raman microscope image of PSZn(tpy)2
PNIPAM/GNR composites on a SiO2 substrate
is shown in Figure 28. The GNRs bead features
(brown) decorated with interconnecting polymer
Web features (yellow), are spatially confined.


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Figure 27. Bright-field/fluorescent confocal microscopy and CLSM photoluminescence images of PSRu
(tpy)2PS polymer and polymer/GNR films. (a) Confocal microscope PSRu(tpy)2PS polymer. Inset:
GFP, DAPI and rhodamine fluorescent images of PS-Ru-tpy2-PS polymer; (b) Confocal microscope
PSRu(tpy)2PS/GNR film. Inset: PS-Ru-tpy2-PS/GNR film GFP, DAPI and rhodamine fluorescent images, (c) CLSM photoluminescence image of PSRu(tpy)2PS/GNR film, Inset: Higher-magnification
CLSM image showing self-assembled GNRs structure. Scale bar in (b-d) and (f-h) is 100 m (Copyright
2012 Royal Society of Chemistry)

Figure 28. Multi-micron PNIPAMZn(tpy)2PS polymer pattern cantered on GNRs and PSRu(tpy)2PS
polymer induced ordering of GNRs. (a) Confocal microscope image of long-range polymer ordering of
PNIPAMZn (tpy)2PS cantered at GNRs, propagating on SiO2. Inset: Micro Raman map spectroscopy
of the peak width of the G (1603 cm-1) line intensity acquired on a 12 24 m2 scan window reveals
coloured features and Raman signatures consistent with chemically prepared GNRs; (c) Confocal microscope image of PSRu(tpy)2PS polymer induced GNR ordering on Si/SiO2surface. Inset: Micro
Raman map spectroscopy of the peak width of the G (1603 cm-1) line intensity acquired on a 20 80
m2 scan window (Copyright 2012 Royal Society of Chemistry)

51


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

Micro Raman mapping with a spatial resolution


of 1 micron was used to characterize the polymer
surface features. The Raman mapping of the G
line (1603 cm-1) peak (inset of Figure 28a) shows
that the beaded features are clearly attributable to
GNRs. As the smaller brown GNR features (<1
m) are coated with polymer, their Raman signal
is obscured. These results show that the GNRs
and PSZn(tpy)2PNIPAM are capable of mutual
self-assembly and propagation over several microns on a SiO2 surface, and the interconnecting
polymer structures retain the approximate width
of the nucleating GNR. The microscope image
of PSRu(tpy)2PS/GNR composites on a SiO2
substrate (Figure 28c) shows that the branched
GNR features (brown) are embedded in a Rupolymer film (yellow). The Raman mapping
of the G line (1603 cm-1) peak (inset of Figure
28a) shows that the branched GNR features are
attributed to GNRs. These results suggest that
hydrophobic PSRu(tpy)2PS self-excludes the
slightly amphiphilic GNRs over tens of microns
to form branched self-assembled structures.
Chemically produced GNRs have characteristic Raman (488 nm laser excitation) peaks of
graphene (G), graphene defect (D) band, and
secondary defect (2D) bands at 1603, 1354, and
2600-3200 cm-1, respectively. GNR, with adhered
Zn-metallopolymer, retains the characteristic Raman spectroscopy G and D peaks. In the case of
the Ru-metallopolymer/GNR composite, there
exists substantial splitting of the G and D peaks
(Figure 28). The Raman splitting of the G and D
peaks is. attributed to donoracceptor interactions between PSRu(tpy)2PS and GNR. The
observed PSZn(tpy)2PNIPAM/GNR supramolecular self-assembly arises from the formation
of donor-acceptor complexes between polymer
and graphene.
An explanation of how metallopolymer interaction with GNR, The electronic characteristic of
the PSZn(tpy)2PNIPAM adsorption on graphene
is shown in the band structure of the hybrid. The
oligomer flat bands have charge primarily confined

52

at Zn(tpy)2 complex. The close proximity of these


flat bands to the charge neutrality point of graphene
implies profound charge transfer between these
components. The unoccupied polymer flat bands
strongly interact with the * band of graphene.
This infers a strong donor-acceptor interaction and
charge transfer between PSZn(tpy)2PNIPAM
and graphene. Specifically, graphene serves as
a charge donor to PSZn(tpy)2PNIPAM, and
PSZn(tpy)2PNIPAM serves as an acceptor. As
a result, the hybrid stability requirement prefers
addition Zn(tpy)2 to graphene in order to shift the
flat bands away from the Fermi level. Ru(tpy)2 has
the same type of band structure interacting with
GNR, although there exist degenerate molecular
levels due to the symmetry of side chains.
These results confirm that the GNRs are capable of controlled propagation of PS-Zn(tpy)2PNIPAM on a SiO2 surface, and the AB copolymer
structure of PS-Zn(tpy)2-PNIPAM has much more
tendency to be self-assembling with GNR than
AA copolymer of PS-Zn(tpy)2-PNIPAM . Specifically, the self-assembling patterns of PS-Zn(tpy)2PNIPAM with GNR are dendrite, while those
of PS-Ru(tpy)2-PS/GNR hybrid are so different
that GNRs function as an ultra-strong adhesion
platform that uniquely promotes the self-assembly
of amphiphilic and hydrophobic metal-contained
diblock copolymers. On a SiO2 surface, the GNRs
are capable of inducing the controlled dendritic
ordering of PSZn(tpy)2PNIPAM, whereas the
hydrophobic PS-Ru(tpy)2-PS copolymer results
in the assembly of GNRs into a pseudo-fractal
branched pattern.

CONCLUSION AND OUTLOOK


The reports on the modification of carbon-based
nanocomposites with ruthenium bipyridine and
terpyridine complexes are very limited. The success and effectiveness of the functionalization enables the attachment of different ruthenium polymer and organic complexes to the surface carbon


Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine

based nanocomposites and enhanced solubility of


Ru-nanohybrid in organic solvents. The photoluminescence properties of Ru-nanocomposites are
due to energy transfer between carbon sp2 network
on the surfaces and ruthenium complexes opens
opportunities for further research, especially in the
development of new carbon based nanomaterials.
The systematic studies of the relationship between
the nature of the active sites in carbon nanocomposite and ruthenium complees are still limited.
This is a direction in which research should be
intensified. The properties of functional carbon
nanocomposite is largely associated with the presence of defects and edge sites, ruthenium complex
type and the interaction between nanocomposites
and metal center . Although conclusive evidence
on the nature of these functionalization and their
properties is still missing, also because in situ/
operando studies are lacking, large progress in
this direction has been definitively made in the
recent years. For example, a lot of dinuclear and
multinuclear ruthenium polymerization complex
have been prepared and the properties of complexes have been well researched and may be the
trends of functionalization carbon nanocomposites
with such multinuclear ruthenium complex for
application as sensors.

Aliev, A. E., Oh, J., Kozlov, M. E., Kuznetsov, A.


A., Fang, S., Fonseca, A. F., & Baughman, R. H.
(2009). Giant-stroke, superelastic carbon nanotube
aerogel muscles. Science, 323(5921), 15751578.
doi:10.1126/science.1168312 PMID:19299612

ACKNOWLEDGMENT

Camp, A. G., Lary, A., & Ford, W. T. (1995). Freeradical polymerization of methyl methacrylate
and styrene with C60. Macromolecules, 28(23),
79597961. doi:10.1021/ma00127a054

The authors thank the National Science foundation (NSF/CFNM/CREST program, grant Award
#HRD-11137751) for financial support for this
research.

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KEY TERMS AND DEFINITIONS


Bipyridine: A bypridine is a family of chemical compounds with the formula (C5H4N)2, which
are formed by the coupling of two pyridine rings.
Six isomers of bipyridine exist, but two isomers
are prominent: 2, 2-bipyridine is a popular ligand
in coordination chemistry. 2, 2-bipyridine is a
chelating ligand that forms complexes with most
transition metal ions.
Carbon Nanotube: A carbon nanotube is a
tube-shaped material, made of carbon and has a
diameter measuring on the nanometer scale. The
graphite layer appears somewhat like a rolledup wire with a continuous unbroken hexagonal
mesh and carbon molecules at the apexes of the
hexagons.
Fullerene: A fullerene is a pure carbon molecule composed of at least 60 atoms of carbon.
Because a fullerene takes a shape similar to a
soccer ball or a geodesic dome, it is sometimes
referred to as a buckyball after the inventor of the
geodesic dome, Buckminster Fuller, for whom the
fullerene is more formally named.
Graphene: A graphene is a 2-dimensional,
crystalline allotrope of carbon. In graphene,
carbon atoms are densely packed in a regular
sp2-bondedatomic-scale chicken wire (hexagonal)
pattern. Graphene can be described as a one-atom
thick layer of graphite.
Ruthenium Complex: Ruthenium forms a
variety of coordination complexes with organic
or inorganic ligands. Ruthenium (II) complex
chelated organic ligands can be utilized for photoillumination and anti-cancer durgs.
Terpridine: A Terpyridine is a tridentate ligand that binds metals at three meridional sites.
2, 2; 6, 2-terpyridine, often abbreviated to
terpy or tpy) is a heterocyclic compound derived
frompyridine. This colourless solid is used as a
ligand in coordination chemistry.

61

62

Chapter 3

Nano Indentation Response


of Various Thin Films Used
for Tribological Applications
Manish Roy
Defence Metallurgical Research Laboratory, India

ABSTRACT
Various thin films used for tribological applications are classified under four heads. Based on their
load vs. displacement curves, which have some characteristics features, the ratio of nanohardness to
elastic modulus and the ratio of cube of nanohardness to square of elastic modulus are evaluated in this
chapter. It is demonstrated that depending on the type of film used, these ratios vary within a certain
range. For soft self-lubricating films, these ratios are very low; whereas for hard self-lubricating film,
these ratios are quite high.

INTRODUCTION
Tribology deals with the study of friction, wear
and lubrication of interacting surfaces in relative
motion. The word tribology is derived from the
Greek word Tribos which means rubbing. Until lately, this study was considered as a branch
of mechanical engineering, and due to its ever
increasing presence in almost every branch of
science, it has now turned into an interdisciplinary field. Rapid growth of science and technology
has created increased demand for materials with
improved performances operated in demanding
environment. This has resulted in development of
several varieties of materials and more importantly

modification of surfaces with different surface


and bulk properties.
Surface engineering is one of the most effective
ways of enhancing the performance of industrial
components to make them suitable for functions
that are different from the primary function of
the bulk substrate. Although surface engineering
has been practiced from the dawn of civilisation,
the science and technology of surface modification has been explored only in recent past. Major
progress in this direction has been achieved only
when a significant gain in performance along with
financial benefit is realised by practicing surface
modification techniques. Even though surface
modification is practiced for several reasons

DOI: 10.4018/978-1-4666-5824-0.ch003

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Nano Indentation Response of Various Thin Films

for protection against degradation such as wear,


corrosion, fatigue etc. surface engineering for
enhanced wear performances is most widely used
tools for performance enhancement. Deposition
of thin film for monitoring the tribology related
surface response has received increased attention
in recent days.
Various tribological thin films can be broadly
classified under four different heads. The first
variety films are hard film with high friction
coefficient. These films are used where the wear
should be low and high friction coefficient is
required. Second variety consists of films with
very high nanohardness and low friction coefficient with excellent inertness. These films are
used for tribological application under circumstances where corrosion or oxidation resistances
plays crucial role. When these films are used as
protective coating, wear of mating surface is an
important problem. Third varieties films known
as self-lubricating film have low nanohardness
along with low friction coefficient. Although
wear rate of these films are not important from
application point of view, the friction coefficients
of these films are very low. Finally forth variety
is films with reasonable nanohardness but low
friction coefficient. These films are used as selflubricating film where wear is also a concern.
The objective of the present chapter is to
critically examine the nano indentation response
of selected films pertaining to each variety of
films mentioned above. In order to achieve the
aforementioned objective, one example of each
variety of films is taken. The load vs. displacement
curves of each film is analysed. Their nanohardness, elastic modulus, ratio of nanohardness to
elastic modulus and elasticity are evaluated. The
characteristics features of these properties of each
variety of films are ascertained.

VARIOUS FILMS
Four different films pertaining to four varieties
referred in earlier section are selected for present
chapter. Nitrides of hard coatings are used for
wear reduction on cutting and die tools for long
time. More recently ZrN has received increased
attention due to its better corrosion resistance
improved mechanical properties and warm golden
colour (Chou, YU, & Huang, 2003; Kolesoguru,
Miterrer, & Urgen, 2002). ZrN is considered to
be an example of first variety of film. Although
the nanohardness of the investigated film is not as
high as reported for other ZrN film, this is a film
with high nanohardness and high friction coefficient. Nanocrystalline diamond film is second
variety film having high nanohardness and low
friction coefficient. Nano crystalline and ultra
nano crystalline diamond (NCD/UNCD) films
can be produced using a modified hot-filament
technique (Braza & Sundarshan, 1992). These
films can be deposited on a broad spectrum of
substrate materials such as tungsten carbides,
titanium and titanium alloys, refractory metals,
ceramics, glass, silicon, quartz, sapphire, graphite
and steel using a passive interlayer. Depending on
deposition parameters, i.e. gas mixture, temperature, pressure and substrate seeding, CVD growth
of diamond results in different types of films.
These are generally classified according to the
crystal grain size as micro crystalline (grain size
5 m), nano crystalline (NCD) (grain size about
50 nm) and ultra nano crystalline (UNCD) (grain
size < 5 nm). Crystallites with sizes down to 3
nm display special advantages. Due to the small
dimensions of nano crystallites, the relation of
volume-to-surface increases dramatically, leading
to an exceptionally high amount of surface atoms
and this results in distinct physical and chemical
properties (Braza & Sundarshan, 1992; Tasi &
Bogy, 1987).

63


Nano Indentation Response of Various Thin Films

Transition metal dichalcogenides films represent today an important variety of self lubricating
films. These films are finding increasing application in space related technologies (Briscoe, 1990;
Singer, Fayeulle, & Ehni, 1996) and other applications in vacuum or in aggressive environment
(Spalvins, 1974). Among various chalcogenides,
tungsten sulphide is considered potential self-lubricating film as this compound is readily available
and it has ability to withstand higher temperature
than molybdenum sulphide. It is noted previously
that, if WS2 film is alloyed with carbon, it results
in reduction of porosities and extent of oxygen
adsorption of the film (Nossa & Cavaleiro, 2001;
Grill, 1993). It is further observed that alloying
with carbon leads to improvement of mechanical
and tribological properties of these films (Grill,
1993; Lince & Hilton, 1995). It is demonstrated
that best combination of mechanical and tribological properties is obtained at around 50 at% C
(Spalvins, 1984). Thus a variety of W-S-C film
having nanocomposite structure has reasonable
nanohardness and low friction coefficient and can
be categorized under third variety films.
Finally, quasi non hydrogenated a-C and and
hydrogenated a-C:H film is taken as an example
of self lubricating film with reasonable nanohardness. Amorphous carbon films also known as
diamond-like carbon (DLC) films have shown
a number of useful properties such as high
nanohardness (Dean & Chalamala, 1999), good
thermal conductivity (Robertson, 2002), low
friction coefficients (Donnet, 1996), excellent
wear resistance (Zehnder & Patscheider, 2000),
ultra-smoothness and chemical inertness (Neuville
& Mathews, 1997). Owing to this unique combination of properties, DLC films have found a
wide range of applications as protective coatings
in magnetic hard disc, microelectromechanical
(MEMS) systems, or reported in recent years, as
biocompatible coatings (Robertson, 1991; Grill,
1999; Miyoshi, Wu, & Garscadden, 1992). In many
of these applications, in particular for magnetic
recording systems, very thin coatings with low

64

friction coefficients accompanied with excellent


wear resistance are desired.

DEPOSITION OF VARIOUS FILMS


Deposition of ZrN Film
ZrN film was deposited using reactive ion nitriding
unit. The coating unit has an annular zirconium
cathode located at the center of the coating chamber and surrounded by an anode. The samples
to be coated are located between the electrodes.
During the coating process the specimens are in a
planetary motion around the cathode. Zirconium
is removed from the cathode in the form of ions
by striking an arc between the cathode and the
anode. The bias voltage drives the ions towards the
samples. Since coating is carried out in nitrogen
atmosphere, Zr ions react with nitrogen to form
ZrN on the samples. The process condition under
which deposition was carried out were 750 volt
arc, 15 V bias voltage, 0.8 to 1.0 mtorr nitrogen
pressure, 850oC cathode temperature and approximately 10 mm/h deposition rate. Further
description about deposition method is available
elsewhere (Sundararajan, Roy, & Das 1997).

Deposition of Nanocrystalline
Diamond Film
Nano-crystalline diamond films are grown by
BeSt coating (rho-BeSt coating GmbH, Innsbruck,
Austria) on silicon substrates by modified hot-wire
chemical vapour deposition from a CH4 (2%)/H2
(98%) mixture. The deposition temperature is
chosen between 550 and 780C, depending on the
substrate specification. After the coating process,
the dangling bonds at the surface were hydrogen
terminated (H-NCD). Thermal treatment of the
nanocrystalline diamond surface at 400C for 4
hours with 21% oxygen, replaced hydrogen for
oxygen containing groups, i.e. ether carbonyl,


Nano Indentation Response of Various Thin Films

or hydroxyl groups (Hllaman, Wanstrand, &


Hogmark, 1998).

Deposition of W-S-C Film


The WSC coatings were deposited by radio
frequency magnetron sputtering of a WS2 target in
a basic ESM 100 Edwards unit following a similar
procedure as presented in a previous research
(Nossa & Cavalerio, 2004). Before deposition, the
substrates were cleaned for 30 min by establishing
the plasma close to the substrate electrode. A Ti
interlayer was deposited to improve the adhesion
of the W-S-C film. CH4 was used as reactive gas
for C containing WSC films. The mass flow
of the reactive gas CH4 was varied from 1 to 5
sccm and the argon flow was adjusted to reach the
final deposition pressure of 1 Pa. The discharge
power was 5.1 W cm-2. The total deposition time
was kept constant at 75 min (15 min for the Ti
interlayer and 60 min for the WSC films). No
substrate bias was applied during the depositions.
The substrate used was 100Cr6 steel.

Deposition of Quasi Non


Hydrogenated (a-C) and a-C:H Film
For deposition of quasi non hydrogenated (a-C) and
a-C:H films, an balanced industrial sized magnetron cathode (coating height: 400 mm) from AJA
(AJA International, North Scituate, MA, USA)
equipped with a graphite target (nominal purity
>99.95%) was used. The magnetron cathode was
powered with a ten kilowatt power supply from
Advanced Energy (Advanced Energy Industries,
Fort Collins, CO, USA) in the power regulation
mode. The pulsing unit was set to 80 kHz, where
a reverse voltage of 15% with a reverse time of 1
s was used. A power density of ~10 Wcm-2 was
applied on the carbon target for all depositions.
For deposition of a-C:H films, C2H2 (nominal
purity >99.96%) was introduced in the coating
chamber together with argon (Ar) (nominal purity
>99.999%) resulting in C2H2/Ar ratios from 0 to

0.43. For deposition of the a-C coatings, a total


flow of 30 sccm Ar was used.
Boron doped silicon wafers (100) with a thickness of 525 25 m were used as substrates. The
wafers were fixed on a grounded substrate holding
carrousel situated at a distance of approximately
10 cm from the sputtering source. In order to study
the influence of substrate bias, a Heiden (Prgen,
Germany) bias power supply was connected to
the carrousel. Films were deposited by oscillation of the carrousel with an amplitude of 9 cm
(left-right) symmetrically through the sputtering
plasma. The substrate temperature was monitored
with an electrically insulated K-type thermocouple
installed at the backside of the substrate holder. For
plasma cleaning of the wafers prior to deposition,
an ALS 340 linear ion beam source from Veeco
(Woodbury, NY, USA) was operated at a voltage
of 2 kV and an Ar flow rate of 20 sccm through
the ion gun. For all depositions, the chamber was
evacuated to a base pressure of 5 10-5 mbar.
During deposition and plasma etching, the pressure
in the chamber ranged from 1 10-3 mbar to 7
10-3 mbar. During deposition no extra heating was
applied to the substrates. The coating temperature
did not exceed 80C for all depositions.

MICROSTRUCTURAL FEATURES
ZrN Film
The SEM image of the cross section of ZrN film
is illustrated in Figure 1. The thickness of the
film is of the order of 5 m although the thickness is not uniform throughout and the film is
essentially crack free. The interface between
the film and substrate is also relatively smooth,
clean and continuous which is indicative of good
adhesion. Some places in the interface some void
like structure can be seen. These are essentially
artifacts of polishing. XRD pattern of the film is
produced in Figure 2. The film is pure ZrN. Few
peaks can be seen for substrate Fe.

65


Nano Indentation Response of Various Thin Films

Figure 1. SEM image of the cross section of the


ZrN film

Figure 2. XRD pattern obtained from the coated


surface

Nanocrystalline Diamond Films


The high magnification SEM images of the morphology of the H-terminated and O-terminated NCD
diamond films are presented in Figure 3. Both the
films exhibit ballas morphology with O-terminated
film particularly showing prominent ballas morphology. Transmission electron microscopy image shown
in Figure 4 clearly proves grain sizes in nanometer
level. Raman spectra obtained from all the films are
presented and described in ref (Liu, Klauser, Memmel, Bertel, Pichler, Knupfer, Kromka, & Steinmuler
Nethl, 2008). Both films show peaks at wave number
(1340 cm-1) corresponding to sp3 bond. The corresponding bond for pure diamond is at 1330 cm-1.
As received H-terminated film exhibits peak at 1160
cm-1 and 1470 cm-1. Both peaks are characterised by
nanocrystalline diamond. In contrast, O-terminated
film exhibits peak at 1330 cm-1 for microcrystalline
diamond and another peak at 1560 cm-1 which can
be identified as G band of microcrystalline graphite.
Thus part of nanocrystalline diamond is possibly
converted to microcrystalline graphite. Three dimensional AFM images showing the topographies
of both films are presented in Figure 5. Topographies
show presence of sharp peaks. There is no apparent
difference in topographies by H-termination and
O-termination. RMS value for O-terminated film
is higher than H-terminated film and is around 13
nm implying very smooth film.

Figure 3. SEM images showing the morphologies of a) H-terminated and b) O-terminated nanocrystalline diamond film

66


Nano Indentation Response of Various Thin Films

Figure 4. TEM image of nanocrystalline diamond


film

W-S-C Film
Figure 6 shows the cross section morphology of
W-S-C coatings with two different C content. It can
be stated that there is a progressive densification
of the coatings with a significant decrease of the
number of pores which results in a decrease of the
exposed surface area where O can be adsorbed.
As a consequence, the final O content decreases
with increasing C. It is also noted that the S content in relation to the stoichiometry (S/W = 2) is
lower. This fact is related to the preferential resputtering of S by energetic species during these
films deposition (Winters, 1982). Furthermore,
the presence of H species in the plasma phase,

due to the use of CH4 as reactive gas, promoted


the formation of H2S compound, which being a
gas is pumped out from the chamber leading to
the depletion of sulphur from the film.
The XRD patterns of the films are illustrated
in Figure 7 The most important points worth
noting is domination of the XRD patterns by a
main broad asymmetric peaks which are indexed
with the general form (10L) corresponding to a
turbostrating stacking of the family of plans (10L)
with L = 0,1,2,3 (Regula, Ballif, Moser, & Lvy,
1996) of the hexagonal WS2 phase. A small peak
close to 2 ~70 can be indexed as the (110) plan
of WC. A progressive decrease in the crystallinity degree with increasing C content as shown by
either the progressive broadening or the decrease
in the intensity of the diffraction peaks can also be
noted. It is hard to detect any vestiges of any other
crystalline phase excepting those related to the
underlying steel substrate (2 ~~52). and the small
features on the right shoulder of the main broad
peak which can be related with the presence of a
W-C phase. The microstructure of the films can,
thus, be described as a nanocomposite consisting
of W-S nanocrystals (and in some cases of W-C
nanocrystals) embedded in a C-rich amorphous
layer, in agreement with the transmission electron
microscopy analysis and X-ray photoelectron
spectroscopy (XPS) study performed in a previous research (Nossa & Cavalerio, 2004; Nossa,
Cavaleiro, Carvalho, Kooi, & De Hosson, 2005).

Figure 5. AFM images showing topographies of a) H-terminated and b) O-terminated nanocrystalline


diamond film

67


Nano Indentation Response of Various Thin Films

Figure 6. SEM images of transverse sections of W-S-C coatings a) 28 at. % C, b) 54 at. % C

Figure 7. X-ray diffraction pattern of various


W-S-C films

to 10 nm except film containing 69 at. % C. The


roughness of this film is quite low and equal to
6.5 nm. However, the RMS values of these films
are comparable to the RMS value of Ti/a-C: H
film and PECVD DLC film (Kvasnica, Schalko,
Benardi, Eisenmenger-Sittner, Pauschitz, & Roy,
2006).

Quasi Non Hydrogenated


(a-C) and a-C:H Film

The three dimensional AFM images showing


the topography of these films are illustrated in
Figure 8 All films exhibit presence of sharp peaks.
The root mean square (RMS) values characterising the roughness of the films indicates that
most of the films are having a RMS value close

68

The high magnification image obtained from


high resolution transmission Electron microscopy
(HRTEM) of a representative quasi non hydrogenated (a-C) film is illustrated in Figure 9. High
amorphicity of the deposited films could also be
proven by HRTEM investigations. Figure 9 shows
the non-crystalline nature of our deposited films.
However, small atomic aggregates in the range
of 2 to 3 nm were found in the DLC matrix. The
three dimensional AFM images showing the topographies of these films are illustrated in Figure
10. Film deposited at high Ar flow rate exhibits
presence of sharp peaks. The sharpness of the
peaks decreases with decreasing Ar flow rate.
A limited number of spikes can be seen in the
deposited film. Various topographical parameters
indicate that the root mean square (RMS) roughness value of these films varies between 0.6 nm


Nano Indentation Response of Various Thin Films

Figure 8. AFM images showing topographies of various W-S-C films containing a) 14 at. 5 C, b) 20 at.
% C, c) 28 at. % C, d) 54 at. % C and e) 69 at. % C

to 1.4 nm authenticating the fact that these films


are ultra smooth films.
Figure 11 illustrates a Raman spectrum (with
additional Gaussian function fits for the D and
G-band) of a quasi a-C film structure, deposited
with pure Ar as sputtering gas. The bands were
found to be at spectral positions of 1356 8
cm-1 (D-band) and 1550 4 cm-1 (G-band). To

investigate the structure of the deposited films in


more detail it is necessary to focus also on the full
width at half maximum of G band (FWHM (G)).
In order to investigate the trends in the C-C sp3
binding content, the FWHM (G) is used to reveal
information about the structural variance induced
by changes in the C2H2/Ar-rate. The variation of
FWHM (G) with C2H2/Ar ratio is presented in

69


Nano Indentation Response of Various Thin Films

Figure 9. High resolution transmission Electron


microscopy (HRTEM) of a representative quasi
non hydrogenated (a-C) film

Figure 12. It can be noted, that the increase of


the C2H2/Ar-rate showed a decreased structural
disorder verified by the decreased FWHM (G)
from 1913 cm-1 to 1731 cm-1.

NANOINDENTATION RESPONSE
ZrN Film
The load vs. displacement curves of ZrN films
is given in Figure 13. The load vs. displacement
curve is smooth without any pop up and pop in.
The maximum depth of indentation is 428.4 nm as
oppose to 335.1 nm residual depth of indentation.
Figure 10. AFM images showing topographies of various Quasi non hydrogenated (a-C) and a-C:H
film deposited under a) C2H2/Ar = 0.0, b) C2H2/Ar = 0.11, c) C2H2/Ar = 0.25 and d) C2H2/Ar = 0.43

70


Nano Indentation Response of Various Thin Films

Figure 11. An exemplary Raman spectrum of a quasi a-C film structure, deposited with pure Ar as
sputtering gas

Figure 12. The variation of full width at half maximum (FWHM) with C2H2/Ar ratio

During the hold at maximum load, the displacement increases in the film indicating drift due
to the creep as the load vs. displacement curves
are plotted after incorporating the correction due

to thermal drift. The plot of load as function of


square of distance is provided in Figure 14. The
nature of curve shows high cohesive strength and
high fracture toughness.

71


Nano Indentation Response of Various Thin Films

Figure 13. Load vs. displacement curve of ZrN film

Figure 14. Load vs. square of displacement curve of ZrN film

Nanocrystalline Diamond Film


The load vs. displacement curves of NCD films
are given in Figure 15. Highly elastic nature of
the curves is evident. The load vs. displacement
curves are smooth and there is no pop up and pop
in ruling out possible failure during indentation.
For NCD-H terminated film the maximum depth of
indentation is 60.7 nm as oppose to 9.5 nm residual
depth of indentation. The corresponding values for

72

O-terminated NCD film are 59.5 nm and 7.8 nm.


The nanohardness of the film increases marginally due to O-termination treatment. According
to the theories of plasticity of contact mechanics,
the load changes with the square of the depth of
penetration. Further to examine the possibility of
failures of these films across the interface of different microstructural features within the film, the
load was plotted against square of the penetration
depth as shown in Figure 16. All the curves show


Nano Indentation Response of Various Thin Films

Figure 15. Load vs. displacement curve of NCD film

Figure 16. Load vs. square of displacement curve of NCD film

a smooth curve with one turning point during


loading and no step is noted before and after the
turning point. Thus, all the film possesses high
cohesive strength and high fracture toughness
(Ding, Meng, & Wen, 2000). Within the range of
applied load, there is no cracking in these films.

W-S-C Film
The load vs. displacement curves of these films
obtained at an applied load of 2 mN are illustrated
in Figure 17. Each curve is obtained by averaging
ten different curves. Similar to nanocrystalline
diamond film, all the curves are smooth and none

73


Nano Indentation Response of Various Thin Films

of the curves shows the presence of pop in or pop


out events indicating no evidence of fracture of
the film. It is clear that, films with lower carbon
content exhibit higher depth of penetration. The
highest depth of penetration of 220.8 nm and the
highest residual depth of 146.0 nm are obtained
for film containing 14 at. % carbon whereas the
lowest depth of penetration of 143.8 nm and the
lowest residual depth of 58.0 nm pertain to the
film containing 54 at. % carbon. Interestingly, film
containing the highest amount of carbon (69 at. %
C) exhibits the highest elastic deformation. Dur-

ing the hold at maximum load, the displacement


increases in all the films indicating drift due to
the creep as the load vs. displacement curves are
plotted after incorporating the correction due to
thermal drift. This feature is completely different
than what is observed for nanocrystalline diamond
film where no such drift is noticed. The extent of
this drift decreases with increasing carbon content,
being minimum at 54 at. % carbon. On further
increase of carbon the drift increases.
The load of these films are also plotted against
square of the penetration depth as shown in Fig-

Figure 17. Load vs. displacement curve of W-S-C film

Figure 18. Load vs. square of displacement curve of W-S-C film

74


Nano Indentation Response of Various Thin Films

ure 18. Again all the curves show a straight line


during loading and no turning point or step is
noted. Thus all the film possesses high cohesive
strength and high fracture toughness (Ding, Meng,
& Wen, 2000). Within the range of applied load,
there is no cracking in these films. As the coating deforms in response to maximum Hertz-like
shear stress lying within the coating depth, it is
apparent that this shear stress is not enough to
make the substrate yield.

Quasi Non Hydrogenated


(a-C) and a-C:H Film
The load versus displacement curves of these films
obtained at an applied load of 0.5 mN are shown
in Figure 19. As usual each curve is obtained by
averaging ten measured curves. All curves are
smooth and none of the curves shows the presence of pop in or pop out events. The highest
depth of penetration of 33.6 nm and the highest
residual depth of 7.21 nm were obtained for the
film deposited at a C2H2/Ar-ratio of 0.43, whereas
the lowest depth of penetration of 28.12 nm and
the lowest residual depth of 2.6 nm pertain to the
film obtained by an applied bias voltage of -100
V. The load was plotted against the square of the

penetration depth as shown in Figure 20. All the


curves show behaviour similar to previous cases
and no step is seen in these curves.

Elastic Modulus and Nanohardness


Variation of nanohardness of H-terminated and
O-terminated nanocrystalline diamond films as
function of contact depth is illustrated in Figure
21. The nanohardness increases with contact depth
with load for both variety of film and then reaches
a constant value at higher contact depth. Initial
increase in nanohardness is certainly not related
to size effect as in that case nanohardness would
have decreased with increase of contact depth.
Rather this effect is due to slipping of the indentor
or invalid indentation test. This is possible given
the depth of indentation as compared to roughness parameters of the film surface. It can also
be noted that the nanohardness of O-terminated
film is higher than the H-terminated film at lower
contact depth and higher contact depth nanohardness of both films are comparable. Thus it can
be concluded that O-termination is near surface
phenomenon and at very low load the influence
of O-termination is visible. This effect do not play
important role at higher load.

Figure 19. Load vs. displacement curve of carbon film

75


Nano Indentation Response of Various Thin Films

Figure 20. Load vs. square of displacement curve of carbon film

Figure 21. The variation of nanohardness with contact depth for NCD films

The variation of nanohardness and elastic


modulus as a function of carbon percentage of
W-S-C films is illustrated in Figure 22. Both the
nanohardness and elastic modulus are improved
with increasing at. % of carbon up to a threshold
value and then drop down with a further increase
of C. The maximum value of the nanohardness

76

is attained for 54 at. % of carbon whereas the


maximum elastic modulus is noted at 28 at. % of
C. As discussed in previous publication (Nossa
& Cavalerio, 2004) such a variation can be attributed to the fact that the film becomes denser with
increasing carbon content. Moreover, the possible
formation of W-carbide nanograins in coatings


Nano Indentation Response of Various Thin Films

Figure 22. Variation of nanohardness and elastic modulus as function of at. % of carbon of W-S-C film

Figure 23. The influence of the applied load on the nanohardness of W-S-C films

with C contents in the range from 40 to 55 at. %,


as demonstrated by XPS measurements (Nossa
& Cavalerio, 2004), can justify the maximum of
nanohardness for that value. Once the amount
of carbon reaches a saturation point a further
increase in carbon results only in a decrease on
the relative amount of W-carbide nanocrystals.
This phenomenon is reflected by a decrease of
both the nanohardness and the elastic modulus.

Figure 23 represents the influence of the applied load on the nanohardness of these films.
Two different trends can be observed. Films with
20 at. % C, 28 at. % C and 69 at. % C exhibit low
nanohardness at low applied loads and the nanohardness increases with the applied up to certain
load. On further increase of load the nanohardness assumes a constant value. In contrast, films
14 at. % C and 54 at. % C possesses minimum

77


Nano Indentation Response of Various Thin Films

nanohardness at applied load of 1 mN. When the


size effect plays an important role in determining
the nanohardness, it decreases with increase of the
applied load. Thus, the size effect is not relevant
for most of the cases in the range of the load used
in this investigation. The depth of indentation at
low load being around 50 to 75 nm and the film
thickness is around 0.85 to 2.5 m. Hence, this
variation of nanohardness is certainly not because
of substrate effect. The lower nanohardness at low
applied load may be related to slipping of indenter
at low load. In order to find the exact reason for
the observed behaviour further investigation needs
to be done. Film with 14 at. % C) and 54 at. % C
showed higher nanohardness at load of 0.5 mN
than at a load of 1 mN. This may be related to
the size effect.
The influence of contact depth on the nanohardness of these films is given in Figure 24. Contact
depth is determined from the load displacement
data using equation given below (Pharr, 1998):
hc = hmax

Pmax

S

(1)

where Pmax is the maximum indentation load, S is


the slope of the initial part of the unloading curve

(in N/m) and is a constant which is dependent on


the geometry of the indenter, for Berkovich tip
= 0.75 (Bhushan & Li, 2003). The dependence of
nanohardness on contact depth follows the same
trend as that of dependence of nanohardness on
applied load signifying minimum substrate effect. It should be stated that all the films exhibit
lower nanohardness at a contact depth of 100
nm. The reason for this is not clear and requires
further investigation in terms of possible formation of soft complex layer or strain induced phase
transformation close to the surface. At very low
contact depth of the order of 50 nm, there is a possibility of size effect and this may be responsible
for slightly higher nanohardness at lower load
of the film with 28 at. % C. Similar variation in
nanohardness with respect to applied load is noted
for film having 28 at. % C for the same reason. It
should be noted that above mentioned size effect
is visible with film having 54 at. % C at a contact
depth of 50 nm whereas size effect can be seen
in the film with 14 at. % C at a contact depth of
80 nm. This difference can be attributed to higher
density of film having 54 at. % C than the density
of film with 14 at. % C.
The variation of nanohardness and elastic
modulus as a function of C2H2/Ar-ratio for Quasi
non hydrogenated (a-C) and a-C:H film is shown

Figure 24. Variation of nanohardness with contact depth for W-S-C film

78


Nano Indentation Response of Various Thin Films

Figure 25. The variation of nanohardness and elastic modulus as a function of C2H2/Ar-ratio for quasi
non hydrogenated (a-C) and a-C:H film

in Figure 25. It can be seen, that the nanohardness


and the elastic modulus decreases with increase
in C2H2/Ar ratio. This decrease is consistent
with the decrease of HWFM (G) of with C2H2/
Ar-ratio indicating that decrease in structural
order responsible for decrease in nanohardness
and elastic modulus

H/E Ratio
Recently it has been shown that the ratio of
nanohardness to elastic modulus (H/E) is a very
important material parameter (Musil & Jirout,
2007). The ratio H/E multiplied by geometric
factor, which is ratio of the diameter of plastic
zone to total deformed zone gives plasticity index. Plasticity index describes the deformation
properties of contacting surfaces. This quantity
also appears in various expressions for fracture
toughness.
The variation of H/E ratio as function of
contact depth of nanocrystalline diamond film
is illustrated in Figure 26. This ratio increases

with increase of contact depth for both varieties


of films. This ratio is higher for O-terminated
film as compared to H-terminated film at lower
contact depth and comparable at higher contact
depth. Thus O-termination improves H/E ratio
at low load. O-termination becomes ineffective
at higher load. It should also be stated that this
ratio is comparable for amorphous carbon film
and Ti containing nanocomposite carbon film at
lower contact depth (Ctvrlik, Stranyanek, Bohak,
Kulikoasky, & Suchanek, 2008). However, this
ratio for nanocrystalline diamond film is significantly higher than this ratio of amorphous and
nanocomposite carbon films at higher contact
depth. Ignoring this ratio at low contact depth,
it is noted that this ratio varies between 0.1 and
0.15. The variation of H/E ratio as function of wt
% of carbon for W-S-C film is presented in Figure
27. It is clear that the ratio H/E increases with
carbon content in the film. This ratio is within
the range of 0.04 to 0.09. Thus with increase in
carbon content the film improves its deformation
properties and fracture toughness.

79


Nano Indentation Response of Various Thin Films

Figure 26. The variation of H/E ratio as function of contact depth of nanocrystalline diamond film

Figure 27. The variation of H/E ratio as function of wt % of carbon for W-S-C film

Bar diagram showing the ratio of H/E for a


series of quasi non hydrogenated carbon film as
function of deposition condition is provided in
Figure 28. It is interesting to note that this ratio is
independent of the processing condition signifying that the fracture toughness or the deformation
properties cannot be altered significantly for pulsed
sputtered deposited non hydrogenated carbon film.

80

H3/E2 ratio
The expression H3/E2 which contains nanohardness and elastic modulus is a measure of the
elasticity exhibited by the film (Charitidis &
Logothetidies, 2005). A high value of H3/E2 is an
indicator of a high elastic behaviour and a low value
of H3/E2 suggests a plastic behaviour of the layer.
This ratio for various films are discussed below.


Nano Indentation Response of Various Thin Films

Figure 28. Bar diagram showing the ratio of H/E for a series of quasi non hydrogenated carbon film

Figure 29. The variation of H3/E2 with the contact depth for nanocrystalline diamond film

Figure 29 represents the variation of H3/E2 with


the contact depth for nanocrystalline diamond film.
It is clear from Figure 29 that H3/E2 increases with
the contact depth indicating that the film becomes
more elastic at higher applied load. The elasticity
is always higher for O-terminated film than Hterminated film. According to some investigators
(Galvan, Pie, & De Hosson, 2006) the toughness

of the film increases with elasticity and hence


O-terminated films are expected to have higher
toughness than H-terminated film. It is clear that
at higher contact depth this ratio is in excess of
1.0. Interestingly, the elasticity of nanocrystalline diamond film is significantly higher than the
elasticity of carbon alloyed W-S-C film (Koch,
Evaristo, Pauschitz, Roy, & Cavaleiro 2009).

81


Nano Indentation Response of Various Thin Films

Figure 30. The variation of H3/E2 with the percentage of carbon for W-S-C film

Figure 31. Bar diagram showing the ratio of H3/E2 for a series of quasi non hydrogenated carbon film

Figure 30 represents the variation of H3/E2


with the percentage of carbon for W-S-C film. It
is clear from Figure 30 that H3/E2 increases with
the carbon content indicating that the film becomes
more elastic. Thus, a higher amount of carbon is
beneficial for a film where wear resistance and
elasticity are expected. The value of this ratio is
around 0.02.

82

Figure 31 illustrates the H3/E2-ratios, of various


carbon films. The elasticity tends to decrease with
increase in C2H2/Ar ratio. The elasticities of these
films are in between 0.17 to 0.20. Examination of
the H3/E2-ratios obtained by various investigators
indicates result of present work is in conformity
with the data reported by Charitidis et al. (2005)
and Ctvrtlik et al. (2008) for amorphous carbon
film but higher than nanocomposite diamond film
obtained by same investigators.


Nano Indentation Response of Various Thin Films

EXAMINATION OF DATA
FROM LITERATURE
Nanohardness elastic modulus, H/E ratio and H3/
E2 ratio of a series of nitride films are listed in
Table 1. It can be seen that for these variety of
coatings nanohardness and elastic modulus being very high, H/E generally vary between 0.11
to 0.15. In contrast, H3/E2 generally around 0.57
to 0.64. However, Cu containing coating exhibit
higher H3/E2 and this value is around 1.06 to 1.08.
Nanohardness elastic modulus, H/E ratio and
H3/E2 ratio of various diamond films as reported
in literature are summarised in Table 2. For diamond films both H/E and H3/E2 ratio are high and
within small range. H/E ratio changes between
0.1 to 0.15 whereas H3/E2 ratio is reasonably high

and in the range of 1.0 to 2.0. Only diamond film


with coarse ballas morphology exhibits low H3/
E2 ratio which is approximately 0.63.
Nanohardness elastic modulus, H/E ratio and
H3/E2 ratio of a series of transition metal dichalchogenide films are listed in Table 3. The H/E
ratio is very low and of the order of 0.05 to 0.07.
In contrast, low value of H3/E2 ratio are found in
the range of 0.01 to 0.06. However, if these films
are made as a nanocomposite film containg metal,
both these ratios increase. These ratios for such
film can be as high as 0.1 and 0.2 respectively.
Nanohardness elastic modulus, H/E ratio and
3
H /E2 ratio of a series of carbon based films are
provided in Table 4. In case of carbon based self
lubricating film the ratio of nanohardness to elastic
modulus tends to vary with in a very close range

Table 1. H, E, H/E and H3/E2 for a series of nitride film


Films

H (GPa)

E (GPa)

H/E

H3/E2 (GPa)

Zr-Y-N, (Musil, Kunc, Zenam and Polakova, 2002)

31.6

229

0.14

0.6

Cr-Ni-N, (Musil, Kunc, Zenam and Polakova, 2002)

39.2

307

0.12

0.64

Ti-Mo-N, (Musil, Kunc, Zenam and Polakova, 2002)

46

413

0.11

0.57

Al-Cu-N, (Musil, and Vicek, 2001)

47

313

0.15

1.06

45.6

405

0.11

0.58

Zr-Cu-N, (Musil, and Vicek, 2001)

56

399

0.14

1.08

CrN

25

375

0.067

0.11

Ti-Al-V-N

Table 2. H, E, H/E and H3/E2 for a series of diamond film


Films

H (GPa)

E (GPa)

H/E

H3/E2 (GPa)

Nano crystalline diamond film, H-terminated, (Roy, Steinmuller


Nethl, Tomala, Tomastik Koch and Pauschitz, 2011)

54.1

403.0

0.13

0.98

Nano crystalline diamond film, O-terminated, (Roy, Steinmuller


Nethl, Tomala, Tomastik Koch and Pauschitz, 2011)

58.7

419.0

0.14

1.2

Microcrystalline diamond film, faceted morphology, (Bogus,


Gebeshuber, Pauschitz, Roy and Haubner, 2008)

82.9

535.5

0.15

1.99

Microcrystalline diamond film, coarse ballas morphology


(Bogus, Gebeshuber, Pauschitz, Roy and Haubner, 2008)

58.5

563.5

0.10

0.63

Microcrystalline diamond film, fine ballas morphology, (Bogus,


Gebeshuber, Pauschitz, Roy and Haubner, 2008)

59.3

379.2

0.15

1.5

Microcrystalline diamond film, (Chowdhury, Barra and Laugier,


2005)

110

1156

0.09

1.06

83


Nano Indentation Response of Various Thin Films

Table 3. H, E, H/E and H3/E2 for a series of of transition metal dichalchogenide film
Films

H (GPa)

E (GPa)

H/E

H3/E2 (GPa)

W-S-C, (Koch, Evaristo, Pauschitz, Roy, and Cavaleiro, 2009)

4.6

66.0

0.07

0.02

WSe2, (Pauschitz, Badisch, Roy and Shtansky, 2009)

5.9

81.5

0.06

0.03

Mo-Se-C, (Tomala, Roy, and Franek, 2010)

4.0

40.0

0.1

0.04

WS2 (Li-na, Cheng-bio, Hai-dou, Bin-shi, Da-ming, Jia Jug and


Gou-lu, 2010)

15.4

354.0

0.05

0.06

MoS2 (Renevier, Lobiondo, Fox, Teer and Hampshire, 2000)

4.7

70

0.06

0.01

CrN-WS2, (Deepthi, Barshilia, Rajam, Konchady, Pai and


Shankar, 2011)

24

250

0.1

0.22

Ti-MoS2, (Renevier, Lobiondo, Fox, Teer and Hampshire, 2000)

15

138

0.1

0.18

Table 4. H, E, H/E and H3/E2 for a series of carbon based self lubricating film
Films

H (GPa)

E (GPa)

H/E

H3/E2 (GPa)

Ti-C:H, (Pauschitz, Kvasnica Jisa, Bernardi, Koch and Roy,


2008)

15.5

164.0

0.1

0.14

a-C, (Krumpiegl, Meerkamm, Fruth, Schaufler, Erkens and


Bohner, 1999)

11.9

117.6

0.10

0.12

a-C: H, (Krumpiegl, Meerkamm, Fruth, Schaufler, Erkens and


Bohner, 1999)

25.0

162.4

0.15

0.59

Ti-C: H, (Krumpiegl, Meerkamm, Fruth, Schaufler, Erkens and


Bohner, 1999)

16.7

113.9

0.15

0.35

a-C:H, (Michel, Muhlen, Achete and Lepiensky, 2006)

14

180

0.08

0.08

Nanocomposite diamond film, (Pauschitz, Schalko, Koch,


Eisenmenger-Sittner, Kvasnica and Roy, 2003)

6.1

76.9

0.08

0.04

a-C, (Charitidis and Logothetidies, 1999)

27

290

0.09

0.23

17.9

148.8

0.12

0.26

18

172

0.1

0.2

a-C, (Huang, Zhou, Xu and Lu, 2002)


a-C, (Tomala, Pauschitz, Roy, 2013)

and it is in between 0.08 to 0.15. The ratio H3/


E2 however, varies over a wide range and can be
taken a characteristics feature.

FUTURE RESEARCH DIRECTIONS


The classification of the tribological thin film as
described in this chapter is in very much rudimentary stage and by no means a last word. There is
enormous scope and demand to classify all thin
film used for tribological application under different category. Naturally the features stated in

84

relation to nanohardness and elastic modulus are


also far from complete. In this chapter, several other
variety of coating such as self adapting thin film,
nanocomposite thin film etc. are not discussed.
Thus there is a need to examine the entire gamut
of coatings available and classify them under a
broader spectrum of features.
The data base on nanohardness and elastic
modulus of thin film meant for tribology, is quite
comprehensive. However, it is very difficult to
carry out a meaningful comparison as these data
are generated under different loading system, for
films with different thickness, under different en-


Nano Indentation Response of Various Thin Films

vironmental condition and for films with different


microstructural features. In view of this, a more
comprehensive data base on these properties can
be contemplated.
Last but not least is the fact that theories of
plasticity of contact mechanics indicates load
scales with the square of penetration. Thus nature
of load vs. square of displacement curve is very
important to understand the deformation behavior
of the film under indentation condition. Unfortunately this aspect of nanoindentation has been
reported by few investigators. There is a genuine
requirement to analyse the load vs. square of
displacement curves of tribological thin films.

CONCLUSION
Various thin films suitable for tribology related
applications are classified under four heads.
The load vs. displacement curves and load vs.
square of displacement curves of these films are
characterized. It is stated by several investigators
previously and the authors also agree with the fact
that H/E and H3/E2 are important parameter for
these coatings. The above discussion brings out
the fact that the value of H/E for nitride coatings
which are very hard and having high friction
coefficient and used for such application where
friction coefficient is either not very important or
high friction coefficient is required, varies between
0.11 to 0.15 whereas H3/E2 ratio is in the range of
0.57 to 0.64. The value of H/E for hard film with
high nanohardness and low friction coefficient
and where wear of counterbody is an issue varies
from 0.1 to 0.15. Interestingly the value of H3/E2
for such film is quite high and is around 1.0 to 2.0.
For soft self lubricating films where wear rate is
not crucial, these ratios are from 0.05 to 0.07 and
0.01 to 0.06 respectively. Finally for reasonably
hard but self lubricating film where wear rate is an
important consideration, H/E ratios vary between
0.08 to 0.15 and H3/E2 vary over a wide range and
no characteristics range can be stated.

