Beruflich Dokumente
Kultur Dokumente
13
Qingbin Zheng
Leibniz Institute of Polymer Research
Dresden
Dresden
Germany
Jang-Kyo Kim
Department of Mechanical and Aerospace
Engineering
The Hong Kong University of Science and
Technology
Kowloon
Hong Kong SAR
Preface
vi
Preface
progress for CVD-grown graphene achieved so far, these important challenges must
be overcome before the industry applications.
Owing to the scalability of production and the convenience in processing,
graphene oxide (GO) has been considered an important precursor for the fabrication
of TCs. GO sheets are hydrophilic and can produce stable and homogeneous colloidal
suspensions in aqueous and various polar organic solvents due to the electrostatic
repulsion between the negatively charged GO sheets. These GO dispersions are easy
to be processed to produce TCs on a substrate. Transparent conducting films (TCFs)
containing GO or chemically reduced GO sheets have been deposited via several
well-established techniques, including spin or spray coating, transfer printing, dip
coating, electrophoretic deposition, and the LangmuirBlodgett (LB) assembly,
followed by chemical reduction and/or thermal annealing.
While there are some books that specialize in fabrication processes and properties
of graphene and GO, very few books are available specifically dealing with the
following topics for their application in transparent conductors: (i) how to produce
TCs by using CVD grown graphene, (ii) how to synthesize GO with different size
and control their surface functionalities to enhance the electrical conductivity,
(iii) how to incorporate these nanostructured materials into thin films with layered
structure, and (iv) how to improve the conductivity and transparency. In light of the
authors experiences on graphene fabrication and application for TCs in the past few
years, this book is aimed to provide a comprehensive overview of traditional and
novel techniques in producing and functionalizing graphene for highly conductive
transparent thin films. It will offer a systematic presentation of the principles,
theories, and technical practices behind the structureproperty relationship of the
thin films, which we believe to be the key for the development of high-performance
TCs.
The book is intended primarily for an audience of graduate students, research
scientists, and professors in the area of carbon materials, transparent conductors,
and related fields, as well as to professionals from the electronic and chemical
manufacturing industries. Nanotechnology, as an emerging new subject, has been
established as a major in postgraduate level in many universities and research
institutes. This book would be well suited as a textbook for an intermediate level
class in nanotechnology and/or materials science and engineering as part of such
a program or as a stand-alone course. It will be accessible equally to readers with
either science or engineering background. At the same time, the unique perspectives
provided in the applications of graphene as TCs will serve as a useful guide for
design and fabrication of these thin film materials for specific applications.
The authors are grateful for the assistance, discussion, and encouragement
offered during the preparation of this book by past and current colleagues and
friends, including Dr. B Zhang, Prof. QZ Xue, Prof. ZG Li, Prof. PC Ma, Prof.
JH Yang, Dr. J Li, Dr. ZD Huang, Dr. Y Geng, Dr. X Shen, Dr. XY Lin, as well
as the research group members who produced the research outputs quoted in this
book. Dr. Zheng was partly supported by the Hong Kong University of Science &
Technology (HKUST) Postgraduate Studentships (PGS), Finetex-HKUST R & D
Center at HKUST, Research Grant Council (RGC) of Hong Kong, Shanghai Pujiang
Preface
vii
Talent Project, and the Alexander von Humboldt Foundation during the course of
completing this book. The authors specially thank Prof. E. Mder, Dr. SL Gao, Dr.
HS Qi, Dr. C Scheffler, and Dr. U Gohs at Leibniz Institute of Polymer Research
Dresden (IPF) for stimulating discussion on this book. The authors are also grateful
to Drs. David Packer, Ho Ying Fan, and Kanchan Kumari at Springer for their kind
reviewing and processing of our manuscript.
Clear Water Bay,
Hong Kong
January, 2014
Contents
Contents
2.3.3Elimination of Sonication 45
2.3.4Size Separation Methods 47
2.4Structures of Graphene and GO 51
2.5Properties of Graphene and GO 55
2.5.1Electrical/Electronic Properties 55
2.5.2Thermal Properties 63
2.5.3Optical Properties 67
2.5.4Mechanical Properties 68
2.6Common Tools for Characterization of Graphene
and Its Derivatives 73
2.6.1Atomic Force Microscopy 73
2.6.2Scanning Electron Microscopy (SEM) 74
2.6.3Transmission Electron Microscopy (TEM) 74
2.6.4Scanning Tunneling Microscope (STM) 76
2.6.5Raman Spectroscopy 79
References 81
3Fabrication of Graphene-Based Transparent Conducting
Thin Films 95
3.1Introduction 95
3.2CVD-Grown Graphene-Based TCs 95
3.2.1Etching Method 95
3.2.2Stamping Method 97
3.2.3Thermal Release Method 101
3.2.4Photoresist Method 101
3.2.5Roll-to-Roll Transfer Method 103
3.2.6Challenges of Transferred CVD-Grown Graphene for TCs 105
3.3Fabrication of GO-based TCs 105
3.3.1Electrophoretic Deposition 109
3.3.2Spin Coating 110
3.3.3Spray Coating 111
3.3.4Dip Coating 112
3.3.5Transfer Printing of GO Films 114
3.3.6LangmuirBlodgett Method 114
3.3.7Rod Coating 117
3.3.8Inkjet Printing 117
References 119
4 Improvement of Electrical Conductivity and Transparency 123
4.1Introduction 123
4.2Chemical Doping 124
4.2.1Chemical Doping of Carbon Materials 124
4.2.2 Chemical Doping of Graphene 127
4.2.3Stability of Doped Graphene Films 136
Contents
xi
4.3Hybridization 138
4.3.1Hybridization with CNTs 138
4.3.2Hybridization with Metal Wires 151
4.3.3Hybridization with Metal Grids 157
4.4Using UL-GO 158
4.4.1Solution Casting of UL-GO 158
4.4.2Dip Coating of UL-GO 159
4.4.3LB Assembly of UL-GO 161
References 173
5 Application of Graphene-Based Transparent Conductors (TCs) 179
5.1Introduction 179
5.2Touch Screen 179
5.3Displays 181
5.3.1Liquid Crystal Displays 181
5.3.2Light-Emitting Diodes 181
5.4Solar Cells 184
5.5Transistors 184
5.6Other Applications 187
5.6.1Electromagnetic Interference (EMI) Shielding 187
5.6.2Functional Glasses 190
5.6.3Transparent Loudspeakers 192
5.6.4Transparent Heaters 192
5.6.5Transparent Actuators 194
5.6.6Transparent Sensors 196
5.6.7Transparent Supercapacitors 198
References 200
6 Conclusions and Perspectives 205
References 210
Index 215
Acronyms
AFM
Atomic force microscopy
Angle-resolved X-ray photoelectron spectroscopy
AR-XPS
Aluminum-doped zinc oxide
AZO
Benzylamine
BA
Bubble deposition method
BDM
Bulk-heterojunction
BHJ
Backscattered electrons
BSE
Carbonaceous byproducts
CB
Cold cathode fluorescent lamp
CCFT
Concentrated graphene oxide wrinkles
CGOWs
Complementary metaloxidesemiconductor
CMOS
Carbon nanoscroll
CNS
Carbon nanotube
CNT
Cathode ray tubes
CRT
C-rUL-GO Chemically doped, reduced ultra-large graphene oxide
Chlorosulfonic acid
CSA
Chemical vapor deposition
CVD
Direct current
DC
o-dichlorobenzene
DCB
Dichloroethane
DCE
Diethylene glycol
DEG
Density gradient ultracentrifugation
DGU
DI Deionized
Dimethylacetamide
DMA
N, N-Dimethylform
DMF
Dimethyl sufoxide
DMSO
Digital single lens reflex
DSLR
Ethylbenzoic acid
EBA
Electron diffraction
ED
Electromagnetic interference
EMI
xiii
xiv
EPD
Electrophoretic deposition
Edge selective functionalization of graphite
EFG
Flat panel display
FDP
Few-layer-graphene
FLG
Fourier transform infrared
FTIR
Fluorine tin oxide
FTO
Fluoroalkyl trichlorosilane
FTS
Full width at half maximum
FWHM
GIC
Graphite intercalation compounds
Graphite nanoplatelet
GNP
Graphene nano ribbons
GNR
Graphene oxide
GO
Graphene oxide paper
GOP
Graphene oxide wrinkles
GOW
Graphene paper
GP
Hydrogen floride
HF
Hydrogen iodine
HI
Nitric acid
HNO3
Highly ordered pyrolytic graphite
HOPG
High-resolution transmission electron microscopy
HRTEM
Indium-doped cadmium-oxide
ICO
Isopropanol
IPA
Indium tin oxide
ITO
LangmuirBlodgett
LB
Layer-by-layer
LbL
Liquid crystal displays
LCDs
Light-emitting diode
LED
Large graphene oxide
L-GO
Magnetron sputtering
MS
Methanesulfonic acid
MSA
Magnetron sputtering deposition
MSD
Molecular dynamics
MDs
Multilayer graphene
MLG
Molecular mechanics
MMs