ACKNOWLEDGMENT
The author is grateful to director DMRL for giving permission to publish this work. The author is
grateful to Dr. Thomas Koch of Vienna University
of Technology and Dr. A. Tomala of Austrian
Center of Competence for Tribology for carrying
out nanoindentation and AFM work, respectively.
The author is also grateful to Prof. A. Cavaleiro
University of Coimbra, Portugal, Dr. Markus
Kahn from Joanneum Research, Laser Center
Leoben, Austria, and D. Steinmller-Nethl of
-BeSt coating GmbH, Innsbruck, Austria, for
providing W-S-C, carbon, and nanocrystalline
diamond films, respectively.

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88

KEY TERMS AND DEFINITIONS


Elasticity: The expression H3/E2 which contains hardness and elastic modulus.
Nanocomposite: Composite materials with
sizes of each phase less than 50 nm.
Nanocrystalline: Crystalline materials with
crystal sizes less than 50 nm.
Nanohardness: Resistance to indentation at
very low load.
Nanotribology: Tribology at low load with
wear rate in nm level.
Self Lubrication Film: Films which provides
lubrication without addition of lubricant.

89

Chapter 4

Synthesis and Characterization


of Iron Oxide Nanoparticles
John M. Melnyczuk
Clark Atlanta University, USA
Soubantika Palchoudhury
Yale University, USA

ABSTRACT
Iron oxide nanoparticles show great promise in bio-applications like drug delivery, magnetic resonance
imaging, and hyperthermia. This is because the size of these magnetic nanoparticles is comparable to
biomolecules and the particles can be removed via normal iron metabolic pathways. These nanoparticles
are also attractive for industrial separations and catalysis because they can be magnetically recovered.
However, the size, morphology, and surface coating of the iron oxide nanoparticles greatly affect their
magnetic properties and biocompatibility. Therefore, nanoparticles with tunable characteristics are
desirable. This chapter elaborates the synthesis techniques for the formation of iron oxide nanoparticles
with good control over reproducibility, surface and magnetic properties, and morphology. The wellknown co-precipitation and thermal decomposition methods are detailed in this chapter. The surface
modification routes and characterization of these nanoparticles are also discussed. The chapter will be
particularly useful for engineering/science graduate students and/or faculty interested in synthesizing
iron oxide nanoparticles for specific research applications.

INTRODUCTION
Recently iron oxide nanoparticles (NPs) have
attracted tremendous attention as candidates
for magnetic resonance imaging (MRI) contrast
enhancer, drug delivery, and magnetic fluid hyperthermia (Mahmoudi, Sant, Wang, Laurent, &
Sen, 2011). Superparamagnetic magnetite and

maghemite based MRI contrast agents like Feridex, Combidex, Resovist, and CLIO have been
approved by the Food and Drug Administration
(FDA) (Bin Na, Chan Song, & Hyeon, 2009).
These dextran-coated iron oxide NPs are used to
dephase the proton magnetic moments of water
surrounding the tumor site to induce a darker
contrast compared to healthy tissues (Pankhurst,

DOI: 10.4018/978-1-4666-5824-0.ch004

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Synthesis and Characterization of Iron Oxide Nanoparticles

Connolly, Jones, & Dobson, 2003). The contrast


agents can be targeted to the tumor and are less
cytotoxic compared to the commonly used gadolinium chelates (Qiao, Yang, & Gao, 2009). Iron
oxide NPs can be passively phagocytosed by the
reticuloendothelial cells or can be actively targeted
to the biomarkers on tumor cells with specific
binding ligands (C. Sun, Lee, & Zhang, 2008).
The large surface and tunable coating of the iron
oxide NPs allow surface conjugation of anti-tumor
drugs like doxorubicine (Xing et al., 2012). This
targeted drug delivery enables accumulation of
therapeutically relevant drug doses at the tumor site
for effective chemotherapy. When the iron oxide
NPs at the tumor site are subjected to an alternating
magnetic field, the magnetic moments reorient.
This magnetic energy is dissipated as heat at the
tumor and elevates the local temperature (42-45
C) to selectively kill the cancer cells (Al-Saie et
al., 2011). The healthy tissues surrounding the
tumor are protected in this form of treatment called
the magnetic fluid hyperthermia (Laurent, Dutz,
Hafeli, & Mahmoudi, 2011). However, iron oxide
NPs with good reproducibility as well as tunable
size and surface properties need to be synthesized
for the above applications (LaConte et al., 2007).
For example, superparamagnetic iron oxide NPs
(< 15 nm) do not aggregate in the presence of a
magnetic field and show a good blood circulation
time. Therefore, these NPs are ideal for MRI and
hyperthermia applications. The surface coating
on the iron oxide NPs is also a major influence
on the proton relaxation rates in MRI. The NPs
with completely hydrophilic surfactant coatings
are most suitable as MRI contrast agents because
they are accessible to the surrounding water protons (Smolensky, Park, Berguo, & Pierre, 2011).
This chapter will focus on the reproducible
synthesis of iron oxide NPs of varying size, morphology, and surfactant coating. The widely used
co-precipitation and thermal decomposition routes
will be elaborated. In explaining these synthetic
techniques emphasis will be given to the condi-

90

tions required for different shapes of iron oxide


NPs. The synthesis of iron oxide nanospheres,
nanocubes, nanoplates, nanoflowers, nanoworms,
and nanowhiskers will be detailed. The methods to
characterize the size, morphology, crystal phase,
and magnetic properties of the NPs via transmission electron microscopy (TEM), x-ray diffraction
(XRD), and alternating gradient field magnetometry (AGM) will be covered next. Finally, the
surface coating and biocompatibility of the iron
oxide NPs will be addressed. The iron oxide NP
products from the thermal decomposition method
are coated with hydrophobic ligands. Surfactant
exchange and polymer encapsulation routes will
be used for aqueous phase transfer of such NPs.

BACKGROUND
Crystal Structure and
Magnetic Properties of Iron
Oxide Nanoparticles
The most interesting crystal phases of iron
oxide nanoparticles are the magnetite (Fe3O4),
maghemite (-Fe2O3), and hematite (-Fe2O3).
(Gubin, Koksharov, Khomutov, & Yurkov, 2005).
Of these hematite is weakly magnetic. However,
the magnetite and maghemite NPs show strong
magnetic properties and are attractive for various
bio-applications (Roca et al., 2009).This could be
attributed to the unpaired 3d electrons (4 or 5) and
the inverse spinel crystal structure of magnetite
and maghemite. Spinel compounds are known
to crystallize in a cubic system and generate an
octahedral crystal structure (Siddiquah, 2008). The
normal spinel has a chemical formula of AB2O4
(A= divalent metal ion and B= trivalent metal ion).
The spinel lattice contains at least eight AB2O4
molecules with the large oxygen anions in a facecentered cubic (fcc) arrangement. This leaves two
types of crystal sites for cation occupancy: the 64
tetrahedral (T-) sites each with four surrounding


Synthesis and Characterization of Iron Oxide Nanoparticles

oxygen anions and the 32 octahedral (O-) sites


each containing six neighboring oxygen anions.
Generally, the larger divalent cations occupy the
T- sites and the trivalent metal ions fill the Osites. However, the inverse spinel structures of
magnetite and maghemite are formed with Fe2+
at the T- sites and Fe3+ distributed equally at both
the T- and O- sites. In maghemite NPs (> 20 nm),
the trivalent cations fill up the O- sites leaving
ordered vacancies to reduce the lattice energy. This
crystallographic arrangement gives magnetite and
maghemite NPs their unique magnetic properties.
Both magnetite and maghemite are ferrimagnetic at room temperature. Ferrimagnetic materials retain the magnetization after removal of the
external magnetic field, similar to ferromagnets
(O Handley, 2000). However, in a ferrimagnet
the anion directly couples two dissimilar cations
(Ma and Mb) via the trademark superexchange
interaction. This induces the Ma-Ma or Mb-Mb
type interactions favoring parallel arrangement
of magnetic moments and the Ma-Mb type interactions favoring anti-parallel arrangements. The
result is a net magnetic moment lower than that of
a ferromagnet. Bulk magnetite shows a saturation
magnetization of 92 emu/g compared to 78 emu/g
for bulk maghemite (S. H. Choi et al., 2008). The
saturation magnetization is lower for the iron oxide
NPs because the surfactant forms a magnetically
dead layer on the NP surfaces (Gangopadhyay et
al., 1992). When the size of the iron oxide NP is
small (< 20 nm), the thermal fluctuations within
the NP is sufficient to flip the magnetic spin energy at room temperature (Krishnan et al., 2006).
Therefore, the small NPs can rapidly magnetize
and demagnetize with an applied magnetic field
(J. Chatterjee, Haik, & Chen, 2003). This unique
behavior called superparamagnetism is attractive for in vivo applications because it prevents
aggregation of the iron oxide NPs through rapid
demagnetization. Additionally, the morphology of
the NP also influences the magnetic properties.
This led to great interest in controlled synthesis
of iron oxide NPs during the last decade.

Synthesis of Iron Oxide


Nanoparticles
The first synthesis of iron oxide NPs was reported
in 1852 (Lefort, 1852). Several physical and wetchemical routes for iron oxide NP fabrication
were developed since then (Laurent et al., 2008).
The physical techniques like gas phase deposition, electron-beam lithography, and mechanical
grinding provide less control over the size of the
NPs compared to the wet-chemical methods. Coprecipitation and thermal decomposition are two
widely used chemical synthetic techniques for the
iron oxide NPs (Lu, Salabas, & Schueth, 2007).

Co-Precipitation Method
Co-precipitation of Fe2+ and Fe3+ salts in an
alkaline aqueous medium is one of the simplest
methods for the synthesis of iron oxide NPs (Gupta
& Gupta, 2005). Hydrophilic capping molecules
such as humic acid, citrate, or polyacrylic acid are
added during or after synthesis to prevent aggregation of the NPs. An oxygen-free environment is
essential for the synthesis otherwise the iron oxide
can be oxidized to ferric hydroxide in the reaction
medium (Zheng, Cheng, Bao, & Wang, 2006).
The following chemical reaction summarizes the
co-precipitation synthesis.

Fe2+ + 2 Fe3+ + 8OH Fe3O4 + 4 H 2O


This method is facile and eco-friendly because
no toxic organic reactants are used. Here, the end
NP product is in aqueous phase and can be used
for biomedical applications. However, the product
is polydisperse and the reaction temperature is
limited by the boiling point of water. As a result,
the NPs show low crystallinity and poor magnetic
properties. Therefore, the thermal decomposition
method was developed to improve the properties
of the iron oxide NPs.

91


Synthesis and Characterization of Iron Oxide Nanoparticles

Thermal Decomposition Method


This approach provides excellent control over
the size, size distribution, yield, crystallinity, and
shape of the iron oxide NPs. Here, an iron precursor
complex is decomposed at elevated temperatures
(~ 300 C) in the presence of capping molecules in
an organic solvent. There are two types of thermal
decomposition method; hot-injection and heat-up.
Hot-Injection: Alivisatos et al. first found
that the hot-injection of iron precursor, Fe(Nnitrosophenylhydroxylamine)3-octylamine into
boiling long-chain amine solvents (250-300 C)
leads to monodisperse maghemite NPs (Rockenberger, Scher, & Alivisatos, 1999). The size
distribution can be improved further using Fe(CO)5
precursor, as shown by Hyeon et al. (Hyeon,
Lee, Park, Chung, & Bin Na, 2001). However,
hot-injection into the boiling solvent at such elevated temperatures raises safety concerns. It also
provides less control over the reaction parameters
because the sudden burst injection can induce
undesired reaction intermediates. Therefore, Sun
et al. developed the heat-up method (S. H. Sun
& Zeng, 2002).
Heat-Up: In this organic phase synthesis, the
reactants are heated up to elevated temperatures
(300- 320 C) at a constant heating rate. This
provides better control over the reaction. Sun
et al. used Fe(C5H7O2)3 precursor complex in
phenyl ether solvent to synthesize monodisperse
magnetite NPs of sizes below 20 nm. However,
the limitation of this precursor is the multi-step
seed-mediated growth required for larger NP sizes.
Therefore, Hyeon et al. used iron oleate precursor for a large-scale synthesis of monodisperse
magnetite NPs of controllable sizes (J. Park et al.,
2004). The heat-up method using iron oleate shows
great potential because the precursor is less toxic
than Fe(CO)5 and the NP product of tunable size
is reproducibly synthesized in one-step.
Modified Heat-Up: In most traditional heatup methods, oleic acid is used as the surfactant
because it prevents aggregation and maintains the

92

spherical morphology of the iron oxide NPs via


a strong surface binding. However, a modified
heat-up method uses a weak binding ligand along
with oleic acid to modify the shape and surface
of the iron oxide NPs (Palchoudhury, Xu, An,
Turner, & Bao, 2010).
The iron oxide NPs from the thermal decomposition route are limited by the toxic organic surface
coating. Therefore, an aqueous phase transfer via
ligand exchange or encapsulation is required before
the NPs are used for bio-applications. Additionally, the size, shape, magnetic properties, and
surface characteristics of the NPs have to be well
characterized prior to the applications to prevent
any harmful effect.

Characterization of Iron
Oxide Nanoparticles
The size, morphology, and a qualitative chemical
composition of the iron oxide NPs is determined
on a TEM because the NPs are too small for the
normal eye or the optical microscopes (Figure
1a). In a TEM (e.g., Tecnai F-20, 200 keV), the
high energy electron beam interacts with the NP
specimen to form bright field (BF) or dark field
(DF) images of the sample (Williams & Carter).
The interacted electron beam contains specimen
information that is displayed using a charge
coupled device camera (CCD). In a BF image, the
NPs appear as dark spots on a bright background
because the image is constructed with the transmitted electron beam. The BF image provides a
general overview of the size, size distribution,
and morphology of the NP sample. However, a
high resolution transmission electron microscope
(HRTEM) image is required to determine the
crystallinity and morphology of the NPs at the
atomic resolution. Here, the heavily diffracted
electron beam interacts with the transmitted beam
to form the high magnification image with visible
parallel phase contrast lines called lattice fringes.
The lattice fringes indicate good crystallinity of
the sample. Additionally, an HRTEM image of


Synthesis and Characterization of Iron Oxide Nanoparticles

Figure 1. Characterization of maghemite NPs via modified heat-up method. (a) BF TEM image, (b) XRD
plot, (c) XPS plot, and (d) M-H curve using AGM

the tilted sample can provide an estimate of the


sample thickness. However, a high angle annular
dark field (HAADF) image is ideal for viewing
ultrasmall NPs (< 5 nm) or surface details because
the image is negligibly affected by the defocus
and sample thickness (Braggs reflections) compared to a BF image. The TEM can also provide a
general chemical composition of the NPs via the
energy-dispersive-spectrophotometry (EDS). The
NP sample preparation for the TEM is relatively
simple. The NPs are washed with ethanol and
hexane to remove the excess organic surfactants
and dispersed in a volatile solvent such as hexane.
The sample is then dropped on a carbon-coated
copper TEM grid (3 mm) with formvar support
for best results.

The XRD (e.g., Bruker AXSD8 Advanced


XRD) is used to determine the crystal phase of the
iron oxide NPs (Cullity & Stock, 2001). Here, the
organic surfactant coating on the NPs is washed
completely to form well-dried powdered NP
sample (Klug & Alexander, 1996). The incident
x-rays (~ 1 ) are elastically scattered or diffracted (Bragg diffraction) by the powdered NPs
towards the detector. The sample and the detector are rotated at and 2 respectively to obtain
a 20- 80 2 scan (Kittel, 1985). The complete
diffraction scan can identify the crystal phase of
the NPs when matched with the reference data
(International Center Diffraction Data, ICDD).
The diffraction profiles of both maghemite and
magnetite are closely related. Maghemite shows

93


Synthesis and Characterization of Iron Oxide Nanoparticles

2 peaks at 35.1, 41.4, 50.4, 63.1, 67.5, 74.4,


and 88.7 on a Co K source ( = 1.79 ) corresponding to the (220), (311), (400), (422), (511),
(440), and (533) crystal planes (Figure 1b). The
(220) peak is not seen for magnetite. This difference is outweighed by the size broadening effect
for small iron oxide NPs. Therefore, XRD patterns
cannot conclusively differentiate maghemite and
magnetite crystal phases (Jia et al., 2008).
X-ray photoelectron spectroscopy (XPS, e.g.,
Kratos AXIS 165 Multitechnique Electron Spectrometer) is used to study the Fe and O valence
states to differentiate these two common iron
oxide crystal phases (Cornell & Schwertmann,
2003). Here, the surface chemical composition
(100 atom% - 0.1 atom% concentration) of the
powdered NP sample is reported as a survey scan
of the emitted photoelectron count corresponding
to the binding energies. The XPS Fe2p core-level
spectra for iron oxide NPs show peaks around 712
and 726 eV corresponding to 2p3/2 and 2p1/2 corelevel respectively (Figure 1c). However, a satellite
peak after 2p3/2 (~ 718 eV) is characteristic to the
maghemite crystal phase (Yamashita & Hayes,
2008). Additionally, the O1s core-level binding
energy of maghemite is lower than magnetite.
Therefore, the O1s shoulder and the satellite peak
around 718 eV can be used to accurately predict
the maghemite from the magnetite crystal phase.
The magnetic property of the iron oxide NPs
is determined with a magnetometer. The AGM
(e.g., Princeton AGM) is the simplest and a highly
accurate magnetometer used for a fast magnetic
measurement of powdered NP samples. The AGM
reports the magnetic moment of the NPs relative
to the applied magnetic field (Figure 1d). Superparamagnetic iron oxide NPs show zero coercivity
at zero magnetic field while a hysteresis loop is
observed for ferromagnetic NPs. The saturation
magnetization of the NPs gives an estimate of
the highest magnetization attainable with the applied field. This value is slightly lower for NPs,
compared to the bulk iron oxide, likely from the
magnetically dead layer of surfactant. The M-H

94

curves provide useful information on the sample.


For example, a ferromagnetic loop in small iron
oxide NPs indicates heavy aggregation. Another
simple method to predict aggregation within the
NP solution is via DLS.
The DLS (e.g., Zetasizer Nano, Malvern) is a
rapid and non-destructive technique to measure
the hydrodynamic diameter of NPs in solution.
Here, the incident laser light is scattered by the
Brownian motion of the NP solution. The diffusion
rate of the NP molecules in solution and hence
the hydrodynamic diameter can be estimated
from the detected fluctuations in the scattered
light. The DLS can determine the surface charge
as well as the extent of polydispersity of the NP
sample. Figure 1 shows the characterization of
organic phase maghemite NPs via TEM, AGM,
XRD, and XPS.

MAIN FOCUS OF THE CHAPTER:


METHODS FOR IRON OXIDE
NANOPARTICLE SYNTHESIS
This section will report the widely used synthetic methods for iron oxide NPs with varying
morphologies and surface coatings. This will be
useful for students and academic personnel aiming to conduct application based research with
iron oxide NPs. The synthesis of engineered iron
oxide NPs is currently an emerging field with
tremendous possibilities.

Iron Oxide Nanospheres


Co-precipitation: This is the most effective route
for the synthesis of aqueous dispersions of iron
oxide NPs. FeCl2.4H2O (2 g) and FeCl3.6H2O (5.46
g, Fe2+:Fe3+ molar ratio 1:2) are mixed with the
surfactant, polyethylene glycol (PEG)-2000 in an
aqueous acid solution (60 mL; 10 mL 1 M HCl in
50 mL de-ionized water). This Fe solution is added
dropwise to 100 mL NaOH (1 M)/PEG-2000 (1 g)
solution mixture under vigorous stirring at 60 C.


Synthesis and Characterization of Iron Oxide Nanoparticles

Figure 2. Iron oxide NPs using modified heat-up method. (a) BF TEM image and (b) HRTEM image

The mixture is stirred for 2 h. The entire reaction


is conducted in an inert atmosphere with nitrogen
purging using the classical Schlenk line technique.
The black NP product is washed multiple times
with de-ionized (DI) water until it is neutral (Gao,
Li, Dong, Zhang, & Yang, 2011).
Modified Heat-up: This method gives iron
oxide NPs with excellent size, shape, yield, and
size distribution compared to the co-precipitation
(Palchoudhury, Xu, Goodwin, & Bao, 2011b).
First, the iron oleate precursor is prepared as follows: FeCl3 (13 g), potassium salt of oleic acid
(192.4 g) is mixed in a solvent mixture (hexane,
280 mL and ethanol, 160 mL) at 65 C for 4 h.
The mixture is phase separated. The upper organic
phase contained the iron oleate complex. This
is washed 3 times with DI water to remove byproducts such as KCl. The paste-like iron oleate
complex is left to dry overnight in the chemical
hood. This precursor complex is used for iron
oxide NP synthesis.
Monodisperse iron oxide NPs (12 nm) are
synthesized via thermal decomposition of the iron
oleate precursor (1.8 g) in the organic solvent,
1-octadecene (13 mL) at 320 C for 2.5 h in presence of oleic acid (OA, 0.1 mL)/trioctylphosphine
oxide (TOPO, 0.2 g; OA:TOPO molar ratio 0.6:1)

surfactant mixture (Figure 2a). The NPs show excellent crystallinity, according to the clear lattice
fringes in the HRTEM image (Figure 2b).

Iron Oxide Nanowhiskers


In a typical synthesis of iron oxide nanowhiskers,
the iron oleate complex (1.8 g) is heated at 150
C in 1-octadecene (13 mL) for 2.5 h using the
usual OA/TOPO surfactant mixture. The product
is ultrathin iron oxide nanowiskers of dimensions
2x20 nm, as seen in the BF TEM image (Figure
3a). The high aspect ratio of the nanowhiskers
makes imaging at high magnification challenging.
However, the clear lattice fringes in the HRTEM
image indicate good crystallinity of the iron oxide
nanowhiskers (Figure 3b) (Palchoudhury, An, et
al., 2011).

Iron Oxide Nanoworms


Co-precipitation: FeCl3.6H 2O (0.63 g) and
FeCl2.4H2O (0.25 g) are mixed in DI water (10
mL) at room temperature. To neutralize this
acidic Fe solution, 1 mL concentrated aqueous
ammonia is added dropwise under vigorous stirring. The reactants are magnetically stirred and

95


Synthesis and Characterization of Iron Oxide Nanoparticles

Figure 3. Iron oxide nanowhiskers. (a) TEM image and (b) HRTEM image

Figure 4. Iron oxide nanoworms via modified heat-up method. (a) TEM and (b) HRTEM

heated at 70 C for 1 h. The complete reaction is


conducted in an oxygen-free environment under
steady nitrogen purge. The magnetic NPs are purified with a centrifuge filtering column (100,000
MW CO, Millipore) and crosslinked in a strong
base (5 M aqueous NaOH) with epichlorohydrin.
The product containing chain-like nanoworms
(NW) is filtered through a 0.1 m pore diameter
membrane to obtain 50-80 nm long NWs (J. H.
Park et al., 2008).
Modified Heat-up: Here, the iron oleate
complex is heated in 1-octadecene (13 mL) in
presence of OA (0.1 mL). During this reaction, a

96

solution of TOPO (0.8 g) in 1-octadecene (7 mL)


is injected to the reaction at 290 C. The reaction
mixture is then heated to 320 C for a total time
of 2.5 h to obtain highly crystalline iron oxide
NWs (~12x100 nm). Figure 4 shows the TEM and
HRTEM images of iron oxide NWs synthesized
via a modified heat-up method (Palchoudhury,
Xu, Goodwin, & Bao, 2011a).

Iron Oxide Nanocubes


The iron oleate precursor complex for the iron
oxide nanocubes is synthesized via an overnight


Synthesis and Characterization of Iron Oxide Nanoparticles

reaction of FeCl3 (1.298 g, 8 mmol) and sodium


oleate (7.3 g, 24 mmol) in a solvent mixture
(hexane, 28 mL; ethanol, 16 mL; water, 12 mL) at
room temperature. The top organic part containing the precursor complex is phase separated in a
separatory funnel and washed five times with DI
water to remove impurities. This black complex
is dried at 105 C under reduced pressure to form
the viscous, brown iron oleate precursor. The
entire process is conducted at room temperature
without inert gas protection.
The iron oleate precursor (1.034 g, 1.15 mmol)
is reacted with sodium oleate (47.5 mg, 0.15
mmol)/oleic acid (168 mg, 0.595 mmol) surfactant
mixture in squalene (10 g). The reaction mixture
is stirred at 150 C for one hour and 175 C for
another hour before heating the reactants to the
boiling point of the solvent (320 C) at 25 C/min
for an hour. An inert atmosphere is maintained
throughout. The resulting iron oxide nanocubes are
about 10 nm in size (Shavel & Liz-Marzan, 2009).

Iron Oxide Nanoplates


and Nanoflowers
The iron oleate complex for the iron oxide nanoplates and nanoflowers is prepared with a slight
modification to the existing route. Potassium
oleate (96.2 g) is mixed to a partial dissolution in
DI water (60 mL) prior to addition of the hexane
(140 mL)/ethanol (80 mL) solvent mixture. The
paste-like potassium oleate is mixed in the solvent
for an additional 1 h for complete dissolution.
FeCl3 (6.5 g) is added to this potassium oleate
complex solution to prevent any reaction of the
iron salt with water. The mixture is reacted for 4
h at 60 C to form the iron oleate complex. The
hexane phase containing the iron oleate complex
is separated and washed with DI water to remove
by-products. The procedure is conducted at room
temperature without inert gas protection. This
iron oleate complex is less viscous and easy to
handle compared to the well-dried iron oleate

waxy paste because the hexane accounted for 6.5%


of its weight. The brown liquid-like precursor is
used for the synthesis of iron oxide nanoplates
and nanoflowers (Palchoudhury, Xu, Rushdie,
Holler, & Bao, 2012).
Nanoplates: Typically, the iron oxide nanoplates are synthesized via thermal decomposition
of the less viscous iron oleate complex (1.8 g) in
1-octadecene (13 mL) for 1 h in the presence of
OA (0.1 mL)/TOPO (0.2 g) surfactant mixture.
The reaction is conducted at the reflux temperature
(290 C) with steady argon purging. The product
is iron oxide nanoplates of dimension 3x15 nm
(Figure 5a). The nanoplates are crystalline, according to the prominent lattice fringes in the
HRTEM image (Figure 5b).
Nanoflowers: Interestingly, iron oxide nanoflowers are formed when a higher percentage of
TOPO (1 g; TOPO/OA molar ratio, 8.35:1) is used
keeping all other reaction conditions the same as
that of the nanoplates. The nanoflowers are made
from an aggregation of small (~ 5 nm) singlecrystalline iron oxide NPs (Figure 5c). However,
the nanoflowers show good crystallinity, as seen
from the HRTEM image (Figure 5d).

Sample Preparation for


Nanoparticle Characterization
The NPs are centrifuged out of the solution using a 1:1 volume ratio of ethanol and hexane
and re-dispersed in hexane for TEM analysis.
This solution is dropped on the TEM grids for
viewing. Alternatively, the dry powder samples
for XRD, XPS, and magnetic measurements are
prepared via magnetic separation. Here, the NPs
are dissolved in a volatile solvent, chloroform.
Acetone is added to induce precipitation of the
iron oxide NPs. The NPs are separated from this
solution using a strong magnet. The clear solution
is discarded and the process repeated two times,
prior to vacuum drying of the NPs.

97


Synthesis and Characterization of Iron Oxide Nanoparticles

Figure 5. Iron oxide nanoplates and nanoflowers. (a) TEM image of nanoplates, (b) HRTEM image of
nanoplates, (c) TEM image of nanoflowers, and (d) HRTEM image of nanoflowers

Aqueous Phase Transfer of


Iron Oxide Nanoparticles
Several promising methods such as ligand exchange, bilayer formation, and lipid/polymer
encapsulation are developed to make the organic
phase iron oxide NPs water soluble (Prakash et al.,
2009). Typically, equilibrium between the 4 attractive and repulsive forces governs the stability of
these NPs in a biological medium. The short-range
Van der Waals forces and the magnetic dipolar
interactions induce inter-particle aggregation.
This can be controlled using electrostatic repulsive forces with a charged NP surface and steric
hindrances of the surfactant coating on the NPs.

98

Ligand Exchange: The iron oxide NPs are magnetically separated out of solution and vacuumdried to completely wash off the organic surfactant
layer. The dried powder sample is dissolved well
in chloroform under sonication to form the stock
solution (5 mg/mL). Freshly prepared polyacrylic
acid (PAA, Mw, 100,000) in dimethylsulfoxide
(DMSO, 4 mL) is mixed with the NP stock solution
and DMSO (45 mL) under sonication (15 min).
The homogeneous solution containing the NPs
and the biocompatible surfactant, PAA is reacted
overnight at 20 C in the shaker for phase exchange.
The iron oxide NPs in solution are magnetically
separated and redispersed in DI water. The final
pH is adjusted to ~ 7-8 using one drop of NaOH


Synthesis and Characterization of Iron Oxide Nanoparticles

solution to stabilize the anionic PAA polymer. The


clear brown solution of aqueous iron oxide NPs
remains stable over a long period (> 1 month)
(Xu, Qin, Palchoudhury, & Bao, 2011).
Lipid Encapsulation: This is a simple technique
to coat the entire hydrophobic iron oxide NPs
with a lipid layer for aqueous phase transfer. The
hydrophobic NPs are first washed and redispersed
in chloroform via sonication. Biocompatible lipid
molecules such as 1,2-dipalmitoyl-sn-glycero-3phosphocholine (DPPC) in chloroform is mixed
with this NP solution. The volatile chloroform
can be easily evaporated overnight under a gentle
stream of argon to form the dried NP/lipid cake.
The phosphate buffered saline is used to rehydrate
the NP/lipid cake under sonication at 50 C for 2
h. The product is a hydrophilic solution of lipid
encapsulated iron oxide NPs or magnetoliposomes
(Gonzales & Krishnan, 2005).
Polymer Encapsulation: Polymer encapsulation is useful to allow iron oxide to have a wider
range of application. Adding a biopolymer like
polyethylene glycol or dextran allows the NPs
not to induce an immune response. Applications
started in the late 1990s were employed in making
smart materials that will behave in a prescribed
way (Ebara, Hoffman, Stayton, & Hoffman;
Kim, Jeong, Lee, Kim, & Park, 2008; Miller
& Peppas, 1988; Nakayama et al., 2006; Song,
Labhasetwar, Cui, Underwood, & Levy, 1998).
The use of smart materials for curing cancer was
adopted in 2004 by The National Cancer institute
(NCI) to target, treat, report, and image tumor
cells (Cancer NANOTECHNOLOGY Plan: A
Strategic Initiative To Transform Clinical Oncology and Basic Research Though the Directed
Application of Nanotechnology, 2004). One of
the current methods for controlled release in deep
tissue can be as simple as encapsulating the drug
into a polymer matrix but the main challenge is
to control the release though an external stimulus
(Lonsdale, 1982). Hydrogels were explored in the

1960s because they held up to harsh conditions


like solvent and recently they are being combined
with NPs to perform controlled release (Kim &
Bae, 1992; Wichterle & Lim, 1960). Hydrogels
are networks that are chemically or physically
cross linked for the express purpose of slowing
down the diffusion of water through the system
(Kinam Park, Waleed .S.W. Shalaby, & H.Park,
1993; Peppas, 1987). These can then be used to
retain the drugs into the pocket. The rate in which
the drugs diffuse out of the system is defined
by the amount of crossing link (Chiellini, 2001)
and the addition of different reactive polymers.
Researchers have exploited the polymer-solvent
lower critical solution temperature (LCST), in
which the polymers will phase separate from the
solvent (Rathbone, Hadgraft, Roberts, & Lane,
2008). There are 2 main polymers explored today
Poly(N-isopropylacrylamide) and the Federal
Drug Administration (FDA) accepted biocompatible hydroxypropyl cellulose polymer that have
LCST of 32 C and 41 C, respectively (Heskins
& Guillet, 1968; Lee & Lawandy, 2002). Since
37 C is normal body temperature research have
found mixing with PNIPAAm different monomers
to form a block co-polymer will tune the LCST
from 32 C to higher temperature. This is useful for
deep tissue hyperthermia and chemotherapy. By
combining the use of NPs with macroporouse gel,
hydrogels or micelles with an AC magnetic field
could induce a controlled release (Kato & Gehrke,
2004; Liu, Wang, Gao, Liu, & Tong; Trapani, Sitterberg, Bakowsky, & Kissel, 2009; Wei, Cheng,
Zhang, & Zhuo, 2009). In 2009 Trapani showed
NPs coated with chitosan could work for controlled
release applications (Trapani et al., 2009). The
Gehrke group showed that HPC in a microporous
gel could be used for magnetothermally-triggered
release (Kato & Gehrke, 2004). Other research
groups use thermally sensitive micelles to achieve
the same results as Gehrke (Wei et al., 2009).

99


Synthesis and Characterization of Iron Oxide Nanoparticles

FUTURE RESEARCH DIRECTIONS


The most attractive features of iron oxide NPs
are the chemical stability and biocompatibility.
The human body contains approximately 3.5 g
of iron in the form of hemosiderin, ferritin, and
transferring (Reimer & Balzer, 2003). Therefore,
water-soluble iron oxide NPs can be potentially
assimilated via normal metabolic pathways such
as liver based excretion. However, the NPs should
be of sizes 5-200 nm to avoid rapid clearance
from the body (H. S. Choi et al., 2007). Despite
the tremendous progress in the synthesis and
reproducibility of iron oxide NPs, it remains a
challenge to fabricate stable aqueous phase iron
oxide NPs with controlled size and shape. The
heat-up method can provide high quality iron
oxide NPs with good size distribution and tunable
properties. However, an additional phase transfer
step is required to coat the NPs with biocompatible
surfactants via ligand exchange or encapsulation.
Increase in the hydrodynamic diameter of the NPs
from inter-particle interaction and aggregation are
the main issues during this phase transfer.
Therefore, a primary direction of future research will be to design an aqueous phase synthesis
for iron oxide NPs with the advantages of the heatup method. Alternatively, the aqueous route should
provide an engineered surface and morphology of
the NPs as that of the heat-up method. Such a facile
route will enable direct synthesis of hydrophilic
iron oxide NPs suitable for MRI contrast agents,
drug delivery, or hyperthermia applications. Ongoing efforts are made towards an aqueous phase
thermal decomposition of inexpensive iron salts
(FeCl3) using high boiling pyrrolidone (Li, Sun,
& Gao, 2005) and polyethylene glycol (Li, Wei,
Gao, & Lei, 2005).
Another aspect of future concern will be the
environmental effect of the NPs (S. Chatterjee,
Bandyopadhyay, & Sarkar, 2011). The impact of
extensive industrial application of the NPs on the
surrounding eco-system must be studied. To this
end, cytotoxicity studies are performed on all new

100

formulations of iron oxide NPs before use (Banerji,


Pramanik, Mandal, Maiti, & Chaudhuri, 2012).

CONCLUSION
This chapter summarized the growing interest in
the synthesis of iron oxide NPs for biomedical
applications such as MRI, drug delivery, and
hyperthermia. The specific focus was on the coprecipitation and heat-up methods. A systematic
report was made on the detailed synthetic procedures for iron oxide nanospheres, nanocubes,
nanoplates, nanoflowers, nanoworms, and nanowhiskers. The methods to characterize the NPs such
as the TEM, XRD, XPS, AGM, and DLS were
also described. While the co-precipitation method
provides a biocompatible aqueous phase synthesis, a better control of the size, size distribution,
shape, and crystallinity of the iron oxide NPs is
achieved with the heat-up method. Therefore, the
future scope lies in a synthetic approach combining the simplicity of the co-precipitation with the
reaction control of the heat-up method.

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KEY TERMS AND DEFINITIONS


Co-Precipitation: Reacting Fe2+ and Fe3+
salts in aqueous solution to form iron oxide
nanoparticles.
Heat-Up Method: Heating up the reactants
in an organic solvent to form the iron oxide
nanoparticles.
Iron Oxide Nanoparticle: Small particles of
iron oxide with at least one dimension < 100 nm
(1 nm = 10-9 m).
Ligand Exchange: Method of partially or
completely replacing the hydrophobic coating
layer (ligand) on nanoparticles with hydrophilic
molecules to render the particles water-soluble.
Nanoflowers: Iron oxide nanoparticles with
flower-like morphology.
Nanoplates: Plate-shaped iron oxide nanoparticles.
Nanowhiskers: Rice whisker-like iron oxide
nanoparticles.
Polymer Encapsulation: Coating the hydrophobic nanoparticles with an additional polymer
layer to render them hydrophilic.

107

108

Chapter 5

Si-NWs:

Major Advances in Synthesis


and Applications
Maha Mohamed Khayyat
Umm al-Qura University, Saudi Arabia
Brahim Assa
MPB Technologies Inc., Canada

ABSTRACT
Surfaces and interfaces have a special significance to nanotechnology because the surface/volume ratio
of nanomaterials is larger than for the bulk ones. Therefore, interfaces of nanomaterials are more important to the properties of the nanomaterials than for larger scale materials. Moreover, crystal growth
and more particularly Nanowires (NWs) growth occurs at the interfaces between the growing crystals
and the supply media. This chapter focuses on the silicon nanowires grown using a Vapor-Liquid-Solid
(VLS) concept. One of the key advantages of VLS is that controlled placement or templating of the
seed metal produces templated NW growth. This templating is required for integration of NWs with
other devices, which is desirable for many applications. The authors discuss issues on the discovery of
fundamentally new phenomena versus performance benchmarking for many of the Si-NW applications.
Finally, the authors attempt to look into the future and offer their personal opinions on the upcoming
trends in nanowire research.

INTRODUCTION
Silicon nanowires (Si-NWs) have recently attracted considerable attention due to the historical
role of Si in devices fabrication and in the integrated circuits (IC) industry. Continued high
performance from Si may require integration of
innovative architectures of NWs with the exciting

functional devices. Si-NWs may provide new avenues in these directions. Recently, Si-NWs have
been used in the fabrication of DNA sensors (Li
et al.,, 2004). The ability to control the unique
morphological and mechanical properties of SiNWs arrays demonstrated by Paulo and coworkers
(Paulo et al., 2007) opens new perspectives for
the development of array based electrical and

DOI: 10.4018/978-1-4666-5824-0.ch005

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Si-NWs

electrochemical systems. In addition, there are


studies (Schmidt and coworkers, 2006 & Cui and
coworkers, 2003) of fabricating Si-NWs vertical
surround-gate field effect transistor (VS-FET).
It has been reported (Huo et al., 2004) that room
temperature electroluminescence has been appeared from undoped Si-NWs that were grown
from disilane at a wavelength excitation of 600 nm.
It has been as well shown recently that Si-NWs
have been used to produce high resolution Atomic
Force Microscope (AFM) (Cohen et al., 2012).
Device applications utilizing Si-NWs have
been demonstrated in many different applications
including optoelectronic and electrical devices, as
well as solar cells (Huang et al., 2004; Kayeset
et al., 2005; Law, 2004; Samuelson, 2004). This
chapter will focus on wires grown using a vaporliquid-solid (VLS) concept or similar three phase
process (Givargizov, 1975; Wacaserand et al.,
2009; Wagner & Ellis, 1964).One of the key
advantages of the VLS process is that the controlled placement or templating of the seed metal
produces templated NW growth. This templating
is required for the straightforward integration of
NWs with other devices which is desirable for
many applications. Templated growth of NWs
have been achieved using various noble metals
like Au, Ag and Cu as the seed sites (Fan et al.,
2006; Kayesand et al., 2007; Westwater, 1997)
but for more reactive metals like Al, Sn and Sb
templating has often proven difficult. The noble
metals can often negatively affect the semiconductor properties of the nanowire from an application
perspective (Fan et al., 2006; Renardand coworkers., 2009; Wacaserand et al., 2009; Whang et al.,
2007; Ke et al., 2009; Chaudhari et al., 2010). For
example Au is a deep level trap in Si. Whereas
the more reactive metals like Al, Sb, and Sn are
less parasitic and can even be positive in terms
of acting as desirable dopants when incorporated
in the semiconductors (Tutuc et al., 2006; Roberts et al., 1981; Krug, 2008).Controlling spatial
placement of VLS grown nanowires with oxygen
reactive seed metals is therefore of great interest

for nanotechnology based applications (Wang and


coworkers2010).
It is our intent to describe in general the growth
of Si-NWs in a three-phase system. Therefore
general terms describing the three phases of the
system to be used throughout this chapter will
first be defined. In this chapter the term supply is
used to indicate the phase that supplies the growth
species to the surfaces. Common supply media are
vapors, solutions, melts, or even molecular beams
through vacuums. The term crystal or wire, as
defined above, will be used to describe the solid
crystalline phase. The term collector is used to
describe the third phase, which is small in comparison to the vapor crystal interface. This term
is used to replace more specific terms like: liquid
droplet, crystalline particle, catalysts, etc. The 1-D
crystal growth occurs at the interface between the
collector and the wire with the collector either at
the base or on the tip of the wire, see the following
figure. Unlike conventional crystal growth with
only two components or phases nanowires are often
grown in a three phase system. The vapor-liquidsolid (VLS) growth mechanism describes such a
three-phase system where the third phase is also
important to the crystal growth. This or similar
growth mechanisms are currently the accepted
mechanism for the enhancement of the epitaxial
growth of most free standing wire-like crystals
(Samuelson et al., 2004; Lauhon et al., 2004; Fan
et al., 2006). The VLS mechanism is based on a
specific system there are three components; a vapor
which supplies the source materials for crystal
growth, a liquid droplet, and the solid crystal. In
order for 1-D growth to result from this three-phase
system, the surface area of the liquid phase must be
physically small in comparison to the surface area
of the vapor/crystal interface. One-dimensional
crystal growth results when the growth rates at
the phase boundary between the liquid phase and
the solid crystal surface is higher than the growth
rate at the vapor/solid phase boundary. The commonality being that there are three phases and the
VLS mechanism is used as a basis to say that the

109


Si-NWs

existence of three phases is sufficient explanation


of the growth mechanism. Some examples are the
vapor-solid-solid (VSS), (Bootsma et al., 1971;
Kamins et al., 2001; Perssonet al.,, 2004) vaporadsorption layer-solid (VAdS), (Bootsma and co
workers1971) solid-liquid-solid (SLS), solutionliquid-solid (SLS) and supercritical-fluid-solid or
liquid-solid (SFSS or SFLS) growth processes,
(Trentler et al., 1995; Fang et al., 2006). The VLS
growth mechanism is therefore examined in order
to reveal the atomistic processes involved in crystal
growth in a three-phase system.

ASPECTS OF SYNTHESIS
Investigation of Si-NWs or Si wiskers dates back
to the pioneering work on vapor-liquid-solid (VLS)
approach by Wagner and Ellis (Zhang and coworkers, 2003; Tian and coworkers, 2006). The key to
NWs growth in any three phase system is that the
nucleation and growth rate at the collector/crystal
(liquid/solid) interface is greater than the growth
rate at the supply/crystal (vapor/solid) interface.
This means that the crystal grows more rapidly
under the collector, forming a nanowire with approximately the same diameter as the collector.
The aspect ratio of the nanowire is dependent on
the selectivity of the growth rates at the different
collector/crystal and supply/crystal interfaces.
The Si-NWs grown via VLS reaction are single
crystals but exhibit growth defects such as bending
and kinking. Lowering the silane (SiH4) partial
pressure leads to an increase in the wire width and
a reduction in the tendency to form kinks. The
VLS reaction using silane as the Si source gas
allows the growth of the very thin wires with high
aspect ratio (length-to-width ratio) (Westwater
and coworkers, 1997).
There are three main production schemes for
forming nanowires. In the top-down approach,
lithography or some other means is used to pattern a planar substrate material. An anisotropic
etch is then used to remove the material between

110

the nanowires. In the bottom-up approach, either


a seed particle or a patterned surface is used to
define where the nanowires will grow. Physical
or chemical vapor deposition (CVD) methods are
then used to supply growth precursors which feed
the growth of crystalline nanowires. Nanowires
can also be produced by forming the crystalline
nanostructures from an amorphous material.
A summary of the VLS growth process steps of
Si-NWs catalyzed for instance with Au is shown
in Figure 1.Similar process can be applied to grow
Si-NWs seeded with Al collector particles over a
relatively wide process window.
Systematic changes in the nanowire morphology have been identified with respect to the Al
film thickness, growth temperature, and pressure.
The Si-NWs can be grown with high growth rates,
good morphology, i.e., epitaxially with low diameter dispersion and tapering), and at high density
over a large range of growth conditions (Wacaser
et al., 2009). In fact, from our experience growing
nanowires with both Au and Al we have found
that it is simpler to achieve high densities, low
diameter dispersion, and good alignment with
Al than it is with Au. However, the key to good
growth with Al is careful deposition and treatment
of the Al layer prior to growth, particularly with
respect to avoiding oxidation; dramatic changes
in the results can be attributed to small changes
in the base pressure used to deposit the Al films.
Post growth and in-situ studies with varied thermal treatment of the Al film allow the state of
the collector to be probed and suggest that the
collector is an under cooled liquid during growth.
This understanding may be important in forming
more complex nanowire-based structures in this
materials system, particularly in terms of the pregrowth conditions. We also confirmed that Al is
incorporated in the nanowires during growth as
an active dopant and as a species that can later
be activated by high temperature treatment of the
nanowires. The incorporation levels are higher
than the projected bulk solid solubility, which
could lead one to conclude that if this high in-


Si-NWs

Figure 1. Schematic representation of growth steps of VLS-assisted growth of Si-NWs. (After Civale et.
al, 2006)

corporation is possible with Al it is also possible


when growing nanowires with other metals. The
structure and electronic characteristics of these
Al grown Si wires are highly relevant to many
applications, for example, in photovoltaics, where
it is advantageous to eliminate Au, where p-type
doping is helpful in forming the structures, and
where novel faceted structures like the pyramidal
structure presented here may be useful in terms of
multiple internal scattering of photons to increase
efficiency.

Catalyst Choice
The metal nanoparticle has a major role in vaporliquid-solid assisted nanowire growth. The metal
particle plays the act of the catalyst and determines
the diameter of the nanostructures. Consequently,
the choice of the metal, based on its physical
and chemical properties, determines many of
the nanowires properties. To be processed via
the VLS growth mechanism, the metal has to

be physically active, but chemically stable. To


find an eligible metal, the phase diagram is first
consulted to choose a material that forms a liquid
alloy with the nanowire material of interest. The
phase diagram (Figure 2) is also helpful for estimating the optimal composition and temperature
for nanowire growth.
In the vapor-liquid-solid process, the GibbsThomson equation places a lower limit on the wire
diameters that can be achieved under a given set
of conditions. Givargizov (1975) studied also in
detail the VLS crystal growth technique in 1975,
according to his study the equilibrium state is
given by the following equation;
NW = B 4
B = B V

(1)
(2)

111


Si-NWs

Figure 2. Binary phase diagram of alloy suitable for VLS mechanism

NW = NW V

(3)

where NW , B , V are the effective chemical


potentials of silicon in the nanowire, in the bulk
material, and in the vapor phase respectively, d is
the diameter of the nanowire, is the atomic
volume of silicon, and is the specific surface
free energy of the wire.
There is a critical nanowire diameter at which
the growth stops completely, the relation is as
follows;
B
4 1

=
kT
kT d c

(4)

where k is the Boltzmans constant and T the


temperature, dc the critical diameter.
Interestingly, the VLS growth is not actually a
catalytic process and the seed metal is not really a
catalyst. The metal droplet just receives the source
material and when super saturation is reached, the
excess material precipitates out of the droplet in
the form of a NW. Thus, the seed metal is only a
soft template (Hutchby et al., 2002; Johansson
et al., 2006) to collect the material and facilitate

112

NW precipitation, guidance, and elongation in


the axial direction.
A catalyst, as well known in chemistry literature and chemical industry, is a material that
increases the rate of a chemical reaction while
remaining intact in the process. The activation
energy for Si-NW growth using Au seeds and Si
thin film growth in microelectronics industry is
about the same at about 130 kJ/mol(Jae-Ryoung
et al., 2002), indicating that Au does not aid in
increasing the reaction rate.
Au is the most favored seed metal in the literature for NW growth due to the ease of handle.
However, Au is viewed as a contaminant in
semiconductor processing. It can modulate carrier
recombination in both n-type and p-type materials
because high-mobility interstitial Au atoms can
transform into electrically active low-mobility
substitutional sites. Gold is not desirable also
in optoelectronics applications since, as a deep
level trap in Si, it causes fast non-radiative decay
of excited carriers. For this reason, Si-NWs with
Au catalyst are not capable of light emission
whereas the NWs produced with other seed metals or oxide-assisted grow this known to produce
light emission in the visible and near IR ranges.
Another disadvantage is the high eutectic composi-


Si-NWs

tion of Au-Si system at 371oC (31 atm. % of Si),


which would make it impossible to obtain abrupt
heterojunctions in a NW by rapidly switching the
gas phase precursors.
For these reasons, several alternatives to Au
have been investigated in Si-NW (Meyyappan
& Sunkara, 2012). Gallium is a metal with low
melting point which forms a eutectic at a low
temperature (29.8 C) with low Si content (only 5
x10-8 atm %). TiSi2 has been successfully used as a
catalyst for Si-NW growth (Guichard et al., 2006).
Titanium sputtered onto a silicon wafer forms
small islands of TiSi2 when annealed at 900 C in
hydrogen for 5 min. Similarly, a thin layer of Pt
on Si wafer obtained by physical vapor deposition
forms PtSi when annealed at high temperatures.
PtSi commonly used as interconnects, has also
been used in Si-NW growth (Baron et al., 2006).

Templated Si-NWs seeded with Au using


standard photolithography is shown in Figure
3 on Si(100) substrate. The work presented in
Figure 3 is carried out by the author as a starting
point to catalyze the growth of Si-NWs, as it is
a well-established material. The knowledge of
parameters determine the diameter of Si-NWs
using Au as a collector was used to grow Si-NWs
using Al. The interest in other metals for Si-NWs
has arisen from the fact that Au historically has
poor compatibility with Si devices because Au
impurities act as a deep level trap decreasing the
carrier mobility, lifetime, and diffusion length.
The cost and the availability of Au is especially
important for photovoltaic applications, leading
to recent efforts using Aland other non-gold metals for NWs growth of photovoltaic Si structures
based on nanowires.