Multi-walled carbon nanotube
MWCNT
Multiple quantum wells
MQW
Nanosized graphene oxide
NGO
Ammonium persulfate
(NH4)2S2O8
N-methyl-2-pyrrolidone
NMP
Nanoparticles
NPs
NWs Nanowires
Organic light emitting diodes
OLEDs
Organic photovoltaics
OPVs
Polyacrylic hydrocarbons
PAHs
xv
PANI
Polyaniline
Polydimethylsiloxane
PDMS
Plasma display panel
PDP
PEDOT/PSS Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
Polyethyleneimine
PEI
Polyethylene glycol
PEG
Polyethylene terephthalate
PET
Pulsed laser deposition
PLD
PMMA
Poly(methyl methacrylate)
PmPV Poly(m-phenylene vinylene-co-2,5-dioctyloxy-pphenylene vinylene)
P2O5
Phosphorus pentoxide
Poly(2,5-dioctyloxy-1,4-phenylene-alt-2,5-thienylene)
POPT
Polyphosphoric acid
PPA
Poly(para-phenylene vinylene)
PPV
Polypyrrole
PPy
Polythiophenes
PTs
Polyvinylidene fluoride
PVDF
Poly(4-vinylphenol)
PVP
Radar absorbing materials
RAM
Reduced graphene oxide
rGO
Radio frequency
RF
Rear-projection
RP
Selected area electron diffraction
SAED
Secondary electrons
SE
Scanning electron microscope
SEM
Sodium dodecyl sulfate
SDS
Small graphene oxide
S-GO
Self-release layer
SRL
Sound pressure level
SPL
Scanning tunneling microscope
STM
Single-walled carbon nanotube
SWCNT
Transparent conductors
TCs
Transparent conductive films
TCFs
Transparent conducting oxides
TCOs
Harmonic distortion
THD
Time-of-flight secondary ion mass spectrometry
ToF-SIMS
Ultralarge graphene oxide
UL-GO
Ultra-high vacuum
UHV
Ultravioletvisible spectroscopy
UV-Vis
Vacuum arc plasma deposition
VAPE
Very large graphene oxide
VL-GO
Width-at-half-maximum
WHM
X-ray photoelectron spectroscopy
XPS
X-ray diffraction
XRD
xvi
Symbols
Rs
t
T
U
Z
DC
Chapter 1
Fig. 1.1 Transparent conductive film markets (US$ millions). a Forecast of TCF markets [4].
b Flat-panel display and transparent conductor markets. ITO indium tin oxide, TCO transparent
conducting oxides, OLED organic light-emitting diodes, RP rear-projection, PDP plasma display
panel, LCD liquid crystal displays, CCFL cold cathode fluorescent lamp, CRT cathode ray tube,
FPD flat-panel display [11]
steel or plastic substrates. Due to the low temperature deposition requirement, ITO
or ZnO is chosen for this purpose [7]. Electrochromic mirrors and windows have
been widely used in automobiles and smart windows with electrically controllable
transmission. The main considerations are chemical inertness, high transparency,
High
High
High
Low
Low
Electromagnetic
shielding
Invisible security
circuits
Protection layer
for glass
High
High
High
Low
Static dissipation
High
Electrochromic
mirrors and
windows
Defrosting
windows
Oven window
Good
Good
Table 1.1 Selection criteria for various transparent conductors (TCs) [7]
Applications
Sheet
Transparency Plasma
Thermal
resistance
wavelength
stability
Flat-panel
Low
High
displays
Touch screens
Low
High
Low-emissivity
Good
High
Long when
windows
cold and short
when hot
Solar cell
Low
High
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good
Good
Chemical
stability
Mechanical
stability
Low
Low
Low (200C)
Low
Low
Low
Toxicity
Low
Low
Deposition
temperature
Low
Low
Low
Low
Low
cost
and low cost, making tin oxide an ideal choice for this purpose [8]. Defrosting windows are required in many areas, such as the display windows in supermarkets and
windshields or windows in airplanes. Low cost and durability are the main factors
and tin oxides are widely used for this application [7]. Laboratory ovens are often
constructed entirely of TCF-coated glass because they need to be transparent while
possessing high temperature stability, chemical and mechanical durability, and low
cost. Static dissipation TCFs are used to dissipate static charges that often grow
excessively on cathode ray tubes (CRT), computer monitors, xerographic copiers,
and television tubes. The main concern here is the mechanical and chemical durability, although the sheet resistance can be relatively high [7]. In order to prevent
the eavesdropping on computers and communications, electromagnetic shielding
TCFs are used to block the stray signals by detecting electromagnetic signals passing through windows [9]. Invisible security circuits can be used for both military
and consumer applications [10]. Very high transparency is the most important factor
for this special purpose. In order to improve the durability of glass, TCFs with good
abrasion resistance are needed.
Hence, different sets of parameters are desired for a wide variety of applications
based on different TCFs [6, 7]. Especially, there are rapidly growing markets for
flexible TCFs such as flexible displays [12], flexible touch screens [13], printable
electronics [14, 15], OLEDs [16], and thin-film photovoltaics [17, 18]. Figure1.2
shows examples of flexible organic optoelectronic devices like OLEDs and organic
photovoltaics (OPVs). OLEDs consume power to emit light, while OPVs absorb
light to store energy for future power output. OLEDs can be used to create digital
displays, such as TV screens, computer monitors, and portable systems [19]. Their
unique flexible and lightweight nature makes them an excellent candidate for use in
emerging technologies, such as roll-up displays. OPV devices convert solar energy
to electrical energy and are promising candidates for meeting the increasing future
energy demands [18]. Flexible and lightweight OPVs can be incorporated into everyday products, such as clothing, backpacks, and other wearable apparel.
ITO has been the dominant material for TCF applications. It has a huge global
market worth US$ 3 billionin 2010 with a 20% growth rate annually [1]. The limited supply of indium and ever-increasing demands, however, have pushed the price
of ITO up continuously [20]. Due to the brittleness of ITO, to apply it in flexible
devices is prohibitively difficult [6]. Several types of new TCF materials, including conductive polymers [21, 22], metallic nanowires [23, 24], carbon nanotubes
(CNTs) [2], and graphene films [25] have been developed as alternative transparent
electrode materials. Graphene, a rapidly rising star on the horizon of materials science [26], is considered the most interesting material to replace ITO benefited from
its exceptional mechanical, optical, and electrical properties [6].
Fig. 1.2 Examples of flexible organic optoelectronic devices. a Example of an organic lightemitting diode (OLED) display (LG Displays 5 plastic-based flexible OLED prototype panel)
[27]. b Example of an organic photovoltaic (OPV) device [28]
Fig. 1.3 Transparent conducting ITO thin films grown by a pulsed laser deposition method. a, b
AFM images of ITO films with thicknesses of 40nm a and 200nm b, respectively. c, d Effect of
film thickness on sheet resistance c and transparency d [40]
been the dominant material for producing TCFs owing to their excellent electrical
conductivity and optical transparency [1]. Several fabrication methods, including
magnetron sputtering [30], radio frequency sputtering [31], molecular beam epitaxy
[32], screen printing [33], pulsed laser deposition (PLD) [34], sol-gel techniques
[35], spray pyrolysis [36], and electron beam evaporation [37], have been developed to produce ITO films. Additional high-temperature annealing is usually needed for the solution-based methods to achieve certain transmittance (T) and resistance standard. ITO nanowires [38] or ITO nanoparticles [39] have been deposited
via solution-based deposition techniques. Figure1.3ab shows the typical atomic
force microscopy (AFM) images of ITO films grown by the PLD method. The rootmean-square roughness of the ITO films with thicknesses of 40 and 200nm were
2.8 and 0.5nm, respectively. The higher surface roughness for the thinner film was
attributed to the formation of islands. It is also noticed that the roughness increased
again when the films were thicker than 200nm due to the crystallinity [40]. It is seen
from Fig.1.3c that the sheet resistance initially decreased with an increase in film
thickness and remained almost constant for films up to 870nm thick. Figure1.3d
shows the variation of optical T and reflectance as a function of film thickness. The
optical T was above 80% for films with thickness from 40 to 300nm in the visible
range (~400700nm), while the reflectance was relatively low [40], which is why
ITO has been the dominant TCF material.
Resistivity
Toxicity
Very good
CdO
In, Sn
Very good
Very high
In2O3
Very good
High
Ga2O3
Sn
Average
Good
Nb, Ta
Average
Average
Sn, Ge
Average
Average
High
Nb, La
Bad
ZnOIn2O3 system
Good
Good
CdOIn2O3 system
Good
High
Good
High
ZnOSnO2 system
CdOIn2O3SnO2 system
SnO2
TiO2
MgIn2O4
Zn2In2O5, Zn3In2O6
In4Sn3O12
CdIn2O4
Cd2SnO4, CdSnO3
Zn2SnO4, ZnSnO3
Zn2SnO4, ZnSnO3
Zn2SnO4, ZnSnO3
Zn2SnO4, ZnSnO3
In2O3SnO2 system
CdOSnO2 system
Average
ZnOIn2O3SnO2 system
Good
Good
High
ZnOCdOIn2O3SnO2 system
Good
High
1.2.2ITO Substitutes
Due to the limited nature of world indium reserves, it is widely believed that a
severe shortage of indium may occur in the near future [41]. This means that a
long-term stable supply of ITO might be difficult to satisfy the expanding TCF
markets. Hence, developing other TCO alternatives to ITO becomes critically important. A number of low-cost alternatives have been proposed recently [1]. TCOs
that contain a reduced amount or no indium, such as Al- and Ga-doped ZnO (AZO
and GZO) and ZnOIn2O3SnO2 (or ZnInSnO) multicomponent oxides, have
attracted much attention [41]. Table1.2 shows typical TCO materials developed as
ITO substitutes. For example, ITO has been prepared on amorphous substrates at
a temperature below 200C by direct current (DC) magnetron sputtering deposition (MSD) for LCD applications. ITO TCFs possess low resistivity in the order
of 104 cm and thicknesses of approximately 15100 nm. Due to the toxicity
of cadmium and the required high temperature heat treatment, it is practically difficult to use cadmium oxide-based and titanium oxide-based TCO materials under
such circumstances [42]. For titanium oxide and titanium oxide-based TCO TCFs,
a high temperature procedure (>300C) is required to reach a low resistivity [43].
Three different kinds of binary compounds (ZnO, In2O3, and SnO2) and multicomponent oxides composed of any combination of these binary compounds may pos-
Fig. 1.4 Stability of resistivity of Al-doped ZnO (AZO) in a humid environment. a Resistivity as a
function of exposure time for AZO films prepared by pulsed laser deposition (PLD). b Normalized
resistivity as a function of exposure time for AZO thin films prepared by (radio frequency (rf) and
direct current (dc)) magnetron sputtering deposition (MSD) and PLD. (Reprinted with permission
from [45]. Copyright (2008) by Elsevier)
sibly be employed as TCFs in LCDs. The usage of indium could also be reduced
by synthesizing multicomponent oxides that contain less indium, e.g., ZnOIn2O3,
In2O3SnO2, and ZnInSnO [44]. The required optoelectrical properties could be
achieved by magnetron sputtering (MS) and vacuum arc plasma deposition (VAPE)
under optimized deposition conditions [44]. Thus, these multicomponent oxides
with an appropriate composition are potential candidates for TCFs in LCDs [41].
The amount of indium used can be reduced to approximately half.
Indium-free oxides, such as ZnO, SnO2, and ZnOSnO2 multicomponent oxides,
are another solution to avoid the use of indium [41]. However, due to the difficulty
of producing low resistivity TCFs at a low temperature and the patterning problems,
impurity-doped SnO2 and SnO2-based materials are unsuitable for use in LCDs. The
current indium-free candidate is impurity-doped ZnO, such as AZO and GZO [41].
In addition, AZO possesses superior electrical stability upon exposure to humid
environments [1, 45]. Figure1.4a shows the electrical stability of the AZO films
prepared with different thicknesses and Al contents, revealing the importance of
these factors. The stability of resistivity was improved as the thickness increased
while the resistivity was dependent on the deposition method, which influenced
the crystallinity of deposited AZO films. It is also worth noting that the stability
was relatively independent of substrate deposition temperatures ranging from 68
to 200C. Figure1.4b shows normalized resistivity (/I, referenced to the initial
resistivity) as a function of exposure time for 200-nm-thick AZO films. It is found
that the AZO films were sufficiently stable for use in practical TCF applications,
irrespective of the deposition method [45].
However, there are still several critical weaknesses in these TCOs, namely (i) ever-increasing material cost due to the limited availability of the elements needed, such
as In, Zn, and Sn, on the earth, (ii) TCO being inherently unable to be etched, patterned, or processed at high temperatures, (iii) TCOs being unable to satisfy property
requirements for emerging applications, such as flexible devices (e.g., flexible LCDs
and organic solar cells) due to its brittle nature, (iv) susceptibility to ion diffusion
into polymer layers, (v) low transparency in the near-infrared region, and (vi) current
leakage caused by structural defects [4650]. In addition to light weight, high flexibility, and low cost, the TCFs required for the next generation optoelectronic devices
should be compatible with the available large-scale manufacturing processes [51].
1.3.1Polythiophene (PT)
Owing to the good electrical properties and environmental stabilities, PT has received much attention from the scientific communities [57]. PTs are conjugated
polymers that can be used for a variety of applications, such as electrical conductors, nonlinear optical devices, polymer LEDs, and smart windows [72]. New types
of PTs with enhanced properties were developed for certain devices by devising
new design strategies. For example, the electronic properties of solution-processable conjugated PTs were modified using self-assembled silane molecules [73].
The electrical conductivities of ultrathin PT films increased by up to six orders of
magnitude by doping with hydrolized fluoroalkyl trichlorosilane (FTS). Because
the interband optical absorption of the polymers in the doped state was drastically
reduced, the doped PT films were highly transparent in the visible range (Fig.1.6).
The PT films were very stable in vacuum and nonpolar environments because the
dopants within the porous polymer matrix were partially cross-linked via a silane
self-polymerization mechanism [73]. The interaction of the silanol groups with po-
10
Fig. 1.5 Molecular structures of PT, PPV, PANI, PPy, and PEDOT. PT polythiophene, PPV
poly(para-phenylene vinylene), PANI polyaniline, PPy polypyrrole, PEDOT poly(3,4-ethylenedioxythiophene). (Reprinted with permission from [53, 57]. Copyright (2013, 1998) by
Elsevier)
Deposition in a polymerizing solution of pyrrole using FeCl3 as the oxidizing agent on PET substrates
Deposition in a polymerizing solution of pyrrole using FeCl3 as the oxidizing agent, with sodium anthraquinone-2-sulfonate and 5-sulfosalicylic acid
as the additives, on PET substrates
Casting of polymerizing solution of methanol-substituted 3,4-ethylenedioxythiophene using ferric tosylate as the oxidizing agent and various
alcohol solvents containing a weak base, imidazole, on glass substrates
PPV
PPy
PPy
PANI
PANI
PEDOT
PEDOT
PEDOT
PEDOT
PEDOT
PEDOT
1362
1325
1000
900
0.61.8
0.010.06
850
200
0.1
0.001
Ha etal. [64]
References
PT
1000
Table 1.3 Electrical conductivities of PT, PPV, PPy, PANI, and PEDOT prepared by various processing conditions [53]
Conducting polymers
Processing conditions
Conductivity (S/cm)
PEDOT
Commercial products
33006740
3400
3065
2084
1418
Conductivity (S/cm)
References
ITO
Vacuum vapor phase polymerization using ferric tosylate as the oxidizing agent with the addition of block copolymers based on poly(ethylene
glycolpropylene glycolethylene glycol) in oxidant solutions on glass
substrates
PEDOT
PEDOT
Processing conditions
PEDOT
12
1 Introduction to Transparent Conductive Films
13
14
Fig. 1.7 Synthetic route for synthesis of PPV. (Reprinted with permission from [75]. Copyright
(1990) by Nature Publishing Group)
1.3.3Polypyrrole (PPy)
PPy is a Nobel Prize-winning organic polymer (in Chemistry, 2000) formed by polymerization of pyrrole [79]. PPy films darken in air due to oxidation, while doped
ones are blue or black depending on the degree of polymerization and film thickness. As seen from Table1.4, the electrical conductivity of PPy thin films increased
by three orders of magnitude when the dopant anion was varied from chloride to
anthraquinone-2-sulfonate [60]. This finding is attributed mainly to the dopant
anions containing fused aromatic rings, enabling the PPy films to have a higher
conductivity than those doped with smaller or bulky dopant anions. Hydrophobic
surface was found to be able to enhance the conductivity of PPy films when a chloride dopant anion was used [80]. The conductivity was also sensitive to the type of
solvents used for PPy. For example, the PPy thin films cast from PPy dissolved in
bulkier alcohol (e.g., oleyl alcohol) had a higher conductivity than that dissolved in
alcohol, such as methanol [81].