Figure 3. Si-NWs catalyzed with Au, patterned growth using photolithography. Experiments were carried
out by one of the authors (Dr. Maha Khayyat) in 2009 at T. J. Watson Research Center

113


Si-NWs

Nanoscale Chemical
Templating (NCT) Using
Oxygen Reactive Materials
Why we need to control the growth place of
NWs? Applications for NWs grown using the
VLS process have been demonstrated in many
optoelectronic and electronic devices. In order
to broaden this application space and make NW
based devices commercially viable, control of
the placement or templating of the nanowires
is desired. Templating is well established using
noble metals like Au, Ag and Cu, but for more
reactive metals like Al, Sn and Sb templating
has been difficult. Array of vertically aligned SiNWs were grown over areas >1 cm2 by standard
photolithography (Kayes and coworkers, 2007).
This is because when the seed metal reacts with
oxygen or oxygen containing materials prior to the
growth, the VLS process is hence impeded. Here
we describe a process we call nanoscale chemical
templating (NCT) which takes advantage of the
reactivity of the seed metal to template the NW
growth. NCT uses oxygen containing mask layer
like SiO2 to prevent the growth of NWs in undesired locations. In the desired growth locations
the mask is removed prior to metal deposition so
that NWs can grow in the holes in the oxide mask.
NCT can have a selectivity of 100%, meaning
that where there is oxide NWs do not grow. The
growth yield depends on the processing parameters and mask dimensions. High yields of single
vertically aligned NWs per sight are possible.
Preliminary optimization produced a 76% yield
of single wires and 97% yield per mask opening.
Most of the excess yield is multiple vertically
aligned wires per sight.
Most of the conventional NW templating
techniques do not work with oxygen reactive seed
materials like Al. The reason is that they require
liquid based chemistries that would oxidize reactive materials rendering the entire layer inactive
for seeding NW growth. In a typical templating
process consists of the following five steps:

114

1. A mask with holes through to the substrate


where NW growth is desired is formed;
2. A metal is blanket layer is deposited over
the mask;
3. The substrate with the over-layer is annealed
and the Au reacts with the substrate in the
holes and forms the NW seeds;
4. A liftoff of the metal is performed by removing the mask;
5. NWs are grown. Depending on the mask the
order of step (III) and (IV) can be reversed.
When the order kept as stated the mask, such
as a SiO2 mask, can prevent surface migration of metal during the annealing process.
If liftoff is performed first, metal migration
during annealing can become a problem for
pattern fidelity. If the metal is not removed
from the areas above mask, NWs will grow
in disordered crystallographic directions
on top of the amorphous mask. Thus for a
typical templated growth process with high
fidelity a liftoff process is required after
the annealing of the seed material with the
substrate.
NTC starts with the same processes as conventional NW templating (see Figure 1).
1. Forming a mask with holes where NW
growth is desired: The only constraint here
is that this mask must be a material that will
chemically react with the desired seed material and render it unsuitable as a NW seed,
2. A blanket deposition of the seed material is also the same: In NCT this layer
must however be protected from oxidation
however. In this paper this is achieved by
depositing the metal layer in the load lock
chamber of the ultra high vacuum- chemical
vapor deposition (UHV-CVD) system and
not exposing the deposited layer to air before
the next steps,
3. Annealing, and


Si-NWs

4. Growth: It is believed that another method


for preserving this layer would be to deposit
an amorphous layer of the desired nanowire
material over the non-oxidized metal layer.
This layer will protect the seed layer from
oxidation but still allow NW growth. In NCT
the metal layer does not require additional
patterning processes like lift off but is only
deposited as a blanket and annealed. This
seed layer could be removed after NW growth
by selective etching of the oxidized metal, or
it can remain as an isolation layer between
the NWs. In fact liftoff is one of the liquid
based processes that would oxidize the entire
reactive seed layer preventing NW growth.
The Si(111) sample, which has opening between a layer SiO2 of 50 nm thick, were placed
in the load lock of a custom built ultra-high
vacuum chemical vapor deposition (UHVCVD)
tool operated under low pressure conditions
(LPCVD). Then a layer of 6 nm thick Al was
thermally evaporated on the oxide patterned Si
(111) sample, where the Al evaporator and a
quartz crystal monitor were installed in the load

lock. The load lock base pressure is in the range1 x


10-7Torr and the growth chamber has a base pressure of 2 x 10-8Torr at 600C. Then the samples
were transferred to the hot growth chamber to be
annealed at 750C, for 20 minutes. The annealing
temperature is higher than the eutectic temperature
(577C) to agglomerate into relatively large islands
on the opening. Then the furnace was cooled to
the desired growth temperature at 490C. Then
the silane (SiH4) was introduced at a fixed flow
rate of 10 sccm (standard cubic centimeter per
minute), along with the diborane (B2H6) with
a flow rate of 1 sccm. The growth time was 60
mins. The growth pressure was 550 mTorr. After
NWs growth the SiH4 and B2H4 were pumped out,
and then the samples were transferred to the load
lock and allowed to cool down for few minutes.
The NWs morphology was studied by scanning
electron microscopy. Figure 4 shows an SEM
image of patterned growth using NCT along with
zones showing non-patterned growth of Si-NWs.
To demonstrate the versatility of NCT we have
used patterns produced with both photolithography
and nanosphere lithography. The type of photolithography used is not thought to be an important

Figure 4. Scanning electron microscopy (SEM) micrograph showing patterned and un-patterned growth
of NWs on Si(111) substrate

115


Si-NWs

parameter in NCT. In order to produce single NW


per opening, holes on the order of 200 nm were
required. This was achievable by the deep UV
lithography, but could have been performed by
e-beam lithography of nano-inprint lithography.
The photolithography substrates were 200 mm
p-type (111) Si wafers which were processed by
first growing a 50 nm thick layer of SiO2 at 950
o
C in a standard oxide growth process. This oxide
layer was then patterned with a 90 nm thick antireflection coating (ARC) followed by 450 nm
thick photo resist (UV1 1 0G) using a 248 nm
ASML UV- excimer laser stepper to expose the
pattern. The pattern consisted of circular holes
with a center to center spacing of 1.95 m and a
nominal diameter of 200 nm. After development
of the resist and ARC open/resist trim by reactive
ion etching in N2/O2, the wafers were subsequently
broken up into samples of approximately 1 cm2
for further individual processing.
The pattern in the resist was transferred into
the oxide by etching the oxide with buffered HF
(BOE 9:1 Seidler Chemical Company) solution,
typically for 60 s. The photo resist and ARC were
removed from the remaining area with acetone
followed by IPA and finally by an O2 ash treatment (100 W, 15 sccm, 1 Torr). This produced
2335 nm openings in the 50 nm oxide, varying the
buffered HF. Directly before loading the substrate
into the load lock of the UHV-CVD chamber the
samples were treated again in the buffered HF
for 4 seconds to remove residual oxides that were
formed during processing and storage. The etch
time was tuned to completely clear the oxide from
the openings without expanding the openings. The
UHV-CVD load lock chamber has been modified
with capabilities for Al evaporation, and after
pumping the chamber to below 10-6torr, 6 nm Al
was deposited as described previously. The sample
was then annealed at 730 C for 10 minutes. This
annealing temperature is higher than the eutectic
temperature (577 1 C) for Si and Al, the Al
deposited on clean Si as in the mask openings
reacts with the Si substrate to form Si:Al eutectic

116

droplets from which nanowires can subsequently


grow. However, thin Al deposited on the SiO2 does
not produce NWs.
After annealing, the growth of nanowires was
carried out by cooling the furnace to the desired
growth temperature at 490 C. Pure silane was
introduced at a fixed flow rate of 10 sccm, along
with a diborane helium gas mixture (B2H6: He
1:1000) with a flow rate of 1 sccm. Following
the procedure used in (Parlevliet et al., 2007),
typical conditions were 60 minutes growth at
a pressure of 550 mTorr. After NW growth the
SiH4 and B2H4 were pumped out and the samples
were transferred to the load lock for cooling. A
schematic flow of NCT is included in Figure 5, in
addition to scanning electron microscopy (SEM)
micrographs of experiments were conducted by
one of the authors (Dr Maha Khayyat).
The substrates for nanosphere lithography were
pieces of a p-type (111) Si wafers ~ 2 cm2 and
were cleaned using standard techniques leaving a
thin oxide on after cleaning. Silica microspheres
are commercially available with narrow size
distributions, and when dispersed properly on a
surface they can form a close-packed array that
defines gaps through which a NW seed material
can be deposited. In our case a drop of solution
taken directly from the bottle was dispersed onto
the substrate. Variable speed spin routines were
used on a resist spinner to remove the liquid
and disperse the particles. After spinning on the
microspheres the substrates were processed like
the photolithography samples after the resist
strip. Namely they were cleaned with O2 plasma,
etched with HF, inserted into the load lock, and
Al was deposited. In Figure 5 a1) and b1) a NCT
scheme using microspheres is illustrated. In this
scheme an Al seed layer forms at the gaps between
microspheres and on top of the microspheres the
Al layer reacts with the oxides in the spheres.
Al deposition, annealing, and NW growth were
performed under the same conditions as with the
photolithography samples.


Si-NWs

Figure 5. (a-c) Illustration of NCT of NWs, and corresponding SEM images, cross sectional (a1, b1,
c1 and c4) and plan view (a2, b2, c2 and c3). (a) Patterned SiO2 layer after photolithography, etching
and resist removal; notice the clean openings and smooth surface. (b) Surface after Al deposition and
730C anneal. Notice the unreacted Al has agglomerated in the openings forming a NW seed per opening
and that the Al in contact with SiO2 has reacted with and roughened the surface. (c) After epitaxial NW
growth. The NWs appear as bright spots in surface view. In the cross sectional view a thin non-seeded
Si layer smaller than 1/100 of the length of the nanowire is also visible. Notice that a single NW per
opening is achieved. c3) and c4) show a larger area containing both a patterned area on the right and
an area with no oxide where random growth occurs on the left. The scale bars are: a1) and b1) 100 nm;
c1) 300 nm; a2), b2), and c2) 200 nm; c3) and c4) 20 m. After Khayyat and coworkers, 2013

In both conventional nanowires templating


and NCT advantages appropriate mask, deposition, and annealing processing conditions can be
found that form well-defined NW seeds. These
seeds control the growth of the NWs with no NW
growth occurring between mask openings. Also
depending on the width of the opening, it is possible to grow a plurality of NWs or a single NW
within each opening. The advantages of choosing NCT with an oxygen reactive material like
Al as the seed material for Si nanowires rather

than conventional templating with Au are: (a)


The fundamental problem of low lifetime due to
deep level traps caused by incorporation of Au
into the Si can be avoided; (b) Al provides lightly
p-doped Si NWs, so that p doped nanowires can
be grown without the morphological changes in
NWs which typically occur during in situ doping
by B2H6 are avoided; (c) The reaction of Al with
the SiO2 mask during an initial anneal avoids the
need for removing the unwanted seed material by
liftoff. No NWs grow between the desired spots

117


Si-NWs

Figure 6. Schematic representation of the use of NCT with silica microspheres. (a) The microspheres dispersed on a Si substrate. (b) After Al deposition and heating, Al reacts with the oxide in the microspheres
but on the substrate in between the microspheres Al seeds form for NW growth. (c) On exposure to silane,
NWs grow from seeds between the microspheres and unseeded growth occurs on the microsphere and
substrate surface. (d) A cross sectional SEM image showing single NW growth between microspheres.
Note the darker contrast at the microsphere surface due to unseeded Si growth and the brighter line at
the interface where the Al was deposited. (The scale bar is 500 nm)

even when the seed material is not removed.


This simplifies the processing by requiring fewer
processing steps; (d) Al remaining post-growth
at the tips of the NWs can easily be removed by
a simple HF treatment. To remove Au from the
tips more exotic etching chemicals are needed that
can affect device performance.

Applications on Silicon Nanowires


It is of great interest to present applications for
Si-NWs, which could benefit in unprecedented
ways from both the unique and tunable properties of nanowires and the small size of these
nanostructures, for use in the miniaturization of
conventional devices. As the synthetic methods for
the production of NWs are maturing and NWs can

118

be made in reproducible and cost-effective ways,


it is only a matter of time before applications will
be explored seriously. This is a timely development, as the semiconductor industry will soon be
reaching what seems to be its limit in feature-size
reduction. At the same time the field of biotechnology is expanding through the availability of
tremendous genome information and innovative
screening assays. Since NWs are of the size of the
shrinking electronic components and of cellular
bio molecules, it is only natural for nanowires to
be good candidates for applications in these fields.
Commercialization of NW devices, however, will
require reliable mass-production, effective assembly techniques and quality-control methods. In
this section, applications of nanowires to Atomic
Force Microscopy (AFM), thermoelectric, and
energy sector will be presented.


Si-NWs

Production-Scale Fabrication
Method of High Resolution AFM Tips
It is a method of fabricating high resolution AFM
tips that have a controllable diameter and a high
aspect ratio (Cohen and coworkers, 2012). The
AFM is one of the foremost tools for imaging, measuring, and manipulating matter at the nanoscale
level. Conventional AFM tips are fabricated by
anisotropic etching of Si. These tips are formed
at the end of a Si cantilever and typically have a
shape of a pyramid with triangular sides defined
by Si (111) surfaces. The drawback of such prior
art AFM tips is their poor lateral imaging resolution due to their low aspect ratio and large radius
of curvature of about 5 nm-30 nm (in the best
case). The present method provides a method of
fabricating high resolution AFM tips including a

single semiconductor nanowire grown at an apex of


a semiconductor pyramid of each AFM tip which
has a controllable diameter (from 5 nm to 200 nm
with additional thinning) and a high aspect ratio,
e.g., length to width ratio, (on the order of greater
than 100), without significant tapering from the
tip of the semiconductor nanowire to its base.
A patterned oxide layer is formed on the
AFM probe (see Figure 7). The patterned oxide
layer has an opening that exposes the apex of the
semiconductor pyramid. A single Si-NW is grown
on the exposed apex of the Si pyramid utilizing
a non-oxidized Al seed material as a catalyst for
NW growth. Since the single Si-NW is grown
from the exposed apex of the Si pyramid, the SiNW grows epitaxial. The Si-NW that is formed
includes a p-doped Si-NW core that is surrounded
by an undoped Si shell. The non-oxidized Al seed

Figure 7. Schematic representations of the various steps of Fabrication of high resolution AFM tips.

119


Si-NWs

material is present at the tip of the p-doped SiNW core. The non-oxidized Al seed material and
the undoped semiconductor shell can be removed
providing a p-doped Si-NW extending from the
apex of the Si pyramid.
Also, the p-doped Si-NW that is provided by
the present method is stiff enough such that it
can be inserted into a biological cell. Moreover,
the method of the present technique can be used
to tailor the dimension and the direction of the
p-doped Si-NW that is produced according to
specific imaging needs. Furthermore, the present
method can also be employed for the mass production of AFM tips which can be easily implemented
into any standard Si AFM cantilever. The method
of fabrication of high resolution AFM tips is a
direct application of NCT explained in the previous section and there are more applications to be
built on the technique of NCT.

Photovoltaic Cells Based on Si-NWs


With the increasing demand for energy and the
detrimental effect of fossil fuels on the environment, renewable energy sources are fast emerging

as an important alternative to traditional energy


sources. Among the alternatives, solar energy
holds great potential due to the enormous amount
of solar radiation the earth receives. It is estimated
that the earth receives about 162,000 TW of solar
energy every hour, which is more than 10,000
times the total worldwide energy consumption in
a year even if 0.1 of the land area is covered with
10% efficient solar cells, we can meet our energy
demands (Office of Science, 2005). In addition to
energy conversion, energy storage devices are also
gaining increased importance due to the emergence
of portable electronic devices and hybrid vehicles.
Si-NWs arrays promise to reduce manufacturing
costs and increase the power conversion efficiency
of photovoltaic devices. In addition to better charge
transport characteristics, nanowires exhibit better
light harvesting properties (see Figure 8).
In Figure 9 we compare the light absorption
and the carrier diffusion length of thin and thick
planar solar cells with a freestanding NW array
solar cell. The main advantages of NWsin terms
of technical performance are illustrated here. The
wires create a shape that promotes scattering,
thus increasing light absorption efficiencies to

Figure 8. The reflectance of bulk Si (pristine) and Si-NWs (C2PV07). A magnified graph of the reflectance of Si-NWs shows that the reflectance is less than 0.006 (a.u.)

120


Si-NWs

Figure 9. (a) Thin Planar Solar Cell: Short carrier length, Poor absorption of light. (b) Thick planar
Solar Cell: Long carrier diffusion length, Good absorption of light (c) Free standing nanowire solar
cell: Short carrier Diffusion length, Good absorption of light

equivalent or better than a similarly thick planar


layer. At the same time core-shell p-n NWs structures can be grown by controlling the doping and
growth parameters during and after the growth of
the nanowires (Kelzenberg et. al, 2010). These
core-shell PV devices allow for shorter carrier
diffusion length than for planar devices of light
absorptive thickness.
Photovoltaic cells based on Si-NWs exhibit
lower power conversion efficiencies than conventional cells due to the enhanced photocarrier
recombination associated with the nanostructures.
It has been identified and separately measured
surface recombination and Auger recombination
in wafer-based nanostructured silicon solar cells
(Oh et al., 2012). By identifying the regimes of
junction doping concentration in which each
mechanism dominates, Oh and coworkerswere
able to design and fabricate an independently
confirmed 18.2%efficient nanostructured blacksilicon cell that doesnot need the antireflection
coating layer(s) normally required to reach a comparable performance level. The results presented
by Oh et al. suggested design rules for efficient
high-surface-area solar cells with nano- and microstructured semiconductor absorbers.

The p-n junction solar cells based on nanowires have been demonstrated in two different
configurations. In the first case, the junction is
radial, while in the other, the junction is planar,
but with the nanowire arrays acting as an antireflecting material. Vertically aligned single
crystal Si NWs were grown on a p-Type Si wafer
and the excellent antireflection properties of the
NWs gave conversion efficiencies of up to 9.31%
(Peng and coworkers, 2005). Further improvement
in the efficiencies to 11.37% was obtained for Si
NW-based p-n junction solar cells by improving
their antireflection properties and better electrical contact of the cells by employing slanted NW
structure (Hui andcoworkers, 2008). Their efficiencies are however; lower than the single-crystal
Si solar cells inspite of higher antireflectivity due
to increased carrier recombination.
A simple method has been developed (Kelzenberg et al., 2008) for cresting rectifying contacts
that yield photovoltaic behavior from single SiNWs. These devices can be used to gain insight
into the performance determining properties for
Si-NWs photovoltaics, such as resistivity and
diffusion length, as well as the rates of bulk and
surface recombination. In radial junction devices,
the tradeoff between small-diameter NWs, which

121


Si-NWs

yield higher photovoltages due to decreased in


junction areas, is optimized when the wire radius
is approximately equal to the minority carrier
diffusion length.
All structures have a fixed wire spacing of
100nm and wire length of 2.33 m, but the wire
diameter varies (Gang &Hu, 2008). It has been
demonstrated that larger filling ratios give higher
absorption at the low-frequency regime, while
in the high-frequency regime NWs with smaller
filling ratios, a NW structure can have overall
absorption efficiency close to that of thin film.
It has been demonstrated that Si-NWs have the
advantages of small reflectance across a wide
spectrum and can be achieved without specially
designed antireflecting coatings.
Another factor in the cost is that VLS growth
is inherently a vapor phase crystal growth scheme
and as such must occur in a closed atmosphere
controlled environment. This usually includes
vacuum transfers and other procedures that can
affect throughput of the samples and thus production costs negatively. This added cost to the solar
cell manufacture can be mitigated somewhat by
the relatively high growth rate of NWs. Compared
to growing planar films, NWs grow at orders of
magnitude higher growth rates in similar growth
systems and parameters. This is due to the fact
that vapor phase crystal growth rates are limited to
some extent by volume growth rate. If one grows
a continuous planar film of a certain thickness,
then a given amount of growth precursors will be
consumed from the vapor. On the other hand,if
one consumes the same amount of precursor to
grow nanowires, their height will be orders of
magnitude taller than the thickness of the planar
film. This is because most of the volume (between
60-90%) between the substrate and the top of the
nanowires is void, i.e. there is no crystal growing
there. Thus, all the precursor material is included
in the crystalline nanowires that comprise the
remaining 10-40% of the volume. In essence the
much higher growth rate of the PV devices will

122

Figure 10. TEM cross section of a core-shell p-n


diode nanowire, showing defects propagating
from the center of the nanowire to the outside.
The original wire had a diameter of ~50 nm and
was defect free

increase the throughput to a level that will allow


for lower production costs.
As mentioned earlier this void volume in the
NW PV devices is not considered dead space
because light scattering can allow the NW-void
layer to absorb as much or more of the incoming
light as an equivalently thick solid layer would absorb. This means that an equivalently thick planar
layer takes much longer to grow than a NW layer.
Even though the processing must include vacuum
based processes that typically add higher costs
due to lower throughput the higher throughput
of the growth process can allow for this process
to be comparably fast and thus more competitive
than other planar PV vapor phase grown devices.
Microscopy and microanalysis are crucial to
improving and understanding NWs growth processes and solar cell performance. The interfaces
and surfaces of the nanowires and what impact
they have on the solar cell device performance?
These interfaces, especially the interface between
the p and n areas of the solar cell diode, are critical
to the quality and efficiency of solar cells. Often


Si-NWs

these interfaces are difficult to control, resulting


in defects (see Figure 10) that can affect the performance of the device.
There is one negative aspect to using NWs in
large scale PV device that is fundamental to the
diode itself. The VOC of any PV devices is dependent on the area of the p-n junction. The VOC
is defined in Equation 5 where is a constant at
constant temperature, IL is the light induced current and ISis the dark saturation current.
VOC

1 I
ln L + 1

I S

(5)

The dark saturation current is directly proportional to the area of the p-n diode. In a NW-PV
device the area of the p-n diode is orders of magnitude larger than for a planar device because of
the core shell structure. This means that the VOC
of the NW device can be lower than for a planar
device. However, as mentioned above, the NW
device has potentially better absorption properties
and carrier collection properties which increase IL
this may not fully compensate for the large increase

in IS, but the increase IL the IS which makes the


NW PV potentially more efficient than its planar
counterpart (see Figure 11).
Extensive theoretical calculations predict that
there are indeed parameter spaces for which the
NW-PV devices outperform planar devices (Kayes
et al., 2005).

Thermoelectric Devices and Sensors


Thermoelectrics are devices for which a temperature gradient causes an electric current in a
closed circuit, or a voltage potential in an open
circuit. Using VLS grown silicon nanowires, it
was established early in the lab that their thermal
conductivity can be significantly reduced from the
bulk value of 150 (at 300 K) to ~8 W/mK (Li et.
al, 2003). The size-dependent reduction in thermal
conductivity is a direct result of strong phonon
boundary scattering at the nanowire surface. It
has been demonstrated recently that the thermal
conductivity in Si-NWs can be further reduced
down to almost the amorphous limit through a
surface defect engineering process (Law et. al,
2004). As a result, these rough Si-NWs behave

Figure 11. Illustrative comparison of I-V characteristics of planar and core-shell NW PV devices.
Although the NW device has lower VOC the maximum power point is higher because of the greater collection efficiency

123


Si-NWs

totally differently from their bulk counterparts.


At room temperature, bulk silicon is considered
to be both a good thermal conductor and electron
conductor, while rough Si-NWs are thermal insulators and at the same time electron conductors,
making them good thermoelectric materials for
waste heat recovery and power generation at a
relevant temperature range.
A sensor is a device that produces some form
of a measurable signal in response to an external
stimulus. The properties of many materials are
influenced by their surroundings. Indeed, there is
a miniaturization effort in progress to reduce the
size and power consumption of various analytical
instruments using the advances in microelecromechanical system (MEMS), and nanotechnology. Nanotechnology offers advantages with
respect to some of the criteria of sensors; such
as, small package, low power consumption. First,
nanomaterials possess a large surface to volume
ratio, leading to large adsorption rates for gases
and vapors; high reactivity. These attributes of

nanomaterials aid with the criteria of increased


sensitivity and response. Certainly, a reduction in
size, weight, and power consumption is possible
due to the small amount of active materials used
in the sensor.

FUTURE RESEARCH DIRECTIONS


The main practical advantage for NWs in large
scale PV applications is that they can potentially
be made to lower cost. One of the possible future
research directions on nanotechnology is Si-NWs
can be grown on cheap substrates. For example
we have grown NWs on common Al foil (see
Figure 12) on reusable substrates. In this process
the NWs are grown on an expensive substrate that
can be reused after the nanowires are removed
(Kayes et al., 2005). In both of these cases the
cost of the substrate has the potential of being
much less than the cost of single crystal material. The efficiency can also be almost as good

Figure 12. (Left) A schematic representation of growing Si-NWs on a cheap substrate. Nanowires grow
on Al foil. (Right) ASEM micrograph of the grown Si-NWs on Al foil, the growth parameters are: 490
C/ 500 mTorr SiH4/ 30 min

124


Si-NWs

or even better in some particular thickness and


application range (Kayes et al., 2005). Thus it is
possible to save on the relatively high cost of the
single crystal substrates and produce cells with
reasonable efficiency. This may have an impact
on the cost per watt production metric.
Growth of NWs on Al foil is a good illustration
of how NWs can be grown, doped, and made on
cheap substrates. In this case the substrate can
also act as the back contact for the solar cell further enhancing the cost savings. In this case the
nanowires where grown with Al as the seed similar
to the procedure published earlier. A sample of
ordinary Heavy Duty aluminum foil approximately
2 cm2 was rinsed with Acetone, alcohol, and then
deionized water (dI). After which it was blown
dry. The substrate was then loaded into the load
lock of the CVD chamber and Al was evaporated
on top of the Al foil. The substrates where then
transferred into the main growth chamber where
they were treated at an annealing temperature
of 600C. The temperature was then lowered to
460C and Silane (SiH4) was introduced into the
chamber. The Si-NWssubsequently grew, as it is
presented in Figure 12. The growth characteristics
of these nanowires are similar to those grown on
Si except that they are not epitaxially oriented to
the substrate, which in this case was not expected
because the substrate is not single crystal.
Having demonstrated that many of the most
interesting discoveries to date relate to nanowire
properties not present in their bulk material counterparts, we can expect future research emphasis
to be increasingly focused on smaller diameter
nanowires, where new unexplored physical phenomena related to quantum confinement effects
are more likely to befound. We can also expect
the development of applications to soon follow.

CONCLUSION
Epitaxial growth of Si-NWs that grows freestanding from the substrate was the topic of this chapter.

With the remarkable progress in research on the


synthesis of Si-NWs over past few years in the
control growth which is accompanied by progress
templating techniques. Detailed analyses have
been presented of the innovative technique of
NCT using oxygen reactive materials. The main
advantages of NCT method are that it works for
reactive seed materials that can be more desirable
for many applications. This method can also have
fewer steps, not requiring lift-off of a metal layer or
removal of the mask. It is also amenable to standard
lithography techniques as well as self-assembled
patterning techniques like nanosphere lithography.
Patterning and growth parameters can be chosen
to achieve a high growth yield and fidelity, where
no NWs grow between openings, most openings
are occupied by one or more NWs and the majority is occupied by a single vertical NWs. We
believe that the methodology used in achieving
controlled placement of single NWs, seeded with
Al is only one example of this technique and that
other oxygen reactive materials such as Sn, Sb, In,
Ga, and Ti and others templated by NCT will have
applications in nanotechnology research as well as
3D CMOS devices(Complementary metaloxide
semiconductor). The production scale method
of high resolution AFM tips represents a direct
application of NCT technique. Nevertheless, for
more applications, an improvement of current
techniques of Si-NWs growth is still needed and/
or an innovative technology should be developed.
With the remarkable progress in research on the
synthesis of Si-NWs over recent years in the
control growth which is accompanied by progress
templating techniques. This is highly desirable to
future nano-manufacturing and applications, and
is in particular an essential step towards in situ
integration of well aligned Si-NWs into devices
with existing technologies. The chapter also covered some concerns and recent demonstrations for
using Si-NWs as solar cells and photonic devices.
There is no doubt that Si-NWs will create
countless new opportunities and hopefully in
technology. Many promising applications are now

125


Si-NWs

at the early demonstration stage, but are moving


ahead rapidly because of their promise for new
functionality, not previously available, to the fields
of electronics, optoelectronics, biotechnology, and
energy conversion and generation, among others.
Many exciting challenges remain in advancing
both the nanoscience and the nanotechnological
promise already demonstrated bythe Si-NWs
research described in this chapter.

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KEY TERMS AND DEFINITIONS


AFM: Atomic force microscope; which is one
of the foremost tools for imaging, measuring, and
manipulating matter at the nanoscale level. The
information is gathered by sensing the surface
with a mechanical probe or tip called a cantilever
with a sharp tip at its end that is used to scan a
sample surface. The cantilever is typically silicon
or silicon nitride with a tip radius of curvature on
the order of nanometers.
ALD: Atomic layer deposition method.
Bottom-Up: Building larger structures from
molecular building blocks.
CVD: Chemical vapor deposition method.
Epitaxy: A type of growth where the growing
crystal retains crystallographic information from
the substrate.

129


Si-NWs

LSMCVD: Liquid source misted chemical


vapor deposition.
MBE: Molecular beam deposition method.
Nanocrystal: Orderly crystalline aggregates of
10s to 1000s of atoms or molecules with diameters
in the range of approximately 100 nm.
Nanolithography: Writing in three dimensions in nanoscale.
Nanoscale Chemical Templating: A method
of fabricating semiconductor nanowires on a
surface of a semiconductor substrate in which the
spatial placement of the semiconductor nanowires
is controlled by using an oxygen reactive seed
material.

130

Nucleation: A term used in crystallography


to describe the process that occurs when two or
more atoms from the supply media chemically
bind to form a molecular unit.
PECVD: Plasma enhanced chemical vapor
deposition method.
PLD: Pulsed laser deposition method.
UHVCD: Ultra high vacuum chemical vapor
deposition method.
VLS: A growth method of semiconductor
nanowire which is based on different phases in
the system; vapor-liquid-solid mechanism.

131

Chapter 6

Principles of Raman Scattering


in Carbon Nanotubes
K. A. Shah
Govt. Degree College for Women, Anantnag, India
M. A. Shah
National Institute of Technology, Srinagar, India

ABSTRACT
Carbon nanotubes have attracted the scientific community throughout the world, and in the past decade,
a lot of work has been reported related with synthesis, characterization, and applications of carbon
nanotubes. This chapter is written for readers who are not familiar with the basic principles of Raman
spectroscopy in carbon nanotubes. The structure of carbon nanotubes, types of the carbon nanotubes,
Brillouin zone of carbon nanotubes, and band structure of carbon nanotubes are discussed at length,
which will serve as foundation for the study of Raman scattering in carbon nanotubes. The Density
of States (DOS) of single walled carbon nanotubes are illustrated by an example which will encourage readers to calculate the DOS of any type of carbon nanotube. The Raman modes of vibration are
discussed, and Raman spectroscopic analysis is presented by considering the typical spectra of singlewalled carbon nanotubes.

INTRODUCTION
For the past several years, great interest has
been devoted to nanosized materials of various
compositions and structures. For example, carbon nanotubes (CNTs) are promising for various potential applications. Precise and reliable
handling of these nanomaterials is important for
bottom-up assembly of nano-devices and considerable efforts employing a variety of approaches
have been made and reported. Characterization

of nanomaterials includes the determination not


only of size and shape, but also of the atomic and
electronic structures and other important properties. A theoretical treatment of Raman scattering
is essential for understanding, interpretation and
appreciation of the experimental Raman spectra
from any type of sample.
Usually the Raman spectra only involve phonons explicitly, being independent of the electronic
structure of the material and the laser energy used
to excite the Raman spectra. Furthermore, the

DOI: 10.4018/978-1-4666-5824-0.ch006

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Principles of Raman Scattering in Carbon Nanotubes

usual Raman scattering signal is weak. However,


the scattering efficiency gets larger when the laser
energy (excitation energy) matches the energy between the optically allowed electronic transitions
in the material and this intensity enhancement
process is called resonance Raman scattering.
The resonance Raman intensity depends on the
density of states (DOS) available for the optical
transitions, and this property is very important
for one-dimensional (1D) systems. Raman spectroscopy is usually among the first experimental
techniques used for the characterization of carbon
nanotubes.
Since carbon nanotube is the most popular
material among the researchers, and is called
the wonderful material of 21st century, therefore
in this chapter we describe the Electronic and
vibrational properties of this nanomaterial. We
start with the electronic properties of carbon
nanotubes. The study is focused on difference
in electronic properties of semiconducting and
metallic nanotubes. Furthermore the vibrational
properties discussed, gives review as well as principles of Raman scattering which is an important
tool for the characterization of carbon nanotubes
and other nanomaterials.

STRUCTURE OF CARBON
NANOTUBE (CNT)
Carbon nanotubes are tubular carbon molecules
provided with very particular properties. Their
structure is similar to fullerenes, but while fullerenes molecules form a spherical shape, nanotubes
are cylindrical structures with the ends covered by
half of a fullerene molecule. Nanotube diameter
is of the order of few nanometers, while their
length is of the order of several millimeters. The
physical properties make them potentially useful
in nanometer scale electronic and mechanical applications. They show unusual strength, unique
electrical properties and extremely high thermal
conductivity. The chemical bonding between

132

carbon atoms inside nanotubes is always of sp2


type. Nanotubes align themselves into ropes held
together by the van der walls force and can merge
together under high pressure. Nanotubes can be
excellent conductors as well as semiconductors,
depending on their structure. The thermal conductivity of carbon nanotubes is also high in the
axial direction. The particular properties of carbon
naotubes make them of great interest for potential
use in biotechnology, since they can be opened
and filled with other molecules. The structure,
electrical conductance and transport properties
of carbon nanotubes has been discussed at length
by Saito, Dresselhaus, and Dresselhaus (1998).
The structure of carbon naotubes has been
explored by high resolution TEM and STM,
yielding direct confirmation that the nanotubes
are cylinders derived from honeycomb lattice
(graphene sheet). As stated earlier the structure of
a SWNT can be conceptualized by wrapping a oneatom-thick layer of graphite called graphene into a
seamless cylinder. The way the graphene sheet is
wrapped is represented by a pair of indices (n, m)
called the chiral vector (Ch) as shown in Figure 1.
The intersection of the vector OB (which is normal
to Ch) with the first lattice point determines the
fundamental one dimensional (1D) translation
vector T. The unit cell of the one dimensional
lattice is the rectangle defined by the vectors Ch
and T (Figure 1). The cylinder connecting the
two hemispherical caps ofthe carbon nanotube
(see Figure 1) is formed by superimposing the
two ends of the vector Ch and the cylinder joint is
made along the two lines OB and AB in Figure 1.
The vectors OB and AB` are both perpendicular
to the vector Ch at each end of Ch .
The integers n and m denote the number of unit
vectors along two directions in the honeycomb
crystal lattice of graphene. If m = 0, the nanotubes are called zigzag. If n=m, the nanotubes
are called armchair. Otherwise, they are called
chiral. In the zigzag conformation, two opposite
C-C bonds of each hexagon are parallel to the
tube axis, whereas in the armchair conformation


Principles of Raman Scattering in Carbon Nanotubes

Figure 1. The (n,m) nanotube naming scheme can be thought of as a vector (Ch) in an infinite graphene
sheet that describes how to roll up the graphene sheet to make the nanotube. T denotes the tube axis,
and a1 and a2 are the unit vectors of graphene in real space.

Figure 2. Left: Different chiral vectors and chiral angle ; Right: a) (5,5) arm-chair-tube, b) (9,0) zigzag-tube and c) (10,5) chiral-tube with matching fullerenes (Dresselhaus, Dresselhaus, & Avouris, 2001)

the C-C bonds are perpendicular to the axis. In


all other arrangements, the opposite C-C bonds
lie at an angle to the tube axis, resulting in a so
called helical nanotube that is chiral (Figure 2).

The Chiral vector Ch is defined by two integers


(n,m) as well as two base vectors a1 and a2 (Dresselhaus, Dresselhaus, & Avouris, 2001; Reich,
Thomsen, & Maultzsch, 2004. The graphite layer

133


Principles of Raman Scattering in Carbon Nanotubes

is bent in such a way that both ends of the vector


lie on top of each other.

Ch = na1 + ma2 = ( n, m )

(1)

These two integers (n, m) determine unambiguously the diameter dt and the chiral angle
of the tube. represents the angle between the
chiral vector Ch and the direction (n, 0) (Figure 2).
3

d t = a n 2 + m2 + nm

(2)

3m


= tan1
2n + m

(3)

where a = 1.44 A is C-C distance. In (n, m) notation for chiral vector, the vectors (n, 0) or (0, m)
denote zigzag nanotube ( = 00) and the vectors
(n, n) denote armchair nanotube ( = 300). All
other vectors (n, m) correspond to chiral nanotubes
(00<< 300). The shape of cross-section are trans
type, cis type and mixture of cis and trans type for
zigzag, armchair and chiral nanotubes respectively.
The unit cell length is given by
0

T= 3

dt

d

(4)

N = 2 (m + n + nm) / dR
2

(5)

where dR = d if n-m is not a multiple of 3d or dR


= 3d, if n-m is a multiple of 3d and d is defined

134

BRILLOUIN ZONE FOR A CNT


The general relationship between a direct lattice
vector, ai, and reciprocal lattice vector, bj, is given
by Brennan (1999):

ai b j = 2 ij

(6)

Here ij is the well known Kronecker delta function defined such that:

1 if i = j

ij =
0 if i j

(7)

Thus for a graphene unit cell, if a1 and a2 are


direct lattice vectors, we may define two indirect
or reciprocal lattice vectors b1 and b2. Figure
3 shows the four vectors. Now, the length of a
reciprocal lattice vector is, given by

bj =

where d greatest common divisor of (2n + m)


and (n + 2m).
The characteristic of semiconducing and metallic nanotubes depends precisely on the values
of m and n. A tube is metallic when (n-m)/3 is an
integer. The number of hexagons N per unit cell
of a chiral nanotube defined by (n, m), is given by
2

as the greatest common divisor of (n, m). Each


hexagon in the honeycomb lattice contains two
carbon atoms. The unit cell area of the carbon
nanotube is N times larger than that for a graphene
layer and consequently the unit cell area of the
nanotube in the reciprocal space is correspondingly 1 / N times smaller.

2

ai

(8)

Similarly if vectors Ch and T define a CNT unit


cell in 2-D, then we may assign two associated
reciprocal vectors K1 and K2 respectively. These
vectors are given by:
K1 =

and

2
Ch

= Ch


Principles of Raman Scattering in Carbon Nanotubes

Figure 3. Direct (a), and indirect (b) lattice structure of graphene. Two atoms, A and B, define the unit
cell with unit vectors a1 and a2. b1 and b2are the reciprocal unit lattice vectors. The high-symmetry ,
K, and M points are also depicted in the reciprocal lattice structure.

K2 =

2
T

(9)

Thus K1 and K2 define a CNT reciprocal unit


cell in 2-D. It is also clear from the definition of
K1 and K2 that the larger the CNT unit cell, the
smaller the 2-D reciprocal unit-cell. For a CNT,
only K2 is the reciprocal lattice unit vector, corresponding to a single direct lattice vector.
The above picture is, however, not complete.
In a CNT, the vector Ch actually folds onto itself,
thus imposing periodic boundary conditions on
the wave function. This means that only certain
values of the component of wave vector k parallel
to K1, are allowed.
Consider the electron wave function for graphene:

( x ) = e ikx u ( x )

(10)

where u(x) is the Bloch function that contains


the periodicity of the lattice. Now by imposing
periodic boundary conditions on the wave function we imply that any translation by a distance in
multiples of |Ch|, and in the direction of Ch on the

graphene lattice should result in the same wave


function. Therefore,

k .Ch = 2 v

(11)

where is in an integer. Expanding out the above


equation in components of kx and ky, we obtain a
linear relationship between kx and ky. Therefore
the application of periodic boundary conditions
on Ch results in the appearance of discrete lines
in the CNT Brillouin zone (BZ) that represent
the allowed values of kx and ky and satisfy Equation 11. These lines are continuous along the K2
direction. The distance between each parallel line
along the K1 direction is 2 / | Ch|.,
The next step in determining the Brillouin zone
for a CNT is to determine the restriction on the
integer , if any. Since any point outside of the
first Brillouin zone of graphene is equivalent to
any point within the zone, we obtain:

y=

graphene reciprocal unit cell area


=N
K1 K 2

( N = Number of hexagons in CNT unit cell)


(12)

135


Principles of Raman Scattering in Carbon Nanotubes

These N lines (0 to N-1, or (N/2 + 1) to N/2


represent the extended zone scheme for a CNT.
Since a CNT is essentially a 1-D material, each
line segment can be translated to the K1=0 line,
resulting in a reduced zone scheme. This is called
the zone folding method.

imposing strictly periodic boundary conditions


for translations by the roll-up vector that defines
the nanotube. In this section we first discuss the
method to obtain the band structure of a CNT from
a simple zone-folding scheme of the electron
band structure of graphene.

ELECTRONIC BAND STRUCTURE


OF CARBON NANOTUBES

BAND STRUCTURE OF
2-D GRAPHITE

The electronic band structure of a CNT depends


very strongly on its diameter and chirality (i.e.
chiral vector). CNTs may be metallic or semiconducting. Even within the broad category of
semiconducting CNTs, vastly different properties
are exhibited by different CNTs. A single wall
carbon nanotube is essentially a single 2-D layer
of graphite (a graphene sheet) rolled into a tube.
Graphene is a sp2 bonded network of carbon atoms
arranged in a hexagonal lattice with two atoms per
unit cell. A nanotube of a particular radius and
chirality may be specified by choosing a roll-up
vector known as Chiral vector Ch that maps two
given hexagons in the lattice on top of each other.
Since any vector connecting two hexagons in the
lattice is a Bravais lattice vector, it is a linear
combination of the primitive vectors with integer
weight. Thus, a given nanotube is associated with
two indices that specify these integers. However
this indexing scheme is one of convention as the
choice of primitive lattice vectors is not unique.
However, this scheme appears to be the most
commonly used in the literature.
For a very large radius tube, one might expect
that the properties of the tube are very similar
to that of graphene. It has been found that even
for very small diameter tubes (~1 nm) that the
basic electronic properties of nanotubes may be
deduced from the band structure of graphene. In
the simplest possible model, the band structure of
nanotubes can be derived directly from the band
structure of graphene. This is accomplished by

The -electron band structure for graphene may be


obtained from the application of the tight-binding
(TB) method (Dresselhaus et al., 2001; Reich et al.,
2004). Figure 3, as mentioned previously, shows
the direct lattice structure (a), and reciprocal or
indirect lattice structure (b) of graphene. Vectors
a1 and a2 define the unit cell, and b1and b2 define
the reciprocal unit cell. The symmetry points, , K,
and M, in the reciprocal lattice are also depicted.
By considering the orbital overlap between the
A and B atoms to be zero (i.e. no overlap), one
obtains a tight-binding (TB) formulation of the
band structure as:

136

3k x a
k a
k a
e ( k ) = 0 1 + 4cos 2 y + 4cos y cos

2
2

(13)

In the equation, 0 is the nearest-neighbor


transfer integral, also called the hopping matrix element, a is the lattice constant for the
graphene direct lattice structure, and e is the
electron energy.
Figure 4 depicts an illustration of the energy
dispersion for graphene over the entire Brillouin zone (BZ). This intersection gives rise to
the semi-metallic nature of graphene. If we do
not consider the overlap to be zero, we obtain
an asymmetric band structure around the Fermi
level. This is depicted in Figure 4, which shows
the band structure of graphene along the high
symmetry directions.


Principles of Raman Scattering in Carbon Nanotubes

Figure 4. Illustration of the electron energy dispersion of the and * orbitals of graphene over the
entire Brillouin zone

BAND STRUCTURE OF
CARBON NANOTUBES
As was mentioned in the previous section, periodic
boundary conditions imposed by the chiral vector
Ch cause the wave vector K1, which is associated
with Ch, to be quantized in a CNT, while the wave
vector K2, which is associated with the vector T,
remains continuous. This gives rise to a set of k
vectors that are parallel to T. These k vectors will
result in cross-sections of the graphene electron
dispersion. These cross-sections result in the
appearance of various sub-bands in a CNT. The
band structure is obtained along the K2 vector.
Figure 4 shows the electron energy dispersion
relations for 2D graphene as a function of the
two dimensional wave vector k in the hexagonal
brillioun zone. The valance and conduction *
bands are seen to meet at the six high symmetry

K points, giving rise to the metallic nature of


graphene. The overlap integral is considered to
be zero. The energy dispersion along the high
symmetry lines between the , K, and M points
is shown in Figure 5. The band (upper part) and
the conduction * band (upper part) are degenerate
at the K points in the hexagonal Brillioun zone
which corresponds to the Fermi energy (EF = 0)
(Dresselhaus et al., 2001; Reich et al., 2004). Since
the energy dispersion near the Fermi energy is
linear, the density of states of metallic nanotubes
is constant at the Fermi energy and is inversely
prepositional to the diameter of the tube.
To distinguish metallic and semiconductor
nanotubes we introduce the Figure 6. In the direction of K1, discrete k values are obtained by
periodic boundary conditions for the circumferential direction of the carbon nanotubes, while in
the direction of K2 vector, continuous k vectors

137


Principles of Raman Scattering in Carbon Nanotubes

Figure 5. Electron energy dispersion of graphene along the high symmetry lines between the , K, and
M points. The overlap integral is non-zero

are in the one dimensional Brillioun zone. If,


for a particular (n, m) nanotube, the cutting line
passes through a K point of the 2D brillioun zone
(Figure 6), where the and * energy bands of
the 2D graphite are degenerate by symmetry, then
one dimensional bands have a zero energy gap.
For metallic nanotubes, the bold line intersects
the K point (corner of the hexagon) at the Fermi
energy of graphite (Figure 6a), where the density
of states are finite as shown below. For the semiconducting nanotubes, the K point always appears
one-third of the distance between two bold lines
(Figure 6b), and thus a semiconducting nanotube
with a finite energy gap appears. For each bold
line, there is an energy minimum (or maximum)
in the valance and conduction energy sub-bands,
giving rise to energy difference Eii (dt). The rule
for being either a metallic or a semiconducting
nanotube is, respectively, that n-m = 3q or n-m
3q, where q is an integer (Dresselhaus, Dresselhaus, & Avouris, 2001).
It is to note that to obtain the band structure for
a CNT, we simply obtain allowed CNT Brillouin
zone K vectors and obtain the associated energy
for each k from the graphene band structure.

138

Figure 6. Wave vector k for one-dimensional


carbon nanotube shown in the two dimensional
Brillioun zone of graphite (hexagon) as bold lines
for (a) metallic and (b) semiconducting nanotubes.
The points K and K` are equivalent


Principles of Raman Scattering in Carbon Nanotubes

ELECTRONIC DENSITY
OF STATES (DOS)
A quantity that enters critically in the experimental
study and the application of the electronic properties is the density of electronic states i.e, the number
of available electrons for a given energy interval.
The density of electrons is known to depend
dramatically on the dimension of a system. For
parabolic bands as found in most semiconductors
it rises as the square root of the energy above the
band gap in the three dimensional case, exhibits
a step like function in two dimensional solids,
diverges as the inverse of a square root in one
dimensional system, and finally, is a delta function in zero dimensions. Carbon nanotubes are
one-dimensional systems and around its minimum
and maximum a band can always be approximated
as parabolic. Thus the density of states varies as
square root of the energy above the band gap.
Some early tight binding and ab-initio calculations confirmed this for armchair nanootubes (Rao
et al., 1997; Mintmire & White, 1998). However it
was generally expected that the electronic density
of states is very different for achiral and chiral
tubes (Dresselhaus, 1998). However this view
changed when Mintmire and White (1998) published their derivation of a universal density of
states for carbon nanotubes Mintmire and White
(1998), given by

n(E) =

4a0

m =+

g(E, E

2d 0 m=

(14)

with density of states function


1

2
2 E > Em
E
/
(
E

E
)
2

g ( E , Em ) =
m
E
<
E

m
0

(15)

where a0 = 2.49 A0 is the lattice constant, 0 =


2.9 eV is the energy overlap integral, m is an

integer, d is the diameter of the tube and Em =


(ia00 31/2)/d is the points of energies of vanishing
slope for different electronic bands, with i = 1,
3, 6, for metallic and i = 1, 2, 4, 5, 7, . for
semiconducting nanotubes (Reich, Thomsen, &
Maultzsch, 2004).
For Em 0, g(E, Em) shows the divergence
at E= Em as expected for a critical point in a
one-dimensional system. For Em= 0, the density
of states functional g = 1, i.e., it is constant and
different from zero. Em= 0 refers to metallic tubes
and the bands that cross at the Fermi energy.
Three methods were successfully used in the
past to confirm the electronic density of states in
single-walled carbon nanotubes. Scanning tunneling spectroscopy (STS) (Wildoer et al., 1998;
Odom et Al., 2001), resonant Raman (Jorio et al.,
2001; Strano et al., 2003) and Optical absorption
and emission measurements OConnell et al.,
2002; Lebedkin et al., 2003). STS was the first
experimental technique that directly demonstrated
the existence of metallic and semiconducting
nanotubes and shows the presence of van-Hove
singularities (vHs). Raman scattering depends
strongly on the nanotube band structure and the
energies with a high density of electronic states.
Raman scattering do not directly measure the
electronic density of states as scanning tunneling
spectroscopy. They rather depend on joint density
of states (JDOS).
An example is given here, how to calculate the
density of states of a (5, 5) armchair nanotube using
Mintmire and White approximation (Mintmire &
White, 1998). Since n-m =0, it is a metallic tube
with diameter d = a/ (n2 + m2 + nm)1/2 =0.686
nm where a =0.249 nm is lattice constant. The
points of energies of vanishing slope for the first
electronic transition i = 1 is Em = 0.607 eV. Since
| E | >| Em |, therefore let us assume the electronic
energy E = 0.7 eV. With this value the density
of states function g(E, Em) =2.005. Substituting
this value along with other constant parameters
in equation (14) the value for density of states
calculated will be n(0.7) = 0.101.