1.3.4Polyaniline (PANI)
PANI is a conducting polymer of the semiflexible rod polymer family, which has
been extensively studied over the past 50 years, focusing mainly on improving its
electrical conductivity [82]. The dependence of color and electrical conductivity
on different oxidation states or doping levels makes PANI a suitable candidate for
sensors and electrochromic devices [83, 84]. Camphorsulfonic acid-doped PANI
15
thin films casted from the PANIs m-cresol solution showed a higher conductivity
than those casted from the PANIs chloroform solution [85]. M-cresol facilitated
the extension of the dissolved PANI polymer chains, while chloroform caused the
dissolved PANI polymer chains to coil [86]. The extended conformation of PANI
also improved the mobility of the charge carriers [87], whereas the vapor-phase
secondary doping, such as m-cresol and o-chlorophenol, enhanced the conductivity of PANI [88]. PANI also has significant advantages over inorganic silicon- and
metal-oxide-based memory materials for the production of both volatile and nonvolatile memory devices [89]. Their dimensions as well as electrical properties can
be easily tailored by controlling the chemical synthesis procedure, producing novel
materials with electrical memory capabilities [90]. Moreover, due to its excellent
electrical conductivity and mechanical stability, PANI finds emerging technological
applications, including rechargeable batteries, solar cells, corrosion devices, and
OLEDs [89].
1.3.5Poly(3,4-ethylenedioxythiophene) (PEDOT)
PEDOT is a conducting polymer based on 3,4-ethylenedioxythiophene monomer
and is highly transparent in its conducting state [91]. Because of the poor solubility of PEDOT, PEDOT:polystyrene sulfonate (PSS) is often used to overcome this
disadvantage [92]. Commercially available PEDOT solutions or dispersions show
electrical conductivities ranging from 0.05 to 10S/cm [9294]. Its conductivity
can be enhanced by mixing with one or more additives, such as methanol, ethanol, isopropanol (IPA), ethylene glycol (EG), glycerol, diethylene glycol (DEG),
sorbitol, dimethyl sufoxide (DMSO), N-methyl-2-pyrrolidinone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide, zwitterions, and ionic liquids
[53]. More approaches to improve the conductivity of PEDOT thin films were reported recently (Table1.3). For example, oxygen-plasma enhanced the conductivity of PEDOT thin films prepared by vapor phase deposition [95]. PEDOT-based
thin films with an excellent conductivity of 900 S/cm were synthesized using
methanol-substituted 3,4-ethylenedioxythiophene [64]. Immersion treatment in
EG further enhanced their conductivities to 1418S/cm [68]. Mixing with an ionic
liquid, 1-ethyl-3-methylimidazolium tetracyanoborate, showed a remarkable conductivity of up to 2084S/cm [69]. Sulfuric acid post treatment also presented an
enhanced conductivity (up to 3065 S/cm) [70]. Ferric tosylate was used as the
oxidizing agent and poly(ethylene glycolpropylene glycolethylene glycol) as
the additive, producing PEDOT-based thin films with a remarkable conductivity
up to 3400S/cm.
Transfer printing
SOBr2
HNO3+ SOCl2
HNO3+ SOCl2
SOCl2
HNO3
HNO3
85
80
77.6
71
80
85
87
56
59
115
80
160
60
340
80
90.9
Rs (/sq)
T (%)
24.9
17.1
13.9
27.8
16.3
64.1
18.8
4.7
Jo etal. [111]
DC / Op Ref.
CBs
Transfer printing HNO3
82
76
23.8
Liu etal. [112]
DCE dichloroethane, SCA superacid chlorosulfonic acid, SDS sodium dodecyl sulfate, TN-PEG terminated poly(ethylene glycol), CBs carbonaceous by
products
Triton X-100
Transfer printing
SDS
Transfer printing
Spin coating
SDS
Spin coating
Transfer printing
DCE
SCA
Table 1.4 Fabrication of SWNT TCs prepared using different approaches [101]
Dispersion method
Solvents or surfactant
Fabrication
Doping agent
method
Using specific solvents
DCE
Dip or spray
coating
16
1 Introduction to Transparent Conductive Films
17
1.4.2Metal Nanowires
As noted above, the fabrication of metal nanogrids is very costly [24]. Thus, randomly distributed metal NWs made of especially copper and silver nanowires (Cu
and Ag NWs) [97, 98] have been investigated as another candidate for TCFs. Cu
NWs were synthesized in gram quantity in aqueous solution and they were assembled into flexible films [101]. The scanning electron microscope (SEM) image in
Fig.1.9a shows long wires of 9010nm in diameter and 103m in length. The
as-produced Cu NW films exhibited a very low sheet resistance (Rs) of 15 /sq
at a T of 65%, along with good stability upon exposure to air for 1 month or after
bending for 1000 cycles. The films consisting of Ag NWs with higher aspect ratios
and uniform dimensions (Fig.1.9b) [98] significantly improved the optoelectrical
properties, i.e., 20/sq at ~80% specular T and 8/sq at 80% diffusive T in the
visible spectral range. Analogous to metal nanogrids discussed above, their high
Fig. 1.8 Metal nanogrids as TCs. a Scanning electron microscope (SEM) image of Au nanogrids
synthesized via a nano-imprinting technique. b Average transmittance plotted as a function of
sheet resistance (Rs) of Au nanogrids. (Reprinted with permission from [96]. Copyright (2007)
by Wiley)
18
Fig. 1.9 Randomly distributed metal nanowires and carbon nanotubes as TCs. a SEM image of
Cu NWs 9010nm in diameter and 103m in length (with inset showing Cu nanowires with
spherical copper particles attached at one end (scale bar=200nm)) [97]. b SEM image of Ag NW
films [98]; and c SEM and d AFM images of single-walled carbon nanotube (SWNT) thin film
deposited on glass [99]. (Reprinted with permission from [9799]. Copyright (2010, 2009) by
Wiley and ACS)
manufacturing and material costs are the main challenges for metal NWs to replace
ITO-based TCFs [24].
19
1.5.2Graphene
A most lately emerging candidate to replace ITO is graphene, a two-dimensional
monolayer of sp2-bonded carbon atoms. The peculiar atomic structure of graphene
allows it to possess unique mechanical, electrical, thermal, and optical properties
that are different from those of CNTs or fullerenes [113]. A few techniques have
been developed to synthesize graphene, such as mechanical peel-off [114], epitaxial
growth [115], and chemical vapor deposition (CVD) [116]. Graphene has attracted
significant interests as the transparent conductive electrodes because of the exceptional electrical transport properties with high optical T. Graphene thin films are
produced by transferring graphene sheets onto transparent substrates through physical contact printing [117] and chemical etching processes [118]. The details of these
techniques for synthesis and transferring are discussed in Chap.2.
Here, the upper and lower bound estimates of the TR curves of graphene were
predicted based on the relation between T and Rs [119]:
T= (1 +
Z 0 G0 2
) ,
2 RS 2 D
(1.1)
20
Fig. 1.10 Outstanding optoelectrical properties of graphene [119]. a Transmittance for different TCs (graphene [121], single-walled carbon nanotubes (SWNTs) [103], indium tin oxide (ITO)
[122], ZnO/Ag/ZnO [123], and TiO2/Ag/TiO2 [124]). b Transmittance (T) versus sheet resistance
(Rs) for different TCs. Blue rhombuses: roll-to-roll graphene TCFs based on chemical vapor deposition (CVD)-grown graphene [121]; red line: ITO [122]; grey dots: metal nanowires [122]; green
triangles: SWNTs [103]. (Reprinted with permission from [119]. Copyright (2010) by Nature
Publishing Group)
where =
Z 0 1/ =
0 c 377 is the free-space impedance, 0 is the free space electric constant, and c is the speed of light. For graphene sheet, 2D = n e , where
n is the number of charge carriers and is the mobility. For an ideal single layer
graphene, the transparency can reach up to 97.7% with a sheet resistance of ~6k/
sq. The sheet resistance can be further reduced to ~400/sq without sacrificing
the transparency by a chemical doping treatment [120]. In additional, as compared
in Fig.1.10a, graphene shows a higher transparency over a wider wavelength range
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than ITO, SWNTs, and thin metallic films [119]. Figure1.10b compares the T and
Rs for different types of TCF materials reported in the literature, including ITO,
SWNTs, Ag NW mesh, CVD grown graphene. In addition to higher transparency,
graphene films have higher mechanical strength, flexibility, and chemical stability
than traditional electrodes made from ITO or FTO [25].
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Chapter 2
2.1Introduction
To develop large-area graphene-based TCFs, one of the foremost challenges is to
produce sufficient amounts of high-quality graphene sheets [1]. The techniques
developed for synthesizing graphene can be grouped into six major methods, i.e.,
mechanical cleavage, epitaxial growth, chemical vapor deposition (CVD), total
organic synthesis, and chemical method. The first attempt to produce graphene
can go back to 1960, when the electron microscopist, Fernandez-Moran, was
looking for a robust, electron-beam transparent, and uniform support membrane
[2]. Millimeter-sized graphene sheets as thin as 5 nm (~15 layers of graphene)
were produced by micromechanical exfoliation from graphite [2]. Single layers
and bilayers of colloidal graphite oxide were observed by electron microscopy
by Boehm et al. in 1962 [3]. Chemical intercalation and exfoliation of oxidized
graphite were extensively investigated in the next decade [4]. Since the discovery
of fullerenes and nanotubes in the early 1990s, great interests were attracted to
study all kinds of carbon materials including graphene [4]. Nanoscale origami-like
structures of one-graphene thickness were observed by atomic force microscopy
(AFM) manipulation of freshly cleaved pyrolytic graphite [5]. Sub-10nm stacks of
graphite were obtained by rubbing micro fabricated graphite pillars on a substrate
in 1999 [6], suggesting a possibility to produce single layer using this technique
[7]. In 2004, Geims group successfully extracted monolayer graphene sheets by
repeatedly cleaving a graphite crystal with an adhesive tape to its limit [8].
The success in mechanical cleavage led to the synthesis of graphene using
other techniques that had reputedly failed in the past [4]. Among others, epitaxial
growth [9] and CVD [10] were shown to produce high-quality graphene. New
methods have emerged to transfer CVD-grown graphene to other substrates for
applications in devices [11, 12]. In order to produce large quantities of graphene
for industry applications, developing large-scale and mass production methods
became necessary [13]. Among those feasible for large-scale production include the
29
30
Table 2.1 Synthesis of graphene. (Reprinted with permission from [15]. Copyright (2014) by
Elsevier)
Method
Figure/illustration
Images
Advantages
Disadvantages
References
Mechanical
cleavage
Less defects
Novoselov et
al.8, 16;
Singh et al. 14
Epitaxial
growth
No defects for
every single
graphene island
Discontinuous
Sutter et al. 17
CVD
Compatible with
the current CMOS
technologies
Kim et al. 18
Total organic
synthesis
Potentially suitable
for mass
production
Many defects
Yang et al. 19
Chemical
method
The majority of
defects can be
removed
Stankovich et
al. 20
total organic synthesis of polyaromatic hydrocarbons (PAH) [14] and the chemical
route to produce reduced graphene oxide (rGO) sheets. At present, the chemical
method has emerged to be a viable route to afford graphene-based single sheets in
considerable quantities [14].
Table 2.1 summarizes the relative advantages and disadvantages of the above
synthesis methods in term of the feasibility to scale-up the process for mass production, materials and production costs, and the presence of defects. The detailed
fabrication processes of these methods are described in Sect.2.2.
31
Fig. 2.1 Micromechanically exfoliated graphene: optical images of a thin graphite, and b fewlayer graphene and single-layer graphene (lighter purple contrast) on a ~300nm SiO2 layer.
Yellow color indicates thicker samples whereas bluish and lighter contrast indicates thinner
samples. (Reprinted with permission from [4]. Copyright (2010) by Elsevier)
32
surface, which may limit the carrier mobility [25]. This technique is neither scalable
nor capable of mass production, even though the samples of graphene thereby obtained could be useful for fundamental studies to characterize their chemistries and
properties.
2.2.2Epitaxial Growth
Epitaxial growth is a substrate-based method, where isolated monolayer of graphene is grown on a single-crystal silicon carbide (SiC) by vacuum graphitization.
Since the thermal treatment of silicon carbide at ~1300C under vacuum results
in sublimation of the silicon atoms while the carbon-enriched surface undergoes
reorganization and graphitization, graphene islands over the entire surface of SiC
wafers were obtained through careful control of the sublimation (Table2.2) [4, 26
29]. The thickness of graphene layers was controlled mainly by annealing temperature and time, and the uniformity of thickness was improved by vapor-phase annealing [30, 31]. A major advantage is that epitaxial-grown graphene can be patterned
using standard lithography methods, a useful property for nanoelectronics. The
physical properties of graphene varied significantly between those grown epitaxially and exfoliated mechanically, due mainly to the influence of interfacial effects in
epitaxial graphene. Similar approach was applied to other metallic substrates, such
as ruthenium (Ru), to produce graphene layers [17, 32]. It is found that the (0001)
faces of Ru crystals were able to grow epitaxial graphene layers, where a very
sparse graphene nucleated at high temperatures. The first graphene layer coupled
strongly to the Ru substrate and the second layer was free of the substrate interaction, which had an electronic structure similar to freestanding graphene. However,
several hurdles must be overcome before real applications are found [14]. First of
all, it is very hard to control the thickness of graphene in the routine production.
Second, unusual rotational graphene stacking were observed in multilayer graphene
due to the different epitaxial growth patterns on different SiC polar faces, which
had profound effects on the physical and electronic properties of epitaxial graphene
[33]. The growth mechanisms need to be further investigated. Third, the relationship between the structure and electronic properties of the interface layer between
graphene and the substrate needs to be clearly understood.
33
References
VanMil etal.
[35]
Camara etal.
[36]
Camara etal.
[37]
Virojanadara
etal. [38]
Unarunotai
etal. [39]
Moreau etal.
[40]
Hibino etal.
[41]
Prakash
etal. [42]
Jernigan
etal. [43]
Ouerghi
etal. [44]
on the substrate. One of the major advantages of the epitaxial and CVD growth
techniques is their high compatibility with the current complementary metaloxidesemiconductor (CMOS) technology. A typical weakness is that controlling the
film thickness is difficult and secondary crystals are easily formed [51], although
some progress has been made to grow uniform graphene layers using the CVD
method [52]. Another important disadvantage is the need of expensive substrate
materials for graphene growth, considerably limiting its applications for large-scale
production. Nevertheless, the CVD approach has emerged as an important method
for mass production of graphene with less structural and electronic disorder or defects, making it an excellent potential for TC applications.
34
Graphene Grown on Ni
The formation of FLG on transition metal surfaces has been known for nearly a
half century [53, 54]. The typical process for CVD of graphene onto Ni film is
shown in Fig.2.2a. In general, the polycrystalline Ni films deposited on SiO2/Si
are first annealed at 9001000C under H2 and Ar flow to grow a smooth surface.
The Ni films are then exposed to a H2 and CH4 mixture so that the carbon atoms
can dissolve into the Ni film to form a solid solution. Finally, the substrate is cooled
down in an Ar atmosphere. As the solubility of carbon atoms decreases as the
temperature goes down, the carbon atoms diffuse out from the NiC solid solution during cooling and precipitate onto the Ni surface to form graphene films.
Fig. 2.2 Graphene grown on a Ni substrate. a Illustration of graphene growth in three different
stages [56]. b Schematic of full-wafer scale deposition of graphene layers on polycrystalline Ni
by chemical vapor deposition (CVD). c E-beam-evaporated Ni film of thickness 100 nm on a
10cm diameter Si/SiO2 wafer. d Atomic force microscopy (AFM) image of a Ni film after CVD
of graphene layers [55]. (Reprinted with permission from [56, 58]. Copyright (2009, 2013) by
Springer and ACS)
35
Fig. 2.3 ac Scanning tunneling microscope (STM) images of graphene on Pd(111) acquired in
situ during growth. d Surface height profile along the white line shown in c; and e atomic model
showing the orientation of graphene. (Reprinted with permission from [57]. Copyright (2009)
by ACS)
36
honeycomb lattice of graphene and the hexagonal lattice of Pd (111), these superstructures are of Moir patterns [57]. Figure2.3e shows the atomic model of such
a commensurate Moir superstructure and the determined epitaxial relationship
between the monolayer graphene and Pd(111).The method of growing graphene
islands on a Pd surface opened up a new avenue of preparing metal-semiconducting
graphene structures and metal-doped graphene-based devices.