139


Principles of Raman Scattering in Carbon Nanotubes

Table 1. Calculated density of states for (5, 5)


nanotube
Em

g(E, Em)

n(E)

0.607

0.7

2.005

0.101

1.821

1.9

3.473

0.176

3.642

3.7

5.642

0.286

Table 1 demonstrates the calculated density


of states for first three electronic transition energies of (5, 5) nanotube using Mintmire and White
approximation Mintmire and White (1998). The
calculated electronic transition energy is shown
in first column of Table 1, however the calculated
electronic energy, density of states function and
the density of states are shown in second, third
and fourth column of Table 1 respectively. The
magnitude for the value of density of states in
the valence band will be equal to its value on
the conduction band. Therefore, by considering
other states in the valance and conduction band,

the density of states can be plotted as a function


of energy similar to as shown in Figure 7.
Figures 7ac shows the DOS for three different SWNTs. Since SWNTs are one dimensional
(1D) systems, their DOS is characterized by the
so-called van Hove singularities (vHSs). The
sharp vHSs define narrow energy ranges where
the DOS intensity becomes very large. Therefore,
in practice, a single carbon nanotube exhibits
a molecular-like behavior, with well-defined
electronic energy levels at each vHS. The three
DOS curves in Figures 7ac come from different
SWNTs as labeled by their (n, m) indices (see
caption). Each pair of indices defines a unique
way to roll up the graphene sheet to form the
nanotube, and each unique (n, m) nanotube has a
distinct electron and phonon structure.
An observable Raman signal from a carbon
nanotube can be obtained when the laser excitation
energy is equal to the energy separation between
vHSs in the valence and conduction bands (e.g.,
see ES11, ES22and EM11in Figure 7), but restricted to

Figure 7. DOS for a (a) armchair (10, 10) SWNT, (b) chiral (11, 9) SWNT and (c) zigzag (22, 0) SWNT
obtained with the tight binding model (d) Shows the electronic transition energies Eiifor all the (n, m)
SWNTs with diameters from 0.4 and 3.0 nm using a simple first-neighbor tight binding model

140


Principles of Raman Scattering in Carbon Nanotubes

the selection rules for optically allowed electronic


transitions. Because of this resonance process,
Raman spectra at the single nanotube level allow
us to study the electronic and phonon structure
of SWNTs in great detail. When Raman spectra
of SWNT bundle samples are taken, only those
SWNTs with Eii in resonance with the laser excitation energy Elaser will contribute strongly to
the spectrum. From Figure 7 it is clear that the
metallic nanotubes (10, 10) has wider energy gapes
between spikes than semiconducting (11,9) and
(22,0) single-walled nanotubes.
For the characterization of nanotubes by Raman
spectroscopy, it is useful to consider plots of the
energies Eii versus the nanotube diameter, dt, as
shown in Figure 7d. Each point in this plot represents one optically allowed electronic transition
energy (Eii) from a given (n, m) SWNT. Crosses
come from semiconducting SWNTs, and circles
from metallic SWNTs. This plot should be considered as a guide for answering the question if
we use a given Elaser to excite our sample, which
(n, m) carbon nanotubes can be in resonance with
my laser line?. In other words, since the observable Raman spectra come predominantly from
tubes in resonance with Elaser, Figure 7 specifies
the nanotubes that will be observable for a given
laser line.

VIBRATIONAL PROPERTIES
OF CARBON NANOTUBES
Many common spectroscopic methods are used
for the study of vibrations in solids, like inelastic
light scattering, far-infrared spectroscopy, and
neutron scattering. Among all methods available,
Raman scattering has been far the most used for
the characterization of carbon nanotubes. However
it is very important to have a general knowledge
of the vibrational properties of carbon nanotubes
using Raman spectroscopy. Raman scattering insitu method is also available. The scattering signal
is so large compared to other spectroscopic meth-

ods that even isolated carbon nanotubes could be


investigated. The ever-growing interest in carbon
nanotube applications like mechanical enforcement, chemical sensor, electronically active and
passive devices etc, demands a thorough and robust
understanding of the vibrational properties. Combined with theoretical work the vibrational spectra
are intimately related to the electronic properties
of the tubes, it is as such that Raman scattering
became a straightforward in-situ non-destructive
tool for the characterization of carbon nanotubes.
From vibrational spectroscopy of carbon
nanotubes one can derive the tube diameter, tube
orientation, metallic or semiconducting nature,
and even attempts to derive tubes chirality has
been reported. Therefore an in-depth analysis of
the spectra is necessary to derive such specific
and important qualities from the spectra. Some
properties of carbon nanotubes indeed follow from
simple analogy to graphite, while others require
more detailed understanding of the nanotubes.
The zone folding approach is widely applied
in work on nanotubes. The folding is obtained by
slicing the graphite Brillouin zone in the appropriate direction. The phonons where the vertical
lines cut the graphite dispersion become -point
phonons in nanotubes. However zone-folding approach has some systematic shortcomings. Firstly
simple zone folding does not yield four acoustic
modes, one of them is the new twiston mode,
where the nanotube performs a twisting type
vibrations. Secondly the out of plane translation,
an acoustic mode in graphene, transforms into the
radial breathing mode (RBM) in carbon nanotubes
with non-zero frequency at the -point. This mode
is an exception to carbon nanotubes and is most
important for determining the tube diameter.
The main features in the Raman spectra of
carbon nanotubes are: the radial breathing mode
(RBM), which is a totally symmetric (in the ring
plane) vibrational mode with A symmetry; the
disorder-induced D-band, also with A symmetry,
and its corresponding second-order G-band;
and the tangential G-band, which is made up of

141


Principles of Raman Scattering in Carbon Nanotubes

a mixture of symmetric and asymmetric in-plane


modes (A and E1 symmetry), and asymmetric
out-of-plane modes (E2 symmetry). We will now
describe each mode by considering typical spectra
of a single walled nanotube.

TYTICAL SPECTRA OF SINGLEWALLED CARBON NANOTUBES


The first order spectra are divided into regions
where the entire tube deforms at low frequency
and where neighboring carbon atoms vibrate out
of phase at higher frequency. The low frequency
range of the radial breathing mode (RBM) is between 100 and 400 cm-1, the intermediate range
with the defect induced vibration (D-mode), which
involves phonons from the graphite K-point, lies
between 1200 and 1400 cm-1, and the high energy
range, (1500-1600 cm-1) belongs to the so-called
high energy mode (HEM). A typical Raman

spectrum of a sample of single-walled nanotube


bundles excited at = 488 nm is shown in Figure
8, the RBM and HEM are very strong.
It is remarkable to note that most Raman spectra
look remarkably similar when excited with Elaser>
2.0 eV, however when excited with lower energy
around 1.9 eV the spectra in the high energy region
broaden, change their shape, and shift somewhat
to lower wave numbers, the maximum intensity
being around 1550 cm-1.
The two types of line shapes are traditionally
referred to as semiconducting and metallic, a notation related to the electronic density of states of
semiconducting and metallic nanotubes believed
to cause corresponding Raman resonances. Hiura
et al. (1993) were the first to publish Raman spectra of nanotubes in (1993). The spectrum looked
exactly like graphite with a single peak at ~1580
cm-1. Holden et. al (1994) reported for the first
time the group of broad Raman peaks just below
~1600 cm-1, which is typical for single-walled

Figure 8. Typical Raman spectrum of single walled nanotubes excited with 488 nm. The RBM, K-point
related D mode and HEM are shown

142


Principles of Raman Scattering in Carbon Nanotubes

nanotubes. A tentative assignment of all Raman


modes to calculated frequencies was made by Rao
et al. (1997). This assignment is still considered
partly correct.
One of the most curious aspects of Raman scattering in nanotubes actually goes back to graphite.
There, the vibrational mode in the region 1200 to
1400 cm-1 has the unusual property that it changed
its energy in the Raman spectrum with excitation
energy (Vidano et al., 1981; Pocsik et al., 1998).
The corresponding mode in nanotubes showed a
very similar behavior (Thomsen, 2000; Kastner
et al., 1999) and so a common explanation was
called for. Raman scattering experiments have
given the impetus to improve the understanding
of both electronic and vibrational aspects of carbon nanotubes. When analyzing Raman spectra
the splitting of electronic joint density of states
can be detected.
The carbon nanotube samples whether single
walled, multi walled, double walled or a bundle
carbon nanotubes often consists of un-oriented
tube ensembles where only the average tube diameters can be controlled by growth conditions,
however the chirality cannot be controlled and
therefore all chiral angles will be present in the
sample. As such the Raman signal is averaged over
different polarizations, diameters and chiralities.
Therefore, the correct interpretation of the Raman
spectra, in particular of the high-energy mode,
posed quite serious challenge.

CONCLUSION
This chapter starts with the discussion of the
structure of carbon nanotubes, so that the readers should understand the types of the carbon
nanotubes and the various parameters which are
necessary for foundations of the subject. Brillouin
zone and band structure of carbon nanotubes is
presented in detail, which will serve as backbone

for studying the vibrational properties of carbon


nanotubes. Density of states of carbon nanotubes
are also discussed with an illustrative example.
The new method presented will help to calculate
the density of states of any type of single wall
carbon nanotube. The importance of the various
modes of Raman spectra are also presented by
considering the typical spectra of single-walled
carbon nanotubes excited with 488nm. In short
this chapter provides a complete background of the
study of vibrational properties of carbon nanotubes
and gives new dimensions to the characterization
of carbon nanotubes by Raman spectroscopy.

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Dresselhaus, M. S. (1998). NanotechnologyNew trick with nanotubes. Nature, 391, 1920.
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Dresselhaus, M. S., Dresselhaus, G., & Avouris,
P. (2001). Carbon nanotubes: Synthesis, structure,
properties, and applications. Berlin: Springer.
doi:10.1007/3-540-39947-X
Dresselhaus, M. S., Dresselhaus, G., & Avouris, P.
(2001). Topics in applied physics. Berlin: Springer.
Hiura, H., Ebbesen, T. W., Tanigaki, K., &
Takahashi, H. (1993). Raman studies on carbon
nanotubes. Chemical Physics Letters, 202(6),
509512. doi:10.1016/0009-2614(93)90040-8
Holden, J. M., Zhou, P., Bi, X. X., Eklund, P. C.,
& Bandow, S. etal. (1994). Raman scattering from
nanoscale carbon generated in cobalt-catalyzed
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Jorio, A., Filho, A. G. S., Dresselhaus, G., Dresselhaus, M. S., Saito, R., et al. (2001). Joint density
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carbon nanotube studied by resonant Raman
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Kastner, J., Pichler, T., Kuzmany, H., Curran, S., &
Balu, W. etal. (1999). Resonance spectroscopy on
single and multi-walled nanotubes under pressure.
Applied Physics. A, Materials Science & Processing, 69(3), 309312. doi:10.1007/s003390051006
Lebedkin, S., Hennrich, F., Skipa, T., & Kappes,
M. M. (2003). Near-infrared photoluminicense of
single-walled carbon nanotubes prepared by laser
vaporization method. The Journal of Physical
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jp027096z
Mintmire, J., & White, C. T. (1998). First-principle
band structures of armchair nanotubes. Applied
Physics. A, Materials Science & Processing, 67(1),
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Mintmire, J., & White, C. T. (1998). Universal
density of states for carbon nanotubes. Physical
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PhysRevLett.81.2506
OConnell, M. J., Bachilo, S. M., Huffman, C. B.,
Moore, V. C., & Strano, M. S. etal. (2002). Band
gap fluorescence from individual single-walled
carbon nanotubes. Science, 297(5581), 593596.
doi:10.1126/science.1072631 PMID:12142535
Pocsik, I., Hundhausen, M., Koos, M., & Ley, L.
(1998). Origin of the D-peak in the Raman spectrum of microsrystalline graphite. J. Non-Crystal.
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Rao, A. M., Richter, E., Bandow, S., Chase, B.,
& Eklund, P. C. et al. (1997). Diameter selective Raman scattering from vibrational modes
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(1998). Physical properties of carbon nanotubes.
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(2001). Scanning probe microscopy studies of
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L., & Lieber, C. M. (Eds.), Carbon nanotubes.
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Strano, M. S., Doorn, S. K., Haroz, E. H., Kittrell, C., Hauge, R. H., & Smalley, R. E. (2003).
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Loehr, T. M. (1981). Observation of Raman band
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doi:10.1038/34139

KEY TERMS AND DEFINITIONS


Band Structure: Band structure describes the
ranges of energy that an electron within a solid
may have or ranges of energy that it may not have.
It provides electronic levels in crystal structure
which are characterized by a Bloch vector k and


Principles of Raman Scattering in Carbon Nanotubes

a band index n. The band theory can be used to


explain many electrical, optical, magnetic, and
physical properties of crystals.
Brillouin Zone: The Brillouin zone is defined
as the set of points in k-space that can be reached
from the origin without crossing any Bragg plane.
Equivalently it can be defined as the Wigner-Seitz
Cell of the reciprocal lattice. In case of single
walled carbon nanotubes the first Brillouin zone
is given by irreducible set of equidistant lines
whose length and spacing are dependent on the
values of two integers n and m.
Carbon Nanotubes: Carbon nanotube can
be thought as a rolled sheet of graphene in the
form of cylinder with diameter of the order of a
nanometre varying from 0.5 to 3nm. The carbon
nanotubes can be metallic or semiconducting depending upon the value of two integers n and m.
They have unique electrical, mechanical, thermal,
optical and magnetic properties.

Density of States: The Density of States (DOS)


of a system can be defined as the number of states
per interval of energy at each energy level that are
available to be occupied by electrons. For a system
a high DOS at a specific energy level means that
there are many states available for occupation and
zero DOS means that no state can be occupied at
that energy level.
Raman Spectroscopy: Raman scattering is
the inelastic scattering of light that provides the
chemical and structural information of a liquid
or crystal. A Raman spectrum is a plot of the
intensity of Raman scattered radiation as a function of its frequency difference from the incident
radiation. This difference in frequency is called
Raman shift. Raman spectroscopy is widely
used for studying carbon nanotube - length and
diameter, whether nanotubes are single- walled or
multi-walled, isolated or bundle, conduction type
of semiconducting or metallic and even chirality.

145

146

Chapter 7

Pharmacokinetics of
Polymeric Nanoparticles at
Whole Body, Organ, Cell,
and Molecule Levels
Mingguang Li
Wayne State University, USA

ABSTRACT
Polymeric nanoparticles have been increasingly studied and applied in a variety of areas, most commonly
in biomedicine. The efficiency and toxicity are two aspects that need to be considered for nanoparticles,
and both are closely related to the pharmacokinetics of nanoparticles. In this chapter, the pharmacokinetics
of polymeric nanoparticles were introduced at the whole body level (including absorption, distribution,
metabolism, and excretion), organism level (transportation within organs and pass through physiological barriers), cell levels (binding to cell surface, endocytosis, intracellular transition, and exocytosis),
and molecule level (protein binding and ligand-receptor binding). Examples were also given to illustrate
the modeling of the pharmacokinetics of polymeric nanoparticles at different levels. A comprehensive
understanding of the pharmacokinetics of polymeric nanoparticles will facilitate the applications in
various areas such as drug delivery and disease diagnosis.

1. INTRODUCTION
Nanoparticles, according to their chemical compositions, could be classified into three categories:
polymeric, non-polymeric, and hybrid particles.
Non-polymeric nanoparticles are commonly
used for imaging and diagnosis in medicine, but
they are very limited to modifications. Polymeric
nanoparticles are very flexible, and could be

prepared using numerous polymers to achieve


very complicated properties and functions, which
make them very advantageous for drug delivery.
Hybrid nanoparticles contain both polymeric and
non-polymeric materials with the purpose to retain
the advantages and functions of both.
It is difficult to distinguish polymeric nanoparticles from non-polymeric and hybrid nanoparticles in terms of pharmacokinetics, although there

DOI: 10.4018/978-1-4666-5824-0.ch007

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Pharmacokinetics of Polymeric Nanoparticles

are certainly some differences such as degradation.


However, it is not in the scope of this chapter to
compare the pharmacokinetics of nanoparticles
with different chemical composition. This chapter
will focus on the pharmacokinetics of polymeric
nanoparticles, while research about non-polymeric
and hybrid nanoparticles will be mentioned only
when they are helpful in understanding the pharmacokinetics of polymeric nanoparticles. On the
other side, most general statements in this chapter
also apply to non-polymeric and hybrid nanoparticles, unless indicated specifically.
Polymeric nanoparticles are increasingly used
in diverse areas, such as cosmetics, foods, and
especially medicine (Nitta & Numata, 2013).
There are two aspects of nanoparticles that need
to be understood thoroughly before they can be
used on human body: how efficient they are for
the purposes and what is the toxicity. Both aspects
are closely related to the fate of nanoparticles
in the human body, which could be generally
described as ADME (absorption, distribution,
metabolism, and excretion). ADME of polymeric
nanoparticles, similar as those of small molecules,
are dynamic processes, involving numerous interactions between the nanoparticles and the human
body. Mathematical description of the kinetics of
these processes enhances our understanding of the
interactions between polymeric nanoparticles and
human body, and further promotes the designation
and optimization of nanoparticles with higher
efficiency and low toxicity (M. Li, Al-Jamal,
Kostarelos, & Reineke, 2010).
The pharmacokinetics of polymeric nanoparticles depends on their properties including
size, surface charge and modifications, chemical composition, and shape. There are a few
comprehensive reviews have discussed this in
full detail (Duan & Li, 2012; Owens & Peppas,
2006). Many studies have been done to show the
relationships between nanoparticle properties and
their ADME within animal bodies and interaction
with cells (Duan & Li, 2012; Moghimi, Hunter,
& Andresen, 2012; Yue et al., 2011). These stud-

ies significantly advanced the understanding of


nanoparticle pharmacokinetics within the human
body. Based on these studies, mathematical models were established or improved to describe and
illustrate the kinetic processes of these particles
inside the living systems.

2. PHARMACOKINETICS OF
POLYMERIC NANOPARTICLES
2.1 The Pharmacokinetics
at Whole Body Level
Nanoparticles entering the human body can be
classified by two ways of exposure: unintentional
and intentional. The former includes airborne
pollutants and nanomaterials in working environments, or in food and cosmetic products. Intentional exposure is mostly for medical applications,
especially drug delivery and imaging. In most
cases, polymeric nanoparticles were engineered
and intentionally given to human for designed
applications such as drug delivery and diagnosis. Nanoparticles may be given through various
routes, such as through the respiratory tract,
gastrointestinal tract, and skin. Nanoparticles can
also be injected into the body, mostly for medical purposes. Numerous studies have shown that
the properties of nanoparticles have complicated
influences on the pharmacokinetics (Figure 1).

2.1.1 ADME of Polymeric Nanoparticles


The most common route is through the respiratory tract, especially for pollutants (Yue et al.,
2011). Due to the physiological structures of the
lungs, pharmacokinetics of inhaled nanoparticles
is very complicated and under numerous studies,
as discussed later in this chapter. According to
the physiological structures, the lungs could be
divided into the airways (trachea, bronchi, and
bronchioles) and the alveoli. Particles could deposit in the airway surface, and then be cleared

147


Pharmacokinetics of Polymeric Nanoparticles

Figure 1. A general view of the influence of nanoparticle physicochemical characteristics (size, shape,
and surface properties) on ADME (absorption, distribution, metabolism, excretion). Abbreviation: RES,
reticuloendothelial system. (Reproduced with permission; Moghimi, Hunter, & Andresen, 2012)

away from the lungs by mucociliary movement,


diffuse through the mucus layer to reach the epithelium cells, or captured by macrophages cells. The
large surface area of the alveoli and the intimate
airblood contact has been taken advantages to
deliver nanoparticles into the blood or lymphatic
system. As part of the respiratory tract, the olfactory region could also allow nanoparticles to pass
through into the central nerve system, as shown
in some animal studies.

148

Nanoparticles enter through the digestive tract


reach the stomach and then transit to the intestine.
The small intestine is the primary location of
nanoparticle absorption, while absorption may
also happen in stomach and colon. While in the
digestive tract, nanoparticles are also cleared out
the body by the movement of the intestines. There
were studies showing that nanoparticles (50 nm
to 200 nm) can pass through Peyers patches in
the wall of small intestine (Yue et al., 2011). In-


Pharmacokinetics of Polymeric Nanoparticles

testinal enterocytes could be another absorption


routes (Florence, Hillery, Hussain, & Jani, 1995).
After that, nanoparticles then further distributed
into other organs and tissues through the blood
and local lymphatic system.
Other route of nanoparticle entrance into human body include the penetration through the
skin, injection directly into the blood circulation
or local tissues. Exposure to the skin has also
drawn increasing attention during the past years
(Pegoraro, MacNeil, & Battaglia, 2012). Studies
have shown that a variety of nanoparticles could
penetrate through the epidermis. For medical applications, nanoparticles could also be given to
the body by injections. No absorption process is
needed for intravenously administered nanoparticles, but nanoparticles administered through
other injection sites still need to be absorbed into
the blood circulation (Maincent et al., 1992).
After the absorption into the blood circulation,
nanoparticles could distribute into all organs and
tissues in the body as shown in many research
works. The concentrations in different tissues or
organs may be much different depending on the
properties of nanoparticles and their interaction
with the living system.
After nanoparticles enter the blood circulation,
they interact with the blood components immediately, including plasma proteins, platelets, red and
white blood cells (Oberdorster, Oberdorster, &
Oberdorster, 2005). Protein binding to nanoparticle surfaces (opsonization) almost instantaneously
once the particle enters a biological medium, and
subsequently change nanoparticle properties and
following interaction with the biological systems
(Aggarwal, Hall, McLeland, Dobrovolskaia, &
McNeil, 2009). Opsonization was reported to be
the major step to facilitate the recognition and
further phagocytosis of nanoparticles by macrophages. The binding kinetics of proteins to the
surface of nanoparticles is further discussed later
in this chapter. Nanoparticle distribution could also
be influenced by the blood supply of tissues. Tissues are divided into two groups by blood supply:

quickly and slowly perfused. The effect of blood


supply depends on the tissue blood supply and the
transportation rates of nanoparticles from blood
into tissues. When the blood supply is very limited,
or nanoparticles distribute into tissues very fast,
the blood flow may become the limiting step of
nanoparticle distribution.
As mentioned before, nanoparticle could
have distribution into almost all organs and tissues, although in most cases not as significant
as into the liver and spleen. A well known factor
that influences distribution of nanoparticles is
the reticuloendothelial system (RES, also called
mononuclear phagocyte system). The RES is composed of a group of cells having the ability to take
up nanoparticles (Otsuka, Nagasaki, & Kataoka,
2003). This includes macrophages, macrophage
precursors, specialized endothelial cells lining
the sinusoids of the liver, spleen and bone marrow, and the reticular cells of the lymphatic tissue
(macrophages) and bone marrow (fibroblasts).
Nanoparticle biodistribution studies have shown
that nanoparticles are accumulating and retained
by the organs compromising of the RES.
Lungs and GI tract could have relatively high
accumulation when they acted as the administration sites (Hillyer & Albrecht, 2001). In most
cases nanoparticles were found at very low levels
or missing in the brain due to the blood-brain barrier (BBB) (Hillyer & Albrecht, 2001). Although
showing low accumulation of nanoparticles
in most cases, the heart is routinely tested for
nanoparticles distribution due to its physiological
importance. The particle distribution into muscle
may be low, but the absolute amount may be quite
high due to the mass of muscles. Unless under
specific circumstances, other organs and tissues,
such as the reproductive tract, skin, and glands are
seldom tested separately, because low distribution
of nanoparticles.
As expected, the metabolism of nanoparticles
depends on their composition and properties. Different particles go through different metabolism
routes. Nanoparticles may be broken down in the

149


Pharmacokinetics of Polymeric Nanoparticles

macrophage cells of RES after being internalized.


The hepatocytes of the liver could also capture
nanoparticles by phagocytosis and digest them.
Nanoparticles prepared using polymers are under
mostly commonly used for drug delivery purposes.
The metabolism of these polymeric nanoparticles
is through the degradation of the matrix polymers.
Biodegradation of natural polymers is generally
faster than that of synthesized ones. One of the
advantages of polymeric nanoparticles is that
their biodegradation rate can be controlled by
modifying the polymer composition and molecular
weight (Shive & Anderson, 1997). Nanoparticles,
especially polymeric ones, could also change their
physical properties which results in the loss of
their original form. Particles could swell, shrink,
dissolve, or break in the biological environment
(M. Li, et al., 2010). These physical changes could
result in removal of nanoparticles from the living system or drifting of their ADME behaviors.
The most studied polymers are PLGA and PLA,
which are approved by FDA to be used in human
body. The degradation of PLGA and PLA is well
documented as depending on molecular weight
and composition. Natural polymers are frequently
chemically modified to obtain certain properties
that may alter their metabolism kinetics within
the body.
Besides metabolism, nanoparticles are also
eliminated out of the body through excretion,
which is also depending on their properties. Studies showed that liver and kidneys are the major
organs for nanoparticle excretion. Nanoparticles
may also be removed from the body through other
excretion routes such as the lungs, the breast milk,
and sweat. In the kidneys, nanoparticles could
enter the urine by glomerular filtration or tubular
secretion. The clearance was shown to be closely
size-dependent, and most studies were done using
inorganic particles. Choi et al,(2007) studied the
renal clearance of Quantum Dots depends on the
size of nanoparticles. Nanoparticles with size less
than 5.5nm showed efficient and complete renal
clearance. Renal clearance of larger nanoparticles

150

could be very slow, but still possible. Liver is


another major organ for nanoparticle clearance
through excretion (Yamago et al., 1995 ;Cho et
al., 2009). The excretion occurs across hepatocytes through the biliary production pathway.
For example, polystyrene nanoparticles were
excreted through hepatic route (Furumoto et al.,
2001). after intravenous administration in rats.
After being taken up by the liver, there particles
were excreted in the bile, about 4% of the dose
after 24 hours.

2.1.2 Pharmacokinetic Modeling


of Polymeric Nanoparticles
at Whole Body Level
Pharmacokinetics has been traditionally applied
to study the ADME of drug molecules. In the recent years, it is also used for nanoparticles. Most
recently, some scientist used other terms such as
particokinetics, or nanokinetics, in the place of
pharmacokinetics for the same type of study for
nanoparticles. The principles of pharmacokinetics
for drug molecules are generally applicable for
nanoparticles, and have been reported in many
studies.
However, as discussed before, ADME of
nanoparticles are very different from that of
drugs especially small molecules. Methods for
drug pharmacokinetics may need to be modified
to be used for nanoparticles. For example, some
nanoparticles have very long retention time in the
body, up to several years. This is very uncommon
for drugs. More importantly, most medical applications of nanoparticles need to understand the
distribution in particular tissues, in most cases, the
diseased ones such as the tumor. Toxicity study
also requires the knowledge of nanoparticles in
those crucial organs such as liver, heart, lungs,
and kidneys. Traditional PK modeling could not
provide sufficient information.
To serve the needs of nanoparticle studies,
physiologically based pharmacokinetics modeling
(PBPK) has been applied to nanoparticle PK stud-


Pharmacokinetics of Polymeric Nanoparticles

ies. PBPK modeling has been widely and successfully applied for drug pharmacokinetics prediction,
as illustrated comprehensively in the review by
Nestorov (2003). These models separate a living
system into compartments based on physiological
information. Time-dependent concentrations of
drugs and metabolites in these compartments are
described by mathematical equations.
The PBPK models have just found application
for nanoparticle during the past several years.
Although only very limited works available
in the literature, they covered various aspects.
Nanoparticle formulations of the same composition or different composition were compared
in the same model. Models were based on data
from both animal models and human. Several
of administration routes were covered including
intravenous, inhalation, and intradermal injection.
Both whole body and region PBPK models
were reported.
Application of PBPK modeling on polymeric
nanoparticles is still at the beginning stage. A very
successful example among a few works in this area
is from Li and coworkers who developed a PBPK

model to simulate the effect of nanoparticle properties on their distribution in the rats (Figure 2). The
biodistribution profiles of PLGA nanoparticles
with various PEG content were mathematically
described by a PBPK model. The model simulated
the experimental results of tissue concentrationtime curves quite well. The model also provided
insights into the kinetics of nanoparticle in vivo
distribution and the influence of multiple properties. The correlation between nanoparticle properties and biodistribution parameters enabled the
relatively accurate prediction of biodistribution
for another nanoparticle formulation. This is the
first work using PBPK modeling to interpret the
effects of multiple nanoparticle properties on their
biodistribution. This illustrates the significance
of a PBPK modeling approach for the building of
nanoparticle property-distribution relationships in
vivo. The applications of this work are far-reaching
including, but not limited to, nanoparticle toxicity
assessment, rational carrier design for drug delivery and imaging, and data interpretation from in
vivo bioimaging/biomarker systems.

Figure 2. A. Schematic diagrams of the membrane-limited PBPK model. Arrows indicate the transportation
of nanoparticles. Triangles represent the intravenous administration. Abbreviation: GI, gastrointestinal
tract. B. Exemplarys imulation of experimental data using the membrane-limited model. (Reproduced
with permission; Li et al, 2012)

151


Pharmacokinetics of Polymeric Nanoparticles

2.2 The Pharmacokinetics at


Organ and Sub-Organ Level
In traditional pharmacokinetics studies and PBPK
studies, most organs and tissues can be considered
as homogeneous in terms of nanoparticle transport
and distribution, without considering the kinetic
processes within the organs and tissues. However,
there are certain organs and tissues in which the
distribution of nanoparticles are not homogeneous
and there are particle transportation and relocation within the same organ or tissue. Lungs and
lymphatic systems are the most significant ones
in this meaning among others.

2.2.1 The Lungs


The kinetics of nanoparticles inhaled into the lungs
remained one the mostly studied topics, in most
cases for the toxicity (Kendall & Holgate, 2012).
The deposition, distribution, retention, and clearance of nanoparticles in the lungs have been in
extensive research and complicated computational
models have been developed to simulate these
processes. Computational modeling of kinetics
of inhaled particles is well developed. Such as
the free public software Multipath Model of
Particle Deposition, MPPD for particle deposition and clearance estimates in humans and rats.
The Human Respiratory Tract Model (HRTM)
of the International Commission of Radiological
Protection (ICRP) provides deposition data of
inhaled particles from 1 nm to 10 m of healthy
adult female and male human subjects, at different
breathing patterns and physiological activities.
The mechanisms, the pattern and the efficiency
of particle deposition in the respiratory tract largely
depend on the aerodynamic or thermodynamic
diameter of the inhaled particles. Nanoparticles
deposit with high efficiency in the entire respiratory tract due to diffusion. Most particles could
be cleared with 48 hours, but prolonged retention
of both micro- and nanoparticles in small airways
of humans were also reported (Wilkey et al.,

152

1980), the probability being inversely correlated


to particle size.
The major pathway for particle clearance from
conducting airways is by mucociliary transport.
The clearance rate depends on both the cilia and
the lung lining layer; faster in the central airways
and slower with increasing airway generation in
rodents. Kinetic studies using iridium nanoparticles showed that about 30% of the deposited
particles were cleared within the first 24 h after
aerosol inhalation. In some cases, a small portion
of nanoparticles could be also cleared from the
lymphatic system or enter the systemic blood
circulation.

2.2.2 Physiological and


Biological Barriers
There are also numerous philological barriers to
nanoparticle transportation, including blood walls,
blood brain barrier, and placental barrier (Pietroiusti, Campagnolo, & Fadeel, 2012). To distribution into other organs, nanoparticles need to pass
through these barriers. The capability for penetrating these biological barriers is mainly determined
by particle size and surface functionalization.
The BBB is a physical and physiological barrier
that regulates the passage of molecules from the
systemic circulation to the brain parenchyma. To
date, efforts to achieve polymeric nanoparticles
that can enter into the brain tissue have provided
promising results (Beduneau, Saulnier, & Benoit,
2007). Surface functionalization with a specific
ligand or cell penetrating peptides facilitates BBB
delivery (Newton, 2006). Biodegradable polymers
are preferred for nanoparticles targeting the brain
due to toxicity concern.
The placental barrier is of particular interest
in terms of protecting the developing fetus during
pregnancy. Only a few studies available in this
area and most of them use inorganic nanoparticles. In one study, it was found that fluorescent
polystyrene particles with a diameter of up to
240 nm were able to cross the placenta in an ex


Pharmacokinetics of Polymeric Nanoparticles

vivo human placental perfusion model (Wick et


al., 2010). These studies show that under certain
circumstances, it is possible for nanomaterials to
penetrate this biological barrier. However, more
studies are needed for better understanding of the
mechanism, extent and consequences of maternofetal transfer of nanoparticles.
Another factor that influences nanoparticle
distribution into tissues from the blood compartment is the blood vessel endothelium. Endothelia
composing the blood vessels have been classified
as continuous, fenestrated, or discontinuous, depending on the morphological features of the endothelium (Gentile, Ferrari, & Decuzzi, 2008). The
fenestrated endothelium exists in glands, digestive
mucosa, and kidneys and has an octagonal symmetry with radial fibrils interweaving in a central
point forming fenestrae of approximately 60 nm.
Discontinuous endothelium is a characteristic of
the liver, spleen, and bone marrow with pores of
50-100 nm. Nanoparticles with different sizes
may selectively diffuse through blood vessel of
different tissues. For example, nanoparticles less
than 60 nm may have easier access into tissues
with fenestrated or discontinuous endothelium.
The higher permeability of tumor vessels has
been taken advantage of for drug delivery using
nanoparticles.

2.2.3 The Tumor


Of special interest is the nanoparticle pharmacokinetics in tumors, because much attention has
been paid to chemotherapy using nanoparticles
(Bhagat, Halligan, & Sofou, 2012). Nanoparticles
have been extensively used for treatment and diagnosis of tumors. Tumors are abnormal organs
and consist of unique physiological features which
may be taken advantage for targeting nanoparticles
into the tumor. Both passive and active targeting
approaches have been investigated. Nanoparticles
can be passively targeted to tumor tissues, taking advantage of their abnormal physiological
features. Tumors are generally divided into two

types for transportation and kinetics studies: avascular and vascular tumors. Avascular tumor has
no blood vessels and the transportation is mainly
by diffusion of particles driven by concentration
gradient. Vascular tumor has blood vessels and the
transportation is influenced by the blood supply.
Avascular model is relatively simple, and
commonly represented using in vitro cultured
3-D tumor cell cluster termed spheroids. Studies
have shown the penetration of nanoparticles into
avascular tumors depends on time, concentration,
particle properties, and tumor properties (Ma et
al., 2012). In general, longer time and higher
concentration lead to more penetration into tumors. Because diffusion depends on the size and
the porosity of the tumor, smaller particles could
penetrate deeper. Nanoparticles within the tumor
could be located in interstitial space, bound to the
cell membrane, or internalized into cells. Binding
and internalization into cells deplete nanoparticle
in the interstitial space and reduce the concentration gradient which drives the particle to penetrate
deeper. The tumor cell density, extracellular matrix
(ECM), and necrotic stage all affect nanoparticle
penetration.
Diffusional model has been applied to simulate
and predict the diffusion of nanoparticles into avascular tumors. Pun et al developed a computational
model to describe the penetration of nanoparticles
into tumor spheroid based on experimental data
(Goodman, Chen, Matveev, & Pun, 2008). The
model accounts for radially dependent changes in
tumor architecture, as represented by the volume
fraction of tissue accessible to nanoparticle diffusion. Parameters such as nanoparticle binding,
internalization rate constants, and accessible
volume fraction were determined experimentally.
Unknown parameters of nanoparticle binding
sites per cell in the spheroid and pore shape factor
were determined by fitting to experimental data.
The model could help to understand how particle
properties and tumor properties could influence
particle penetration into tumor.

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Pharmacokinetics of Polymeric Nanoparticles

For vascular tumors, the distribution is much


more complicated than avascular ones. The
transportation of nanoparticles could be driven
by particle extravasation, convection, hydraulic
pressure, and diffusion. Tumor blood vessels are
leaky, tortuous, and dilated, and their endothelial cells lining have aberrant morphology with
the basement membrane often being abnormal.
Their high vascular density, vascular leakiness,
and impaired lymphatic recovery lead to an enhanced permeability and retention (EPR) effect
for nanoparticles. At the same time, hydraulic
pressure inside tumor is reported to be higher due
to hindered lymphatic drainage, which may reduce
the diffusion of particles. Convection is another
factor that is not clearly understood in terms of
particle transport in tumors.

2.3 The Pharmacokinetics at


Cellular and Subcellular Level
The kinetics of nanoparticle transportation
within the living system is very complicated and
still poorly understood. The most basic process
nanoparticles experience within the body is interaction with various types of cells, including
epithelium, endothelium, tissue cells, and macrophages. The kinetics of the nanoparticle-cell
interaction (adhesion, endocytosis, intracellular
transport, and exocytosis) depends on the properties of both nanoparticles and individual cells
(Mailander & Landfester, 2009; Rivera-Gil, Clift,
Rutishauser, & Parak, 2012). There are multiple
pathways for nanoparticles entering the cells as
indicated in Figure 3, although the knowledge in
this area is expanding daily.

Figure 3. Model of endocytic mechanisms and intracellular transport. EE, early endosomes; MP, phagosomes or macropinosomes; MVB, multivesicular bodies/late endosomes; Lys; lysosomes; RE, recycling
endosomes. (Reproduced from with permission; Iversen, Skotland, & Sandvig, 2011)

154


Pharmacokinetics of Polymeric Nanoparticles

2.3.1 Binding to the Cell Surface


Binding to cells is necessary for endocytosis of
nanoparticles into cells. The binding kinetics
to cells surface depends on the properties of
nanoparticles and the cells. In general, there are
specific and nonspecific binding. Specific binding
depends on certain receptors on the cells surface
while nonspecific binding is proportional to the
extracellular nanoparticle concentration. After
binding to the surface, nanoparticles could be
internalized into cells. Due to the importance of
this step, many studies have been done to control
the binding of nanoparticle to cell surface, and
the most common method is modify the particle
surface with targeting ligands which have high
affinity to specific receptor on certain types cells
(Holgado, Martin-Banderas, Alvarez-Fuentes,
Fernandez-Arevalo, & Arias, 2012). The strength
of interaction between the surface ligand and
membrane receptors can be controlled by various
parameters, including the type of ligand (i.e., affinity) and by changing the surface ligand density
(i.e., avidity) (Tassa et al., 2010).
Research has been done to use mathematical
modeling to predict the optimal design of nanoparticles for cell binding. A stochastic approach for
predicting the adhesion strength of nanoparticles
to a cell layer under flow has been coupled to a
mathematical model for the receptor-mediated
endocytosis of nanoparticles (Decuzzi & Ferrari,
2008). The study examined the main geometrical,
biophysical and biological parameters governing
both binding and endocytosis and analyzed their
relative importance. Based upon the geometrical
and biophysical properties of the particle and the
biological conditions at the site of adhesion, the
model predicted that there are three different situations for particle-cell interaction: no adhesion,
adhesion with no endocytosis, and adhesion with
endocytosis. Based on the model, nanoparticles
could be designed for better binding and entering cells.

2.3.2 Cellular Uptake


(Endocytosis) Kinetics
Nanoparticles can enter cells through either
endocytic dependent or endocytic-independent
(direct penetration) pathways. There are five
pathways reported in literature for nanoparticle
endocytic-dependent internalization by mammalian cells: phagocytosis, macropinocytosis,
clathrin-mediated, caveolin-mediated, and clathrin/caveolin-independent endocytosis (Mailander
& Landfester, 2009). Cellular uptake mechanisms
of nanoparticles are mainly influenced by their
hydrophobicity/hydrophilicity, surface charge,
surface functionalization, size and shape. Hydrophobic nanoparticles generally have short circulating half-lives and low bioavailability in vivo. The
hydrophobic surfaces are not physically stable and
do not remail well-dispersed in the bloodstream,
thus tending to agglomerate formation and are
therefore recognized by macrophages and removed
from circulation by the reticuloendothelial system.
Besides the surface properties, size and shape
are also shown to affect cellular uptake of nanoparticles. Many studies have indicated that size and
shape are crucial parameters in both specific and
non-specific cellular-uptake processes. Particles
larger than 500 nm could be recognized and
taken up by phagocytosis, whereas smaller ones
may escape from phagocytosis. Internalization of
larger particles by non-phagocytic cells is mainly
through macropinocytosis via hydrophobic and
electrostatic interactions. Direct cell penetration
could also happen for very small sized cationic
nanomaterials (such as metal nanoclusters and
dendrimers) by passing through cell membranes
without disrupting the integrity of the membrane
barrier.
Nanoparticle-cell interaction kinetics was
mostly studied using non-polymeric nanoparticles
due to their easy detection and stability. Based on
the results of pharmacokinetic models, the halflives of internalization for nanoparticles could

155


Pharmacokinetics of Polymeric Nanoparticles

be from minutes to hours. Chithrani et al. studied


kinetics of both endocytosis and exocytosis using
gold nanoparticles with sizes from 14 to 74 nm
(Chithrani & Chan, 2007). They reported that
the internalization half-lives were from 1 to 3 h,
depending on the nanoparticle sizes and the cells
tested. The half-lives of removal of the internalized
gold nanoparticles were faster (from 0.33 to 0.75
h). Serda et al.99 studied the internalization of
silica nanoparticles by vascular endothelial cells
and reported the half-life to be 15.7 min.
Mathematical models were also applied to
simulate the endocytosis kinetics (Y. Li, Yue,
Yang, & Zhang, 2012). An N-varied dissipative
particle dynamics (DPD) simulation technique
is developed for endocytosis kinetics for ligandcoated nanoparticles with different shapes. The
results indicate that the rotation of nanoparticles
regulates the competition between ligand-receptor
binding and membrane deformation. There are
two stages of particle internalization including
membrane invagination and nanoparticle wrapping. The kinetics of the first wrapping stage is
mainly dominated by the part of nanoparticles
with the largest local mean curvature, at which
the membrane is most strongly bent. The study
showed that nanoparticles with various shapes
have different favorable orientations for these two
stages, and one or two orientation rearrangement
may be necessary for endocytosis.

lysosomes contain proteases and other enzymes


that degrade most biological substances.
Metabolism and biotransformation of nanoparticles may happen during all the dynamic processes
of nanoparticles cell interaction. Biotransformation of nanomaterials leads to continuous changes
of physicochemical properties and subsequently
alters their interaction with the biological environments.
After particle wrapping in the sorting endosomes, acidification occurs maintaining a slightly
acidic environment (pH 6.2-6.5) within the early
endosomes and a more strongly acidic environment in the late endosomes and in lysosomes (pH
4.5-5.5). This process is always accompanied by
recruitment of digestive enzymes into the vesicle
to digest the vesicular contents.
Polymeric nanoparticles are frequently surface
modified such as conjugated with targeting ligands
or other function groups. These ligands or function
groups may be cleaved off in early endosomes.
For biodegradable polymers, such as PLGA and
PLA, the hydrolytic degradation is accelerated
in the endosomal or lysosomal environment. The
metabolic products of PLGA are lactic acid and
glycolic acid, and those of PLA are lactic acid,
which can be incorporated into cell metabolic
pathways. The biodegradation rate is determined
by the particle size, composition and molecular
weight and ultrastructure of the shell polymer.

2.3.3 Intracellular Traffic and


Biotransformation Kinetics

2.3.4 Exocytosis Kinetics

Nanoparticles internalized into cells through the


formation of early endosomes (EE), phagosomes
or macropinosomes (MP). These vesicles with particles then mature down the degradative pathway
and become multivesicular bodies/late endosomes
(MVB) which fuse with lysosomes (Lys). Alternatively, the nanoparticles may be transported
back to the cell surface either directly from EE
or through the recycling endosomes (RE). The

156

Most of those studies about exocytosis of nanomaterials used inorganic particles, due to their
stability and easy detection. However, research on
polymeric nanoparticle exocytosis has increased
in the past several years due to high interests in
their biomedical applications. The physicochemical properties which regulate the exocytosis of
nanoparticles are still not clear, but appear to be
impacted by size, shape, surface functionalization
and cell type.


Pharmacokinetics of Polymeric Nanoparticles

In general, exocytosis depends clearly on


particle size, surface properties, and geometry. In
general, nanoparticle exocytosis is much slower
than endocytosis. For particles of 20-50 nm,
the rate of endocytosis seems to be faster, and
the rate of exocytosis decreases with increasing
particle size . Chithrani and Chan reported that
the fraction of endocytosed nanoparticles varied
for different cell lines and that the percent of cellular nanoparticles being exocytosed within 1 h in
HeLa cells was approximately 35, 10 and 5% for
nanoparticles of 14, 50 and 74 nm, respectively.
One study showed that exocytosis of PLGA
nanoparticles occurred with about 65% of the
internalized fraction undergoing exocytosis in
30 minutes. Exocytosis of nanoparticles was
slower than the exocytosis of a fluid phase marker,
Lucifer yellow. Furthermore, the exocytosis of
nanoparticles was reduced after the treatment
of cells with the combination of sodium azide
and deoxyglucose, suggesting that exocytosis of
nanoparticles is an energy-dependent process (Panyam & Labhasetwar, 2003). It is also possible that
polymeric ones may be break down within cells,
and would not be exocytosed in the same form.
Mathematical models were also developed to
describe the kinetics of exocytosis of nanoparticles. Hong Jin and coworkers investigated
the endocytosis and exocytosis rates of lengthfractionated single-walled carbon nanotubes
(SWNT) (Tassa, et al., 2010). Interestingly, the
endocytosis rate constant of SWNT is found to be
nearly 1000 times that of Au nanoparticles but the
recycling (exocytosis) rate constants are similar
in magnitude for poly(d,l-lactide-co-glycolide),
SWNT, and Au nanoparticles across distinct cell
lines. They also develop a quantitative model
to correlate endocytosis rate with nanoparticle
geometry that accurately describes this data set
and also literature results for Au nanoparticles.
The model asserts that nanoparticles cluster on
the cell membrane to form a size sufficient to
generate a large enough enthalpic contribution
via receptor ligand interactions to overcome the

elastic energy and entropic barriers associated


with vesicle formation.

2.4 The Pharmacokinetics


at Molecular Level
2.4.1 Protein Binding
Once in the blood vessels, nanoparticles interact
with the proteins (termed opsonization). Protein
binding leads to the recognition of nanoparticles
by the immune cells and subsequently captured
and cleared from the circulation. The formation
of a protein corona could significantly alter the
nanoparticle surface properties, and subsequently
influence the uptake, biotransformation and biocompatibility of the particles. The composition
of the protein corona may vary over time due to
continuous protein association and dissociation as
well as local environmental changes. The composition of the protein corona also depends on particle
surface characteristics (primarily hydrophobicity
or charge), particle size, and composition.
Characterization of the protein binding kinetics
onto nanoparticle surface is important for understanding the fate of nanoparticles in the body.
Rates of protein binding to and dissociation from
nanoparticles are critical parameters determining
their interaction with receptors, and biological effects. A tightly associated protein that exchanges
slowly may follow the particle into intracellular
locations, whereas a protein with fast exchange
will be replaced by an intracellular protein during or after such transfer. The biological outcome
may also differ depending on the relative protein
exchange rates between nanoparticles and cellular
receptors.
Depending on the protein and particle properties, the association and dissociation rates
may vary significantly (Cedervall et al., 2007).
Proteinprotein complexes may have lifetime for
microseconds to weeks, while proteinligand
complexes may last microseconds to days. Studies using silica, polymer and TiO2 nanoparticles

157


Pharmacokinetics of Polymeric Nanoparticles

Figure 4. Numerical simulation of the time evolution of the interaction between three human plasma
proteins and nanoparticles. The concentrations of NP (black-dotted), NP HSA (red), NP HDL (blue) and
NP Fib (green) as a function of time are shown. (Reproduced with permission; DellOrco et al., 2010)

showed the exchange of adsorbed proteins may


take 100 s to many hours (Cedervall et al., 2007).
The highest mobility proteins arrive first
and are later replaced by less motile proteins
that have a higher affinity for the surface, in a
process that may take several hours. DellOrco
et al. (2010) developed a mathematical model
to describe the kinetics of the corona formation
around a copolymer nanoparticle. Nanoparticle
interaction with three proteins were simulated:
high density lipoprotein (HDL) which has low
mobility by high affinity; human serum albumin
(HSA) which has high mobility by low affinity;
and fibrinogen (Fib) which has low mobility and
low affinity. The results indicated that the temporal
development of the corona strongly depends on
the association/dissociation rates of each protein.
The simulation showed that the time required to
reach equilibrium, which depends on the association/disassociation rates, is determined by size of
protein and particles. (see Figure 4)
By understanding the binding kinetics and
mechanisms of proteins on nanoparticles, scientist
may be able to control the binding kinetics for
particular purposes. Looking into the fundamental
influencing factors of nanoparticle-protein interactions, it also was demonstrated that increased

158

hydrophobicity favors blood protein binding. When


nanoparticles were more densely coated with
polyethylene glycol (PEG), less protein was bound.
Thus, surface modifications like PEG coating are
widely applied to prolong the circulating half-life
and to allow escape from phagocytosis. It has been
reported (Hoshino Y, Nakamoto M, Miura Y, 2012)
that temperature-responsive binding kinetics was
used to monitor the association/disassociation
rates of protein-nanoparticle binding, which may
be applied in targeting nanoparticles to certain
tissues by temperature control.

2.4.2 Ligand-Targeting
There is increasing interests in using Nanoparticles with surface-conjugated targeting ligands
for a variety of biomedical applications. The
main purpose of applying targeting ligands is
to enhance nanoparticle binding to the desired
tissues or organs, which express higher levels of
corresponding receptors. For example, Carlos
Tassa and coworkers (Tassa, et al., 2010) used
surface plasmon resonance (SPR) to directly
and quantitatively study the affinity and binding
kinetics of nanoparticles with small molecules
conjugated to their surface. They studied the


Pharmacokinetics of Polymeric Nanoparticles

interaction between a single protein target and a


series of targeting ligands whose intrinsic affinity varies over a 4500-fold range and performed
SPR at protein densities that reflect endogenous
receptor densities. The results showed that even
weak small molecule targeting ligands can significantly enhance target-specific avidity through
multivalent interactions.
While ligand-receptor binding kinetics has
been under study for many years, the binding
kinetics could be different when the ligands were
conjugated on the particle surface, instead of being free ones. The interaction between conjugated
ligands and receptors on cells surface is still far
from well understood. Multiple factors contribute
to the complexity of the interaction, including the
chemical structures and density of ligands, the size
and shape of particles, and expression levels of
receptors, binding entropy, and others.
For example, nanoparticle size may affect
the ligand/antibody to nanoparticle ratio, surface
ligand conformation, ligand binding capacity,
surface curvature, and relative orientation of
ligands during nanoparticle membrane docking.
It is assumable that the spatial position of ligands
on the particle surface will is a major factor affecting binding with receptors on cells surface.
Ligands connected with chains to the particle
surface have flexibility and may be more effective in binding to receptors. One study showed
(Wang & Dormidontova, 2012) that the onset of
nanoparticle adsorption has a universal character
for a range of nanoparticles: the onset receptor
density decreases exponentially with the energy
of ligand-receptor binding and inversely with the
ligand density. The same study also showed that a
bimodal tether distribution, which permits shielding ligands by longer nonfunctional tethers, leads
to extra loss of entropy at the adsorption onset,
enhancing the selectivity.
While ligant-targeting is very promising, it is
not always effective in vivo due to much more complicated environments. Ligands may be cleaved

off and the targeting ability will be weakened.