Graphene Grown on Cu
Due to the grain boundaries of Ni or Pd surface, the grown graphene films usually contain both monolayer and few-layer graphene [58]. Because carbon has extremely low solubility in Cu, Cu has become a potentially outstanding substrate for
the growth of monolayer graphene [54]. Ruoffs group at the University of Texas
at Austin first reported the growth of high-quality monolayer graphene on polycrystalline Cu foils, which attracted great attention due to the advantages of good
control of graphene layers, low cost, and ability to transfer [10]. The Cu foil was
annealed at 1000C in a hydrogen atmosphere. A mixture of H2/CH4 was then introduced into the system to initiate graphene growth on the Cu foil. The system was
cooled down to room temperature after a continuous graphene layer was formed
[10]. The SEM image in Fig.2.4a clearly shows Cu grains with color contrast. The
high-resolution SEM in Fig.2.4b indicates that these Cu surface steps were formed
during thermal annealing. The darker flakes indicate multilayer graphene, while
the wrinkles originated from the different thermal expansion coefficients between
graphene and Cu. The wrinkles went across the Cu grain boundaries, confirming
that the graphene film was continuous. The inset of Fig.2.4b shows TEM images
of single and bilayer graphene. The grown graphene films can be transferred to another substrate using various transfer methods. Figure2.4c, d shows the transferred
graphene film on a SiO2/Si or glass substrate. It is seen that the graphene film on
the glass substrate was optically uniform. The quality and uniformity were evaluated by Raman spectroscopy and Fig.2.4eg shows the SEM and optical images
with the corresponding Raman spectra. The Raman spectra (Fig.2.4g) indicated by
a red circle has a G-to-2D intensity ratio (IG/I2D) of ~0.5 and a symmetric 2D band
centered at ~2680cm1 with a full width at half maximum (FWHM) of ~33cm1,
confirming the monolayer graphene [10]. The blue circle and green arrow represent
bilayer- and trilayer-graphene sheets, respectively.
37
38
2.2.5Chemical Methods
The most common source of graphite used for oxidation is flake graphite, which can
be produced by removing heteroatomic contaminations from naturally occurring
graphite [60]. Due to the spaces between graphene layers in graphite, the intercalating agents are able to reside between the graphene layers under chemical reactions,
forming graphite intercalation compound (GIC) [61]. The experiments to investigate the insertion of additional chemical species between the basal planes have been
performed extensively since the successful formation of the first intercalation compound using potassium [51]. GICs have layered compounds with different stages,
which are defined as the number of graphitic layers in between adjacent planes
of intercalant [51]. Figure 2.6ad shows the structures of second- to fifth-stage
bromide GICs, which correspond to approximate compositions of C16Br2, C24Br2,
C32Br2, and C40Br2 [62].
The interlayer spacing of GIC can increase from 0.34 nm to more than 1 nm
depending on the intercalant, leading to a significant reduction in the van der Waals
forces between adjacent sheets [61]. The weak van der Waals forces make GICs
much easier to be further exfoliated, offering a possible route to fabricate single
layer graphene or graphene oxide (GO). The interlayer spacing in GICs can be expanded by thermal shock (~1000C) to produce expanded graphite (EG). As shown
in Fig.2.6e, the halogen intercalants, such as iodine chloride (ICl) (to form Stage-2
ionic GIC) and iodine bromide (IBr) (to form Stage-3 ionic GIC), can be introduced
into the host material of highly ordered pyrolytic graphite (HOPG) and sequentially
to form layered structures [63]. Upon high-temperature annealing, the volume of
the obtained Stage-2 and Stage-3 GICs (Fig.2.6f, g) increases rapidly due to the
volatilization of the IBr or ICl intercalants between the graphene layers [63].
Graphite oxide was first prepared almost 150 years ago by Brodie, who treated
graphite repeatedly with potassium chlorate and nitric acid [64]. The oxidizing agent
39
was changed to a mixture of sulfuric acid, nitric acid, and potassium chlorate [64]. A
less hazardous and more efficient method for graphite oxidation was later devised by
Hummers and Offeman [65], who employed a mixture of sodium nitrate, potassium
permanganate, and concentrated sulfuric acid. The latter two modified methods are
at present most widely employed [66]. Graphite oxide in water hydrolyzes to form
40
Fig. 2.6 Interlayer ordering in graphite intercalation compounds (GICs) with different stages and
the expanded graphite (EG) [6163]. ad Second to fifth stage structure of bromine-intercalated
GICs. The dashed lines indicate bromine intercalate layers; the solid lines indicate carbon layers
[61, 62]. e 3D computer-generated molecular models of highly ordered pyrolytic graphite (HOPG)
(top), iodine bromide (IBr) Stage-3 GIC (middle), and chloride (ICl) Stage-2 GIC (bottom).
f Photographs of HOPG (top), Stage-3 GIC (middle), and Stage-3 EG (bottom). g Photographs of
HOPG (top), Stage-2 GIC (middle), and Stage-2 EG (bottom) [63]. (Reprinted with permission
from [61, 63]. Copyright (2002, 2011) by Springer and Nature Publishing Group)
negatively charged thin platelets that consist of single- to multilayer carbon. Monolayer graphite oxide is now widely acknowledged and recognized as GO [20, 67].
The term sheets usually indicate monolayer to several layers, while platelets
is often used to describe thicker multilayer GO or rGO [68]. Figure2.7 shows the
41
process involved in the exfoliation of graphite oxide into individual GO sheets. The
exfoliation is facilitated by rapid heating [69] or ultrasonic agitation [70, 71], while
excessive ultrasonication often results in breakage or fragmentation along with a
significant reduction in lateral dimensions of GO sheets [72, 73]. Individual GO
sheets can be viewed as graphene decorated with oxygenated functional groups on
the basal plane and around the edges [74]. Due to the ionization of carboxyl groups
present at the edges, GO can be electrostatically stable to form a colloidal suspension [70] in water, alcohols, and certain organic solvents [75] without surfactants.
To restore the inherent electrical conductivity of graphene, GO should be reduced either in solutions [20, 71, 7779] or after films are formed on a substrate
(Fig.2.8a). Many different reducing agents have been identified, including hydrazine [20, 80, 81], dimethylhydrazine [67], hydroquinone [82], hydrogen iodine (HI)
[83, 84], and NaBH4 [85, 86]. The reduced GO sheets become less hydrophilic and
instantly aggregate in the solution because of the removal of oxygenated groups
(Fig. 2.8bd). However, charge-stabilized colloidal dispersions were obtained by
raising the pH value during reduction, even for deoxygenated sheets [87]. More
recently, the reduction step was further improved by preparing dispersions directly
in anhydrous hydrazine [80, 81, 88]. It should be noted, however, that anhydrous
hydrazine is highly toxic and potentially explosive, thus a great caution should be
exercised when using it.
The solution-based exfoliation method involves direct exfoliation of natural
graphite (NG) flakes in organic solvents, such as methanesulfonic acid (MSA)
[90], ionic liquids [91], benzylamine (BA), N-methyl-2-pyrrolidone (NMP),
and N,N-dimethylacetamide (DMA) with the addition of NaOH [92]. Dispersion and exfoliation of graphite are simultaneously achieved with the aid of
sonication and the sonication energy required for exfoliation is balanced by the
42
Fig. 2.8 Reduction of graphene oxide (GO). a Oxidation of graphite to GO and reduction to
reduced graphene oxide (rGO) [14]. bd Aberration-corrected TEM images of the following materials. Scale bar, denoting 2 nm, is valid for all images. b Single suspended sheet of graphene.
c Single suspended sheet of GO. d Suspended monolayer of rGO [89]. (Reprinted with permission
from [14, 89]. Copyright (2011, 2010) by Elsevier and Wiley)
43
2.3Preparation of Large-Size GO
2.3.1Mild Oxidation and Sonication
Due to the presence of a large number of intersheet junctions, small-size GO sheets
may result in high intersheet contact resistance in the reduced GO films [101].