Another possibility is that biological molecules
such as plasma proteins may bind to the ligands
or the particle surface and block the binding of
ligands to their receptors. For example, one study
has shown that transferrin-targeted nanoparticles
lose their targeting capabilities when a biomolecule corona adsorbs on the surface (Salvati A,
Pitek AS, Monopoli MP, Prapainop K, Bombelli
FB, et al., 2013).

3. CONCLUSION
Understanding the controlling pharmacokinetics
of polymeric nanoparticles will lead to improvements in biomecial applications such as drug
delivery and diagnosis, and lower toxicity. The
pharmacokinetics of polymeric nanoparticles
should be viewed at multiple levels for clear understanding, including whole body, organ, cell,
and molecule levels. The experimental findings
and computational models for understanding polymeric nanoparticle pharmacokinetics will have
significant impact in designation, optimization,
and administration of these particles for clinical
applications.

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bm101482r PMID:21657799

KEY TERMS AND DEFINITIONS


Biodistribution: The determination of compounds of interest travel and retaining in organs
and tissues of an animal or human subject.

Computational Model: A mathematical


model that simulates the behavior of a complex
system based on knowledge of that system.
Ligand: A substance (usually a small molecule), that forms a complex with a biomolecule
to serve a biological purpose.
Nanoparticles: Solid particles that have at least
two dimensions within 100 nm. In broad meaning,
solid or semi-solid particulate materials with at
least two dimensions within 1000 nm.
Opsonization: The process by which nanoparticles are altered by opsonins so as to become
more readily and more efficiently engulfed by
phagocytes.
PBPK Modeling: Physiologically based pharmacokinetic (PBPK) modeling is a mathematical
modeling technique for predicting the absorption,
distribution, metabolism and excretion (ADME)
of substances animals or human beings.
Pharmacokinetics: The determination of the
fate of substances administered externally to a
living organism.

163

164

Chapter 8

Applications of Nanomaterials
in Construction Industry
Salim Barbhuiya
Curtin University of Technology, Australia

ABSTRACT
The application of nanomaterials in various applied fields has gained worldwide recognition. Nanomaterials
have the ability to manipulate the structure at nano-scale. This leads to the generation of tailored and
multifunctional composites with improved mechanical and durability performance. Recognizing this, the
construction industry recently has started to use a variety of nanomaterials. The use of these materials is
found to improve various fundamental characteristics of construction materials including the strength,
durability, and lightness. In this chapter an attempt is made to review the use of various nanomaterials
in cementitous system. This is followed by a discussion of the challenges related to their use. Finally, the
strategies for using nanomaterials in construction industry for the next ten years are identified.

INTRODUCTION
When the physicist and Nobel laureate Richard
Feynman presented, in late 1959 at the California
Institute of Technology, USA the lecture There is
plenty of Room at the Bottom (Feynman, 1960),
he outlined what today is known as Nanotechnology. He stated that when we have some
control of the arrangement of things on a small
scale we will get an enormously greater range of
possible properties that substances can have, and
of different things that we can do,. Years later,
the chemist and Nobel laureate Roald Hoffman, at
Cornell University, stated that: Nanotechnology
is the way of ingeniously controlling the buildDOI: 10.4018/978-1-4666-5824-0.ch008

ing of small and large structures, with intricate


properties. It is the way of the future, a way of
precise, controlled building, with incidentally,
environmentally benignness in by design. The
physics and chemistry of nanomaterials are fundamentally different from those of their micro-scale
counterparts. Dramatic changes and improvements
are brought about not only by size reduction, but
also by new properties only apparent at the nanoscale. In fact, nanotechnology has changed and
will continue to change our vision, expectations
and abilities to control the materials world.It is
for these reasons, nanotechnology has recently
become one of the hottest areas in Research and
Development worldwide, and attracted considerable attention in the media and as well as in the
investment community.

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Applications of Nanomaterials in Construction Industry

The advances in productivity of the construction industry in the 20th century were slow, and
development of its technology lagged behind that
of other industry sectors. Nanotechnology is a
route to achieving real competitive and sustainable
growth and innovation within the construction
industry. This scientific approach is essential if the
potential for a new generation of materials which
are of both high performance and more economically viability is to be realised. Nanomaterials are
defined as those materials which have at least one
dimension (length, width or thickness) below
100 nanometer (1nm), 1nm being s thousand of
a micron, or about 100,000 times smaller than a
human hair.
One of the challenges in the field of construction
materials has been, and still is, the development
of concrete with improved durability. Concrete
is a complex multi-phase composite material.
The properties, behaviour and performance of
concrete are dependent on the nano-structure of
the cementitious matrix that glues together and
provides integrity. Therefore, the study of the
structure of the cement pastes and phenomena
in the nanoscale is crucial for the development
of new construction materials and applications
(Beaudoin, 1999). However, the common approach for the development of durable concrete
has mostly consisted of varying the macroscopic
parameters which are used to produce concrete.
i.e., basically working on the concrete mix design
and using different types of SCMs (Mehta, 2000;
Mehta & Manmohan, 2006; Concrete Centre,
2007). To a great extent, this approach, motivated
mostly by the inertia of the construction industry
itself, has slowed down the advance in the deep
understanding of construction materials. Within
the new paradigm of Nanoscience and Nanotechnology this can no longer continue. Construction
materials must be investigated within a scientific
approach if a new generation of materials that are
both of higher performance and more economically viable is to be created.

NANOMATERIALS IN
GENERAL APPLICATIONS
Nano particles are the cornerstones of Nano science and nanotechnology. Nano materials bridge
the range of micro and nano scales and their
presence enhances the mechanical properties of
the material. Over the years nanomaterials have
seen widespread acceptance and utilization in
various fields of science and technology. Owing
to its nano size, this technology has allowed us to
fabricate enormous products having advantages
over conventional ones; ranging from the materials
(nano-fuel cells, catalyst, lubricant, aeronautics,
automobiles, telecommunications, energy production, mechanics, biology, medicine etc.
Epoxy resins embedded with nanomaterials are
now being developed for better mechanical characteristics. Researchers are also trying to analyze
the changes in properties of epoxy-based coatings
filled with nanoparticles.Shi et al. (2009) added
nanoparticles of Zn, SiO2, Fe2O3 and halloysite clay
in a commercial epoxy resin and found enhanced
mechanical and chemical properties.In another
study Woo et al. (2008) investigated the residual
mechanical properties of epoxy organoclay composites after they were exposed to moisture and
UV light. Li et al. (2008) analyzed epoxy resin
containing various percentages of coiled carbon
nanotubes and single-walled carbon nanotubes.
The coating formulations were prepared by reacting diglycidyl ether of bisphenol-A (DGEBA) and
isophoronediamine. The coating was modified
with nanoalumina, silanizednanoalumina and
organo-modified montmorillonitenanoclay. It was
found that the Youngs modulus and hardness
increased considerably on addition of nanomaterials.The wear resistance of nanocomposite coating containing nano-TiO2 and other fillers were
studied by Chang et al. (2007). The authors found
that the addition of TiO2 reduces the coefficient
of friction but increased the wear resistance and
load bearing capacity.

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Applications of Nanomaterials in Construction Industry

Gold nanoparticles are used in numerous biomedical applications. A review article by Khan et
al. (2013) discusses the biomedical applications
of gold nanoparticles in drug delivery, imaging
and treatment of major life threatening diseases.
Iron oxide nanoparticles are also used in various
biomedical applications. Nano TiO2 is finding
applications in cosmetics, sunblock creams and
self-cleaning windows. A number of nanoparticles
are now being explored for developing dental
fillings and artificial bones.Various memory
chips are now being manufactured using nanoparticles. Silicon nanocrystal memory and nanowire
memory are used in devices with flash memory
applications. Nanomaterials are also used for
energy applications. Nanostuctured metal-oxide
thin films are receiving a growing attention for
the realization of gas sensors (NOx, CO, CO2,
CH4 and aromatic hydrocarbons) with enhanced
sensitivity and selectivity. Nanostructured MnO2
finds application for rechargeable batteries for
cars or consumer goods. Nanomaterials are also
explored for use in environment friendly energy
sources and emission control.

NANOMATERIALS IN
CEMENTITIOUS SYSTEMS
While talking about the use of nanomaterials in
a cementitious system, it is not always easy to
span the bridge between the modern advanced
technology and know-how that exist for the last
2000 years. From nanotechnology point of view,
cement itself is clearly a nanomaterial without
any modification. This is because it has a hierarchical structure ranging from sub-millimeter
dimension down to nanometer scale. Moreover,
it is also well established that most of its material
properties mainly depend on the microstructural
development below 100nm (Taylor, 1997). In
a cementitious system, it is expected that the
strength and durability properties should improve
if the overall porosity and capillary pore sizes in

166

cement paste are reduced or the diffusion of pore


solution and aggressive chemicals are hindered
by the incorporation of some additives having a
similar range of sizes. Nanomaterials have the
potential to reduce the pore size of cement paste
and, hence, improve the strength and durability
of the system. They have a high surface area to
volume ratio (Figure 1). Therefore, they have
the potential for tremendous chemical reactivity
within a cementitious system.
In cement matrix, most of the research works
to date was conducted on nano-silica (nano-SiO2)
(Bjornstromet et al., 2004; Ji, 2005; Jo et al., 2007;
Li et al., 2004,2006; Qing et al., 2007; Lin et al.,
2008; Sobolev et al., 2009; Qing et al., 2008) and
nano-titanium oxide (nano-TiO2) (Li et al., 2006;
Li et al., 2007). A few studies on the incorporation if nano-iron (nano-Fe2O3) (Li et al., 2004),
nano-alumina (nano-Al2O3) (Li et al., 2006) and
nano-clay particles (Khuo et al., 2006; Chang
et al., 2007) in cement matrix are also reported.
Research (Sobolevand Ferrada-Gutirrez,
2008; Li et al., 2004) showed that nano-SiO2
(Figure 2) improves the workability and strength
of concrete. They are also found to increase the
resistance to water penetration of concrete (Ji,
2005). Gaitero et al. (2008) have demonstrated that
use of nano-SiO2can help to control the leaching
of calcium leaching in concrete. It is also reported
that nano-SiO2 is more effective than microsilica
in enhancing the strength properties of concrete
(Jo et al., 2007; Qing et al., 2007). According to
Jo et al., (2007) particles of nano-SiO2not only act
as a filler material, but also they act as an activator to promote the pozzolanic reaction. Li (2004)
reported that significant increase in compressive
strength at early age can be obtained using nanoSiO2 in high volume fly ash concrete, which is
one of the drawbacks of this type of concrete.
However, in order to achieve good performance
and to use nano-SiO2in economical way, it is better to use nano-SiO2in a combination of fly ash
and microsilica.


Applications of Nanomaterials in Construction Industry

Figure 1. Particle size and specific surface area related to concrete materials (Sobolev and FerradaGutirrez, 2005)

The addition of nano-Al2O3 was found to be


very effective to increase the elastic modulus of
mortar. With the addition of 5% nano-Al2O3having
size in the range of 150 nm, Li, et al., 2006 found
that there was an increase of 143% in the elastic
modulus. However, the authors reported that they
had a limited effect on the compressive strength.
Nano-Fe2O3 is reported to provide concrete the
self-sensing capacity (Li et al., 2004). Their inclusion also improves the compressive and flexural
strength of concrete. The sensing capabilities
of concrete are invaluable not only for real time
structural health monitoring, but also for the
construction of smart structures. This is simply
because they do not invoke the use of embedded
or attached sensors.
Nano-TiO2 has been identified as a potential
nanomaterial with wide range applications. This
is mainly because of its strong oxidizing capacity

under U-V radiation, chemical stability, chemical


inertness in absence of U-V light and absence of
toxicity. Studies (Jayapalam et al., 2009) have
shown that nano-TiO2 can accelerate early age
hydration of Portland cement. They are also found
to improve the compressive and flexural strengths
of concrete (Li et al., 2007). The authors alsofound
that the abrasion resistance of concrete containing
Nano-TiO2is better than that containing the same
amount of nano-SiO2. Nano-TiO2has proven to
be very effective to produce self-cleaning and
depolluting concrete (Murata et al., 1999; Vallee et al., 2004). Nano-TiO2based self-cleaning
concrete products are commercially available. Figure 3 shows the Church Dives in Misericordia,
Rome, Italy, which was built using self-cleaning
concrete. In Tokyo (Figure 4) several areas of
roads have been coated with nano-TiO2 in order
to reduce the pollution.

167


Applications of Nanomaterials in Construction Industry

Figure 2. Spherical nano-SiO2 particles of uniform distribution observed using TEM

Figure 3. Church Dives in Misericordia, Rome, Italy

168


Applications of Nanomaterials in Construction Industry

Figure 4. Use of nano-TiO2 on roadway for pollution reduction: left coating application; right finished
road showing a lighter colour

CARBON NANOTUBES/
NANOFIBRES IN
CEMENTITIOUS SYSTEMS
Carbon nanotubes/nanofibres (CNTs/CNFs) are
potential candidates for use as nano-reinforcements in cement-based materials. CNTs/CNFs
exhibit extraordinary strength with moduli of
elasticity on the order of TPa and tensile strength
in the range of GPa, andthey have unique electronic
and chemical properties (Ajayan, 1999; Thomson
et al., 1999; Srivastava et al., 2003). CNTs/CNFs,
thus, appear to be among the most promising
nanomaterials for enhancing the mechanical
properties of cement-based materials and their
resistance to crack propagation while providing
such novel properties as electromagnetic field
shielding and self-sensing (Makar et al., 2005;
Li et al., 2007). Single-wall CNTs (SWCNTs),
multi-wall CNTs (MWCNTs), and CNFs are
highly structured graphene ring-based materials
with very large aspect ratios (of 1000 or more)
(Xie, 2005) and very high surface areas. SWCNTs
are single graphene cylinders and MWCNTs are
multiple, concentric graphene cylinders coaxially
arranged around a hollow core. Unlike CNTs,
CNFs present numerous exposed edge planes

along the surface that constitute potential sites


for advantageous chemical or physical interaction.
While CNTs/CNFs have been extensively studied
in polymeric composites (Coleman et al., 2006;
Lau et al., 2006; Hammel et al., 2004), their use
in cement has, to date, remained limited. One
of the main challenges is the proper dispersion
of CNTs/CNFs into cement paste, partly due to
their high hydrophobicity and partly due to their
strong self-attraction. Incorporating the unique
mechanical properties of CNTs/CNFs in cement
composites has proven to be rather complex and to
date mixed results have been obtained. A number
of methods have been investigated to improve
dispersion and to activate the graphite surface in
order to enhance the interfacial interaction through
surface functionalization and coating, optimal
physical blending, and/or the use of surfactant
and other admixtures.
Researchers (Baoguo et al., 2009) have developed a self-sensing nanotechnology composite
material for traffic monitoring by using piezoresistive multi-walled carbon nanotubes (CNTs) as
an admixture. The authors studied the response
of the piezoresistive properties of this composite
to compressive stress and they investigated with
vehicular loading experiments the feasibility of

169


Applications of Nanomaterials in Construction Industry

Figure 5. Illustration of self-sensing concrete pavement for traffic flow detection

using self-sensing CNT/cement composite for


traffic monitoring. The results indicate that there
are good corresponding relationships between
compressive stress and the electrical resistance of
the self-sensing CNT/cement composite (Figure
5). The self-sensing CNT/cement composite also
presented remarkable responses to vehicular loadings. These findings indicate that this self-sensing
nano-composite cement has great potential for
traffic monitoring use such as in vehicle detection,
weigh-in-motion measurement and vehicle speed
detection. An interesting aspect of this work is
that, from the eventual traffic applications point
of view, the pavement itself would become the
traffic detection, thus eliminating the need for
separate traffic flow detection sensors.

CHALLENGES RELATED TO THE


USE OF NANOMATERIALS
The primary challenge related to the use of
nanomaterials is to manufacture the nanomaterials itself. The second challenge is the heat of
hydration. Due to many folds increase in specific

170

surface areas the nanoparticles are very reactive


and results in enormous amount of heat of hydration. Special organic and inorganic additives are
needed to be developed to control the setting and
heat of hydration. For the nano-coatings, the properties of the coatings themselves need extensive
investigation. Durability of coatings under various
exposure conditions, abrasion resistance, friction
resistance, high temperature resistance, failure
modes and electrical characteristics need to be
proven by using exhaustive experiments.
Huge amount of expenditure is needed for the
equipment to study the behaviour of nanoparticles
and nano-additive in cement based materials.There
are issues concerning the potential toxicity of
nanomaterials as well. Investigationsshowed that
nanoparticles can cause symptoms like the onescaused by asbestos fibres. Grassian et al. (2007)
studied the effects relatedto the inhalation of TiO2
particles with a primary particle sizebetween
2 and 5 nm, reporting lung inflammation for a
concentrationof 8.8 mg/m3. These symptoms have
been confirmed by otherauthors (Yu et al., 2008;
Liu et al., 2008; Poland et al., 2008; Donaldson
& Poland, 2009; Pacurari & Castranova, 2010).


Applications of Nanomaterials in Construction Industry

Hallock et al. (2008)recommend that the use


ofnanoparticles should be made with the same
care already used in Universities for materials
of unknown toxicity, i.e., by using airextraction
devices to prevent inhalation and gloves to prevent
dermalcontact. Singh et al. (2009) mentioned the
possibility of DNA damage resulting in later cancer
development. Some authors (Dhawan et al., 2009)
believe that the nanotoxicity risk depends on the
nanoparticlestype, concentration volume superficial characteristics. Others (Tyshenko & Krewski,
2008) suggest that several categories and new
parameters must beformulated to better analyze
this subject. Some questions that deserve further
investigation are presented elsewhere (Hirano,
2009; Walker & Bucher, 2009).BystrzejewskaPiotrowska et al., (2009)have recently carried out
an extended literature review on this subject. These
authors mentionedthat Environment Protection
Agency has considered that carbon nanotubes are a
new form of carbon that must be treatedunder the
toxic products Act. These authors also mentioned
that nanoparticles may be responsible for a new
kind of problem, the appearance of nano-wastes.
They suggest that products containing nanoparticles should be labelled in order to facilitate future
separation and recycling procedures.

STRATEGIES FOR USING


NANOMATERIALS FOR
THE NEXT TEN YEARS
The filed encompassed by the term nanomaterials has changed dramatically over the past 10
years. While it was useful, 10 years ago, to describe
nanomaterials on the sole basis of our ability to
understand and to control matter at the nanoscale
where material properties possess a distinct sizedependence, the filed has now grown well beyond
that earlier definition. For example, it is evident
now that additional factors beyond constituent
nanoparticles are also playing major roles. The

past decade has seen an evolution in scientific


understanding and capabilities, from working with
isolated nanoparticles, nanotubes and nanowires
to working with hybrid nano-composites whose
particles are controlled not only by the constituentnanomaterials, but also by their morphology,
spatial anisotropy and relative proximity with
respect to one other and the host matrix.
Over the next ten years, nanoscience researchers will focus on a range of issues to improve the
performance, multi-functionality, integration and
sustainability of nanomaterials in a variety of
emerging and converging technologies. In particular, methods are required for nanomaterials and
nano-systems by design; scaling up high-quality
and mono-disperse nanomaterial production;
for rapidly measuring and characterizing quality
and reproducibility of manufacturing processes
incorporating nanomaterials and for manufacturing nanostructures into bulk materials, coatings
and devices while retaining enhanced nanoscale
properties. Through controlled assembly of
nano-constituents that have distinct properties,
the next generation nano-composite materials
are expected to have the unique and powerful
attribute of independent tunability of previously
coupled properties. For example, bulk materials
with high electrical conductivity typically possess high thermal conductivity, whereas these
properties have the potential of being decoupled
in next-generation nano composites. This specific
example has broad implications for thermoelectric devises that convert waste heat into useful
electricity. Similarly, the decoupling of electrical
conductivity and optical reflectivity would enable
a new class of transparent conductors that could
serve as the basis of improved photovoltaic and
display technologies. Ultimately, the rational assembly of nanomaterials into nano-composites
will yield high-performance materials with new
combinations of properties, thusunderpinning
the development of previously unrealizable applications.

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Applications of Nanomaterials in Construction Industry

CONCLUSION
Nanotechnology application in construction
industry is still a very small, fragmented pursuit and unknown outside the scientific circle.
Nanoparticles are not cost-efficient materials,
and this prevents their commercial applications
in a near future. However, some nano-based
materials & products are now used or ready to
be adopted by the industry, and many others are
coming to the market. Photo catalytic applications
of nanomaterials are already a reality, still more
research efforts are needed in order to find other
semiconductors apart from TiO2 and conductors
that can be activated with visible light. Huge
potential has been predicted for nanotechnology
application in construction. This is because even
minor improvements in materials and process
could bring large accumulated benefits. However,
further research is also needed in the field of
nanotoxicity, be there as it may, extreme caution
must be used when using nanoparticles. While
nano-engineering of cement-based materials is
seen as having tremendous potential, nonetheless,
several challenges will need to be solved to realize
its full potential, including the proper dispersion
of the nanoscale additives, scale-up of laboratory
results and implementation on larger scale, and a
lowering of the cost benefit ratio.

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KEY TERMS AND DEFINTIONS


Carbon Nanofibre: Cylindric nanostructures
with graphene layers arranged as stacked cones,
cups or plates.
Carbon Nanotubes: Allotropes of carbon
with a cylindrical nanostructure.
Nano-Fe2O3: Oxide Particles typically 20-40
nanometers with specific surface area in the 3050 m2/g range.
Nanomaterials: Describe in principle materials the single units of which is sized in at least
one dimension between 1 and 1000 nanometers
(109 meter).
Nano-SiO2: Single particles of silica dioxide,
an inorganic metal oxide, with a diameter less
than 100 nm.
Nano-TiO2: Spherical or faceted high surface
area oxide magnetic nanostructure particles, typically 20-80 nanometers with specific surface area
in the 10-50 m2/g range.
Pozzolanic Reaction: Chemical reaction that
occurs in Portland cement containing pozzolans.

175

176

Chapter 9

Silicon NanostructuresGraphene Nanocomposites:


Efficient Materials for Energy
Conversion and Storage
Chaitanya Krishna Kamaja
National Chemical Laboratory (CSIR), India
M. Rajaperumal
National Chemical Laboratory (CSIR), India
Rabah Boukherroub
Universit Lille 1, France
Manjusha V. Shelke
National Chemical Laboratory (CSIR), India

ABSTRACT
Global demand of energy is increasing at an alarming rate, and nanotechnology is being looked at as
a potential solution to meet this challenge (Holtren, 2007). Although the efficiency of energy conversion and storage devices depends on a variety of factors, the overall performance strongly relies on the
structure and properties of the component materials (Whitesides, 2007). Compared to conventional
materials, silicon (Si) nanostructures and graphene nanosheets possess unique properties (i.e. morphological, electrical, optical, and mechanical) useful for enhancing the energy-conversion and storage performances. Graphene can enhance efficiency of nano-Si based solar cells and battery due to its
high electronic conductivity, ultrahigh mobility, high transparency, and strong mechanical property.
This chapter provides a comprehensive review of recent progress and material challenges in energy
conversion (solar cells) and storage (batteries/supercapacitors) with specific focus on composites of Si
nanostructures-graphene nanosheets.

DOI: 10.4018/978-1-4666-5824-0.ch009

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Silicon Nanostructures-Graphene Nanocomposites

INTRODUCTION
The increasing energy demand due to increase in
population, industrial activity, etc. led to decrease
in fossil fuel. According to US energy information
administration (EIA), for the year 2011, energy
consumed for electricity generation from fossil
fuel is about 87% and 13% from renewable energy
(Figure 1) [http://www.eia.gov/electricity].
Among renewable energy sources, solar energy is the most important because the amount
of energy that reaches the earth surface in one
hour is about 18TW, and the global consumption
of energy per year is about 15TW (Kalyanasundaram, 2012). Solar energy has to be converted
to different convenient forms of energy and the
conversion efficiency is the measure of practicality of this energy source. Materials and devices to

convert solar light energy into electrical energy


efficiently are the immediate concerns. Most of
the conventional solar cells in the market are based
on Si p-n junction diodes and their efficiency
had reached 25% (Green, 2009). Advantages of
Si are high abundance (second most abundant
element in the earth crust), non toxic, and long
term stability. But the main disadvantage of Si is
that the process of making ultrapure crystalline Si
is very costly, but also it is an indirect band gap
semiconductor, so for absorbance of sunlight a
very thick layer of Si is required. To reduce the
cost of the solar cell, researchers started to evaluate
heterojunctions of Si. Among the heterojunctions,
Schottky diode holds advantage over p-n junction diode. In Schottky diode the thickness of Si
layer can be decreased, that eventually decreases
the cost of the device. The condition for Schott-

Figure 1. The percentage of electrical energy generation from different resources (Source: U.S. Energy
Information Administration, Annual Energy Outlook 2013 Early Release, December 5, 2012)

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Silicon Nanostructures-Graphene Nanocomposites

kydiode is that the semiconductor should have


moderate doping (high doping results in electron
flows from semiconductor to metal and forms
ohmic contact). When metal and semiconductor
brought too close to each other, electrons flow
from the conduction band of the semiconductor
to metal until thermal equilibrium is reached i.e.
the Fermi level becomes the same for both metal
and semiconductor. This forms a depletion region
with the absence of electrons at the junction, and
results in barrier for further electron transition at
the junction (Lutz, 2011). The Schottky barrier
height (SBH) is given by:
b = M
where b = Schottky barrier height, M = metal
work function and = electron affinity of the
semiconductor. The built in potential separates
the electron hole pair by the incident light photon.
The net current density (j) in the solar cell is
given by:
j = jlight jdark

j =jsc jo e

qV / nk B T

1

where jsc = short circuit current density, n=


diode ideality factor, V = voltage across the diode,
q = elementary charge, kB = Boltzmanns constant,
T = absolute temperature and jo = reverse current, corresponding to thermal generation of
carriers, which can be expressed as:
(qb / kBT )

jo = Aeff A**T 2e

The efficiency of the solar cell depends mainly


on the series resistance and shunt resistance. The
series resistance includes the contact resistance
between the metal and top electrode, the contact

178

resistance between Si and bottom electrode and


the bulk resistance of both Si and metal. For better
efficiency, the solar cell should have low series
resistance and high shunt resistance.
In the conventional Schottkydiode a thick
metal layer is required, which results in absorbing most of the radiation and thus limits the
efficiency of the cell. In order to increase the
absorbance of the semiconductor a thin layer of
indium doped tin oxide (ITO) is used. However
due to less abundance and high cost of indium,
it became less usable (Ye, 2012). So, in order to
decrease the cost of device, new materials have
to be developed in such a way to replace indium.
Si and graphene form Schottky junction. In this
chapter, we will discuss the strategies reported to
increase the efficiency of Si-graphene Schottky
junction solar cell.
As solar energy source is climate dependent,
effective energy storage systems are also essential. The electrochemical energy storage systems
are one of the clean, green, economically valuable methods. In this respect, electrochemical
supercapacitors (ECs), batteries and fuel cells
are considered as important key components
of modern electronic devices/tools. These three
electrochemical devices critically depend on the
electrochemistry at the electrode material and
electrode/electrolyte interface. For real applications, the performance of these electrochemical
devices are evaluated in terms of energy and power
density. Figure 2 shows the comparative performance of these devices with combustion engine.
Moreover, energy and power density of ECs and
batteries covered a large area in the Ragones plot,
which clearly states their significant technological
importance (Yu, 2013; Padbury, 2011).
Supercapacitors are electrochemical devices
that can provide high power for a short time period. The typical energy density is 5 Whkg-1 and
power density is 5-10kWkg-1(Miller, 2008). The
power density of a supercapacitor is two orders of
magnitude higher than the current Li ion battery.


Silicon Nanostructures-Graphene Nanocomposites

Figure 2. Ragones plot comparison of various electrochemical devices and (a) internal combustion
engine, (b) schematic diagram of Li ion battery, and (c) supercapacitor

The energy storage mechanism of a supercapacitor is near surface charge storage. Therefore,
only slight structural change is observed in the
active materials during cycling. Hence, the life
time of a supercapacitor may exceed more than
50,000 cycles and better heat management could
be achieved. Based on the storage mechanism,
supercapacitors can be classified into two types.
One is double layer capacitor (EDLC) that can
store the energy in the form of non faradic reaction and the other is pseudo capacitor which stores
the energy in the form of faradic reaction. Based
on the device fabrication, supercapacitors can be
further classified as symmetric supercapacitors,
wherein both electrodes store the energy in same
mechanism, or as asymmetric supercapacitors
where one electrode can store the energy in form
of EDLC and the other electrode is used to store
faradic energy.

In contrast to supercapacitors, batteries are high


energy density devices, which utilize almost all
active material present in the electrode. Hence,
large structural changes are observed during the
cycling, as a result the power density and cycle
life of batteries are lower than those of supercapacitors. Among many batteries, Li Ion Battery
(LIB) has been successfully commercialized and
extensively used in portable electronics due to
their high energy, power density, rate capability
and better cycle life.

BACKGROUND
Since the discovery of graphene in 2004, it became
the hot topic in current research because of its
wide applications in different fields (Novoselov,
2004; Guo, 2011; Luo, 2012). A graphene is a

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Silicon Nanostructures-Graphene Nanocomposites

two dimensional hexagonal crystal of carbon atoms with high transparency, approximately zero
band gap, low sheet resistance, high mechanical
strength, flexibility and highly stable. Because of
its high transparency, it can be used as electrode
in photoelectric devices and it can also separate
electron-hole pair at the junction. It is mostly
synthesized by CVD (Kim,. 2009) or solution
process methods and transferred to the Si surface
(Hernandez, 2008).
In the year 2007, carbon nanotubes (CNT)Si heterojunction concept was first introduced
in solar cells (Wei, J. 2007). Later on, the same
group modified the device structure and compared
the efficiencies of multi-walled carbon nanotubes
(MWCNT) and double-walled carbon nanotubes
(DWCNT) (Jia, 2008). There are two main disadvantages of CNT-Si heterojunction: first they
form both Schottky and p-n junctions because
CNT exist as both metallic and semiconducting
nanotubes, and second the conductivity of CNT

is low because of the space between the bundles


of CNT network.
Graphene has advantages over CNT because of
its high surface coverage over Si surface (100%),
the conductivity of the film is high because it consists of multiple layers of Graphene Sheets (GS)
which are overlapped and interconnected; it also
acts as an antireflective layer. In 2010,grapheneSiheterojunction concept was used for solar cell
application (Li, X. 2010). GS were coated on
patterned n-Si/SiO2 substrate with a Si window,
the front and back contacts were made by sputtering of Au on SiO2 and Ti/Pd/Ag on n-Si. The
band structure and schematic representation of
the device are shown in figure 3a, b. Si absorbs
light and the photo generated holes and electrons
are separated by built in potential, the holes move
to the graphene and electrons diffuse to the Si
surface. Two cells are demonstrated with an area
of 0.1 and 0.5 cm2 with efficiencies of 1.65 and
1.34%, respectively.

Figure 3. a) The band structure of graphene with n-Si, b) Schematic representation of the device. Bottom
left inset shows that at the junction holes and electrons are separated, and bottom right inset displays an
optical image of the device (Reproduced from Li, Zhu, Wang, Cao, Wei, Li et al., 2010 with permission
from WILEY-VCH Verlag GmbH & Co. Weinheim)

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Silicon Nanostructures-Graphene Nanocomposites

In case of materials for energy storage, currently graphite is used as anode material in commercial lithium ion batteries and has quite low
capacity of 372mAhg-1, which is insufficient to
satisfy certain high energy requirements (Dimov,
2007). Si is considered as one of the most promising substitutes for graphite; it has a capacity of
4200 mAhg-1 due to Li22Si5 alloy formation and
relatively low working voltage (0.5 V vs Li/Li+)
(Kasavajjula, 2007). In order to improve the cycle
life of Si-based anode, many strategies have been
proposed. The most attractive strategy is to reduce
the host size and form a Si-carbon nanocomposite.
It has been reported that Si nanowires (SiNWs)
and nanotubes possess better capacity retention
over many hundredth of cycles (Chan, 2008; Park,
2009; Cui, 2009; Wu, 2012). Although, this kind
of morphology has better cycle life, it requires
quite expensive synthetic methods which limit
their practical utility. At the same time, the energy density of grapheme based supercapacitors
showed to be enhanced up to 85Wh/kg, which is
comparable to that of nickel metal hydride batteries
(Liu, C. 2011).This enhancement is attributed to
the unique morphology of curved graphene sheets,
which maintain their high surface area even after
reduction thereby reducing the restacking tendency
of graphene sheets. Graphene enhances Li storage
capacity of Si nanostructures when grapheme is
used as conducting agent (Wang, X. L. 2010).In
this chapter, we will review the recent progress
in the cost effective synthesis of various Si and
graphene composites for energy production and
storage. Even though fuel cells will fall into the
energy production area, this will be out of the
scope for this composite material. So only solar
cells, photoelectrochemical water splitting, batteries and supercapacitors are discussed throughout
this chapter.

MAIN FOCUS OF THE CHAPTER


1. Graphene-Si Nanocomposites
for Energy Conversion
An untreated Si solar cell only absorbs 67.4%
of sunlight shone upon it, meaning that nearly
one-third of that sunlight is reflected away and
thus unharvestable. From an economical and
efficiency perspective, this unharvested light is
wasted potential and a major barrier hampering
the proliferation and widespread adoption of solar
power. In conventional solar cells, anti-reflective
coatings are used to trap the light and to increase
the efficiency. To further address this problem,
researchers started to use patterned Si pillar arrays
(SPA). The advantage of SPA is that they provide
more surface area for light harvesting and also act
as an anti-reflective coating. The highest reported
efficiency for only Si nanostructures is 18.2%(Oh,
J. 2012).The other factor that can enhance the efficiency of Schottky junction solar cell is coating
with p-type graphene. The p-doping increases
the work function of graphene, which results in
enhanced conductivity of GS and increases the
built in voltage of graphene-Si junction. However,
the performance of Si/graphene composite is low
because of the high density of defects present at the
interface of Si and graphene hetero junction, which
increases the electron-hole recombination rate,
leading to a decrease of the solar cell efficiency.
So far, various approaches have been developed
to increase the work function of GS by p-doping.
AuCl3 acts as p-type dopant for most of organic
semiconductors because it takes electrons from the
semiconductor and forms Au particles, so it can be
used for p-doping of graphene. The efficiency of
AuCl3 doped graphene with Si heterojunction is
about 0.08% (Shi, 2010). When graphene is doped
with thionyl chloride (SOCl2) vapor and the device

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Silicon Nanostructures-Graphene Nanocomposites

is made with SiNWs, the efficiency increased


up to 2.86% (Fan, 2011). Doping graphene with
HNO3 vapor for integration in solar cell device
with both Si and n-Si SPA raised efficiencies to
3.55% and 4.35%, respectively (Feng, 2011,2012).
It was found that after doping, the series resistance of solar cell decreases from 6.11 to 4.07
cm-2. It was concluded that with the increase of
doping time the efficiency and fill factor of solar
cell increase to certain limit and then decrease.
Indeed, prolonged doping causes degradation of
GS, built up the series resistance of the solar cell
and oxidation of the Si surface. In order to have
better understanding of the device performance,
theoretical and experimental studies on the effect
of doping on graphene and the number of graphene
layers that influence the efficiency of G-Si solar
cell have been carried out (Lin, 2013). From the
simulation results, it was proposed that a maximum
conversion efficiency of 9.2% can be achieved.
Figure 4a suggests that increasing the number
of grapheme layers decreases the transmittance
linearly; this indicates that the graphene will
harvest the sunlight and the amount of sunlight
absorbed by the Si decreases, which will decrease

the performance of the solar cell. Figure 4b shows


that the sheet resistance of graphene decreases
with increasing the number of graphene layers.
So for a good solar cell efficiency, the number of
graphene layers has to be optimized in such a way
that it should have low series resistance and high
optical transmittance. Finally experiments showed
that the G-Si solar cell with 2-3 layers of graphene
and HNO3 doping achieves efficiency of 7.72%.
Ihm et al. studied how the open circuit voltage of
the device changes with the number of graphene
layers (Ihm, K. 2010).Li et al. synthesized borondoped graphene (BG) and made a device with
n-Si to achieve an efficiency of 2.3%. To further
improve the device performance, they doped BG
with HNO3 vapor and achieved 3.4% efficiency (Li,
X. 2012). Recently, an efficiency of graphene/n-Si
solar cell of 8.6% was reported by doping graphene with bis-(trifluorometanesulfonyl)amide
(TFSA). As seen in Figure5, the Jsc, Voc, FF and
all increased from 14.2 to 25.3mA/cm2, 0.43 to
0.54V, 0.32 to 0.63, and 1.9 to 8.6%, respectively
and the series resistance decreased from 14.9 to
10.3 cm-2 upon doping (Miao, 2012).

Figure 4. Theoretical calculation dependence of the number of grapheme layers with a) transmittance,
b) sheet resistance (Reproduced from Lin, Li, Xie, Feng, Chen, Song et al., 2013 with permission from
Royal Society of Chemistry)

182


Silicon Nanostructures-Graphene Nanocomposites

Figure 5. a) The J-V characteristics of pristine and bis-(trifluorometanesulfonyl)amide (TFSA) doped


graphene under AM1.5 illumination at 100mW/cm2, b) the sheet resistance values of pristine and TFSA
doped graphene(Reproduced from Miao, Tongay, Petterson, Berke, Rinzler, Appleton, & Hebard, 2012
with permission from American Chemical Society)

In the future, nanoscale power devices will play


a vital role in nano-electronics. Xie et al. (2012)
prepared a solar cell with grapheme and multiple
SiNWs and achieved an efficiency of 1.47%.
Although Si can be effectively used for photoelectrical conversion, the real problem arises when
Si is applied for the conversion of solar energy
to chemical energy, because it forms an insulator layer by oxidation in the electrolyte solution.
Hence, the protection of Si surface is essential.
Generally, noble metals, wide gap semiconductors
and polymers are employed as protective layers.
The high cost of noble metals, low conductivity
of wide band gap metal oxides and low stability
of polymers restrict the practical application for
photo-electrochemical water splitting.
Graphene alone cannot generate hydrogen
because its work function lies below the reduction potential of water. However when it forms
a heterojunction with p-Si, the electrons from
Si flow to the graphene and the Fermi level of
graphene moves upwards in such a way that it
generates hydrogen. In 2010 Hongtao et al. inves-

tigated macroporous Si/graphene composite for


photo-electrochemical water splitting (Hongtao,
2010). The nanocomposite was produced through
electrodeposition of graphene on macroporous
Si substrate and the photoelectrochemical measurements were performed in 0.05M H2SO4. The
onset potential of pristine macroporous Si was
-0.24V, which is shifted to 0.3V for macroporous
Si/graphene composite. These results indicate
that using the composite material the graphene
Fermi level shifted upper wards for easier hydrogen evolution. Wu et al. (2011) studied pristine
Si/graphene composite for hydrogen evolution
and found that without annealing the composite
material, the photocurrent density was low. This
has been attributed to weak adhesion between
graphene and Si, which is responsible for Si oxidation due to electrolyte diffusion. Huang et al.
synthesized SiNWs by using Ag assisted chemical etching and grapheme by two steps, first they
synthesized grapheme oxide (GO) by Hummers
method, followed by the reduction of GO in hydrazine. The obtained graphene was dispersed in

183


Silicon Nanostructures-Graphene Nanocomposites

Figure 6. a) Schematic representation of SiNWs and grapheme heterojunction device for photoelectrochemical water splitting, b) photo electrochemical behaviour of SiNWs and SiNWs/graphene composite.
(Reproduced from Huang, Zhong, Wang, Zhang, & Zhang, 2013 with permission from American Chemical Society)

ethanol and spin coated on SiNWs and the photo


electrochemical measurements were performed
in aqueous H2SO4 containing K2SO4 (pH=1.8).
Figure 6a shows the schematic representation of
the device for hydrogen generation. From figure
6b, it was found that both SiNWs and SiNWs/
graphene exhibited larger light current when
compared to the dark current. The photo current
density was 4 times greater than pristine SiNWs
alone and 600 times larger than SiNWs/graphene
composite compared to planar Si/graphene composite at -0.05V.The open circuit potential of
SiNWs/graphene composite was shifted positively
by 20mV in comparison to that of SiNWs. The
enhanced photo current density was due to fast
electron transfer from Si to graphene and from
graphene to electrolyte (Huang, 2013).
In order to decrease the number of recombination sites and thus enhance the efficiency of the
solar cell, surface passivation of Si is required. For
example, a thin layer of SiO2, formed by keeping
the Si wafer in air for 2 h, enhances the device
performance due to oxygen passivation of dangling
bonds on the Si surface. The preparation of SPA
and SiNWs from Si wafer introduces roughness

184

on the Si surface, while acting as recombination


sites. Nearly 15% efficiency is reported for planar
Si-CNT hetero-junction solar cell by using TiO2
as an antireflection coating (Shi, E. 2012). Conclusively, the efficiency of planar Si-graphene
solar cell can be increased by using the concept
of antireflective coating. Even after doping, the
sheet resistance of grapheme remains quite high.
In order to decrease the sheet resistance, new
dopants have to be employed. To optimize the
number of GS layers, layer by layer removal of
grapheme can be used (Dimiev, 2011). Finally, the
device fabrication should be improved in order to
expand the device area.

2. Graphene-Si Nanocomposites
for Energy Storage
The successful commercialization of Si-based
energy storage devices is handicapped because
Si anodes experience large volume change upon
battery operation, leading to pulverization of electrode materials and fast capacity fading. Cheaper
synthesis techniques need to be developed for Si
nanostructured anodes.


Silicon Nanostructures-Graphene Nanocomposites

As mentioned earlier in the text, the capacity


fading in Si based Li-ion battery can be surpassed
by the use of Si nanostructures, which can tolerate
the strain induced during the use of Li ion batteries due to the better mechanical properties of the
nanostructures. The electronic conductivity and
mechanical stability can be further enhanced by
preparing graphene composites. In this section,
first we will discuss varieties of nanostructured
Si and graphene or tailored graphene composites for Li-ion battery followed by discussion on
nanostructured Si as electrode for supercapacitor
applications.

2.1 Si Nanostructures and Graphene


Composites for Li-Ion Battery
2.1.1 Si Nanoparticles (Si NPs) and Graphene
Composite in Powder Form
For the practical application of Si-based anode,
it remains a key challenge to achieve favorable
structure beneficial to both high capacity and
long-term cyclability. To alleviate these problems,
Zhou et al. (2012) prepared silicon nanoparticles/
graphene composite using a simple and straightforward method combining freeze-drying and
thermal reduction. The Si NPs intercalated into
the graphene sheets form a typical hierarchical
micro-nanostructure in which graphene plays the
roles of both electronically conducting network
and an elastic buffer for the silicon nanoparticles.
Figure 7aillustrates the synthesis process of Si NPs
inserted into graphene sheets. Figure 7b shows
the X-ray diffraction (XRD) patterns of Si NPs
inserted into thermally reduced grapheme composite, Si NPs and thermally reduced graphene
(TRG). The XRD pattern of the composite is
similar to that of pure Si NPs, indicating that the
Si nanocrystals are not destroyed during the high
temperature heating process. The XRD pattern of
TRG displays a characteristic peak at 2 = 26.4,
corresponding to d-spacing of 0.338 nm, close to
the d-spacing of graphite (ca. 0.335 nm). This peak

is absent in the XRD pattern of the composite,


suggesting that the Si NPs are nicely dispersed
within the micrometer graphene sheets. These
results are corroborated by transmission electron
microscopy (TEM) analysis (figure 7d), revealing
micrometer sized aggregates made of Si NPs and
graphenesheets. HRTEM analysis shows a single
Si crystal intercalated between graphene sheets
(figure 7e).The electrochemical performance
of the Si NPs inserted in graphene and pristine
Si NPs was investigated through cyclic voltammetry and discharge/charge profiles (figure 7c).
This composite material showed initial discharge
capacity of 3060mAhg-1with a reversible charge
capacity up to 1866 mAhg-1. After 100cycles,
the reversible capacity dropped to 1153 mAhg-1
at a current density of 200 mAg-1, which is more
than 3 times than that of the theoretical specific
capacity of currently used graphite anode (LiC6,
372 mAhg-1), while that of pristine Si NPs is as
low as 13 mAhg-1. The composite displayed also
an improved rate capability with stable and reversible capacities of 1304, 1014, and 803 mAhg-1 at
current densities of 1000, 2000 and 4000 mAg-1.
The capacity is calculated based on the total
composite weight.
Reassembled graphene-platelets encapsulated
Si NPs, prepared in large scale, have been evaluated as an anode material for lithium ion battery
(Yoon, T., 2011). The incorporation of SiNPs into
graphene platelets was performed by using simple
solution dispersion method. Robust electrical integrity provided by the flexible graphene sheets
led to improved electrochemical performance. This
electrode exhibited reversible lithiation capacity
of 802 mAhg-1 with excellent capacity retention
up to 30 cycles.
2.1.2 Si NPs/SiNWs-Graphene Composites
as Free Standing Flexible Film
A free standing Si nanoparticles-graphene composite flexible film was prepared by simple filtration technique and used as anode material without

185


Silicon Nanostructures-Graphene Nanocomposites

Figure 7. Schematic illustration of the synthesis of Si NPs inserted into graphene (a), XRD patterns of
Si NPs inserted into thermally reduced graphene composite and their pristine constituents (b), Anode
performance of Si NPs/graphene composite and pristine Si NPs versus lithium (c), TEM images of the
composite at low magnification (d), and high magnification (e) (Reproduced from Zhou, Yin, Wan, &
Guo, 2012 with permission from Royal Society of Chemistry)

current collector. Interestingly, the absence of


current collector reduces the total weight of batteries. Hence, the performance of the full device
significantly increased. Recently, many research
groups reported flexible film anode materials.
Graphene oxide (GO) sheets were first prepared
from natural graphite and then mixed with commercial Si powder followed by vacuum filtration
to obtain flexible film. Then thermal reduction
was performed at different temperatures to yield
the final anode material. The anode film prepared
from reduced GO and Si NPs showed discharge
capacity of 708 mAhg-1 after hundred cycles at a
current density of 50 mAg-1 (Wang, 2010). The
anode film thermally reduced at 700C showed

186

charge capacity of 1500 mAhg-1 after 300 cycles


in the case of constant current-constant voltage
(CCCV) cycling mode (Lee, 2010). However, the
powder form of the same composite exhibited
quite low capacity in the constant current mode.
Similar free standing film anodes prepared by
thermal reduction at 700C displayed discharge
capacity of 768 mAhg-1after 300 cycles at a current density of 50 mAg-1 (Tao, H. C., 2011).Very
recently, SiNWs-graphene composite prepared
by the same simple filtration technique was used
as anode film (Chockla, 2012). The authors attributed the better capacity at very high current
to graphene present in the composite rather than
only SiNWs. SiNWs-graphene film anode was pre-


Silicon Nanostructures-Graphene Nanocomposites

pared by simple filtration of SiNWs and grapheme


oxide, followed by heat treatment at 600C.The
SiNWs-rGO electrode delivered a significantly
higher specific capacity of about 3350 mAhg-1 at
840 mAg1 and retained relatively same capacity
up to 20 cycles (Wang, 2013).
2.1.3 Electrostatic Self-Assembly of Si NPs/
SiNWs and Grapheme Sheets
Electrostatic self-assembly of nanoparticles provides intimate contact between oppositely charged
nanoparticles. Figure 8 shows the schematic portray of electrostatic self-assembly of Si NPs on
graphene sheets. GO sheets are negatively charged
due to the presence of many oxygen containing
functional groups. The presence of native oxide
on the Si surface provides a negative charge for Si
NPs. Positively charged Si NPs are prepared via
functionalization with poly (diallyldimethylammomium chloride) (PDDA).After functionaliza-

tion with PDDA, the Si NPs surface charge changed


from original negative (zeta potential = 33 mV)
to positive (zeta potential = + 41 mV).Positively
charged Si-PDDA nanoparticles assemble with
negatively charged GO sheets by electrostatic
attraction. Subsequently, the aqueous dispersion
was freeze-dried and thermally reduced, followed
by HF treatment to produce graphene encapsulated
Si nanoparticles composite (Zhou, 2012). This
new synthetic strategy of graphene encapsulated
Si nanoparticles composite is supported by TEM
analysis (figure 8a,b), revealing the small size Si
NPs completely encapsulated within micrometer
size graphene sheets. HRTEM image clearly
shows a single Si NP completely encapsulated
by graphene sheets (figure 7c). Survey spectra
of Auger electron spectroscopy (AES) analysis
of single Si NPs graphene composite shows that
absence corresponding signal for silicon suggest-

Figure 8. Schematic diagram of the formation of Si nanoparticles encapsulated in graphene sheets and
TEM images of the resulting composite (Reproduced from Zhou, Yin, Wan, & Guo, 2012 with permission
from WILEY-VCH Verlag GmbH & Co. Weinheim).

187


Silicon Nanostructures-Graphene Nanocomposites

ing that Si NP was completely encapsulated by


graphene sheet.
This nanocomposite material exhibits initial
discharge capacity of 2920 mAhg-1 with a reversible capacity of 1720 mAhg-1. The reversible
capacity of the nanocomposite is maintained as
high as 1205 mAhg-1 even after 150 cycles at a
current density of 100 mAhg-1, which is more
than 3.2 times higher than that of the theoretical
specific capacity of commercial graphite anode.
A similar approach, based on self-assembly of
positively charged Si NPs and negatively charged
GO, was applied for the preparation of SiNWs and
graphene composite (Zhu, Y., 2012). Here, the
positive charge on the SiNWs was acquired through
chemical functionalization with (3-aminopropyl)triethoxysilane (APTES). Electrostatic interaction
between NH2-SiNWs and GO leads to their self
assembly. Subsequent heat treatment reduces GO
to graphene in the composite. As synthesized
SiNWs/graphene composite showed a discharge
capacity of 2142 mAhg-1 initially and after 80
cycles the capacity was still maintained above
1000 mAhg-1.

anchoring of Si nanoparticles onto the surface


of graphene sheets via phenyl linkers. This was
achieved by successively diazotizing two amines
of p-phenylenediamine, and the in situ generated
aryl radicals grafted spontaneously to the graphene
sheets and Si nanoparticles. The resulting SiPhG
nanocomposite exhibited delithiation capacity of
1079 and 828 mAhg1 in the initial and 50th cycle
at a current density of 300 mAg1.This graphene/
SiNPs composite showed better performance
because Si was well connected with the conductive matrix. Carbon coated Si on graphene was
recently prepared (Evanoff, 2011). First, a few
layers of graphene was synthesized from natural
graphite and uniformly coated with Si via SiH4
decomposition at 500C followed by coating with
a thin amorphous carbon by thermal decomposition of propane. Carbon coating was deposited to
reduce Si oxidation and improve anode stability.
High reversible discharge capacity of 2300 mAhg1
was obtained for this composite at a low current
density of 140mAg-1. This reversible capacity is
six times greater than the commercial graphite.

2.1.4 Direct Attachment of Si Nanostructures


onto Graphene

Effective 3D conductive network was built by the


combination of graphene, carbon nanoparticles
and SiNPs to achieve better performance anode
material (Zhou, 2012).The capacity fading of
graphene, carbon and Si nanoparticles tertiary
composite is lower than any binary composite
of graphene and Si or carbon nanoparticles. This
might be the result of effective 3D conductivity
and low aggregation in the tertiary composite.
3D porous architecture of SiNPs/grapheme was
prepared by thermal reduction of SiO2 coated GO
by magnesium (Xin, 2012). This 3D porous SiNPs/
grapheme nanocomposite maintained reversible
capacity of ~900 mAhg1at charge rates up to
1000 mAhg1whereasthe Si/graphene composite
delivered a capacity below 100mAhg1at a 1000
mAg1 charge rate.

Recently, SiNWs are synthesized in situ on graphene sheets (Lu, Z., 2012). Graphene prepared
from GO, was decorated with gold nanoparticles
and used for catalytic growth of SiNWs. Thermal
decomposition of diphenysilane in hexane was
utilized for simultaneous growth of SiNWs and
reduction of GO to graphene. The first insertion
of lithium gave a discharge capacity of 3506
mAhg1 and a subsequent charge capacity of
2009 mAhg1. Acoulombic efficiency of about
57.3% was obtained at the rate of 0.1C in the
first cycle. Similarly, Si nanoparticles were attached onto functionalized graphene by covalent
functionalization (Yang, S., 2012). In this study,
a novel nanocomposite was fabricated by covalent

188

2.1.5 3D Si NPs/Grapheme Nanocomposite


Silicon Nanostructures-Graphene Nanocomposites

2.1.6 Tailored Graphene and Si NPs/SiNWs


Composite

2.1.7 Si NPs/Graphene Composite Prepared


by Mechanical Blending

Plane vacancy present on the graphene/Si NPs


composite shows excellent rate capability. The
plane vacancy present in the graphene allows
lithium ion transport throughout the structure
thereby reducing the diffusion length as confirmed
by impedance spectroscopy. Electrochemical impedance spectroscopy is one of the better-known
techniques used to quantify the solution and charge
transfer resistance of electrode materials. The
charge transfer resistance and Warburg coefficient
of plane defective graphene/Si NPs composite
was lower than their counterpart of non plane
vacant graphene (Zhao, 2011).Thin film of this
plane defective graphene/Si NPs composite was
subjected to the anode performance evaluation.
It displayed better performance, suggesting that
the defective graphene still has better conductivity and mechanical stability. The solid electrolyte
interface can be controlled by forming crumpled
graphene-Si NPs composite (Luo, 2012). The
coulombic efficiency of this crumpled grapheneSi NPs composite reached up to 95% during the
second cycle and 99% after the fifth cycle. The
coulombic efficiency of the electrode with only
Si particles reached up to 95% at the tenth cycle,
but the capacity was completely lost after the
twentieth cycle. Recently, nitrogen doped graphitic
layer, prepared by thermal CVD of CH4/H2/NH3,
was coated as shell on vertically aligned SiNWs
synthesized by Ag metal assisted chemical etching
(Cho, 2012).It was found that by increasing the
thickness of the nitrogen doped graphitic layer on
SiNWs, high charge capacity of 1260mAhg1could
be achieved as compared to undoped graphitic
layer where it is initially 2100 mAhg1and further
drops to 1040mAhg1after 45 cycles. This reveals
that doping of graphitic layers on SiNWs can be
effective for lithium ion battery performance,
which eventually increases the charge storage
capacity and cycle life of a battery.

Xiang et al. reported that Si NPs (50 nm)-graphene


(prepared from thermal expandable graphite)
composite gave better performance than graphene prepared by chemical method (Xiang, H.,
2011). Pristine Si NPs anodes showed highest
charge capacity of 3170 mAhg1 in the first cycle.
However, it drops to 434 mAhg1 after 30 cycles.
Even though Si NPs-graphene composites have
lower capacity than the pristine Si NPs, the cycle
life was improved significantly. In this study all
of the Si NPs and chemically derived graphene
composites have reversible capacity less than
2000mAhg1. SiNPs and thermally expanded
graphene composites display initial reversible
capacity of about 2753mAhg1. They retained
83% of the initial capacity after 30cycles. The
entire cycling test was performed at 300mAg1.
This was attributed to the low density of defects
of graphene obtained from thermal expandable
graphite, which enhances the conductivity of the
composite therefore exhibits better performance.
Chou et al. prepared graphene-Si NPs composite
by mechanical mixing of graphene prepared by
solvo thermal method and Si NPs (40nm) (Chou,
2010).They demonstrated that the composite
had a discharge capacity of about 2158 mAhg1.
After 30 cycles, the charge capacity dropped to
1168mAhg1.
2.1.8 SiNPs/Grapheme Electrode as a BinderFree Anode
Ethanol suspension of Si NPs-graphene oxide
was spin coated on copper foil; subsequent heat
treatment at 700C yields the binder-free anode.
The resulting composite displays initial discharge
capacity of 2813mAhg1at a current density of
1A/g(ref. 68:Zhou, X. 2012).After 200cycles it
retains a capacity of 1611mAhg1 and also exhibits
better rate performance at various current densities. Another group developed a new synthetic

189


Silicon Nanostructures-Graphene Nanocomposites

route for Si/graphene composite film on Cu foil


using simple electrophoretic deposition of grapheme sheets followed by RF sputtering of Si (Zhang,
Y. Q., 2012).The anode film showed capacity of
2204mAhg1, and after 150 cycles it retained a
capacity of about 87.7% of initial capacity.

2.2 Si-Based Supercapacitors


Although considerable research is dedicated for
designing micro-supercapacitors with electrode
materials like carbon and metal oxides, their integration in microelectronics is still a challenge.
Si plays ubiquitous role in electronic and microelectronic devices, and supercapacitors based on
Si can facilitate its integration in microelectronic
devices. In this regard, SiNWs are subjected to
Li-battery cycles to generate porous SiNWs as
excellent supercapacitor electrodes at high power
operations (Choi, J. W. 2010). The porous SiNWs
based supercapacitor device displayedenergy and
power densities of ~20 Wh/kg and ~22 kW/kg,
respectively. The symmetrical electrochemical
capacitor based on porous Si (PS) electrodes was
demonstrated to giving the highest series capacitance of 320 F/cm2(Desplobain, S. 2007). In this
study, surface electrical conductivity of PS was
increased by metallization with gold. Chemical
vapor deposition (CVD) grown SiNWs-based
electrodes display a promising cycling stability
in an organic electrolyte and a quasi-ideal pure
capacitive behavior (Thissandier, 2012). The same
research group investigated the influence of SiNWs length on symmetrical micro-ultracapacitor
devices (Thissandier, 2013). They demonstrated
that the capacitance increases with the length of
the SiNWs electrode and has been improved up
to 10 Fcm2 by using 20 mSiNWs, i.e.10-fold
bulk Si capacitance. This device exhibits promising galvanostatic charge/discharge cycling stability with a maximum power density of 1.4 mW
cm2.Sihollow nanostructures are recently used as
electrode material for supercapacitors (Liu, M.P.,
2012). Nanostructured Si hollow spheres with a

190

thin shell have been synthesized by magnesium


reduction of silica spheres. The electrode showed
maximum specific capacitance of 193 F g1 in the
neutral Na2SO4 aqueous solution at a scanning
rate of 5 mV s1, comparable to carbon capacitors. Alternatively, SiNWs coated with NiO (Lu,
2011; Tao, 2010), or SiC (Alper, 2012) have been
studied as potential materials for supercapacitor
electrodes, but so far no research work has been
demonstrated with Si and graphene composite
supercapacitor electrode.

FUTURE RESEARCH DIRECTIONS


As we know that solar energy plays a vital role
for the sustainability of the world. In order to
increase the solar cell efficiency, new materials
have to be developed and among them graphene
plays an important role. Because of its optical
properties and highly conducting nature, it can be
used as transparent electrodes in solar cell and will
replace other electrodes due to its low cost and ecofriendly. Entirely different optical and electronic
properties of graphene and Si provided interesting
platforms for exploring structure-activity relations of Si/grapheme nanocomposites. Surface
modifications of these materials to incorporate
organic linkers with fast charge transfer rates or
strategies to couple with plasmons can enhance
photocurrent generation in these composites.
In the future, graphene/Si composites might
replace the graphite anode thereby electric vehicle
dream may be possible. Graphene/Si composites
for lithium ion batteries are still in the infant
stage so more active research is required in this
area. New strategies and synthetic routes to develop graphene-Si based multilayer structures
can provide several advantages for Li-ion battery
electrode. Chemically modified graphene-Si
nanocomposites can be synthesized to tailor the
end application of the specific composite. Also
more detailed studies are expected using molecular
dynamic simulations for better understanding.


Silicon Nanostructures-Graphene Nanocomposites

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ADDITIONAL READING

Zhou, X., Cao, A. M., Wan, L. J., & Guo, Y. G.


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KEY TERMS AND DEFINITIONS


Energy Density: Total energy available from
per unit weight of the system.
Open Circuit Voltage: Maximum voltage at
zero current in the solar cell.
Power Density: Total energy available per unit
time from per unit weight of the system. It refers
to the rate of energy transfer.
Schottky Diode: Metal/semiconductor heterojunction diode.
Short Circuit Current: Current at zero voltage in the solar cell.

195

196

Chapter 10

Metal Oxide-Graphene
Nanocomposites:
Synthesis to Applications

Ponchami Sharma
CSIR-North East Institute of Science and
Technology, Jorhat, India

Ashvini B. Deshmukh
CSIR-National Chemical Laboratory, India

Najrul Hussain
CSIR-North East Institute of Science and
Technology, Jorhat, India

Manjusha V. Shelke
CSIR-National Chemical Laboratory, India

Manash R. Das
CSIR-North East Institute of Science and
Technology, Jorhat, India

Sabine Szunerits
Institut de Recherche Interdisciplinaire
Universit Lille 1, France

Rabah Boukherroub
Institut de Recherche Interdisciplinaire
Universit Lille 1, France

ABSTRACT
Graphene is one of the most interesting materials in the field of nanoscience and nanotechnology. Metal
oxide nanoparticles exhibit unique physical and chemical properties due to their reduced size and high
density of corner or edge surface sites. The metal oxide-graphene nanocomposites not only possess
favorable properties of graphene and metal oxide, but also greatly enhance the intrinsic properties due
to the synergistic effect between them. These composites are used for catalysis, supercapacitors, lithium
ion batteries, solar cells, sensors, removal of pollutants from water, etc. There is a very broad scope of
further research for the development of metal oxide-graphene nanocomposites with enhanced properties for different applications. This chapter deals with a comprehensive review of the current research
activities from the viewpoint of chemistry and materials science with a special focus on the synthesis,
characterization, and applications of metal oxide-graphene nanocomposite materials.
DOI: 10.4018/978-1-4666-5824-0.ch010

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Metal Oxide-Graphene Nanocomposites

INTRODUCTION
In the recent years, graphene the mother of all
the graphitic materials has drawn the attraction
of researchers worldwide (Geim & Novoselov,
2007). Graphene is a single layer of carbon atoms
closely packed into honeycomb two dimensional
(2D) lattice with a carbon-carbon distance of
0.142 nm. The sp2 hybridized carbon network
as well as its high electron mobility at room
temperature (250,000 cm2/Vs), exceptional thermal conductivity (5000 W m-1K-1) and superior
mechanical properties with Youngs modulus of
1 TPa make it the material of choice for a wide
range of applications in the field of materials
science, physics, chemistry and nanotechnology
(Novoselov, Geim, Morozov, Jiang, Katsnelson,
Grigorieva, et al., 2005; Li, Wang, Zang, Lee, &
Dai, 2008; Stankovich, Dikin, Dommett, Kohlhaas, Zimney, Stach, et al., 2006; Schedin, Geim,
Morozov, Hill, Blake, Katsnelson, et al., 2007;
Singh, Singh, Nayak, Kumari, Grcio & Dash,
2011). Two dimensional, atom-thick graphene can
be considered as the ideal substrate for the synthesis of hybrid composites with three-dimensional
(3D) architectures with unique chemical, physical and structural properties (Zhao, Song, Song,
Yin, Wu, Zhou, et al., 2010). The fabrication of
metal and metal oxide-graphene/graphene oxide
(GO) nanocomposites has drawn special interest
in this regard. The presence of metal and metal
oxide nanoparticles (NPs) on reduced graphene
oxide (rGO) sheets prevents the restacking of
the individual graphene sheets which arises due
to strong Van der Waals interactions between
the sheets (Zhao et al., 2012). Metal oxide NPs
exhibit unique physical and chemical properties
upon a decrease of their particle size and structural
geometry. The decrease of the particle size has
a direct influence on the band gap of the oxide
particles and is reflected on their conductivity
and chemical reactivity. However, these properties are greatly affected by the aggregation of the

NPs. Therefore, prevention of such aggregation


is necessary when synthesizing metal oxide NPs.
Graphene or GO nanosheets can effectively stabilize such NPs to prevent their aggregation, and
the properties of the NPs could be enhanced by
anchoring them onto the graphene sheets (Bai &
Shen, 2012). Therefore, current research trends
are focused on the preparation and application of
metal oxide-graphene nanocomposites. A number
of research activities have been carried out in
this area in recent years. This chapter consists of
a comprehensive review of current research activities in the synthesis and applications of metal
oxide-graphene nanocomposites.

BACKGROUND
Recently, many efforts have been focused on the
preparation of metal oxide-graphene nanocomposites using different strategies such as precipitation
from a mixed solution, hydrothermal/solvothermal
method, microwave-assisted synthesis, photoassisted synthesis, sol-gel method, atomic layer
deposition, electrostatic interaction, layer-bylayer self- assembly, covalent interaction, etc.
(Yao, Miao, Liu, Ma, Sun & Wang, 2012; Yang,
Zhang, Ma, Huang, Wang & Chen, 2009; Zhang,
Dwivedi, Chi, & Wu, 2010; Chandra, Park, Chun,
Lee, Huwang, & Kim, 2010; Ji, Wu, Shen, Zhou
& Xi, 2011; Seo, Lee, Kim & Kim, 2013; Wu,
Feng, Wang, & Wan, 2013; Xu, Wang, Zhu,
Yang & Lu, 2008; Zhu, Zeng, Nie, Xu, Chen,
Han, et al., 2010; Zhang, Chen, Zhang, Huang,
Chen. Yang, et al., 2010; Wu, Shen, Jiang, Wang
& Chen, 2010; Chang, Lee, Hu, Chang, Liu &
Yang, 2010; Wu, Ren, Wen, Gao, Zhao, Chen, et
al., 2010; Zhang, Lei, Yin, Chen, Li, Wang, et al.,
2010; Zou, Zhu, Sun & Wang, 2011; Wu, Wang,
Wang, Ren, Zhao, Zhou, et al., 2010; Zhou, Zhu,
Yang, Jiang & Li, 2011; Zhou, Zhu, Yang, &
Li, 2011; Liu, Pan, Zhao, Liu, Zhu, Chen, et al.,
2012; Li, Zhang, Wang, Han, Liu, Zheng, et al.,

197


Metal Oxide-Graphene Nanocomposites

2010; Ng, Iwase, Bell, Kudo & Amal, 2011; Hu,


Zhao, Zhou, Gogotsi & Qiu, 2011; Zhang, Li,
Cui & Lin 2010; Yan, Fan, Wei, Qian, Zhang &
Wei, 2010; Chen & Wang, 2010; Meng, Geng,
Liu, Li & Sun, 2011; Alles, Aarik, Aidla, Fay,
Kozlova, Nilisk, et al., 2011; Yang, Feng, Ivanovici
& Mullen, 2010; He, Fan, Ma, Zhang, Leung &
Chan, 2010; Bai & Shen 2012; Li, Cao, Shao, Li,
Qu & Yin, 2011; Li, Wang, Liu, Liu, Ou & Yang
2011; Ren, Huang, Fan & Liu, 2011; Sreeprasad,
Shihabudheen, Maliyekkal, Lisha & Pradeep,
2011; Zhou, Zhu, Cheng, Liu, Yang, Cong, et al.,
2011; Nethravathi, Rajamathi, Ravishankar, Basit
& Felser, 2010; Liu, Meng, Hu, Geng, Banis, Cai,
et al., 2013; Wu, Zhou, Yin, Ren, Li & Cheng,
2012; Xue, Chen, Yu, Wang, Yardeni, Dai, et al.,
2011). Each of these techniques possesses some
unique characteristics, which lead to the formation
of functional metal oxide-graphene nanocomposites. In this chapter, different synthesis processes
commonly applied for the production of metal
oxide-graphene nanocomposites are described
in detail. The resulting metal oxide-graphene
nanocomposites have found a wide number of
applications in various fields such as Li-ion battery, supercapacitors, photovoltaic cell, water
purification, biomedicine, etc. which are also
discussed in this chapter.

Preparation of Metal OxideGraphene Nanocomposites


A number of procedures are available for the synthesis of metal oxide-graphene nanocomposites.
Broadly, they can be classified into two categories:
in situ and ex situ methods. The in situ process
involves the formation of nanomaterials in the
presence of pristine or functionalized graphene or
GO nanosheets, while the ex situ approach involves
prior synthesis of nanomaterials in the desired
dimensions and morphology, and subsequently
connected to the surface of pristine or functionalized graphene or GO nanosheets.

198

In Situ Process
The in situ process is the most commonly used
strategy for the synthesis of metal oxide-graphene
nanocomposites. This process has the advantage
of avoiding the use of protecting surfactants or
extra linker molecules, which may imply a tedious experimental procedure and may also affect
the properties of the nanocomposites. Another
advantage of this process is that a variety of
chemical and physical synthesis techniques can
be used, including solution chemistry methods,
direct decomposition of precursors, hydrothermal/
solvothermal techniques, gas-phase deposition,
solgel processing, template method, and so on.

Precipitation of Metal OxideGraphene Nanocomposites


from a Mixed Solution
A variety of metal oxide-GO nanocomposites have
been synthesized by precipitating the mixed solution of metal salts and GO, followed by subsequent
reduction to metal oxide-graphene nanocomposites. The general procedure for the synthesis of
metal oxide-graphene nanocomposites can be
schematically represented as in Figure 1.
Synthesis of Fe3O4-graphene nanocomposites
by precipitation of Fe3+/Fe2+ ions and GO in an
alkaline solution followed by reduction with
hydrazine hydrate is reported in a number of
studies (Yao et al., 2012; Yang et al., 2009; Chandra et al., 2010). Independently, CuO-graphene
nanocomposites were obtained by addition of
CuSO4.5H2O, NH4OH, and NaOH to an aqueous
solution of dispersed graphene nanosheets followed by hydrazine reduction (Seo et al., 2013).
Similarly NiO/graphene nanocomposites were
also synthesized using nickel chloride and graphite
oxide as starting materials and hydrazine hydrate
as a reducing agent in a basic pH range (Ji et al.,
2011). However, the use of hydrazine hydrate as
reducing agent is often not preferred due to its
toxicity. Ethylene glycol was thus investigated


Metal Oxide-Graphene Nanocomposites

Figure 1. Schematic representation of the synthesis of metal oxide-graphene oxide/graphene nanocomposites by the precipitation approach

as an alternative reducing agent for the synthesis


of Fe3O4-graphene nanocomposites with FeCl3 as
iron source (Wu et al., 2013). Typically, FeCl3 was
mixed with GO followed by addition of sodium
acetate. The mixture was autoclaved at 200 C
for 8 h to yield Fe3O4-graphene nanocomposites.
Co3O4-graphene (Xu et al., 2008), CuO-graphene
(Zhu et al., 2010), SnO2-graphene (Zhang, Jiang,
Yan, Wang, Wang, Song, et al., 2010), and RuO2graphene (Wu et al., 2010b) nanocomposites were
synthesized using a similar approach. A two step
strategy for the synthesis of metal oxide-graphene
nanocomposites was reported by Chang, Lee,
Hu, Chang, Liu & Yang (2010). It is based on
precipitating hydroxides onto GO nanosheets
followed by microwave-assisted hydrothermal/
solvothermal annealing (Chang, 2010) to produce
a number of unitary and binary metal oxides
(Mn3O4, TiO2, SnO2, NiCo2O4, Zn2SnO4)-graphene
nanocomposites.
Teo, Kim, Huang, Chia & Harrison (2012)
described a green and energy efficient method for
the synthesis of Fe3O4-graphene nanocomposites
based on the redox reaction between Fe2+ ions and
GO nanosheets at room temperature in basic medium. The pH of the GO suspension was adjusted
to 11-12 using 25% NH4OH solution followed by
a slow addition of FeSO4 as iron precursor under
magnetic stirring. The resulting Fe3O4-graphene
nanocomposite was collected by centrifugation
and washed with water to remove excess of ammonia. The probable reaction mechanism for the
formation of metal oxide-graphene nanocomposites in alkaline medium can be described as follows.
Mx+ + xOH- M(OH)x

M(OH)x + xOH- M2Ox + xH2O + xeGO + xe- Graphene


The formation of Fe3O4-graphene nanocomposite was confirmed by SEM-EDX analysis.
The SEM image of GO nanosheets displayed a
smooth surface with a distinctive layered appearance (Figure 2a), while that of Fe3O4 nanoparticles
showed agglomeration of the particles (Figure
2b). The SEM image of Fe3O4-graphene nanocomposite showed uniform distribution of the
nanoparticles over the graphene surface (Figure
2c). The elemental mapping of C, O, and Fe using
energy dispersive X-ray (EDX) analysis clearly
indicated the presence of Fe in the nanocomposite
(Figure 2d).
Zhao et al. (2012) investigated the synthesis
of CuO-graphene nanocomposites by such redox
reaction in alkaline solution. The CuO-graphene
nanocomposites were characterized by XRD,
FTIR, Raman spectroscopy, TGA, SEM and TEM
analysis. The structural features of CuO-graphene
nanocomposites were thoroughly identified using
Raman spectroscopy (Figure 3). Graphite oxide
exhibits two characteristic peaks at about 1581 cm-1
(G band), corresponding to an E2g mode of graphite,
related to the vibration of the sp2-bonded carbon
atoms in a two-dimensional hexagonal lattice, and
at about 1333 cm-1 (D band) related to the defects
and disorder in the hexagonal graphitic layers.
The G band peak was blue shifted to 1594 cm-1
after formation of CuO-graphene nanocomposite
which may be due to a decrease of the number
of layers in the solid state. In addition to the Gand D-bands, three extra weak peaks at 281, 342
and 612 cm-1 corresponding to one Ag and two

199


Metal Oxide-Graphene Nanocomposites

Figure 2. SEM images of (a) graphene nanosheets, (b) Fe3O4 nanoparticles, (c) Fe3O4-graphene nanocomposites, (d) EDX of Fe3O4-graphene nanocomposite. ( 2012 Elsevier Ltd. Reprinted with permission
from Teo, Lim, Huang, Chia, & Harrison, 2012)

Figure 3. Raman spectra of (a) GO, (b) CuO-graphene nanocomposite ( 2012 The Royal Society of
Chemistry. Reprinted with permission from Zhao, Song, Song, & Yin, 2012)

200


Metal Oxide-Graphene Nanocomposites

Bg modes of CuO were observed in the Raman


spectrum of the CuO-graphene nanocomposite.
The Raman ID/IG ratio was increased from 1.14
for GO to 1.24 for CuO-graphene nanocomposite,
indicating that more defects have been introduced
into the CuO-graphene nanocomposite. At the
same time, the change of D/G intensity ratio for
CuO-graphene nanocomposite as compared with
GO nanosheets suggests partial reduction of the
GO nanosheets.
The thermal stability of the CuO-graphene
nanocomposite was further investigated by using TGA. Figure 4 displays the thermal behavior
of the CuO-graphene nanocomposite, GO and
graphene, respectively. The TGA curve of the
CuO-graphene nanocomposite shows 3% weight
loss from 50 to 150 C, which is due to the loss
of water or some organic solvent. Increasing the
temperature resulted in 10% weight loss around
200 C and 20% weight loss around 450 C, at-

tributed to the decomposition of residual oxygencontaining functional groups and carbon skeleton
from graphene, respectively. As can be seen, the
weight loss of the CuO-graphene nanocomposite
in the removal of residual oxygen functional group
process is much lower than that of GO (29.5 wt%),
which indicates the oxygen-containing functional
groups are largely eliminated during the reduction process. Compared to GO and graphene,
which show a complete decomposition of carbon
at about 650 C, full carbon decomposition of
CuO-graphene nanocomposite occurred at a lower
temperature (450 C), indicating that the thermal
stability of graphene was decreased after forming
a composite with CuO nanoparticles.
The morphology of the resulting nanocomposite was investigated using TEM and SEM.
Figure 5a and b display TEM and SEM images
of rGO (prepared by chemical reduction of GO
with hydrazine) sheet, respectively. It can be seen

Figure 4. TGA curves of (a) CuO-graphene nanocomposite, (b) GO nanosheets, (c) reduced GO nanosheets
(prepared by hydrazine reduction of GO) in air (2012 The Royal Society of Chemistry. Reprinted with
permission from Zhao, Song, Song, and Yin, 2012)

201


Metal Oxide-Graphene Nanocomposites

Figure 5. TEM (a) and SEM (b) images of graphene nanosheets; TEM (c) and SEM (d) images CuOgraphene nanocomposite (2012 The Royal Society of Chemistry. Reprinted with permission from Zhao,
Song, Song, & Yin, 2012)

that the rGO sheet exhibits a typical rippled and


crumpled morphology and paper-like structure
with single or very thin layers. TEM and SEM
analysis of CuO/rGO nanocomposite show that
the CuO nanoparticles are homogeneously distributed on the rGO surface without any apparent
aggregation. The inset in Figure 5c corresponds to
a high magnification image of CuO/rGO, in which
spindle-like CuO nanoplates (30 nm in diameter
and 60 nm in average length) are visible.

SolGel Method
The solgel process is a cheap and low-temperature
technique, which undergoes a series of hydrolysis
and polycondensation reactions and its use for the
synthesis of metal oxide-graphene nanocomposites

202

is widely adopted. However, the product obtained


by this method consists typically of an amorphous
phase rather than defined crystals and therefore
it requires crystallization and post-annealing
steps. Wu et al. (2010b) applied this method for
the synthesis of RuO2-graphene nanocomposites.
Zhang et al. (2010c) synthesized in this manner
TiO2graphene nanocomposites using tetrabutyl
titanate and GO nanosheets as starting materials.
They first dispersed GO nanosheets in ethanol by
ultrasonication and then reduced it to graphene
using NaBH4. The as-synthesized graphene was
again dispersed in ethanol and tetrabutyl titanate
was added dropwise followed by addition of glacial
acetic acid and water. The mixture was stirred and
dried at 80 C for 10 h to yield the precursor. The
TiO2-graphene nanocomposites were produced by


Metal Oxide-Graphene Nanocomposites

Figure 6. Schematic illustration of the synthesis of TiO2-graphene nanocomposites by sol-gel method


(2010 The Royal Society of Chemistry. Reprinted with permission from Zhang, Li, Cui, & Lin, 2010d)

annealing the precursor at 450 C. The synthetic


route is schematically represented in Figure 6.

Hydrothermal/Solvothermal
Technique
Hydrothermal and solvothermal techniques are
other frequently used strategies for the synthesis
of metal oxide-graphene nanocomposites. In
this fabrication process, the synthesis is generally carried out in an autoclave under high vapor
pressure and high temperature. Nanocomposites
can be obtained by this process without the need
of post-annealing and calcination. However, the
requirement of high temperature and long reaction
times are the two major drawbacks of this process
when compared to other energy efficient and short
term processes. In spite of such drawbacks, a
number of metal oxide-graphene nanocomposites
such as ZnO (Zou et al., 2011; Wu et al., 2010a),
TiO2 (Zhou et al., 2011a; Fan, Shi, Wang, Shi,
Wang, Xu, et al., 2011; Shen, Shi, Yan, Ma, Li
& Ye, 2011; Shen, Yan, Shi, Ma, Li & Ye, 2011),
Fe3O4 (Zhou et al., 2011b; Wang, Zhong, Wexler,
Idris, Wang, Chen et al., 2011; Shen, Wu, Bai &
Zhou, 2010; Shi, Zhu, Sim, Tay, Lu, Zhang, et al.,
2011), SnO2 (Huang, Zhou, Zhou, Qian, Wang,
Liu et al., 2011; Jung, Myung, Cho, Shon, Jang,
Kim, et al., 2010), Co3O4 (Li et al., 2011a), Bi2O3

(Wang, Hu, Chang, Chen, Lei, Zhang, et al., 2010),


Fe2O3, CoO (Zhu, Zhu, Zhou, Zhang, Lou, Chen,
et al., 2011) have been prepared by this approach.
Hwang, Lee, Kim, Han, Kim, Park, et al. (2011)
prepared transparent ZnO nanowires on graphene
sheets by this method. The GO nanosheets were
synthesized by the Hummers method and then
transferred onto a flexible PDMS substrate to
constitute a mechanically flexible/stretchable,
electro-conductive, and optically transparent
substrate. Vertical ZnO nanowires were then
grown by hydrothermal/solvothermal process on
the flexible substrate, as illustrated in Figure 7.

Photo-Assisted Reduction
Photo-assisted reduction is another green process,
which provides a uniform reducing environment in
solution without the need of any additional reducing agent. Semiconductors with large band gaps
are photo-catalytically active under UV-visible
light irradiation and can be used to reduce GO
through a photogenerated electron transfer process
to produce semiconductor-graphene nanocomposites. TiO2 and ZnO are used to generate metal
oxide-graphene nanocomposites by this process.
Williams, Seger, & Kamat (2008) reported the
photocatalytic reduction of GO nanosheets with
TiO2 nanoparticles (NPs) in an inert atmosphere at

203


Metal Oxide-Graphene Nanocomposites

Figure 7. A schematic illustration of the fabrication process of ZnO nanowires on graphene film/PDMS
substrates (2011 The Royal Society of Chemistry. Reprinted with permission from Hwang, Lee, Kim,
Han, Kim, Park, No, & Kim, 2011)

room temperature using ethanol as hole scavenger


for TiO2 photocatalyst. Under UV irradiation,
TiO2 NPs were excited to generate electronhole
pairs. The holes are scavenged by ethanol to
produce ethoxy radicals leaving the electrons to
accumulate within TiO2 particles (reaction 1).
The accumulated electrons serve to reduce the
GO sheets into graphene (reaction 2).
C2 H 5OH

TiO2 + hv TiO2(h e ) TiO2(e )


+

+ C2 H 4OH + H +

TiO2(e) + GO TiO2 + Graphene

(1)
(2)

Photo-assisted production of TiO2-graphene


nanocomposites without any scavenging agent was
also investigated (Li et al., 2010). The photogenerated holes react with surface adsorbed water to

204

generate oxygen and protons, whereas the electrons


are efficiently captured by the sp2 regions of GO
nanosheets. The electrons delocalized in the sp2
regions of GO nanosheets may initiate the reactions
to dissociate oxygenated functional groups at the
boundary of sp2 regions, together with protons, as
shown in Equations (3) and (4) (Li et al., 2010).
4h+ (TiO2) + 2H2O O2 + 4H+

(3)

4e (TiO2) + GO + 4H+ Graphene + 2H2O


(4)
This photocatalytic reduction was carried in
air atmosphere although the dioxygen in air competes with GO nanosheets for electron capture. In
a similar manner, ZnO-graphene nanocomposites
were successfully prepared (Liu, Pan, Zhao, Lv,
Zhu, Chen, et al., 2012).


Metal Oxide-Graphene Nanocomposites

One of the greatest advantages of the photoassisted reduction of GO nanosheets is that it allows
the preparation of patterned graphene areas by
UV irradiation. Since UV irradiation has a little
thermal effect, the shapes of the graphene patterns
can be well controlled by limiting the thermal
diffusion effect (Li et al., 2010). Photo-assisted
reduction using visible light is carried out for
WO3-graphene and BiVO4-graphene nanocomposites (Ng et al., 2011). However, this process
only applies for semiconductors with narrow band
gaps i.e. absorbing visible light.

Microwave-Assisted Synthesis
Microwave irradiation is widely used as a green
and efficient technique for the production of
metal oxide-graphene nanocomposites. Unlike
photocatalytic reduction, this method can be
utilized as a general procedure for all types of
metal oxides. Microwave energy is transformed
into heat energy upon absorption by the substrate,
which is believed to be the driving force for the
reduction of GO nanosheets and metal salts (Hu
et al., 2011). However, the exact mechanism is
not yet clearly understood. Microwave synthesis
has the advantages of very short reaction time
and production of small particles with narrow
size distribution in comparison to conventional
methods. Zhang et al. (2010b) generated Fe3O4graphene nanocomposites by microwave heating
a Fe(NO3)3/GO mixture in the presence of urea
and ascorbic acid under reflux condition for
1 h. A similar reaction was performed by the
same group for the synthesis of SnO2-graphene
nanocomposites, starting with GO nanosheets,
tin chloride and urea with variable concentrations (Zhang, Lei, Yin, Chen, Li, Wang, et al.,
2011). Yan, Wei, Qiao, Shao, Zhao, Zhang, et al.
(2010) prepared Co3O4-graphene nanocomposites
by microwave irradiation of a mixture of cobalt
nitrate hexahydrate and GO nanosheets in the
presence of urea in a domestic microwave oven
for 10 min. Similarly, Co3O4- (Chen, 2010a) and

ZnO-graphene nanocomposites (Liu et al., 2011)


have been synthesized by this method.

Atomic Layer Deposition (ALD)


While the solution-based methods offer potentially
low cost and scalability, they have the disadvantage in precisely manipulating the deposition of
metal oxides (Meng et al., 2011). Atomic layer
deposition (ALD) is a layer-by-layer technique
of gassolid synthesis route having two sequentially cyclic self-limiting half-reactions. Metal
oxide-graphene nanocomposites with excellent
uniformity and conformity can be obtained by
precisely controlling the deposition parameters
at the atomic level. Meng et al. (2011) have prepared TiO2-graphene nanocomposites by ALD
method. Graphene nanosheet powders were
first loaded into a commercial preheated ALD
reactor. Then, titanium isopropoxide (TTIP) and
deionized water were introduced into the ALD
reactor in an alternating sequence to perform
ALD of TiO2. TiO2-graphene nanocomposites
were produced in six sequences at three growth
temperatures namely 150, 200 and 250 C, as the
phase change, morphology and deposition rate
of the TiO2 nanoparticles deposited on graphene
sheets depend on the growth temperature. From
the SEM images in Figure 8 of a TiO2-graphene
nanocomposite grown at 150 C, the deposited
layer is uniform and smooth. At 200 C, the layer
is smooth except the presence of some nanoparticles of around 15 nm, while at 250 C this layer
becomes totally rough and bumpy.
The absence of diffraction peaks in the XRD
spectrum of TiO2-graphene nanocomposites deposited at 150 C suggests that the as-deposited
TiO2 is amorphous. However, the sample grown
at 200 C exhibits a clear peak at 25.28o as well
as two weak but uncertain peaks at 38.58o and
48.05o, corresponding to the (101), (112), and
(200) planes of anatase TiO2, respectively. Furthermore, more peaks are visible in the XRD spectra
of the sample grown at 250 C with increased

205


Metal Oxide-Graphene Nanocomposites

Figure 8. High-magnification SEM images of (a) pristine graphene nanosheets, and ALD-TiO2 on graphene nanosheets at 150 C (b), 200 C (c), and 250 C (d). ( 2011 IOP Publishing Ltd. Reprinted with
permission from Meng, Geng, Liu, Li, & Sun, 2011)

intensities, corresponding to different characteristic planes of anatase TiO2 as denoted in Figure


9. Such observations in XRD spectra prove the
phase transitions in the growth of ALD-TiO2 with
temperature.
Alles et al. (2011) also found a similar trend
in surface morphology during the synthesis of
HfO2-graphene nanocomposites. Smooth nanocomposites were prepared at 180 C, while nanocomposites with comparatively rougher surface
were obtained by a two-step (170/300 C) growth
process as evidenced from the AFM imaging. This
is due to crystallization of HfO2 during the film
growth at higher temperature.
Meng, Geng, Liu, Li & Sun (2010) adopted
this approach to prepare amorphous and crystalline SnO2-graphene nanocomposites.

206

Ex Situ Method
In the ex situ approach, metal oxide NPs are synthesized separately and then attached to the surface
of graphene nanosheets via linking agents that
utilize covalent or noncovalent interactions such
as Van der Waals interactions, hydrogen bonding, stacking or electrostatic interactions. In
this approach, either the metal NPs or graphene
nanosheets or both are modified with functional
groups. This self-assembly based method can
overcome the incompatibilities between metal
oxide and graphene nanosheets. Compared to
in situ growth, better control of the distribution,
size, and feeding amount of the metal oxide NPs
on graphene nanosheets can be achieved by this
method (Bai & Shen, 2012).


Metal Oxide-Graphene Nanocomposites

Figure 9. XRD spectra of ALD-TiO2-graphene nanocomposites prepared at 150, 200, and 300 C. (
2011 IOP Publishing Ltd. Reprinted with permission from Meng, Geng, Liu, Li, & Sun, 2011)

Non-Covalent Interactions
Metal oxide-graphene nanocomposites can be
synthesized by non-covalent interactions such as
electrostatic interactions, layer-by-layer assembly
between the metal oxide NPs and the graphene or
GO moiety (Yang et al., 2010a; He et al., 2010;
Bai & Shen, 2012; Li, Wang, Liu, Liu, Ou &
Yang, 2011; Zhang, Chen, Zhang, Huang, Chen,
Yang, et al., 2011).

Electrostatic Interactions
Electrostatic interactions between metal oxide and
GO/graphene nanosheets are utilized for the preparation of metal oxide-graphene nanocomposites.
GO and graphene are negatively charged due to
ionization of the oxygen functional groups present
on their surface. The net negative charge is used

to assemble them with positively charged metal


oxide NPs through electrostatic interactions. Yang
et al. (2010a) have synthesized Co3O4-graphene
nanocomposites by this method. They have first
modified the oxide NPs by surface grafting of
3-aminopropyltrimethoxysilane (APS) to make
the oxide surface positively charged. The modified oxide NPs were assembled with negatively
charged GO by electrostatic interactions. Under
optimal conditions, almost all the GO and modified oxide NPs co-assembled to give a transparent
aqueous solution. Finally, the resulting aggregates
were reduced with hydrazine hydrate to give
Co3O4-graphene nanocomposites. The overall
procedure for the synthesis of Co3O4-graphene
nanocomposites can be schematically represented
as in Figure 10.
However, precise control of the size of the
NPs is still a challenge using this method. An-

207


Metal Oxide-Graphene Nanocomposites

Figure 10. Fabrication of Co3O4-graphene nanocomposites including (1) modification of the Co3O4 by
grafting aminopropyltrimethoxysilane (APTS) to render the oxide surface positively charged, (2) hybrid
assembly between positively charged oxide nanoparticles and negatively charged graphene oxide by
electrostatic interactions and (3) chemical reduction (2010 Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim. Reprinted with permission from Yang, Feng, Ivanovici, & Mullen, 2010a)

other disadvantage of this process is that since


the metal oxide NPs are attached to the GO or
graphene nanosheets by electrostatic interaction,
they may be easily leached out during application
(He et al., 2010).

Layer-by-Layer (LBL) Self-Assembly


LBL self-assembly is also an effective method
for the synthesis of metal oxide-graphene nanocomposite films. Such films are generated by
alternating layers of graphene nanosheets with
the metal oxide component. The simplicity and
thickness controllability at the nanoscale range are
the major advantages of this process. Moreover,
the blending of two components into composites
and the fabrication of composites into films can

208

be carried out simultaneously by this method


(Bai & Shen, 2012). Yao, Wu, Cui, Fang & Yu
(2010) applied this technique for the preparation
of GO/PDDA/TiO nanocomposite films (PDDA:
poly[diallyldimethylammonium], TiO: Titania)
through photothermal and photocatalytic reduction
of GO to graphene nanosheets by TiO nanosheets.
First, a high quality GO/PDDA/TiO hybrid film
was fabricated on glass substrate through alternating LBL self-assembly of GO and TiO nanosheets
with PDDA. The obtained hybrid film was then
illuminated under the 300 W Xe lamp through
a shadow mask for desired time intervals. The
photoconductive patterns were formed at the area
where it was exposed to the light illumination due
to the photodegradation of PDDA and reduction
of GO nanosheets. The graphene nanosheets acted


Metal Oxide-Graphene Nanocomposites

Figure 11. Schematic illustration of the fabrication procedure of LBL assembled multilayered composite
films consisting of PDDA/GO/PDDA/TiO (DIW: deionized water). (2011 The Royal Society of Chemistry. Reprinted with permission from Yao, Wu, Cui, Fang, & Yu, 2010)

as electrodes on the glass substrate due to their


high electronic conductivity, the TiO nanosheets
acted as photo conversion medium in the hybrid
films and ultrafast photocatalytic electron transfer
took place between TiO nanosheets and graphene
nanosheets to yield GO/PDDA/TiO nanocomposite films. A schematic illustration of this synthetic
procedure is summarized in Figure 11.
Li et al. (2011a) synthesized 3D multilayer
architectures of (PDDA/PSS-graphene/PDDA/
MnO2)10 using negatively charged species of
poly(sodium-4-styrenesulfonate) (PSS) modified graphene, negatively charged MnO2 sheets
and positively charged PDDA as building blocks
(Figure 12).
However, as this method is also based on noncovalent interaction of oppositely charged species,
the problem of leaching out during application
time still persists.

Covalent Interactions
In covalent interactions, GO nanosheets rather than
graphene is preferred in immobilizing metal oxide
NPs due to its large amount of oxygen containing
groups that facilitate the linkage with other functional groups. The main advantages of this technology are its capability of pre-defining the loading
amount of metal oxide and the metal oxide NPs

that can be grafted on graphene surface firmly by


covalent bonding. He et al. (2010) have synthesized
Fe3O4-graphene nanocomposites by this method.
They have first functionalized Fe3O4 NPs sequentially with tetraethyl orthosilicate (TEOS) and
3-aminopropyltriethoxysilane (APTES). Fe3O4
NPs tended to form nanoscale aggregates during
surface functionalization because of the magnetic
dipolar interaction among the magnetite NPs. With
the aid of N-hydroxysuccinnimide (NHS) and
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
(EDC), a GOFe3O4 hybrid was obtained from the
condensation reaction between amino groups of
APTES-modified Fe3O4 and carboxylic groups
of GO nanosheets through amide bond formation
(He et al., 2010). The functionalized Fe3O4 NPs
and GO nanosheets were then mixed together and
stirred for 1 h at 80 C. The Fe3O4-graphene nanocomposites were isolated by magnetic separation
and washed with water (Figure 13).
The functionalization of GO nanosheets with
magnetic Fe3O4 NPs was confirmed by FTIR
spectroscopy (Figure 14). The peak at 1723 cm-1
corresponds to C=O stretching in carboxylic acid
and carbonyl moieties terminating GO nanosheets.
After amidation reaction, three new characteristic peaks of the amide carbonyl group for GO
Fe3O4 hybrid at 1647 (CONH amide band I),
1533 (NH amide band II), and 1455 cm-1 (CN

209


Metal Oxide-Graphene Nanocomposites

Figure 12. A schematic view of the synthesis of multilayer films on substrate (2011 The Royal Society
of Chemistry. Reprinted with permission from Li, Wang, Liu, Liu, Ou, & Yang, 2011b)

Figure 13. Schematic illustration of the synthesis of Fe3O4-graphene nanocomposites by covalent interaction

stretching of amide) appeared, suggesting that


Fe3O4 nanoparticles were linked to GO surface
by covalent bonding.
To confirm the covalent bonding between
Fe3O4 NPs and GO nanosheets via amidation

210

reaction, GO nanosheets were mixed with NH2terminated Fe3O4 NPs at 80 C for 1 h in the
absence of NHS and EDC and the mixture was
subjected to an external magnetic field. The
solution remained brown colored even though it


Metal Oxide-Graphene Nanocomposites

Figure 14. FTIR spectra of (a) GO and Fe3O4-GO nanocomposites with different ratios of Fe3O4 to GO:
(b) 1:9 and (c) 1:1 (2010 Elsevier Ltd Reprinted with permission from He, Fan, Ma, Zhang, Leung,
& Chan, 2010)

had been influenced by a magnet for a long time.


In the presence of NHS and EDC, the resultant
Fe3O4-GO nanocomposites could be immediately
separated from the reaction mixture once a magnet was placed nearby and the solution became
colorless, indicating the formation of chemical
bonding between Fe3O4 NPs and GO nanosheets
through amide bond. They have further reduced
Fe3O4-GO nanocomposites by NaBH4 to form
Fe3O4-graphene nanocomposites. The chemical
changes brought by NaBH4 reduction were investigated by X-ray photoelectron spectroscopy (XPS).
The C1s XPS spectrum of GO with peak-fitting
curves is displayed in Figures 15a and b. The
peaks at 284.9, 287.0, 288.3, and 289.3 eV were
assigned to carbon atoms in C=C/CC, CO, C=O
and OC=O, respectively. This result suggested
that GO nanosheets contained large numbers of
functional groups on their surface. In comparison
to GO nanosheets, the C1s XPS spectrum of Fe3O4-

graphene nanocomposite obviously exhibited


a decreased intensity for peaks corresponding
to GO functional groups, indicating effective
deoxygenation of GO nanosheets. Besides, an
additional component at 286.1 eV was observed
for Fe3O4-graphene nanocomposites resulting
from the formation of CN bonding during the
amidation reaction. The reduction of Fe3O4-GO
nanocomposites to Fe3O4-graphene nanocomposites was also evidenced by UVVis absorption
spectra (Figure 15c). GO nanosheets exhibit a
characteristic peak at 224 nm corresponding to
* transitions of aromatic CC bonds. For
Fe3O4-graphene nanocomposite, the absorption
peak blue-shifted to 213 nm, suggesting that the
covalent attachment of Fe3O4 onto the GO surface
by the amidation reaction changed the structure
of GO nanosheets. After reduction, the Fe3O4graphene absorption peak red shifted to 248 nm

211


Metal Oxide-Graphene Nanocomposites

Figure 15. C1s XPS spectra of (a) GO, (b) Fe3O4-graphene nanocomposites, and (c) UVVis spectra of
GO, Fe3O4-GO nanocomposites and Fe3O4-graphene nanocomposites. (2010 Elsevier Ltd. Reprinted
with permission from He, Fan, Ma, Zhang, Leung, & Chan, 2010)

as the electronic conjugation in the graphene was


restored by the reduction with NaBH4.
Zhang et al. (2011a) reported another route
to synthesize Fe3O4 graphene nanocomposites
by covalent bonding. Fe3O4 nanoparticles were
modified with hydrophilic 2,3-dimercaptosuccinnic acid (DMSA), followed by assembling
them onto polyethylenimine (PEI)-grafted GO
nanosheets via the formation of amide bonds
between COOH groups of DMSA molecules and
amine groups of PEI.

Applications of Metal OxideGraphene Nanocomposites


Graphene and graphene-based nanocomposites
are the most appealing matrices because of their
unique properties and potential applications as
electronic and photonic devices (Du, Skachko,
Barker & Andeei, 2008; Wang, Ang, Wang, Tang,
Thong & Loh, 2010; Eda, Fanchini & Chhowalla,

212

2008; Xia, Muller, Lin, Garcia & Avouris, 2009),


sensing platforms (Schedin et al., 2007; Jung,
Cheon, Liu, Lee & Seo, 2010; He et al., 2010)
and clean energy systems (Wang, Zhi & Mullen,
2008; Yin et al., 2010). In particular, graphene or
a few-layers graphite decorated with metal oxides
including titania, cobalt oxide, zinc oxide or tin
oxide have been intensively investigated, and
have shown promising applications in capacitors,
batteries, catalysis, and biomedicine. Moreover,
graphene and its metal oxide nanocomposites have
also found applications in wastewater purification
(Chandra & Kim, 2011; Sun, Cao & Lu, 2011).