Because of the needs to synthesize large-size graphene sheets with uniform size
distributions, many studies have been directed towards optimizing the parameters
employed in various steps of the chemical method. Table2.3 summarizes the representative methods of producing large-size GO by controlling the oxidation and
sonication parameters.
44
GO size
References
Up to ~200m
Up to
~40,000m2 in
area
Approximately
millimeter
Up to 50m
~20m
Up to~200m
Zheng etal.
[107] Aboutalebi
etal. [108] Jia
etal. [109]
Su etal. [104]
45
Fig. 2.10 SEM images of ultralarge graphene oxide (UL-GO) sheets. a Large graphene oxide
(GO) sheets obtained via a mild oxidation and sonication method [103]. b UL-GO sheets obtained
by avoiding sonication process [104]. (Reprinted with permission from [103, 104]. Copyright
(2010, 2009) by ACS)
2.3.3Elimination of Sonication
Efficient and highly reproducible chemical methods have been developed which
involve intercalation, thermal exfoliation, and chemical oxidation to produce gramscale large-size GO sheets, up to ~50200m in lateral size with a yield exceeding
50% [107, 108]. The UL-GO stable suspension was obtained through oxidation and
washing processes without any sonication step. It is found that the GO size produced
through chemical method mainly depended on three factors: namely, (i) to control the
degree of oxidation; (ii) to completely eliminate damaging ultrasonication process;
46
Fig. 2.11 Transparent graphene films produced via a simple solution casting of exfoliated platelets from edge-selectively functionalized graphite (EFG). a Schematic presentation of pristine
graphite, EFG in solid state and EFG in dispersed solution. b As-cast EFG film. c Heat-treated
EFG (HEFG) film on a SiO2 surface. (Reprinted with permission from [106]. Copyright (2011)
by ACS)
and (iii) to use the inherently large NG flakes as the precursor material [109]. Because the use of large graphite flakes as the precursor material does not necessarily
guarantee large-size GO sheets, the pre-exfoliation process and the use of exfoliated
graphite are necessary to avoid the damaging ultrasonication process, and thus ensure minimum breakage of the GO sheets during fabrication. As shown in Fig.2.12a,
the fabrication process includes three steps: (i) intercalation of acid molecules into
NG to obtain GICs, (ii) expansion of the interlayer space by thermal shock at a
high temperature (~1000C), and (iii) chemical oxidation by modified Hummers
method. Graphite was sufficiently exfoliated before oxidation, thus individual GO
sheets were easily obtained by gentle shaking. Figure2.12b, c shows that the sizes of
the as-prepared GO sheets varied from several to hundreds of micrometers.
To further understand the effects of ultrasonication, thermal shock expansion,
degree of oxidation, and precursor NG flake size on final GO size, well-planned
parallel experiments were performed [109]. As shown in Fig. 2.13, different
47
Fig. 2.12 a Flow chart for the synthesis of ultralarge graphene oxide (UL-GO) [110]. bc SEM
images of as-prepared graphene oxide (GO) sheets deposited on a Si substrate at b low and c
high magnifications [107]. GIC graphite intercalation compound. (Reprinted with permission from
[107, 110]. Copyright (2011, 2012) by ACS and RSC)
48
Fig. 2.13 Effects of processing and material parameters on the size of final graphene oxide
(GO) sheets. The flowchart shows the preparation of GO sheets from nano-graphene (NG) flakes
based on three different approaches. (Reprinted with permission from [109]. Copyright (2014) by
Elsevier)
High-Speed Centrifugation
Several different size groups 4 of GO sheets were obtained after sequential highspeed centrifugation of GO polydispersion, and Fig.2.14 shows the flow chart for
the sequential centrifugation at gradually slower speeds. Typically, the unsorted,
as-prepared GO dispersion was centrifugated initially at 8000rpm for 40min, dividing GO into supernatant and precipitate, and the supernatant was collected to
label as small GO (S-GO). The precipitate was re-dispersed for the second run
of centrifugation at 6000rpm for 25min, producing supernatant and precipitate.
The supernatant obtained in this run was designated as large GO (L-GO). The
precipitate was re-dispersed in water for the third run of centrifugation at 4000rpm
for 25min, producing very large GO (VL-GO) (supernatant) and ultralarge GO
(UL-GO) (precipitate). Figure2.15 presents the area distributions of the different
49
Fig. 2.14 Flow chart for high-speed centrifugation method. (Reprinted with permission from
[110]. Copyright (2012) by RSC)
groups obtained, namely, S-GO, L-GO, VL-GO, and UL-GO, which were measured
by counting more than 200 sheets for each group.
Density Gradient Separation
GO Dispersions containing monodispersed GO sheets can also be separated by density gradient centrifugation [73, 111, 113]. The separation method is based on the
isopycnic density gradient ultracentrifugation and involves balancing the density
of colloids of the material with that of a supporting medium. The technique was
successfully employed to separate graphene sheets by the number of layers [95,
113] and carbon nanotubes (CNTs) by the diameter/chirality/wall thickness [114,
115]. As illustrated in Figure 2.16a, GO or rGO can be separated into a specific
size range, which has particular properties for different applications by optimizing
the separation parameters [73, 111]. According to the Stokes Law [111], larger
sheets have a higher sedimentation rate after balancing the centrifugal force against
buoyancy and viscous drag. The density and viscosity increased at the gradient
boundaries, causing smaller GO sheets to move slowly, allowing larger and heavier
sheets to pass through. Therefore, GO sheets with different lateral sizes and surface
chemistries were captured along the centrifuge tube at appropriate positions when
the centrifugal force was removed. Figure 2.16b shows the centrifugation tubes
after separation using different conditions, and the horizontal dark bands/lines correspond to the gradient boundaries fixed before centrifugation. Figure2.16c shows
the images of an ultracentrifuge tube after density gradient separation of functionalized GO, confirming that the separation method offers an effective way to obtain
GO or rGO sheets with suitable sizes in bulk quantities.
50
Fig. 2.15 Size distributions of a UL-GO, b VL-GO, c L-GO, and d S-GO; and e average areas of
graphene oxide (GO) sheets. UL-GO ultralarge graphene oxide, VL-GO very large graphene oxide,
L-GO large graphene oxide, S-GO small graphene oxide. (Reprinted with permission from [107,
110]. Copyright (2011, 2012) by ACS and RSC)
51
Fig. 2.16 Density gradient separation method: schematic a and picture b of separation of reduced
graphene oxide (rGO) sheets into different sizes via density gradient centrifugation [111]; and
c area sorting of polyethyleneglycol-functionalized graphene oxide (GO) after density gradient
separation [73]. (Reprinted with permission from [111, 73]. Copyright (2010, 2008) by ACS and
Springer)
groups with decreasing GO size [112]. Thus, the technique involves selective precipitation of GO sheets with sizes larger than 40m2 at a pH of 4.0 which contain
larger hydrophobic planes and fewer hydrophilic oxygenated groups. The zeta potentials of GO dispersions decreased with increasing pH because of the ionization
of COOH functional groups, see Fig.2.17a. GO dispersions became stable when
their zeta potential values were lower than about 30mV. It is worth noting that
there was a pH window between 3.34 and 4.24, where the zeta potential of the
large GO was higher than 30mV, and that of the small GO was lower than this
value. By controlling the pH value of a GO dispersion, one can realize the fractionation of GO sheets (Fig.2.17b).
52
/DUJHVL]H*2
6PDOOVL]H*2
Fig. 2.17 pH-assisted selective sedimentation method. a Zeta potentials of large and small graphene oxide (GO) aqueous dispersions as a function of pH value. b SEM images of unsorted GO
before fractionation, large and small GO monolayers after fractionation. (Reprinted with permission from [112]. Copyright (2011) by ACS)
edge can also be directly determined by TEM, which is capable of producing movies of the dynamics of carbon atoms at the edge of a hole in a suspended graphene
sheets (Figs.2.19h, i) [118]. As the first truly 2D crystal, it is particularly important
to understand the mechanisms of the stability of graphene. By means of atomistic
Monte Carlo simulations based on a very accurate many-body interatomic potential
for carbon [119], it is found that that ripples spontaneously appear arising from
thermal fluctuations with a size distribution peaked at about 80 (Figs.2.19j, k), a
reflection of the multiplicity of chemical bonding in carbon [120].