Li-Ion Battery
Currently for Li ion battery (LIB), there is a great
demand to provide high efficiency, low cost and
green solution for energy storage devices. Graphite
with a theoretical capacity of 372 mAhg-1 is commonly used as anode material for LIB (Winter,


Metal Oxide-Graphene Nanocomposites

Besenhard, Spahr & Novak, 1998). Graphene has


great potential as anode for Li-ion battery due to
its special Li ion storage mechanism i.e. lithium
can be stored on both sides of graphene sheets
and also on the edges of graphene sheets, which
eventually leads to larger practical capacity than
that of graphite. Even though graphene shows
higher capacity, it fails after a few cycles due to
restacking of graphene sheets. To overcome this
issue, metal oxide-graphene nanocomposites e.g.
SnO2-graphene (Kim, Kim, Park, Gwon, Seo, Kim,
et al., 2010; Wang, Choi, Li, Yang, Nie, Kou, et
al., 2009) and Fe3O4-graphene (Zhou, Wang, Li,
Zhang, Li, Wu, et al., 2010) electrodes have been
applied in LIB. Among these, SnO2-graphene
nanocomposites, prepared by hydrothermal
method, shows the first reversible specific capacity of 729 mA h g1 at a current density of 50 mA
g1, and remains at 646 mA h g1 after 30 cycles
at a current density of 100 mA g1 (Fan, 2013).
In these type of hybrid electrodes, incorporation
of graphene helps to maintain the conductivity.
Moreover, direct growth of metal oxide NPs on
graphene sheets improved the contact between the
NPs and the 3D network of graphene; this comprehends efficient conduction of charge carriers.

capacitors, commonly used electrode materials


are metal oxides and conducting polymers which
offer higher specific capacitance compared to the
porous carbon based EDLC electrode. But the
high cost and low conductivity of these materials
have restricted their applications. Therefore, metal
oxide-graphene nanocomposites are efficiently
being used as hybrid materials for supercapacitors. Recently, many research groups reported
nanocomposites of graphene with metal oxide
such as ZnO (Zhang, Chen, Zhang, Huang, Chen,
Yang, et al., 2009), SnO2 (Li et al., 2009), Co3O4
(Yan, Wei, Qiao, Shao, Zhang & Fan, 2010), MnO2
(Chen, Zhu, Wu, Han & Wang, 2010; Yan, Fan,
Wei, Qian, Zhang & Wei, 2010), and RuO2 (Kim,
Luo, Cruz-Silva, Cote, Sohn and Huang, 2010)
as electrodes for supercapacitors. MnO2-graphene
composite electrode shows a high specific capacitance of 310 F g-1 at 2 mV s-1 (228 F g-1 at
even 500 mV s-1), about 3 times higher than that
given by pristine graphene or MnO2 (Figure 16).
Higher specific capacitance is achieved for this
metal oxide-graphene composite as compared to
pure graphene electrode.

Supercapacitors

Waste water generated by industrial, domestic


and agricultural activities can be purified by technologies like adsorption, precipitation, membrane
separation, amalgamation, and ion-exchange.
To remove the pollutants from dilute solutions,
adsorption which is economical and efficient
over other technologies is widely used. Graphene
and its composites have large surface area and
present surface functional groups, which make
them an attractive adsorbent candidate for water
purification. Due to difficulty large scale synthesis, graphene materials have limited applications
in water purification. To avoid these problems,
several attempts have been made to synthesize
graphene and its nanocomposites (Stankovich et
al., 2006; Zhou, Huang, Qi, Wu, Xue, Boye, et al.,
2009). Recent literature survey reveals that, for the

Supercapacitors are alternative energy storage


devices with high rate capability, low cost and
long cycle life. There are two types of supercapacitors based on their charge storage mechanism: 1)
electrical double layer capacitor (EDLC), which
stores energy via electrostatic process, 2) pseudocapacitors, which store energy through surface
redox reaction.
Generally in EDLC, porous carbon materials
are used as electrode materials but this restricts
their applications in high power density supercapacitors due to their low conductivity. Graphene
is one of the best candidates with high electrical
conductivity and large surface area to replace the
porous carbon materials for EDLCs. In pseudo-

Water Purification

213


Metal Oxide-Graphene Nanocomposites

Figure 16. Graphene-based supercapacitor. (2013 American Chemical Society. Reprinted with permission from He Chen Li Zhang Fu Zhao & Xie 2013)

removal of arsenic from water, magnetite-graphene


and ferric hydroxide-GO nanocomposites were
successfully used (Chandra et al., 2010; Zhang
et al., 2010a). Zhang, Liu, Zhang, Wei, Jang, &
Oh (2012) synthesized high crystalline Fe3O4graphene composite via one-step thermolysis
reaction which proved to be a promising sorbent
material for wastewater treatment. The zero band
gap of graphene helps to display high catalytic
activity for the degradation of organic pollutants
when traditional photocatalysts, such as ZnO,
TiO2, and CdS, are incorporated with graphene.

Photovoltaic Cells
In the dye sensitized solar cells (DSSC), graphene
and its composites with metal oxide NPs are used
to enhance the interface area of dye/electrolyte,
to increase the loading of dye molecules and
to improve the conductivity of electrons at the
semiconductor layer to compete with charge
recombination. In TiO2-graphene, the band gap
of graphene is about 4.4 eV situated between the

214

conduction band of TiO2 (anode) and the work


function of ITO (cathode), which allows for the
fast collection of electrons at the anode to suppress charge recombination (Tang, Lee, Xu, Liu,
Chen, He, et al., 2010). Under visible light irradiation, valence electrons are directly excited from
graphene into the TiO2 conduction band at the
TiO2-graphene interface giving rise to separated
electronhole pairs. Moreover, the enhancement
of light scattering at the photoanode is achieved by
forming TiO2-graphene porous network. A TiO2
graphene nanocomposite based dye sensitized
solar cell is depicted in Figure 17. By using TiO2
rGO nanocomposites as photoanode, a photo
conversion efficiency (PCE) of about 47% is
obtained, which is at least 39% higher as compared
to the commercial P25 TiO2 (Yang, Zhai, Wang,
Chen & Jiang, 2010). Ng, Iwase, Bell, Kudo &
Amal (2010) and Ng et al. (2011) achieved higher
photoelectrocatalytic efficiencies by fabricating
the composites of graphene and TiO2, WO3, or
BiVO4 via a one-step UV or visible light inducedphotocatalytic reduction process.


Metal Oxide-Graphene Nanocomposites

Figure 17. Metal oxide-graphene nanocomposite


based dye sensitized solar cell. (2010 American
Chemical Society. Reprinted with permission from
Yang, Zhai, Wang, Chen, & Jiang, 2010c)

Biomedicine
Nanostructured metal oxides have recently attracted much attention due to their high surfaceto-volume ratio, high surface reaction activity,
high catalytic efficiency, and strong adsorption
ability. Great efforts have been devoted to explore
potential applications of metal oxide-graphene
nanocomposites in biomedicine. The graphene
nanosheets act as an advanced support with large
surface area for immobilizing different target biomolecules. Moreover, it effectively promotes the
electron transfer between electrode and analytes.
Iron oxide-graphene nanocomposites are widely
studied for magnetically targeted drug delivery,
photothermal therapy, and magnetic resonance
imaging (Yang et al., 2009). Yang, Zhang, Ma,
Huang, Wang & Chen (2009) reported the use
of iron oxide-graphene nanocomposites as drug
carriers. Recently, Chen, Zhang, Zhang, Deng
& Zhang (2011) demonstrated the use of magnetic aminodextran coated iron oxide-graphene
nanocomposites as the T2-weighted magnetic
resonance imaging (MRI) contrast agent for in
vitro cell labeling. Taking advantages of the su-

perparamagnetic properties, high drug loading


capacity, and strong optical absorption of iron
oxide-graphenePEG (PEG=polyethylene glycol)
nanocomposites, they demonstrated magnetically
targeted drug delivery and photothermal therapy
(PTT) in vitro to selectively destroy cancer cells
in highly localized regions.
SiO2-graphene nanocomposite was successfully used for highly selective and sensitive detection of cancer biomarkers (Myung, Solanki, Kim,
Park, Kim & Lee, 2011).
Copper and copper oxide-based nanomaterials were of great interest for their extensive applications in gas sensing and biosensing. Qian,
Ye, Xu & Le (2012) demonstrated the excellent
electrocatalytic activity of Cu2O-graphene nanocomposites towards glucose. The electrocatalytic
activity of Cu2O-graphene nanocomposites was
compared with graphene and Cu2O alone as
electrode modifying material for oxidation of
glucose in 50 mM NaOH solution (Figure 18). The
nanocomposites exhibited typical current response
for the oxidation of glucose (curve 3), while no
obvious oxidation peak for glucose can be found
at the graphene (curve 2) and Cu2O nanoparticles
(curve 1) modified electrodes. Such excellent
electrocatalytic activity of the Cu2O-graphene
nanocomposites may be attributed to high catalytic
active sites for the glucose oxidation provided by
the Cu2O nanoparticles and increase of the efficient
electroactive surface area due to introduction of
graphene, which also provides conductive bridges
for accelerating the electron-transfer.

FUTURE RESEARCH DIRECTIONS


Metal oxide-graphene nanocomposites are promising materials for a number of applications in
many fields. The properties and efficiency of the
composites are dependent on a number of factors
such as size, shape, distribution of the NPs, thickness of the GO/graphene nanosheets, purity of the

215


Metal Oxide-Graphene Nanocomposites

Figure 18. Linear sweep voltammetry of Cu2O (curve 1), graphene (curve 2), and Cu2O-graphene composites (3) modified GC electrodes in 50 mM NaOH solution containing 2 mM glucose at a scan rate of
50 mV s1 ( 2012, ESG. Reprinted with permission from Qian, Ye, Xu, Le, 2012)

material, etc. Though a number of methods have


already been reported for the synthesis of metal
oxide-graphene nanocomposites, the development
of a method bridging several aspects such as cost
effectiveness, eco-friendly, control of properties,
etc. is still a challenge. The development of a
process that can fulfill all these requirements and
which can be utilized for large scale production of
such composites is a promising research area. The
interaction mechanism and structural-properties
relationship between the metal oxide NPs and
graphene sheets need to be studied from both
theoretical and experimental aspects so as to help
future developments in this area. The composites
are studied for applications in a number of fields.
However, there may be some more fields in which
they have the possibility of potential applications.
Proper study in this regard may open up a new
window for practical applications of these composites in different fields.

216

CONCLUSION
GO and graphene nanosheets have been utilized
as a very good support for incorporating metal
oxide NPs. A number of procedures are studied
for the synthesis of metal oxide-graphene nanocomposites. These composites have applications
in various fields. Further proper and systematic
studies in this area will open up new directions
for large scale production of such nanocomposites
for practical applications and new fields in which
these composites can be efficiently used.

ACKNOWLEDGMENT
The authors thank the DST New Delhi, the CNRS,
the Universit Lille1 and Nord Pas de Calais
region for financial support and also the Director, CSIR-North East Institute of Science and


Metal Oxide-Graphene Nanocomposites

Technology Jorhat, India for the interest in this


work. PS acknowledges CSIR, New Delhi, India
for Senior Research Fellowship grant.

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KEY TERMS AND DEFINITIONS


Aggregation of Nanoparticles: Nanoparticles
bind each other to form larger aggregates.
Ex Situ Method: A method in which different
precursors are generated separately and then mixed
together to generate the final product.
Graphene Oxide: Oxidized form of grapheme.
Graphene: A single layer of sp2 hybridized
carbon atoms closely packed into a two dimensional honeycomb lattice.
In Situ Method: A method in which all the
reactions take place in the same reacting vessel
to give the product.
Metal Oxide: Compounds of metal with
oxygen.
Metal Oxide-Graphene Nanocomposites:
Hybridized form of metal oxide nanoparticles
and graphene nanosheets.

225

226

Chapter 11

In2X3 (X=S, Se, Te)


Semiconductor Thin Films:

Fabrication, Properties, and Applications


Mahieddine Emziane
Masdar Institute of Science and Technology, UAE
Rahana Yoosuf
Masdar Institute of Science and Technology, UAE

ABSTRACT
Indium chalcogenide thin film semiconductor compounds In2X3 (with X being a chalcogen atom, i.e., S,
Se, or Te) are important materials in many current technological applications such as solar cells, microbatteries, memory devices, etc. This chapter reviews the recent progress in In2X3 (X = S, Se, or Te) thin film
research and development, with a particular attention paid to their growth and processing methods and
parameters, and the effects that these have on the films microstructure. The intimate relationship between
their fabrication conditions and the resulting physico-chemical and functional properties is discussed.
Finally, results pertaining to the fabrication and characterization of these thin film materials, as well
as the main devices and applications based on them are also highlighted and discussed in this chapter.

INTRODUCTION
Remarkable advances have taken place during the
past few decades in semiconductor materials and
devices. The semiconductor compounds of In2X3
family, where X is S, Se or Te have attracted particular interest in recent years due to their promising technological applications including a wide
variety of devices. Among the important In2X3
devices that have been developed are solar cells
(Yu et al, 1998), dry cells (Dalas & Kobotiatis,

1993), photochemical cells (Hara et al, 2000), solid


state batteries (Julien et al, 1985), phase change
memory devices (Lee & Kang, 2005; Lee & Kim,
2005; Hirohata et al, 2006), thin film strain gauge
(Desai et al, 2005a), gas sensors (Desai, et al,
2005b), etc. Some In2X3 compounds can be used
in Schottky diodes, capacitors, heterojunctions,
and micro batteries (Kobbi, B., et al, 2001), and
they also have a potential application as passivating layer for III-V semiconductor devices (Barron

DOI: 10.4018/978-1-4666-5824-0.ch011

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


In2X3 (X=S, Se, Te) Semiconductor Thin Films

1997). Many of the devices based on In2X3 have


already found their way into industry.
A number of books, book chapters, and
topical reviews are dedicated to semiconductor
compounds such as II-VI, III-V and group IV
(Adachi, 2005; Ahrenkiel, 1993; Chu & Chu,
1995; Shay & Wernick, 1975). However there is
no review on In2X3 semiconductor compounds
available in the literature. This article reviews the
status of research on In2S3, In2Se3 and In2Te3 thin
films, and focuses on their fabrication methods
and functional properties. It also summarizes the
recent advances in their relevant applications in
many devices.
The interest in In2S3 thin films has increased
during the last decade or so because of the high
potential demonstrated by this material. With
optimal physical properties, this material can meet
the requirements for use as a window material or
a buffer layer for photovoltaic device structures
(Barreau et al, 2003). In2S3 can be used as an
effective replacement for CdS in Cu(In,Ga)Se2
(CIGS) based solar cells (Spiering et al, 2003).
Though the highest conversion efficiency in thin
film solar cells has been reported for CIGS with
CdS buffer layer, it is desirable to replace CdS
with cadmium free buffer layers for environmental reasons (Hariskos et al, 2005; Naghavi et al,
2003a; Naghavi et al, 2003b; Sakata, 2000; Lee,
et al, 2007).
Indium selenide (In2Se3) is another promising
In2X3 material. In thin film form, it has valuable
optical and electrical properties and is thus of
interest for low-cost photovoltaic applications
(Sahu, 1995; Lakshmikumar & Rastogi, 1994;
Brahim-Otsmane et al, 1994; Hasehawa & Abe,
1982; Jayakrishnan et al, 2008). This is because
of its high absorption coefficient as well as optimum energy band gap, suitable for solar energy
conversion (Former et al, 1985; El-Sayed, 2004;
Lee, et al, 2008; Bernede & Marsillac, 1997;
Segure, et al, 1983; Qasrawi, 2007; Konagai et
al, 1996). In2Se3 can also be used as a precursor
for the growth of CuInSe2 absorber layer (Kim et

al, 2005). The hexagonal layered structure of this


material allows the change of the physical properties without destroying the initial structure. This
characteristic makes it feasible to use this material
in batteries (Balkanski, 1998; Julien, et al, 1989).
In2Te3 is also drawing attention due to its photoconducting properties (Guettari et al, 2003; Bose
& De Purkayastha, 1981) and for its switching and
memory effects (Balevicius et al, 1975; Balevicius
et al, 1976; Afifi et al, 1996). The research and
development of highly sensitive In2Te3 as gas
detector and thin film screw gauge have attracted
growing interest (Desai et al, 2005a; Afifi et al,
1995; Lakshminarayana et al, 2002; Hussein &
Nagat, 1989).

FABRICATION PROCESSES
The properties of In2X3 thin films usually show
a strong dependence on the film deposition
technique and conditions as well as on the postdeposition heat treatment. The deposition method
also has an impact on the overall fabrication cost.

In2S3 Thin Films


Deposition Methods
A wide range of methods exist for growing In2S3
thin films. In2S3 thin films are deposited using
both wet and dry processes. Prominent among
them are low pressure metal-organic chemical
vapor deposition (MOCVD) (Horley et al, 1999),
atomic layer chemical vapor deposition (ALCVD)
(Spiering et al, 2003), spray pyrolysis (Jayakrishnan et al, 2005; Bhira et al, 2000; Pai et al, 2005),
chemical bath deposition (CBD) (Barreau et al,
2002), atomic layer epitaxy (ALE) (Yousfi, et
al, 2000a; Yousfi et al, 2000b; Asikainen et al,
1994), photochemical deposition (Kumaresan et
al, 2002), annealing of elemental layers (Barreau
et al, 2000a; Barreau et al, 2001), physical vapor
deposition (PVD) (Barreau et al, 2002; Trigo

227


In2X3 (X=S, Se, Te) Semiconductor Thin Films

et al, 2008; Timoumi et al, 2006), sulfurisation


of metallic electrodeposited indium (Herrero &
Ortega, 1988; Data et al, 2008), etc.
CBD method which uses chemical reactions in
solution as the driving force for the film growth
is a low-cost method which can operate at low
processing temperature and provides large area
deposition (Bernede et al, 2002). CBD involves
the controlled precipitation from the solution of
a compound on a suitable substrate. The method
consists of a complex metal ion of interest, a source
of chalcogen ions, and a stability equilibrium that
provides a concentration of ions small enough for
controlled homogenous precipitation of material
in thin film form on the substrate. Various reports
on the deposition of In2S3 thin films from a bath
containing In salt and thioacetamide as sulfide
ion source were published (Yahmadi et al, 2005;
Yamaguchi et al, 2003). The most common In
salt used for the preparation was indium chloride
(InCl3) (Asenjo et al, 2004). Indium sulfate was
another alternative (In2(SO4)3) (Lokhande et al,
1999). Nanoporous network of In2S3 platelets
were grown by CBD method on ITO substrates
(Puspitasari et al, 2008).
Attempts were made to deposit In2S3 thin films
by using successive ionic layer adsorption and
reaction (SILAR) method (Kundakci, 2008). This
method is mainly based on the immersion of the
substrate into separate cation and anion precursor
solutions and rinsing between every immersion
with ion exchanged water. Indium chloride could
be used as cationic precursor and sodium sulfide
could be used as anion source (Ranjith, et al, 2007).
Utilization of triethanolamine and hydrazine
hydrate complexed indium sulfate and sodium
sulfide as precursors resulted in nanocrystalline
In2S3 thin films (Pathan, et al, 2005).
A systematic study of -In2S3 thin films grown
by ALCVD was carried out by various groups.
ALCVD is based on the surface reaction of the
precursors. The main advantage of this deposition
method is that it allows the deposition of highly
homogenous thin films with controlled layer

228

thickness. The non metal precursors used in the


preparation were usually hydrides like H2S for S
and metal halides (especially chlorides) or alkyls
were used as In precursors (Naghavi, 2004). A
recent result showed that -deketonate precursors such as indium acetylacetonate gave better
results and seemed to be more favorable for low
temperature deposition (Yousfi et al, 2001).
MOCVD, a chemical vapor deposition process
based on metal organic precursors, is the most
advantageous method for the thin film growth of
In2S3. MOCVD provides a single in-line process
without interruption for device fabrication, independent control of III/VI ratio, and easy mass
production. The synthesized dimeric indium
thiolates were used as single source precursors
for MOCVD, while trimethyl-indium and t-butylthiol were applied as precursor sources in another
work (Spiering et al, 2009). Thin films of -In2S3
were deposited using low pressure MOCVD with
air stable precursors In(S2CNMenButyl)3 and
In(S2CNMenHexyl)3 (OBrien et al, 1998).
Better quality In2S3 films can be obtained by
electrochemical synthesis, where the deposition
of In and S may take place by direct electronic
exchange with the substrate. Electrochemical
methods have demonstrated the possibility of obtaining In2S3 films by electrodeposition followed
by a sulfurisation process (Herrero & Ortega,
1988), one-step cathodic deposition (Asenjo et
al, 2005), and two-step electrodeposition (Tacconi & Rajeshwar, 1998). Electrodeposition is
a liquid phase method with the advantage of
up-scaling feasibility to large substrate areas for
production. In2(SO4)3 was used most commonly
as the In source and Na2S2O3 as the S source
(Abdel Haleem & Ichimura, 2008). Tacconi &
Rajeshwar (1996) reported another approach for
the electrosynthesis of In2S3 films over a sulfurmodified gold substrate by an alternating use of
two baths; one contained sulfide ions and the other
contained In ions (Tacconi & Rajeshwar, 1998).
Electro chemical synthesis gives a wide range of
parameters that can be changed independently to


In2X3 (X=S, Se, Te) Semiconductor Thin Films

Figure 1. Schematic showing the different phases of In2S3

obtain better quality films (Pandey et al, 1996).


(see Figure 1)
With respect to industrial integration, the high
vacuum growth techniques are attractive and their
main advantage is the easy control of the growth
rate through various process parameters. There
were a number of reports on the preparation of
In2S3 by PVD either by sequentially evaporating In
and elemental S (Nagavi et al, 2003b; Barreau et
al, 2000; Robles et al, 2005) or by co-evaporation
(El-Nahass et al, 2006; Gall et al, 2005; Barreau
et al, 2009). Single source vacuum evaporation
using pre-synthesized powder of In2S3 was also
employed for thin film preparation (Timoumi
et al, 2005; Timoumi et al, 2006). However, an
additional annealing step was required to form
high-quality In2S3 (Spiering et al, 2004; Yoosuf
& Jayaraj, 2005).
It is possible to use spray pyrolysis to deposit
In2S3 with good uniformity, which also allows the
production of large area films. In this method, gas
atomizes the solution containing the constituents
into a fine mist with a spray nozzle. The reactant
in the droplets is pyrolysed on the heated substrate.
Ideally, a pyrolysis reaction leads to the deposition of films of the desired compound while other
products evaporate as gaseous species. In2S3 thin
films prepared by the spray pyrolysis technique
showed optoelectronic properties that depend
on the deposition parameters. By controlling the
deposition parameters, In2S3 thin films could be
produced with optimized optoelectronic properties (John et al, 2003). Most of the research
works on In2S3 prepared by spray pyrolysis were
carried out by using InCl3 and thiourea as start-

ing materials but there were reports on the use of


other precursor materials as well. Indium acetate
and thiourea were used as precursor compounds
(Calixto-Rodrigueza et al, 2005) for the In rich
In2S3 thin films that are optimal for application
as a window material in photovoltaic structures.
Indium nitrate and thiourea were used as precursor
solutions in the preparation of In2S3 thin films in
another work (John et al, 2005).
Reports of In2S3 thin films successfully synthesized by other techniques like spray ions layer
gas reaction (ILGAR) (Allsop et al, 2005), RF
sputtering (Hariskos et al, 2004), modulated flux
deposition (MFD) (Asenjo et al, 2007; Sanz et
al, 2006), etc. are also available in the literature.
Kumaresan et al. reported the growth of In2S3
thin films by photochemical deposition from an
aqueous solution by means of UV illumination
(Kumaresan et al, 2002).

Post-Deposition Annealing
The annealing temperature is a critical parameter
for In2S3 window layers, as excessive temperature
results in copper diffusion and decreased solar
cell performance (Gall et al, 2005; Spiering et
al, 2004; Bedir & Oztas, 2008). Several groups
have optimized the annealing conditions that
are favorable for the good crystalline growth of
In2S3 for PV applications. Timoumi et al. (2006).
optimized the annealing temperature and duration
in nitrogen and air atmospheres (Timoumi et al,
2006). The as-deposited films were amorphous
in nature and the annealing treatment induced the
crystallization of the layers, but showed additional

229


In2X3 (X=S, Se, Te) Semiconductor Thin Films

In6S7 phase for higher annealing temperature. For


different annealing times, the chemical analysis
showed the presence of these same elements, but
with less S content. The film annealed in air was
found to be optimum for PV applications.
The structural and electrical properties of
In2S3 films prepared using the spray pyrolysis
technique were shown to improve considerably
through annealing at 400C. The films showed
good homogeneity with 80% transmission (John
et al, 2006). Annealing at 500C led to the phase
transition from InS to In2S3 in the films grown
by photochemical deposition (Bedir & Oztas,
2008). For the In2S3 thin films prepared by thermal
evaporation, the as-deposited In2S3 thin films were
non-crystalline, while they were found to have a
polycrystalline nature after being annealed for
1 h at both 150C and 200C (El-Shazly et al,
1998). Similar characteristics were observed for
the films prepared by the MFD procedure. After
being annealed for one hour at 150C, the films
showed the polycrystalline -phase, which had
amorphous nature while as-deposited (Guillen
et al, 2004).
A two-stage process consisting of the evaporation of In in the first step followed by an annealing
in S atmosphere in the second step for the growth
of In2S3 was reported (Yoosuf & Jayaraj, 2005).
In2S3 films synthesized by solid-state reaction of
sequentially deposited In and S thin layers were
followed by annealing in argon atmosphere for
30 minutes and it was observed that in order to
obtain the films with the best crystalline properties
and the best purity, the optimum temperature was
400C (Barreau et al, 2000a). The same results
were obtained for studies carried out on different
substrates such as glass coated with SnO2, In2O3
and ZnO transparent conductive oxides (TCOs)
(Barreau et al, 2000b). The effect of annealing
on CBD grown In2S3 films was studied under
nitrogen (Yahmadi et al, 2005) and argon atmospheres (Sandoval-Paz et al, 2005). In both cases
all annealed thin films showed an improvement
in their structural and morphological properties.

230

Ranjith et al. (2007) observed a color change


from yellow for the as prepared sample to reddish
black after annealing due to the formation of In
rich phases (Ranjith et al, 2007). The color was
changed from yellow to orange after annealing
in nitrogen atmosphere for electrodeposited In2S3
films (OBrien et al, 1998).

Effect of Deposition Parameters


The processing parameters such as deposition
temperature, deposition time, pH of the solution,
thioacetamide (TA) concentration, and the nature
of substrates have strong influence on the properties of thin films grown by CBD method. The
deposition temperature between 50C and 70C
was found optimum for the growth of good quality films (Barreau et al, 2002; Trigo et al, 2008;
Lokhande et al, 1999). The studies showed that well
crystallized films with good surface homogeneity and roughness were deposited on glass slides
using [TA] = 0.10 M, pH = 2.35 and tD = 60 min
as deposition conditions (Bernede et al, 2002).
However the films grown on SnO2/glass substrate
under the same deposition conditions contained
the unwanted In6S7 phase even after annealing
treatment. Kamoun et al. (2001) claimed that they
obtained the best crystalline -In2S3 films on SnO2/
glass substrate out of the different substrates they
used for the spray pyrolysis deposition (Kamoun
et al, 2001). Na free lime glass could be used to
prevent diffusion of Na in the films during the
synthesis process (Barreau et al, 2002b).
The substrate temperature (Ts) has a significant
influence on the stoichiometry of the grown In2S3
films. The films deposited at Ts < 300C were S
rich, whereas the films deposited at Ts > 300C
were rich in In (Revathi et al, 2008). It was proved
that the rate-determining step for the film growth
at the higher substrate temperature was not identical to that at lower temperature (Yamaguchi et
al, 2003). The best deposition rate for ALD films
was obtained at a deposition temperature of 180C
with a source temperature of 135C (Naghavi


In2X3 (X=S, Se, Te) Semiconductor Thin Films

et al, 2004). The studies on the variation of Ts


during the deposition of In2S3 as the buffer layer
in a CIGSe/In2S3 solar cell structure showed that
the chemical nature of the interface was changed
as Ts varied (Gall et all, 2005). The increase of
Ts resulted in a higher Cu content in the buffer
layer thus affecting all of the solar cell parameters
and decreasing its overall conversion efficiency.
The preparation temperature, i.e., the temperature of the deposition bath (Tp) also has influence in the film growth. It was found that films
prepared by spray pyrolysis at Tp > 400C were
either amorphous or nanocrystalline, whereas
those prepared at Tp 400C were polycrystalline
(Calixto-Rodrigueza et al, 2005). Prolongation of
reaction time in CBD process led to the formation of nanocrystalline In2S3 films together with a
slight increase in the crystallite size (Yamaguchi
et al, 2003).

In2Se3 Thin Films


Deposition Methods
A number of deposition methods for growing
single-phase In2Se3 thin films have been reported,
and the popular ones are evaporation techniques
such as elemental evaporation, (Thomas, 1992;
Watanabe et al, 1989), evaporation of indium
selenide powder (Kenawy et al, 1990), electron
beam evaporation (Manno et al, 1995), flash
evaporation (Persin et al, 1972), but also pulsed
laser deposition (PLD) (Ye et al, 1998; Hrdlicka
et al, 2007), spray pyrolysis (Bouzouita et al,
2002), molecular beam epitaxy (MBE) (Emery
et al, 1992; Ohtsuka et al, 1999), chemical vapor
deposition (Park et al, 2003), MOCVD (Gysling
et al, 1992; Gordillo & Calderon, 2003), etc.
The growth of In2Se3 by the evaporation of
In2Se3 powder or co-evaporation of In and Se
was a classical deposition method. Single-phase
-In2Se3 with a preferential orientation along (113)
plane was obtained by the evaporation of In2Se3
powder (Marsillac et al, 1995). Single-phase

-In2Se3 oriented along (004) plane was grown by


the evaporation of -In2Se3 crystals at a substrate
temperature of 200C (Qasrawi, 2006). The films
deposited by the co-evaporation of In and Se
showed (006) as the preferred oriention (Amory
et al, 2003a; Amor et al, 2003b). Clavijo et al.
(2009) prepared -In2Se3 thin films with a band
gap of 1.47 eV by co-evaporation and they could
convert it into -In2Se3 films with a band gap of
2.11 eV by thermal annealing in Se atmosphere
(Clavijo et al, 2009).
The formation of In2Se3 thin films by solidstate reaction induced by annealing of vacuum
deposited In-Se stack layers was reported (Marsillac et al, 1996; Bernede et al, 1997; Emziane
et al, 1997). Promising IV characteristics were
obtained with TCOs such as SnO2 and ZnO for
-In2Se3 grown by a similar method (Marsillac
& Bernede, 1998). Bindu et al. (2002) obtained
polycrystalline -In2Se3 with a band gap of 2.09
eV by annealing stack layers consisting of amorphous Se and In, where Se was deposited by
CBD and In by vacuum evaporation (Bindu et
al, 2002). Negative conductivity was observed
at room temperature in In2Se3 films prepared by
annealing In/Se bilayer at 100C (Sreekumar et
al, 2006). The films produced by the evaporation of In2Se3 powder and by solid-state reaction
between In and Se sequentially deposited were
compared, and it was indicated that the best films
were obtained by the solid-state reaction followed
by annealing (Marsillac et al, 1995). The growth
of In2Se3 polycrystalline thin films by electron
beam evaporation was also reported (Manno et
al., 1995; Micocci et al, 2006).
The most common chemicals used for the preparation of In2Se3 thin films by CBD were indium
chloride (InCl3), tartaric acid, hydrazine hydrate
and sodium selenosulphate (Lincot et al, 1999;
Ortega-Borges, 1993; Gorer & Hodes, 1994). The
reaction between these chemicals in an aqueous
alkaline medium at room temperature gave In2Se3
(Asabe et al, 2008). Pathan et al. (2005) reported a
modified chemical bath deposition (M-CBD) for

231


In2X3 (X=S, Se, Te) Semiconductor Thin Films

the growth of In2Se3 thin films. In M-CBD, each


reaction was followed by rinsing, which enabled
the heterogeneous reaction between the solid phase
and the solvated ions in the solution (Pathan et al,
2005). They obtained nanocrystalline films with
a band gap of 2.5 eV higher than the usual band
gap obtained by CBD (2.35 eV). The resistivity
of M-CBD prepared films also showed a higher
value of electrical resistivity of 106 cm, while
the CBD films had a typical resistivity of the order
of 102 cm (Asabe et al, 2008).
Electrodeposition technique is another lowcost, simple and low-temperature liquid phase
method used for the growth of In2Se3. The lowtemperature deposition minimizes the inter diffusion of the materials at the grain boundaries
(Park et al, 1998) so that the films of high quality
can be produced for device applications such as,
heterojunctions devices, switching devices, etc.
(Massaccesi et al, 1996; Valdes et al, 2008). Highly
crystalline films were obtained by the electrodeposition technique from a mixture of InCl3 and
SeO2 in an aqueous solution (Gopal et al, 2005). A

TiO2/In2Se3/CuInSe2 heterojunction was reported


with electrodeposited In2Se3 (Valdes et al, 2008).
Nathan et al.(2003) developed an electrochemical
method analog to atomic layer deposition allowing
the formation of one atomic layer at a time. In2Se3
thin films and nanostructures were fabricated by
this method (Vaidyanathan et al, 2003).
Spray pyrolysis was chosen by several authors
to prepare In2Se3 thin films due to its simplicity
and versatility. It was observed that the properties of In2Se3 sprayed films depended mainly on
Se/In molar concentration ratio in the solution
(Bouzouita et al, 2002). Spray pyrolysis was
also used as a first step of a low-cost two-stage
process for preparing In2Se3 thin films. The spray
pyrolysed In203 thin films were allowed to react
with elemental Se vapor at atmospheric pressure
in nitrogen ambient to yield In2Se3. (see Figure 2)
The most important aspect of MBE is the slow
deposition rate, which allows the films to grow
epitaxially. In2Se3 epitaxial films were successfully
grown on (001) GaAs substrates by MBE. From
the studies carried out by Ohtsuka et al. (2000),

Figure 2. Raman scattering spectrum of -In2Se3 thin films (Emziane et al, 1997)

232


In2X3 (X=S, Se, Te) Semiconductor Thin Films

it was revealed that the crystallinity of the films


was improved by using slightly disoriented (001)
GaAs substrates (Ohtsuka et al, 2000). In2Se3
epitaxial films with zincblende structure were
successfully grown on (001) GaAs substrates at
low substrate temperatures and polycrystalline
In2Se3 films with defect wurtzite structure were
grown at high substrate temperatures (Okamoto
et al, 1997).
Polycrystalline In2Se3 films with a columnar
structure were grown by different groups (Huang
et al, 2008; Lyu et al, 2010) using MOCVD.
Homogeneous -In2Se3 thin films with a band
gap of 1.87 eV were reported using single source
MOCVD. Afzaal et al. (2005) fabricated In2Se3 by
low pressure (LP) MOCVD and aerosol assisted
(AA) CVD processes using a single source approach (Afzaal et al, 2005). By employing AACVD
they were able to reduce the growth temperature
to a few hundred degrees below that needed for
the growth by LP MOCVD. The growth of In2Se3
by AACVD was also reported (Park et al, 2003).
The MOCVD growth of In2Se3 films using the
volatile In[SeC(SiMe3)3]3 as the single-source
precursor was also reported (Cheon, J., et al,
1995). Another MOCVD method proposed to
prepare single-phase In2Se3 films was by using
dual-source precursors, trimethylindium (TMI),
and hydrogen selenide (H2Se) (Chang, 2007).
The flow rate of these two precursors could be
adjusted independently to obtain a different VI/
III ratio (Chang, 2007).
There were also reports of the growth of In2Se3
thin films by PLD, but the prepared films were
found to be amorphous in nature (Hrdlicka et al,
2007). Beck et al. (2007) reported the growth of
vacancies ordered in screw form (VOSF) and
layered In2Se3 thin films by laser back ablation
(LBA), which was analog to PLD (Beck et al,
2007). The growth by electron beam evaporation of polycrystalline -In2Se3 with a band gap
of 1.41 eV [111], and the growth of -In2Se3 by
flash evaporation of powdered single crystals of
In2Se3 [110] were reported.

Post-Deposition Annealing
The difficulty with the deposition of In2Se3 is often the coexistence of more than one InSe phase
and the amorphous nature of the as-deposited
films. Indeed, most of the deposition methods
yield amorphous thin films, and a heat treatment
of the as-deposited films is necessary to obtain
polycrystalline In2Se3 thin films. Such an annealing also helps eliminate the unwanted phases and
favors the existence of single-phase In2Se3.
The already mentioned evaporation techniques
and solid state reaction between the sequentially
deposited In and Se were completed by a postdeposition annealing treatment. The In-Se stacked
layers deposited were subjected to an annealing
treatment in vacuum in closed ampoules to obtain
single-phase -In2Se3 with a good texture. The
optimized annealing conditions were found to be
300C for 24 hours to obtain nearly stoichiometric
-In2Se3 thin films (Gordillo & Calderon, 2003;
Marsillac et al, 1996; Bernede et al, 1997). But an
annealing under a dynamic vacuum at 250C for
6 hours was necessary at the end of the process
to sublimate the Se deposited on the sample surface during the annealing. In a subsequent work
(Emziane et al, 1997), an open reactor was used
with an argon atmosphere during the annealing
process and the excess Se left was removed from
the samples following this process. The optimum
annealing temperature was 400C for a duration
of 30 minutes. It was also proved from studies
carried out by Emziane et al. (1999) that a higher
annealing temperature was needed to start the
crystallization for the films deposited with Se/In
ratio greater than 1.5 (Emziane & Le Ny, 1999).
Studies were carried out using nitrogen as a substitute for argon as the annealing atmosphere and
resulted in good crystalline quality -In2Se3 thin
films with the same annealing conditions, i.e.,
400C and 30 minutes (Marsillac et al, 1999).
Single-phase -In2Se3 films were obtained using
the same technique for an annealing temperature
of 587C for 40 minutes followed by quenching

233


In2X3 (X=S, Se, Te) Semiconductor Thin Films

to room temperature instead of a slow cooling


(Emziane et al, 2000c). The temperature was high
enough to obtain the single-phase which can
be kept at room temperature due to the quench
(instead of changing to the room temperature
stable -phase).
The post-deposition annealing was essential
for the process of preparation of -In2Se3 thin
films from InSe stacked layer also (Bindu et al,
2002), and the best crystalline films obtained for
an annealing temperature of 400C. The postdeposition annealing treatment also resulted in the
conversion of as-deposited -In2Se3 into -In2Se3
(Amory et al, 2003b). The -In2Se3 phase grown
by co-evaporation of In and Se was converted
into the -In2Se3 phase through thermal annealing at 550C in Se atmosphere. Sreekumar et al.
(2006) observed a phase transition from -In2Se3
to -In2Se3 upon annealing of In-Se stacked layers
at 400C (Sreekumar et al, 2006). Single-phase
-In2Se3 was formed on annealing at 200C with
grain orientations along (410) and (500), and
annealing at 400C resulted in the formation of

highly crystalline -In2Se3 having grains oriented


along (110) and (006). (see Figure 3)
The preparation of -In2Se3 thin films by
electron beam evaporation also necessitated
post-deposition annealing treatment in argon
atmosphere at a temperature of 427C (Manno et
al, 1995). Herrero et al. studied the (1987) effects
of post-deposition annealing on the properties of
the films prepared by alternate electrodeposition
of In and Se from separate baths. They observed
that when the temperature ranged between 300C
and 500C, the films were of -phase. At 600C
the thin films lost some Se and the ratio Se/In
decreased (Herrero & Ortega, 1987).

Effect of Deposition Parameters


The substrate temperature usually influences the
phase in which the In2Se3 films grow. At lower
substrate temperatures around 300C, the deposition of the -phase occur, while temperatures
higher than 500C resulted in the -phase. It was
also found that the samples deposited at tempera-

Figure 3. XRD patterns of -In2Se3 thin films (Emziane et al, 2000c)

234


In2X3 (X=S, Se, Te) Semiconductor Thin Films

tures ranging from 300C to 550C grew with a


mixture of -In2Se3 and -In2Se3 phases (Clavijo
et al, 2009).
The study of Julien et al. (1986) showed that
In2Se3 thin films grew with a good stoichiometry
at a substrate temperature around 187C in the
-phase, but were seen remained in the -phase
above 207C (Julien et al, 1986). The influence
of the substrate temperature and post-deposition
vacuum heat treatment on the properties of the
films was examined by Persin et al. (1972) for
films prepared by flash evaporation. Large agglomerates of defects were present in the films
formed at lower substrate temperatures, which
could not be removed by post-deposition heating
(Persin et al, 1972).
From the studies of In2Se3 prepared by electrodeposition from indium sulfide and selenious
acid solutions at 22 and 82C, it was found that
the higher deposition temperature caused a better
crystallization while the as-grown films showed a
small excess of elemental Se (Valdes et al, 2008).
(see Figure 4)

Figure 4. Cross-section of -In2Se3 thin films grown


on (a) glass substrate, (b) SnO2-coated glass, and
(c) gold-coated glass (Marsillac et al, 1999)

In2Te3 Thin Films


Deposition Methods
Techniques such as thermal evaporation, electron
beam evaporation, molecular beam epitaxy, and
flash evaporation are some of the methods used
for the growth of In2Te3 polycrystalline thin films.
Most of the researches on In2Te3 were done
on thin films grown by evaporation technique
(Rousina & Yousefi, 1990; Barua & Goswami,
1970; Peranantham et al, 2007; Mathur, 1981).
-In2Te3 thin films were grown by the sequential
evaporation of In and Te layers (Emziane et al,
1999) and by co-evaporation (Guettari et al, 2003).
-In2Te3 thin films were obtained by annealing the
films prepared by thermal evaporation (Hegab
et al, 1998). Balevicius et al. (1975) studied the
nanosecond switching and memory behavior
of In2Te3 thin films prepared by direct thermal

evaporation (Balevicius et al, 1975; Balevicius et


al, 1976). The films deposited by the electron beam
evaporation technique were found to be of -In2Te3
phase and no -In2Te3 phase could be observed
(Balevicius et al, 1976). Golding et al. reported

235


In2X3 (X=S, Se, Te) Semiconductor Thin Films

the studies of the molecular beam epitaxial growth


of In2Te3 (Golding et al, 1989), and the formation of In2Te3 thin films by the evaporation from
independent sources of elementary components
in a quasi-closed volume on InAs substrates was
also reported (Bezryadin et al, 1998). Thin films
of In2Te3 were prepared by the conventional flash
evaporation method onto freshly air cleaved single
crystal surfaces of NaCl (Desai et al, 2005). In2Te3
for use in thin film screw gauge (TFSGs) and gas
sensors was grown by flash evaporation (Desai et
al, 2005a; Desai et al, 2005b).
The depositions of In2Te3 by electrodeposition from propylene carbonate solutions containing InCl3 and tri-n-butyl phosphine telluride
(Wynands & Cocivera, 1988), and -In2Te3 by
the direct synthesis of this compound from In
and Te in a calorimetric bomb with an electrical
micro-furnace, were also reported (Lavut et al,
1997). Pure cubic In2Te3 films were deposited by
AACVD of a single-source precursor, {In(m-Te)
[N(iPr2PTe)2]}3 (Shivram et al, 2006).

Deposition Parameters and


Post-Deposition Annealing
The influence of the annealing conditions on
vacuum evaporated In2Te3 thin films was studied. The as-deposited indium telluride films had
an amorphous structure but annealing at 200C
resulted in the -phase polycrystalline structure
(Hegab et al, 1998), whereas the as-deposited
amorphous films showed InTe phase only on annealing at 250C in another study (Peranantham et
al, 2007). From the compositional analysis it was
observed that the films annealed at 400C were
In rich In2Te3 films due to the re-evaporation of
Te at elevated temperature. Similar observations
were also made by Emziane et al. (1999) where
the films subjected to a post-deposition annealing
at 390C resulted in Te deficient films. The results
were the same regardless of the annealing atmosphere (i.e. argon or nitrogen), and an annealing

236

temperature higher than 420C resulted in surface


oxidation (Emziane et al, 1999).
The effect of substrate temperature on the
preparation of thin films of In2Te3 was studied and
a substrate temperature of 180C was found to be
optimum for the preparation of In2Te3 thin films
(Balevicius et al, 1976). The growth of -In2Te3
at 227C was reported by Guettari et al. (2003).
It was also reported that a substrate temperature
of 200C favored the growth of -In2Te3 on glass
substrates, while -In2Te3 thin films were obtained
at 250C on NaCl substrates (Bezryadin et al,
1998).

PROPERTIES OF In2X3 THIN FILMS


An understanding of the fundamental properties
of thin films is an important prerequisite for the
fabrication of device quality materials. The film
functional properties depend on its chemical
composition and structure and the way it interacts
with its environment: light, electric and magnetic
fields, chemicals, mechanical force, heat, etc. This
section deals with the various properties of the
In2X3 thin films.

In2S3 Thin Films


Structural Properties
In2S3 is one of the In2X3 materials that crystallize
in cubic or hexagonal closed packed structure,
similar to II-VI compounds upon the replacement
of the divalent cation by the trivalent In. As one
third of the cation site remains empty, it causes a
defect structure (Becker et al, 1986). Three major
crystal modifications are known for In2S3 (Joint
Committee on Powder Diffraction, cards 5-731,
32-456, 25-390, 33-623). The low temperature
metastable -phase has a cubic structure with a
lattice constant a of 5.358 . It is a cubic closed
packed structure of sulfur, where 70% of the In
atoms are randomly distributed on octahedral


In2X3 (X=S, Se, Te) Semiconductor Thin Films

sites and the rest remain in tetrahedral sites (Diehl


& Nitsche, 1973). The -phase transforms irreversibly at 360 C to the -phase having a defect
spinal lattice (a = 10.73 ) in which eight of the
tetrahedral sites are occupied by In, and four are
randomly left empty (Kambas et al, 1985). Thus
the chemical formula of -In2S3 can be written
as [In(t)2/31/3]In2(o)S4 where (t), (o) and ()
represent the tetrahedral, octahedral and vacant
sites, respectively. Under certain conditions, a
high ordering of this vacancy at the tetrahedral
sites occurs, establishing a tetragonal super cell
containing spinel blocks along the c-axis (Kambas et al, 1981). This phase transition from the
tetragonal structure to the less ordered -phase
takes place at 420 C (Diehl & Nitsche, 1973;
Gilles et al, 1962). At a temperature of 754 C
-In2S3 is reversibly transformed to the -In2S3,
which has a layered structure with a hexagonal
unit cell (a = 3.85 , c = 9.15 ). The following
relation can be suggested for the phase transition
of In2S3.
Beside these phases, there is a high pressure
-phase, which is rhombohedral (a = 6.0561
and c = 17.5 ) (Joint Committee on Powder
Diffraction, card 33-624). Several reports were
published regarding the growth of different phases
of In2S3. The higher temperature cubic -phase
was observed in chemically deposited films onto
glass substrates as a mixture with the cubic -phase
(Gillen et al, 2004; Bayon & Herrero 2000). The
transmission electron microscopy (TEM) studies of CBD films showed that the initial growth
on glass corresponded to the -phase of In2S3
while the films deposited on FTO coated glass
substrate corresponded to the -phase (Lokhande
et al, 1999).
Among the different phase modifications,
-In2S3 is the stable form with a tetragonal structure
(Rooymans, 1959). Various groups studied the
structures of -In2S3 thin films by X-ray diffraction
(XRD) and scanning electron microscopy (SEM).
Cubic structures were reported for the CBD thin
films annealed under nitrogen atmosphere (Ber-

nede et al, 2002) and for films grown by SILAR


method (Kundkei et al, 2008). Films were found
to be composed of a mixture of the cubic and
-In2S3 phases for films grown by CBD technique
(Bayon & Herrero, 2000). The investigations of
films prepared by closed vapor evaporation showed
a combination of tetragonal and cubic structures
of -In2S3 phases at lower substrate temperatures
of less than 200 C (Revathi et al, 2008). XRD of
thermally annealed In2S3 films deposited by CBD
revealed that the thermal annealing on the films
produced the conversion of the cubic crystalline
phases to the tetragonal -phase and a crystalline reorientation of the latter phase (Gillen et
al, 2004). Similar characteristics were observed
for In2S3 prepared by annealing In in S pressure
(Benchouk et al, 2009).
Most of the as-deposited PVD films were noncrystalline and they were found to have polycrystalline nature belonging to the tetragonal -phase after
annealing (Timoumi et al, 2005; El-Shazly et al,
1998; Lee et al, 2009). Same trends were observed
for films obtained by some SILAR (Ranjith et al,
2007) and CBD (Bernede et al, 2002). Electrodeposition also required a subsequent annealing step
for best results (OBrien et al, 1998; Tacconi &
Rajeshwar, 1998), and it was also found that the
degree of crystallinity increased as the temperature
of annealing increased (Barreau et al, 2002; Barreau et al, 2000a; Yoosuf & Jayaraj, 2005; Revathi
et al, 2010). Indeed, the crystallinity increases
with increasing the annealing temperature as
well as the film thickness for -In2S3 deposited by
thermal evaporation (El-Nahass et al, 2006). The
increase of S concentration in the spray pyrolysis
also caused an increase in crystallinity.
In general, the (103) peak is the preferred
orientation for most of -In2S3 films that grow
in the tetragonal structure (Barreau et al, 2003;
Naghavi, 2003b; Sanz et al, 2006). But different
preferential orientations were observed by various
researchers depending on the method and substrate
used for the growth. The (109) preferential orientation was observed for films deposited by CBD

237


In2X3 (X=S, Se, Te) Semiconductor Thin Films

on TCO and glass substrates. The films prepared


by MFD presented different preferential orientations depending on the substrate used. On glass,
the films had a (103) preferential orientation, and
the films on TCO substrate exhibited the (109)
preferential orientation (Asenjo et al, 2007). The
preferential orientation was observed along (220)
plane for films prepared by spray pyrolysis (Pai
et al, 2005; John et al, 2005; John et al, 2006).
Guillen et al. (2004) reported that the (103) preferential orientation was achieved only when the S
source temperature was adjusted in a narrow range
between 220 and 230 C (Guillen et al, 2004).
Substrate temperature has a strong impact on
the film morphology and grain size. The surface
topology studies carried out by atomic force microscope (AFM) measurements on close spaced
evaporated films showed that the granularity was
improved by 25 nm with an increase in substrate
temperature (Revathi et al, 2008). A similar observation of variation in grain size with substrate
temperature was reported for the spray pyrolysed
films (Pai et al, 2005). The variation in grain size
by 20 nm was reported also by post-deposition
annealing (Revathi et al, 2010). A decrease in a
and c lattice parameters with substrate temperature
was observed for the films grown by close spaced
evaporation (Sotelo-Lerma et al, 2006).
The surface studies of In2S3 prepared by CBD
at room temperature showed a cauliflower-like
morphology, while the films deposited at a higher
temperature resulted in a fibrous structure (Yamaguchi et al, 2003). The film deposition at lower
reaction temperature was by the sedimentation of
particles formed in the bath, and the film growth
was by the heterogeneous precipitation on the
substrate at higher temperature. A microcrystalline
morphology was observed in the sample deposited by plasma-assisted co-evaporation (PACE)
at 350 C with an average grain size around 100
nm, while a nanocrystalline film morphology was
observed at lower temperatures with a reduction
in grain size to 10 nm at 100C (Sahu, 1995). A

238

significant variation in surface morphology with


the reaction temperature was also reported.
Deposition time also affects the morphology
of the films. The films prepared by CBD were
composed of nanometric round shape grains for
lower deposition time, whereas the films deposited
were composed of a porous layer formed by larger
and irregular agglomerates for higher deposition
time (Yahmadi et al, 2005). Similar growth stages
were reported by some other authors as well. The
layer grown at a shorter deposition time was constituted by rectangular-shaped crystallites whose
growth was combined with the sticking of large
colloidal agglomerates formed in the reaction
solution at longer deposition times. The number
and size of the agglomerates on the film surface
increased with deposition time (Asenjo et al,
2009). The presence of In6S7 phase caused some
fibre structures along with large lumps (Bernede et
al, 2002). Irregular shaped platelet-like structures
were obtained for films grown by CBD (Asenjo
et al, 2004) and different film morphology was
observed depending on the substrate used. On
glass the films were composed of large nanometric
round shape grains, whereas the films deposited
on PET and Arylite were composed of irregular
agglomerates (Bouguila et al, 1997).
The composition of the films usually depends
on the growth process. It was generally observed
that when the deposition was based on chemical
methods, the residual precursor elements were
found within the films. Typically, chlorine was
frequently detected in the films grown by ALD
with InCl3 precursor (Asikainen et al, 1994),
ILGAR (Allsop et al, 2005), and spray pyrolysis
(Hariskos et al, 1996; Vaidynathan et al, 2003). In
the case of CBD and electrodeposition, the layers
contained In(S, OH) compound (Bayon & Herrero,
2000; Kim & Kim, 1986; Datta et al, 2008). Sulfur
composition in excess of the stoichiometric value
in spray pyrolysed In2S3 films caused an increase
in the lattice parameters a and c (John et al, 2005).
Similar observations were reported with EDX studies for the films grown using a two-stage process


In2X3 (X=S, Se, Te) Semiconductor Thin Films

(Yoosuf & Jayaraj, 2005) with a suggestion that


the expansion of the lattice parameters was due
to the occupation by sulfur of the interstitial sites
of defect spinal structure.

Optical Properties
-In2S3 thin films exhibit a direct optical transition
with a band gap energy (Eg) around 1.98-2.3 eV
(Naghavi et al, 2003b; John et al, 2003; Guillen et
al, 2004; Nomura et al, 1991; George et al, 1998).
An indirect optical transition (with Eg = 2.2 eV)
was also reported (Kim & Kim, 1986; Timoumi et
al, 2006; Sterner et al, 2005). Several values greater
than 2.3 eV have been reported in the literature.
A higher band gap of 2.84 eV was obtained for
CBD grown films (Asenjo et al, 2004), and similar
values were reported for -In2S3 films deposited
on several kinds of TCO by PVD. A band gap
energy of ~2.6 eV was obtained for -In2S3 thin
films deposited onto glass substrates by CBD and
SILAR (Kundakci et al, 2008; Sanz et al, 2006).
Several authors studied a widening in the
band gap by an increase in oxygen content in the
films (Barreau et al, 2002c; Tacconi & Rajeshwar, 1998; Barreau et al, 2002b). An increase in
band gap was observed due to Na content in the
films, and this was explained by the fact that Na
increased the ionicity of the tetrahedral cationic
sulfur bonds which increased the optical band
gap. Some authors attributed the gap broadening
to an excess of S (Naghavi et al, 2004). The blue
shift of the optical transmission was interpreted
by the broadening due to an excess of S in the
bulk (Kim & Kim 1986). But contrary to these
reports, John et al. observed a decrease in band
gap when the S concentration increases (Pai et al,
2005). Some authors explained the broadening
of the optical band gap of In2S3 by quantum size
effect induced by the small grain size (Yasaki et
al, 1999). The higher band gap obtained for the
spray pyrolysed films was explained both by the
presence of oxygen and the quantum size effect
(Pai et al, 2005). The broadening or shift of the

short wavelength absorption of In2S3 thin films


was also explained by the presence of secondary
phases and disordered structure (Kamoun et al,
1998).
Higher band gaps were generally observed in
vacuum deposited In2S3 thin films after annealing (Timoumi et al, 2006; El-Nahass et al, 2006).
The band tails observed in the optical spectra of
vacuum deposited In2S3 thin films after air annealing were interpreted as defects introduced
by the thermal evaporation process (Timoumi
et al, 2006). In contrast, there were reports of a
decrease in band gap on annealing (Yousfi et al,
2001; Revathi et al, 2010). The sharp decrease of
energy band gap at higher annealing temperatures
could be explained by structural defects.
A strong effect of the film thickness on the
optical absorption coefficient and the band gap
energy was observed for films grown by MFD
where values above 3.0 eV were obtained for very
thin In2S3 films (Guillen et al, 2004).
A broadening of the band gap of the films
with the increase of substrate temperature up to
300 C was observed for evaporated films, and
further increase in substrate temperature caused a
reduction in band gap. The initial bad gap increase
was explained by the decrease of mid band gap
defects while the subsequent decrease was thought
to be due to the larger compositional deviations
in the films as indicated by the compositional
analysis. The band gap of the films deposited by
PACE was reduced by the increase in substrate
temperature (Sahu, 1995) and a red shift in band
gap was observed for In2S3 thin films on swift
heavy ion irradiation (Kumar et al, 2006).

Electrical Properties
The electrical properties of -In2S3 phase were
studied by Rehwald et al. (1965). They found it
to have a n-type electrical conductivity, however,
the conductivity strongly depended on the S concentration. A deficiency in S relative to the In2S3
stoichiometry increased the electron density, and

239


In2X3 (X=S, Se, Te) Semiconductor Thin Films

thus the n-type nature. It was also observed that


the annealing of In2S3 films in air or vacuum at
temperatures around 150 C for 2 hours resulted
in an increase in conductivity by more than an
order of magnitude.
The large increase in conductivity observed
for the spray pyrolysed films on annealing was
explained by the modification of the properties
of the grains or their boundaries by the presence
of oxygen (John et al, 2006).
For photovoltaic device applications, it is
essential to know the photosensitivity of the
material. The processing parameters such as
substrate temperature, reaction temperature, and
S/In concentration in the reaction solution have
influence on the film photosensitivity. The photosensitivity was found to be decreasing by an
increase in substrate temperature. The increase in
S concentration caused an increase in photosensitivity, while the increase in In concentration had
a negative impact (Pai et al, 2005). The increase
in reaction temperature during the sulfurisation of
In films to obtain In2S3 films showed an increase
in photosensitivity (Yoosuf & Jayaraj, 2005). The
post-deposition annealing of the spray pyrolysed
films led to the reduction in photosensitivity (John
et al, 2006).

The Presence of Other Elements


Recent investigations dealt with the effect of the
introduction of foreign atoms within In2S3. The
presence of Al atoms in the compound noticeably contributed to the growth and structure of
the deposited films. The presence of Al caused
an increase in adsorption of oxygen in the spray
pyrolysed films (Kamoun et al, 2001). The study
of Na containing -In2S3 films proved that the
introduction of Na in the -In2S3 crystalline matrix induced an increase of the lattice parameter
a and an increase of InS and NaS bond lengths
(Barreau et al, 2002d). Ag and Cl doping resulted

240

in samples with enhanced crystallinity and photosensitivity (Mathew et al, 2009; Cherian et al,
2010). The substitution of a third element also
helped in stabilizing the phases. The stabilization of -In2S3 at room temperature was achieved
through replacing about 510% of In atoms by
As, Sb or Bi (Pandey et al, 1996).
The partial substitution of In by another element like Al (Bhira et al, 1998; Couzinie-Devy
et al, 2010), or a partial substitution of S by O
(Hariskos et al, 1996; Brauger et al, 1996), were
widely accepted methods of making wide band gap
In2S3 films. Sn doping investigated by introducing Sn into the spray solution also resulted in a
widening of the optical band gap through oxygen
incorporation (Mathew et al, 2010).
The presence of a third element can lead to
drastic changes in the electrical properties. Indeed,
the conductivity was found to increase with Na
content. When Na was introduced in the crystalline
matrix, it created a disorder by the non-periodic
occupation of the tetrahedral sites and this could
explain the increase in electrical conductivity
(Barreau et al, 2002a). But reportedly when the Na
content was increased above a particular value, a
total filling of the tetrahedral sites resulted, leading
therefore to a perfectly ordered material having
a very low electrical conductivity (Barreau et al,
2003). The introduction of oxygen in the thin films
could modify the properties of grain boundaries,
which induced an increase in conductivity of the
films approximately by two orders of magnitude
(Barreau et al, 2002b). The effect of the substitution of S by O in -In2S3 films also induced an
increase in conductivity (Bessergenev et al, 1996).
The conductivity of the samples was enhanced
by five orders of magnitude through Sn doping
done by thermal diffusion for the films grown by
spray pyrolysis (Mathew et al, 2010). Sn doping of
In2S3 films also increased the conductivity of the
films prepared by chemical vapor phase transport
(Becker et al, 1986).


In2X3 (X=S, Se, Te) Semiconductor Thin Films

In2Se3 Thin Films


Structural Properties
In2Se3 is an interesting material because of its
polymorphism and related metal-ion defect structure. Though there are relatively five well known
phases , , , , and , there are only two basic
phases for this compound. One is the -phase that
crystallizes in a layer structure and is metastable at
room temperature but stable at temperatures higher
than 550 C, and the other is the -phase which is
stable phase at room temperature and crystallizes
in a defect wurtzite-like structure with one third of
the cation sites being vacant (Emery et al, 1992;
Ohtsuka et al, 1999; Ye et al, 1998b; Popovic et al,
1979; Pfitzner & Lutz, 1996; Manolikas, 1988).
Such structural vacancies behave as one atomic
species and should be arranged in a screw form
along the c axis (Ye et al, 1998a). (see Figure 5)
-In2Se3 with a rhombohedral structure is
metastable and can be obtained by heating
-In2Se3, that will transform back to -In2Se3 at
room temperature. -phase can be stabilized by Sb
doping which makes it stable (Eddike et al, 1998).
The -phase is found to be stable above 750 C

(Marsillac et al, 1995). The different phases and


their properties are given in Table 1.
The -In2Se3 phase with an anistrophic structure was reported by De Groot et al. (2001) and
Jasinky et al. (2002). Although the conditions of
deposition are similar to that of the -phase, doping is necessary to obtain and stabilize -In2Se3
thin films at room temperature. However, the
-phase transforms to -phase on annealing at
higher temperatures (Eddike et al, 1998). -In2Se3
has a flake like structure, whereas -In2Se3 has a
columnar structure (Huang et al, 2008).
There were studies carried out to understand the
phase transition during the preparation. Annealing
In/Se bilayer films at lower temperature resulted in
the formation of In6Se7 and -In2Se3 phases. The
growth of the -phase with a good stoichiometry
was observed at a substrate temperature around
187 C and shown to remain in the -phase above
187 C (Julien et al, 1986). The suitable annealing
temperature for the growth of single-phase -In2Se3
was found to be 200 C by another study, and a
phase transformation from -In2Se3 to -In2Se3 as
well as a structural re-orientation of planes was
also observed at an annealing temperature of 400
C (Sreekumar et al, 2006). A high Se/In ratio in
amorphous multilayers or a high Se overpressure

Figure 5. Photoluminescence spectra of a -In2Se3 thin film at different temperatures [Marsillac et al,
1999].

241


In2X3 (X=S, Se, Te) Semiconductor Thin Films

Table 1. The characteristic phases of In2Se3 films


Phase

a ()

c ()

Structure

Characteristic

4.025
4.025

19.235

Hexagonal

Stable

28.762

Rhombohedral

Stable

4.0157

28.33

Rhombohedral

Metastable

7.1286

19.382

Hexagonal

Stable

8.09

19.8

Hexagonal

metastable

hexagonal

Stable at higher
temperatures

4.014

during the annealing of amorphous films was


found to promote the formation of the singlephase -In2Se3 (Emziane et al, 2000a; Bernede
et al, 1997). A high Se overpressure during hot
depositions resulted in the -phase (Emziane et
al, 1999; Ohtsuka et al, 2001). At substrate temperatures ranging from 300 to 550 C, the In2Se3
films grew with a mixture of the -In2Se3 and
-In2Se3 phases (Amory et al, 2003b).
XRD studies showed that the -In2Se3 films
were highly orientated along the (006) plane
(Afzaal et al, 2005; Afifi et al, 2001). To improve
the crystallinity, it was suggested to remove the
excess of Se by the heat treatment of the asdeposited films at temperatures above 300 C in
flowing nitrogen (Emziane et al, 1999). The same
observations were reported for films prepared by
vacuum evaporation of InSe crystals (Ates et al,
2008). The solution temperature was found to
influence the crystallinity for the electrodeposited
films (Valdes et al, 2008). Another suggestion for
improving the crystallinity of the films prepared
by electrodeposition was to increase the concentration of InCl3 in the reaction solution (Gopal et
al, 2005). A similar observation was reported by
another group that improved the crystallinity of
In2Se3 films by increasing the In concentration
during the fabrication process of In2Se3 films by the
stacked elemental layer (SEL) technique (Deepa
et al, 2006). The growth of In2Se3 films on AlN
buffer layers also resulted in a better crystallinity
(Chang et al, 2007).

242

9.646

The morphology of the In2Se3 films depends


on the deposition parameters and the substrate
on which the film is grown. Investigations using reflection high-energy electron diffraction
(RHEED), Raman spectroscopy, and SEM showed
that low growth temperatures (500 C) resulted
in the formation of a zincblende structure, and at
high temperatures (> 540 C) the films grew in a
defect wurtzite structure on GaAs (001) substrates
(Okamoto et al, 1997). Similar structural characteristics were observed for MOCVD films grown
at different temperatures. XRD analysis revealed
that In2Se3 had a wurtzite structure at a growth
temperature below 450 C, while a rhombohedral
structure was obtained above 450 C (Huang et al,
2008). SEM showed a vertical columnar structure
of -In2Se3 on Si (111) substrates (Huang et al,
2008; Chang et al, 2007), and a horizontal lamellar
structure on Si (100) substrates (Chang et al, 2006).
The film morphology was observed to improve
by introducing an AlN buffer layer for the films
grown by MOCVD (Chang et al, 2007). The CBD
grown films appeared to be made of small grains
with an average size of 21nm (Asabe et al, 2008).
AFM measurements showed that the phase of
the In2Se3 thin films and their thickness significantly affect their morphology. The and phases
grown by the same method showed different visual
appearances, and it was found that the increase
of the film thickness affected both the average
roughness and the average grain size (Amory et
al, 2003b). Furthermore, the grain size and the


In2X3 (X=S, Se, Te) Semiconductor Thin Films

growth rate were drastically increased with the


increase in substrate temperature (Lyu et al, 2007).

Optical Properties
In2Se3 films have a high optical absorption coefficient and a direct band to band type optical
transition. The band gap of -In2Se3 at room
temperature is estimated to be in the range 1.7-2
eV (Lyu et al, 2010; Lyu et al, 2007), while the
band gap of -In2Se3 is in the range of 1.2-1.3 eV
(Qasrawi et al, 2001; Emziane et al, 2000c). A
direct band gap of 1.55 eV was obtained for the
-phase (Julien et al, 1986) and 1.75 eV for the
-phase (Eddike et al, 1998).
A higher band gap of 2.35 eV was reported
for all the films prepared by CBD at room temperature showing a n-type conduction mechanism
(Asabe et al, 2008; Hankare et al, 2008). A band
gap of 2.5 eV was observed for indium selenide
compound formed with InSe, In2Se3 and In6Se7
phases (Pathan et al, 2005), and oxygen was also
present in the films. The annealing resulted in an

increase in optical band gap with temperature due


to the formation of the -In2Se3 phase (Afzaal et
al, 2005; Ates et al, 2008). A maximum band gap
of 2.08 eV was obtained for evaporated films annealed at 400 C. Contrarily, the band gap energy
of In2Se3 thin films prepared by SILAR seemed
to decrease with increasing temperature (Astam
et al, 2007).
A decrease in optical band gap was reported
by the substitution of Te for Se (Hrdlicka et al,
2007). A decrease in optical band gap was also
shown for electrodeposited In2Se3 films with an
increase in the concentration of InCl3 which, in
turn, caused an increase in the In content in the
films (Gopal et al, 2005).
The optical studies of In2Se3 films showed that
in the films grown in the -phase the transmittance was caused by photon absorption via states
within the gap, which contributed to the absorption process simultaneously with the fundamental
absorption. Whereas, in -In2Se3 films the photon
absorption was mainly through the fundamental
absorption mechanism (Amory et al, 2003b).

Figure 6. Photocurrent spectra of a 1m thick -In2Se3 film with the beam incident on the film (a), and
on the substrate (b) [Marsillac et al, 1999].

243


In2X3 (X=S, Se, Te) Semiconductor Thin Films

Photoluminescence spectra of single-phase


-In2Se3 films prepared by AP-MOCVD showed
an exciton emission at 580 nm (Lyu et al, 2010;
Lyu et al, 2007). Strong emissions were observed
at around 580 nm for films grown by MBE. The
emission consisted of three well-resolved lines
that were identified with a free exciton (Ex) and
bound excitons (Ix0, Ix1) at 579.2 nm (Ex), 579.8
nm (Ix0) and 580.2 nm (Ix1), respectively (Ohtsuka et al, 1999).
Photoluminescence investigation of films
prepared by annealing In/Se bilayer system at 100
C showed that as the In concentration increased
the intensity of the emission decreased sharply.
A strong emission with a maximum intensity was
observed at 802 nm, i.e. and energy of 1.55 eV
(Sreekumar et al, 2006).

Electrical Properties
It is reported that the type of conductivity of In2Se3
thin films depends on the annealing temperature.
Low temperature annealed films showed n-type
conductivity due to the presence of undiffused
In, while films annealed at higher temperatures
showed a p-type conductivity (Bindu et al, 2002).
Qasrawi et al. (2001) reported p-type -In2Se3 by
thermal evaporation followed by annealing at 200
C. The annealing increased the conductivity for
electron beam evaporated and vacuum evaporated
films (Manno et al, 1995; Afifi et al, 2001). The
conductivity was controlled by the grain boundaries and was very sensitive to oxygen contamination
(Bernede et al, 1997). The increase in the electrical
conductivity of the -phase after thermal treatment above 200 C and its irreversibility were
explained in terms of structural changes at high
temperatures (Julien et al, 1986).
The dark and photoconductivity were found to
be decreasing with temperature when annealing Se
and In stacked layers to obtain In2Se3 thin films.
The films synthesized by annealing the layers at
100 C resulted in a maximum photoconductivity,

244

while those formed at 450 C showed a minimum


photoconductivity (Bindu et al, 2002).
Negative photoconductivity in -In2Se3 thin
films was reported at room temperature (Sreekumar et al, 2006). The trapping of photo excited
carriers, recombination of minority carriers, and
capture of conduction band electrons ultimately
resulted in negative photoconductivity at room
temperature. The same work also revealed that
the photoconductivity of the films decreased
gradually and became negative upon increasing
In concentration.

The Presence of Other Elements


Doping with a third element helped in stabilizing
the -phase of In2Se3. Indeed, Zn doping was found
to stabilize -In2Se3 thin films at room temperature
(De Groot & Moodera, 2001). A small addition
of Ag also resulted in stabilizing the -In2Se3
phase formed both with and without capped films
(Eddike et al, 1998). Mn doping of -In2Se3 was
implemented by depositing a Mn layer of ~ 10
nm thickness prior to the co-evaporation of In and
Se, and the insertion of Mn in the film strongly
influenced its crystallization (Amory et al, 2006).
Doping of p-type -In2Se3 thin films by Cd
was observed to significantly alter their structural, electrical, and photoconductive properties
(Qasrawi et al, 2002). The hexagonal structure of
-In2Se3 was transformed to hexagonal InSe due
to a change in the lattice parameters, reflection
lines, and stacking orders upon Cd doping. The
values of the room temperature dark electrical
conductivity, carrier concentration, and Hall
mobility increased when the samples were doped.
However, the activation energy and the barrier
height at the grain boundaries were decreased
by Cd incorporation due to a higher density of
traps in the band gap and at the grain boundaries.
The temperature dependence of the electrical
conductivity and Hall mobility of S and Li doped
In2Se3 films were studied by Julien et al. (1986).


In2X3 (X=S, Se, Te) Semiconductor Thin Films

In2Te3 Thin Films


Structural Properties
A systematic XRD investigation of In2Te3 has
shown that there are two phases and , and the
former transforms to the latter at a temperature of
about 620 C. The high temperature disordered
-In2Te3 has a zinc blende structure (Hahn &
Klinger, 1949) with a lattice parameter of a =
0.6158 nm, whereas the low temperature -In2Te3
phase has a defect antifluorite structure with a
lattice parameter of a = 1.6548 nm. It has been
reported that the to transition is fully reversible.
These two phases are characterized by one-third
or two-thirds, respectively, of the In sub-lattice
sites being vacant.
The electron microscopic studies revealed that
the ordered -In2Te3 phase was actually composed
of two different ordered phases, namely -In2Te3-I
and -In2Te3-II (Karakostas & Economou, 1975).
The -In2Te3-II was a super structure of the
-phase with a high density of stacking faults.

The -In2Te3-I was of a hyper-stoichiometric


type, whereas the -In2Te3-II was of a hypostoichiometric type.
Different phase growths were observed with
respect to the substrate on which the films are
deposited. In2Te3 thin films grown on glass substrates were of -phase, whereas those formed
on crystalline NaCl substrates were of -phase
(Desai et al, 2005). The annealing of amorphous
In2Te3 films at 300 C resulted in polycrystalline
-In2Te3 films (Hegab et al, 1998).

Optical Properties
The direct band gap values reported in the literature for In2Te3 vary between 1.03 and 1.23
eV (Rousina & Yousefi, 1990; Peranantham et
al, 2007; Emziane et al, 1999; Afifi et al, 2000).
The transmittance and the band gap were found
to increase with the annealing temperature for
the vacuum evaporated films (Peranantham et al,
2007). (see Figure 7)

Figure 7. Absorption coefficient and band gap determination for a typical -In2Te3 thin film [Emziane
et al, 1999].

245


In2X3 (X=S, Se, Te) Semiconductor Thin Films

A band gap of 1.02 eV was reported for


-In2Te3, and the effect of annealing on the
band gap was interpreted by the density of states
(Hegab et al, 1998). A band gap of 0.8261 eV
for as-deposited films increased to 1.1480 eV
for films annealed at 250 C (Peranantham et
al, 2007).
A band gap of 1.19 eV was observed at room
temperature for -In2Te3 grown by MBE, and
the refractive index was found to be 2.85 at a
wavelength of 1100 nm (Bezryadin et al, 1998).

Electrical Properties
The electrical measurements show that In2Te3
films are p-type semiconductors (Matheswaran
et al, 2010). An irreversible change in electrical
conductivity was observed above 252 C hinting to the possibility of decomposition (Mathur
et al, 1981). DC electrical conductivity and
Hall effect measurements were carried out for
-In2Te3 thin films obtained by direct thermal
evaporation on sapphire substrates (Afifi et al,
2000). The variation of the DC electrical conductivity of In2Te3 thin films with temperature
was studied at different substrate temperatures
(Desai et al, 2006). The AC and dielectric
properties were also studied for In2Te3 films
grown by vacuum evaporation (Seyam, 2001;
Matheswaran et al, 2010). Both the dielectric
constant and the dielectric loss increased with
temperature and decreased with frequency in
the investigated range.
The junction studies showed that Ag, Sn, In
and Zn provided good ohmic contact for In2Te3
thin films (Desai et al, 2006). Finally, it was
shown that the thermoelectric power of -In2Te3
was temperature independent (Lakshminarayana
et al, 2002).

246

APPLICATIONS OF In2X3 THIN FILMS


In2S3 Thin Films
In2S3 is among the interesting candidates for the
replacement of CdS as buffer layer in Cu(In,Ga)
Se2 (CIGS) as well as in CdTe based solar cells
due to the possible gains in efficiency associated
with an increase in the short circuit current. To
avoid the toxic heavy-metal Cd containing waste
in the module production, a Cd free buffer layer
is desirable. Wide band gap (>2.5 eV) In2S3 thin
films have the potential to be used as a better
buffer layer with an improved light emission in
the blue region compared to CdS that has a band
gap of 2.4 eV.
The development of Cd free devices started in
1992 with an efficiency of about 9% and intensively
continued to the current efficiency level of 16.4%
(Naghavi et al, 2003a) for CIGS solar cell prepared
with atomic layer chemical vapor deposited In2S3
as a buffer layer. Comparing the results with those
using a CdS buffer layer, the initial difference was
about 4% absolute and became almost negligible
following more investigations (Hariskos et al,
2005). The ALD process for the In2S3 deposition
was up-scaled to a substrate size of 3030 cm2 with
best efficiencies up to 10.8% (Brahim-Otsmane
et al, 1994) and 12.9% (Spiering et al, 2004) for
such a CIGS sub-module. The cell parameters of
some CIGS modules with In2S3 buffer layers grown
by different methods are summarized in Table 2.
The best cell efficiencies obtained so far with
In2S3 buffer layers by PVD as an in-line compatible dry vacuum deposition method are: 15.2%
(Pistor et al, 2009) by depositing the buffer layer
on industrially developed Cu(In,Ga)Se2 absorber,
and 14.8% (Strohm et al, 2005) by depositing the
buffer and absorber layers in the same chamber
without vacuum breaking.
An efficiency of 7.9% was reported for the
buffer layer with a mixed ZnS-In2S3 composition
(Sakata, 2000), with the introduction of Zn in
proportion around 1% in the reaction mixture. The


In2X3 (X=S, Se, Te) Semiconductor Thin Films

Table 2. Performance of some CIGS modules of different sizes with In2S3 buffer layer grown using different methods
Deposition method

Efficiency (%)

JSC (mA.cm-2)

VOC (V)

FF (%)

Area (cm2)

ALCVD

16.4

31.5

0.665

78

0.1

ALCVD

14.9

30.8

0.648

74.7

0.5

PVD

15.2

29.8

0.667

75.6

0.528

PVD

14.8

31

0.65

71

0.48

Ultrasonic CSP

12.4

34.7

0.502

71

Not specified

CSP

9.5

48.2

0.588

33.5

0.009

ALCVD

12.9

45.7

0.278

72.6

714

ALCVD

10.8

29.5

0.591

62

724

Zn introduction favored the JV characteristics


of the cells, open circuit voltage (Voc), fill factor
(FF), and efficiency (). The deposition of a small
amount of zinc sulfide (ZnS) at the absorber/buffer
interface was also used to improve the performance
of CIGS solar cells. ZnS helped increase Voc of
the cell by approximately 20 mV and raised its
overall efficiency (Allsop et al, 2007).
An annealing step (~ 5-10 min at 200 C in air)
of the complete cell was shown to be beneficial
for the cell performance (Todorov et al, 2008;
Buecheler et al, 2009). An efficiency of 12.3%
was reported after annealing the laboratory cells
with CIGS/MOCVD indium sulfide structure,
although the composition of the In2S3 buffer layer
was not specified. A cell efficiency of 12.4% was
achieved with an ultrasonically sprayed In2S3 buffer layer on a CIGSSe absorber after heat treatment
(Buecheler et al, 2009).
The substrate temperature during the deposition of the In2S3 buffer layer turned out to be a
crucial parameter with regard to CIGSe/PVD-In2S3
solar cell efficiency (Barreau et al, 2009). The
chemical nature of the interface changed as the
substrate temperature varied, which affected all
the solar cell parameters and caused a decrease
of its efficiency.
In2S3 thin films can also be used as precursors
for the preparation of CuInS2, which is one of the

most widely used absorber layers in solar cells


(Sakata et al, 2000).
The surface sulfurisation by sequential evaporation of In2S3 after CIGS deposition improved by
1% the performance of ZnO:Al/CdS/CIGS/Mo/
glass solar cell without anti- reflection coating
(Ohashi et al, 2001).
The possibility of using n-type In2S3 in photoelectrochemical cells (PECs) also attracted some
interest recently. In a PEC using In2S3 and In2O3
multilayer composite, single walled carbon nanotubes (SW-CNTs) led to an increase in power
conversion efficiency by reducing the recombination rate (Lee et al, 2007). The polymer-sensitized
PECs based on In2S3 nanorods in thin film form
were recently reported (Lee et al, 2008), where
the PECs were prepared by the adsorption of
acetylene-polymer photosensitizers on In 2S3
nanorods in aqueous solution which demonstrated
a power conversion efficiency of 1.63%.
In2S3/TiO2, In2S3/ZnO, and In2S3/ZnS photoelectrode structures were fabricated using In2S3
colloidal thin films grown by spin coating. A
photocurrent sensitized by In2S3 was observed for
ZnO and TiO2, but not for ZnS (Yasaki et al, 1999).
The use of In2S3 in polymer heterojunction solar
cells was reported (Dalas et al, 1993; Tang et al,
2008), and the effect of each layer thickness in an
inverted polymer solar cell using spray pyrolysed
In2S3 and MEH-PPV polymer was carried out.

247


In2X3 (X=S, Se, Te) Semiconductor Thin Films

The optimum layer thickness was found to be


200 nm for In2S3 and 100 nm for MEH-PPV, and
the maximum efficiency obtained was 0.075%
(Menon et al, 2010).

In2Se3 Thin Films


In2Se3 can be used as a window layer (Former et
al, 1985) in CIS/In2Se3 solar cells as well as an
absorber layer (El-Sayed, 2004; Lee et al, 2008) in
CdS/In2Se3 solar cells depending upon the optical
band gap of the film. -In2Se3 with a wider band
gap of 2.15 eV (Clavijo et al, 2009) can be used
as window layer, while -In2Se3 having a band gap
of 1.3 eV (Segure et al, 1983) can be used as an
absorber layer in solar cells. Its cleaved surfaces
do not need any additional treatment for pn
junction formation and are chemically inert under
ambient conditions (Qasrawi, 2007). In2Se3 has a
low surface recombination velocity resulting from
its low density of dangling bonds on the surface.
An efficiency of 13% was reported for CIGS
based solar cells with In2Se3 window layers grown
by co-evaporation (Konagai et al, 1996), while a
Mo/CIS/In2Se3/ZnO solar cell with an efficiency
of 8.3% was reported using the co-evaporated
In2Se3 as a the window layer (Gordillo et al, 2003).
The composition effect on the JV characteristics of -In2Se3 based diodes was investigated
for Mo/-In2Se3/ZnO:Al diode structures. When
-In2Se3 was doped with Mn there was no photovoltaic effect that is seen for pure -In2Se3,
which could be attributed to the presence of a
band of localized states present in the band gap
of Mn-doped -In2Se3 (Morsli et al, 2007). The
rectifying contact SnO2/In2Se3 was investigated
using n-type -In2Se3 with a band gap of 1.8 eV
(Bernede et al, 1997).
The formation of CuInSe2 from a migration
enhanced MBE deposited In2Se3 was reported
(Kim et al, 2005). The complex layered structure of
In2Se3, which makes it possible for ions to diffuse
and alter its physical properties without changing
its structure, allows this material to be used as

248

cathode in micro-batteries and as solid solution


electrodes in micro-capacitors (Balkanski, 1998).
The phase change characteristics and the
wider variation in electrical resistivity associated
with the crystallization of In2Se3 films have an
advantage in the multi-bit per cell operation of
PRAM devices (Lee & Kang, 2005; Ahrenkiel
et al, 1993; Segure et al, 1983). An In2Se3 based
PRAM device switching between amorphous and
crystalline states was fabricated and exhibited a
switching dynamic range as high as 100 (Lee &
Kang, 2005).

In2Te3 Thin Films


The gas sensing feature of In2Te3 thin films with
respect to CO2 was investigated and they were
found to be useful in monitoring the CO2 concentration (Desai et al, 2005b). With increased
CO2 concentration, the sensitivity of the sensor
increased.
The application of In2Te3 as a possible thin
film screw gauge (TFSG) was also studied, and
the resulting TFSGs had a high gauge factor and
a good temporal stability. They exhibited a linear
response for both tensile and compressive strains
and a negligible hysteresis (Desai et al, 2005a).
The study of the switching behavior in amorphous In2Te3 thin films revealed that it was typical
for a memory switch. The thickness dependence
of the mean value of the switching voltage Vt was
linear in the investigated range, and Vt decreased
exponentially with a temperature rise from 25 to
100 C. The switching voltage activation energy
was about 0.25 eV and the conduction activation
energy was 0.51 eV (Afifi et al, 1996).
In2Te3 was also found to be of interest as a radiation stable particle due to its suitable direct band
gap and large stopping power as a consequence
of high atomic mass and low defect migration
energy (Afifi et al, 1995).


In2X3 (X=S, Se, Te) Semiconductor Thin Films

TERNARY COMPOUND THIN


FILMS BASED ON In2X3
In addition to the binary compounds, there are
also some ternary phases of group In2X3, such as
In2(Se,Te)3, (In,Ga)2X3 that have band gaps and
photoconductive properties suitable for solar cell
absorber layer applications. (see Figure 8)

Thin films of In2Se3-xTex (x = 01.5) were prepared by pulsed laser deposition (PLD) however
the obtained films were amorphous (Hrdlicka
et al, 2007). The growth of -In2(Se2.5Te0.5)3 by
alternate thermal evaporation of In and (Se, Te)
layers on glass substrates was reported. Although
the as-deposited films were amorphous, the postdeposition annealing treatment resulted in their

Figure 8. XPS spectra of In2(Se1xTex)3 (x~0.11) films. In 3d: from top to bottom, respectively, after 0, 1,
3 and 6 min of sputtering. Se 3d and Te 3d: from bottom to top, respectively, after 0, 1, 3 and 6 min of
sputtering (Emziane & Le Ny, 2001)

249


In2X3 (X=S, Se, Te) Semiconductor Thin Films

Figure 9. The spectral distribution of the transmittance of In2(Se1xTex)3 (x~0.17) films with 600 nm
thickness in the visible and near-infrared (a). The transmittance of -In2Se3 films with 900 nm thickness
is also shown for comparison (b) (Emziane & Le Ny, 2001).

crystallization. A band gap of 1.45 eV was obtained


for the -In2(Se2.5Te0.5)3 films, and the substitution
of Se atoms by Te improved the photocurrent
intensity. The photocurrent was increased about
three orders of magnitude when the Te substituted
Se (Emziane & Le Ny, 2000a; Emziane & Le Ny,
2001; Emziane & Le Ny, 2000b). The growth
of In2x,Ga2(1-x)Te3 layers on InAs substrates by
evaporation from independent sources of elementary components in a quasi-closed volume was
proposed (Bezryadin et al, 1998).
Ternary indium sulfide compounds like CuInS2
with an improved photosensitivity and In2-xGaxS3
offering the possibility to tailor the band gap are
attractive materials for photovoltaic and optoelectronic devices (Naghavi et al, 2003b). (see Figure 9)
250

SUMMARY AND OUTLOOK


In2X3 compound semiconductor thin films, with
X being a chalcogen atom S, Se, Te, are promising candidates for applications in a variety of
devices. The different deposition and processing
methods used for the growth of these thin films
were reviewed, and various effects of fabrication
parameters, such as temperature, heat treatment,
doping, etc. were presented. The structural,
physico-chemical and functional properties of
these thin films were also extensively reviewed and
discussed in light of the many device applications
that such thin film have demonstrated.
A particular attention was paid to the intimate
relationship between their fabrication conditions


In2X3 (X=S, Se, Te) Semiconductor Thin Films

and the resulting microstructure and functional


properties, with an emphasis on the obvious use of
these materials in a variety of thin film solar cells.
We have shown the wide spectrum of compound
materials (i.e. binary, ternary and quaternary) that
can be synthesized based on the In2X3 semiconductor group, and the many devices and applications
that can be achieved by using them.
It is hoped that our review will contribute to
a better understanding of these thin film materials and help further investigate them in order to
improve the performance of the existing devices,
but also the demonstration of more efficient and
cost-effective devices in many areas of technology.

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In2X3 (X=S, Se, Te) Semiconductor Thin Films

KEY TERMS AND DEFINITIONS


Characterization: The study and analysis
of a material or a device in order to determine
its characteristics and properties. These can be
physical, chemical, electrical, optical, magnetic,
mechanical, catalytic, thermal, etc.
Functional Properties: The properties that
some materials can have and that make them useful
for specific applications such as electrical, optical,
magnetic, thermal, mechanical, etc.
Growth: It is often referred to the process of
depositing or growing a layer on a given material
used as a substrate.
Indium Chalcogenides: Compound semiconductor materials that have indium as well
as chalcogen atoms (like S, Te and Se) in their
chemical composition.
Junction: The physical contact of a semiconductor material with another material that
may be a semiconductor or a metal. The typical

example is the p-n junction used as the basis for


many devices.
Microstructure: The physic-chemical structure of a material at the microscopic level.
Photovoltaics: The process of converting light
directly into electricity using the photovoltaic
effect.
Processing: Treating a material thermally
or chemically or mechanically or otherwise in
order to alter its microstructure and, ultimately,
its functional properties.
Solar Cell: A device based on a typical semiconductor p-n junction and that converts photons
directly into electricity. Solar cell can be made
using a variety of semiconductor materials.
Thin Films: Materials with a thickness in
the nanometer or micrometer range, grown or
deposited on a substrate using a given physical or
chemical method. They are used as active layers
in devices or as coatings.

267

268

Chapter 12

Carbon Nanotubes
for Photovoltaics
Ayoola Brimmo
Masdar Institute of Science and Technology, UAE
Mahieddine Emziane
Masdar Institute of Science and Technology, UAE

ABSTRACT
Recent developments show that the exceptional physical, optical, and electrical properties of Carbon
Nanotubes (CNTs) have now caught the attention of the Photovoltaics (PV) industry. This chapter provides an updated and in-depth review of some of the most exciting and important developments in the
application of CNTs in photovoltaics. The chapter begins with a discussion of the underlying properties
of CNTs that make them promising for PV applications. A review of the literature on the application
of CNTs in the photoactive layer of Silicon (Si)-based heterojunctions, as anchors for light harvesting
materials in Dye Sensitized Solar Cells (DSSCs) and as components of other organic solar cells (OPVs),
is then presented. Findings portend the promise of CNTs in bridging the gap between the two classes of
solar cells currently in the market. Since the technology is in its early stages, it is generally limited by a
general lack of understanding of CNTs and their adequate growth mechanisms.

INTRODUCTION
The PV effect in simple words refers to the creation of voltage and electric current by a diode
upon exposure to light. In an ideal case, light
(photons) absorbed by a photovoltaic material
excite electrons into a higher state of energy, allowing them to act as charge carriers for electric
current. However, the efficiency of this process
is highly dependent on the materials ability to
successfully absorb photons in the light sources

spectrum, allow excitation of its electrons/holes


and then safe guard the delivery of these electrons/
holes to the electrodes before recombination
occurs. In reality, ensuring the success of these
processes is very difficult hence the relatively low
efficiencies of most commercial solar cells today.
Over the years, Si has proven to be the leading
material used in the PV industry with crystalline
Si wafer based PV responsible for the majority
of the worlds annual solar cell production (Mller, Ghosh, Sonnenschein, & Woditsch, 2006;

DOI: 10.4018/978-1-4666-5824-0.ch012

Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.


Carbon Nanotubes for Photovoltaics

Laird, 2010). This is the case as the Si wafer


based PV has long been a proven and robust PV
technology. The cost of high efficiency Si wafer
PV devices, limits this technologys potential of
performing well in the energy market; traditional
mono crystalline Si PV and the most efficient
multijunction PV (performing at about 40.7%
under 240 sun illumination) can cost upwards
of several dollars per installed watt (Kammen
& Pacca, 2004; King et al., 2007; Camacho et
al., 2007), with kWh cost several times higher
than energy from traditional fossil fuel sources.
In contrast, due to greatly reduced semiconductor material consumption and the ability to (i)
fabricate the solar cells on inexpensive largearea foreign substrates and (ii) to monolithically
series-connect the fabricated solar cells, thin-film
PV has the potential of achieving module costs
of well below $1.4 per W (Aberle, 2009). As
thin film materials are typically polycrystalline
or amorphous, they experience a high reduction
in efficiency due to interface recombination and
degradation under light illumination (StaeblerWronsky effect) (Galloni, 1996), making them

less efficient than their wafer based counterparts.


Evidently, the present trend in the PV industry
divides cells into two categories: cells which
are affordable but of relatively low efficiency
and cells which are of good efficiency but very
costly. Figure 1 shows the efficiency and cost
projection of these categories of cells. As it is
expected that the PV market will continue to
rise, it is of great interest to the PV industry to
bridge the gap between these two categories of
cells currently available and produce units which
are not only of decent efficiency but also affordable enough to compete with other sources of
secondary energy. Approaches in this line aims
to decrease the cost to well below the $1/W
level of the second-category PVs potentially to
$0.20/W or better, by significantly increasing
efficiencies but maintaining the economic and
environmental cost advantages of thin-film deposition techniques (Conibeer, 2007). In order
to establish a third category of PV devices, a lot
of methods have been explored to bridge this
and CNT unsurprisingly has been a well cited
candidate in the field.

Figure 1. Efficiency and cost projections for first- (I), second- (II), and third category (III) PV technologies (wafer based, thin film and advanced technologies respectively) (Green, 2001)

269


Carbon Nanotubes for Photovoltaics

The abundance of carbon and the unique properties of its nanostructures which include high
transparency (Kaempgen, Duesberg, & Roth,
2005), excellent electrical conductivity (Sarno
et al., 2013), outstanding thermal properties
(Balandin et al., 2008), direct band gap (Avouris,
Freitag, & Perebeinos, 2008) and high predicted
mobility (Durkop, Getty, Cobas, & Fuhrer, 2004),
make it attractive for solar energy conversion.
Unfortunately, CNTs are currently extremely
expensive, making them unviable for applications in commercial PV devices (Baughman,
Zakhidov, & De-Heer, 2002). However, recent
advances in synthesis techniques, in particular
Chemical Vapor Deposition (CVD) methods,
show promise for being scalable (ton/day), low
cost (<$100/kg), and able to produce high purity
CNTs (Sinnott & Andrews, 2001). This prospect
coupled with the remarkable properties of CNT
has made it difficult to neglect CNTs as a candidate for facilitating the production of affordable
and efficient PV devices.
The aim of this study is to review major works
that have attempted to integrate CNTs in PV
devices. The next section briefly discusses the
CNTs properties which have enticed professionals in the PV field. This is followed by the main
focus areas of this review which includes: CNT
applications in the photoactive layer in Si based
heterojunctions; as anchors for light harvesting
materials in DSSCs and as components of other
OPVs. The roles played by CNT in these PV
cells are discussed and criticized in these sections. As the cost of resulting solar cells largely
depends on the fabrication technique applied,
the fabrication of CNT based PV devices are
highlighted. Finally, general technical challenges
and prospects in the field of CNT applications
in PV are discussed.

270

BACKGROUND
Physical, Electrical and
Optical Properties of CNTs
CNTs have a unique pseudo-one dimensional
tubular structure which can be envisaged as rolled
single sheets of graphene. They form spontaneously and efficiently under well-defined conditions either as single-wall nanotubes (SWNT) or
nested multi-wall nanotubes (MWNT). Contiguous carbon nanotubes exhibit a high degree of
atomic scale perfection (Jorio, G. Dresselhaus,
& Dresselhaus, 2008). The nanotubes are constructed with a length-to-diameter ratio of up to
132,000,000:1 (Wang et al., 2009), significantly
larger than that of any other material. The quantum
size nature of this material makes it possible to
exhibit special physical configurations which are
largely responsible for its outstanding properties
(Zhu, Klein, Schmalz, Rubio, & March, 1998).
Since their discovery by Iijma (1991) CNTs have
incited a great number of researches due to their
fascinating properties; Figure 2a shows that the
strength of an individual MWNT is about 100
times that of typical structural steel (Brimmo,
Hassan, Ibrahim, & Shatilla, 2013) and Figure 2b
shows that the electrical resistivity of a SWNT is
about an order of magnitude lower than that of a
copper nanowire (Liu et al., 2012). Also, CNTs
exceptional mechanical (Coleman, Khan, Blau,
& Gunko, 2006; Yu et al., 2000; Ciurea et al.,
2009; Treacy, Ebbesen, & Gibson, 1996), electrical (Venema et al., 1999; Jishi, Bragin, & Lou,
1999; Durkop, Getty, Cobas, & Fuhrer, 2004;
Gao, Chen, Fuhrer, Glattli, & Bachtold, 2005)
and optical properties (Movlarooy, Kompany,
Hosseini, & Shahtahmasebi, 2010; Chen, 2010;
Zhao & Mazumdar, 2005; Shan & Bao, 2006; Fa,
Yang, Chen, & Dong, 2004; Chen, Lee, Chang,
Lue, & Lin, 2006; Kataura et al., 1999) are well
cited in the literature as such, it is of no surprise
that CNTs are considered ideal for a wide range of
applications (Baughman, Zakhidov, & De-Heer,


Carbon Nanotubes for Photovoltaics

Figure 2. (a) Plot of stress versus strain curves for an individual MWNTs(Yu et al., 2000); (b) I-V characteristics of a SWNT at 20K and 298K (Ciurea et al., 2009)

2002) and a test bed for fundamental science (Cao,


Wang, Rolandi, & Dai, 2004).
CNTs are electronically distinguished by how
the combination of the rolling angle and radius
decides if the resulting individual nanotube shell
is metallic or a semiconductor. Electron transport
in CNTs is described as ballistic, i.e. the resistance
of the nanotube does not depend on its length as
the mean free path m is longer than the nanotube
itself (Brown, Hao, Gallop, & Macfarlane, 2005).
The electrical resistivity of individual CNTs has
been measured to be as low as 106 cm (McEuen,
Fuhrer, & Park, 2002; Gao, Chen, Fuhrer, Glattli,
& Bachtold, 2005) for SWNTs and 3105 cm
(Bachtold, et al., 1998; Berger, Yi, Wang, & deHeer, 2002) for MWNTs. Semiconducting CNTs
are, unlike Si, direct band gap materials that have
the same effective mass for holes and electrons
which suggests their great potential in photonics
and related applications (Kuo, Tzolov, Straus, &
Xu, 2009).
The unusual and potentially useful optical
characteristics of CNTs can be traced back to the
nanotubes electronic structure (Weisman & Subramoney, 2006). A typical feature of the high aspect

ratio, quasi one-dimensional CNT is their discrete


density of state (DOS): their DOS as a function of
energy depicts a curve with discontinuous spikes as
shown in Figure 3. The sharp peaks as observed by
scanning tunneling spectroscopy (Li et al., 2001),
typically in one-dimensional materials, are called
the Van Hove singularities (Kataura, et al., 1999;
Kim, Odom, Huang, & Lieber, 1999). The peaks
signify discrete energy sub-bands which fall within
the broad visible-near-IR range (Bachilo, et al.,
2002; OConnell et al., 2002), with the band gap
magnitude depending on the nanotubes physical configuration (Rao, et al., 1997; Faga, et al.,
2007). This opens up the possibility of tuning the
optical properties of CNTs. Such fine tuning has
been experimentally demonstrated (Iakoubovskii
et al., 2006), often leading to innovative optical
applications of CNTs (Murakami, Einarsson,
Edamura, & Maruyama, 2005).
The optical properties of CNTs usually mentioned in the literature are absorption (Kataura,
et al., 1999; Sinnott & Andrews, 2001), photoluminescence (PL) (Iakoubovskii, Minami, Ueno,
Kazaoui, & Kataura, 2008; Iakoubovskii et al.,
2006; Tan et al., 2007; Oyama et al., 2006), and

271


Carbon Nanotubes for Photovoltaics

Figure 3. Schematic density of electronic states


pattern in a semiconducting SWNT. The sharp
maxima are van Hove singularities. Arrows show
the dominant optical absorption and emission
transitions (in a one-electron model) (Weisman
& Subramoney, 2006).

Raman spectroscopy (Dresselhaus, Jorio, Hofmann, Dresselhaus, & Saito, 2010; Hennrich et
al., 2005; Zdrojek, Gebicki, Jastrzebski, Melin,
& Huczko, 2004) with the isolation of individual
nanotubes cited as critical for decoupling the
optical response of one nanotube from another
(Hartschuh et al., 2005). Typical SWNTs absorption spectra show perturbations (Naumov,
Ghosh, Tsyboulski, Bachilo, & Weisman, 2011)
as opposed to an absorption threshold followed by
an increase in absorption, as experienced by most
3-dimensional materials. The absorption spectra
of SWNT bundles contain three broad absorption
regions corresponding to the first and second allowed transitions for semiconductor SWNTs, and
the first allowed transition for metallic SWNTs
(Hartschuh et al., 2005). This trend can be seen
in Figure 4a which is the absorption spectra of
SWNTs produced by the laser-oven method. In
Figure 4a, the peaks at 1700 and 950 nm are due

272

to semiconducting nanotubes while the peak at


650 nm is due to metallic nanotubes (Hartschuh
et al., 2005).
PL of CNTs is a process whereby CNT absorb photons and then re-radiates them almost
immediately, with a light emission effect. This
phenomenon only occurs in semiconducting CNTs
as the hole created in metallic CNTs, by an excited
electron, is immediately filled up by one of the
large number of high energy electrons available
in the metallic material. Also, the luminescence
efficiency of SWNTs has been shown to increase
with decreasing temperature (Lauret et al., 2004).
The observation of structurally dependent PL
from SWNTs represented a major breakthrough
(Bachilo et al., 2002), as the electronic transition
energies was shown to depend on the nanotubes
description matrix ((n, m) values) explicitly and
not simply on the SWNT diameters (Hartschuh
et al., 2005). PL in CNT occurs within a wide
wavelength range (Iakoubovskii et al., 2006) and
has been observed in both isolated (OConnell et
al., 2002) and bulk (Lebedkin, Hennrich, Skipa,
& Kappes, 2003) SWNTs. While ensemble measurements are complicated by the superposition
of many PL peaks from many different species,
single nanotube spectra clearly isolate a single
peak and are thus simpler to interpret (Lefebvre,
Fraser, Finnie, & Ho