The structure of GO is largely different from that of pristine graphene because
of the attachment of oxygenated functional groups. The nonstoichiometric chemical composition of GO makes it a challenging task to determine the structure of GO
[64]. One of the most credible and well-known models of GO was proposed by Lerf
[74] and Klinowski [65, 122], who focused on a nonstoichiometric and amorphous
structure. As schematically shown in Fig. 2.20a, b, three major features including graphitic regions (with an original honeycomb structure), disordered regions
53
Fig. 2.18 2D building material for other dimension carbon materials. (Reprinted with permission
from [121]. Copyright (2007) by Nature Publishing Group)
(with high oxidation), and defect regions (with holes) are presented on GO sheets.
The oxygenated functional groups attached on GO sheets have been studied using
different characterization techniques, such as high-resolution TEM, STM, XRD,
XPS, and Fourier transform infrared spectra analyzer (FT-IR) [64].
It is found that partial oxidation was thermodynamically favored over complete
oxidation according to both experimental observations and density functional calculations [123]. The variations in the degree of oxidation caused by the difference
in graphite source or oxidation procedure may cause considerable modifications in
the structure and properties of GO. In addition, the precise nature and distribution
of these oxygenated groups were determined by the level of coverage and GO size
[65, 124]. A low O/C ratio is normally associated with a large GO area, suggesting
that a smaller GO contains relatively more oxygenated groups given the GO surface
area [124]. It is also found that the epoxide to alcohol ratio increased with more
oxidation [123]. Characterizing the degree of oxidation is necessary to understand
the structureproperty relationships because the optical and electrical properties of
GO are controlled mainly by -electrons from the sp2 carbon atoms [125].
To reveal further structural information, the surface of GO was examined [90, 91]
under an STM. Although the hexagonal lattice of the sheets was partially preserved,
the GO sheets were distinguishable from pristine graphene by the appearance of
54
Fig. 2.19 Structure of graphene. ac Schematics of crystal structure a, Brillouin zone b and dispersion spectrum (c) of graphene [116]. dg Raman imaging results from edges with angles d 30,
e 60 (zigzag), f 90, and d 60 (armchair) [117]. h, i Aberration-corrected TEM image of h an
armchair, and i zigzag configurations of carbon atoms at the edge of a hole in graphene [118]. j, k
A representative configuration of graphene j and the bond length distribution k [120]
55
Fig. 2.20 Structure of GO sheets. a Structural model [128]. b 3D view [124] of graphene oxide
(GO) showing hydroxyl and epoxy groups on the basal plane and carboxylic acid groups mainly at
the edges. c STM image of a GO monolayer on a highly oriented pyrolytic graphite (HOPG) substrate, taken under ambient conditions (oxidized regions are marked by the line contours) [129].
d AFM image of a GO monolayer deposited on a SiO2 substrate, showing a backfolded edge [129].
e AFM section profiles along the three different lines in d, showing a mono-, bi-, and trilayer structure [129]. STM scanning tunneling microscope, AFM atomic force microscopy. (Reprinted with
permission from [124, 128, 129]. Copyright (2012, 2009, 2007) by ACS)
bright regions that correspond to the destruction of ordered lattice features due to
the presence of oxygenated functional groups (Fig.2.20c). Because of the oxygenated functional groups, the thickness of a monolayer GO sheet is much thicker than
~0.34nm of an ideal monolayer of graphene. The thickness of a monolayer GO
sheet is shown ~1 nm, while that of double layer GO is ~2 nm (Fig. 2.19d, e).
However, the thickness of GO sheets may largely vary depending on the degree of
oxidation [20, 126, 127].
56
Table 2.4 Comparison of electrical properties of pristine graphene, GO, and rGO
Type of graphene or
GO
Graphene
Sheet resistance (/
sq)
301000
GO
rGO
Insulator
1200
>1012
103107
References
[8, 45, 121, 132, 133,
143 ],
[141]
[104, 128, 141,
144146]
paradox, and weak antilocation [130, 131]. The carrier mobility of graphene can
reach up to 200,000cm2v1s1 when graphene is suspended on a clean surface,
which can be extremely useful for ultrafast electronics and optoelectronics [132]. In
reality, however, its mobility is largely limited to 200015,000cm2v1s1 because
of the presence of microscopic ripples, scattering, and defects [8, 121, 133]. Since
graphene is a zero gap semimetal, many efforts have been directed towards opening
a band gap using several methods, such as narrowing 2D graphene to 1D nanoribbon, forming nanomesh and hydrogen patterning [134137]. An on/off ratio of over
104 was observed in very narrow GNRs [138]. Due to the high charge mobility, the
quantum Hall effect was observed even at room temperature [139].
In sharp contrast, however, the electrical properties of GO sheets are significantly different from those of the pristine graphene. The long-range conjugated network
of the graphitic lattice is the main reason for the excellent conductivity of pristine
graphene sheets, while the functional groups and defects on GO sheets break the
conjugated structure and localized -electrons [140]. As compared in Table2.4, owing to the much reduced carrier mobility, GO film is insulating with Rs values typically higher than about 1012/sq [141]. The reduction of GO is the key to restore
the excellent electrical conductivities of graphene. Chemical and thermal reduction
methods are known as the two main strategies to reduce GO [142]. The relation
between sheet resistance (Rs) (unit: /sq) and bulk conductivity () (unit: S/m) can
be described by the following equation:
Rs =
1
t
(2.1)
57
Conditions
C/O ratio
Hydrazine
Hydrazine
100C, 24h
DMF/H2O, 80C,
12h
RT, 24h
80C, 1h
RT, 2h
RT, 30min
RT, 6h
RT, 1min
RT, 2h
RT, 7h
RT, 20min
RT, 5min
RT, 10min
RT, 6h
RT, 20min
40C, 40h
100C, 1h
10.3
11
Conductivity References
(S/m)
2420
Stankovich etal. [20]
Park etal. [150]
1700
9.5
4.8
8.6
18.6
7.9
33.5
21.2
7.6
21.1
3.9
7.6
17.9
5.3
11.5
12
4700
82
45
2100
2300
15,000
3416
12,530
10
7540
1120
30,400
29,800
Phenylhydrazine
NaBH4
NaBH4
Al/HCl
Fe/HCl
Zn/HCl
Zn/H2SO4
Sn(II)/HCl
Al foil/HCl
Mg/HCl
Zn/NH3
Zn/NaOH
Al foil/NaOH
HI/AcOH
HI
water. Although hydrazine has been one of the most widely used agents in industry,
it is highly toxic and dangerous, especially the anhydrous hydrazine, thus extreme
care has to be taken in using it.
Figure 2.21a shows the fabrication process of rGO by hydrazine. The direct
dispersion of hydrophobic graphite or graphene sheets in water without the assistance of dispersing agents has generally been considered to be an insurmountable
challenge. To avoid the serious aggregation of GO after reduction, soluble polymer surfactants [71] or ammonia [87, 126, 144] have been employed to retain the
colloidal state in water. Li etal. [87] discovered that it is easy to produce stable
aqueous rGO dispersions by adding ammonia to the reaction solution to increase the
pH value (Fig.2.21b). This method is a facile approach to large-scale production
of aqueous rGO dispersions without the need of polymeric or surfactant stabilizers,
making it possible to process graphene materials using low-cost solution processing
techniques [87]. The derivatives of hydrazine, such as dimethylhydrazine [67] and
phenylhydrazine [147], were also shown effective reducing agents for GO. Metal
hydride, such as NaBH4, was shown comparable with hydrazine as a reducing agent
[148, 149]. It is also found that an additional dehydration process using concentrated sulfuric acid at 180C after reduction by NaBH4 further improved the reduction
efficiency of GO [148].
However, these chemicals are not suitable for the reduction of GO films, especially for those needing high flexibility for applications in flexible devices, because
of the stiffening effect and disintegration of the films during reduction. Figure2.22a
shows optical photographs of the reduction process by immersing GO films into
58
Fig. 2.21 Chemical reduction by hydrazine. a Scheme showing the chemical route to the synthesis
of aqueous graphene dispersions. 1 Oxidation of graphite (black blocks) to graphite oxide (lighter
colored blocks) with greater interlayer distance. 2 Exfoliation of graphite oxide in water by sonication to obtain graphene oxide (GO) colloids stabilized by electrostatic repulsion. 3 Controlled
conversion of GO colloids to conducting graphene colloids through deoxygenation by hydrazine
reduction. b Effect of ammonia on dispersion state of CCG sheets, characterized by measuring
average particle sizes over a long period of time. The photographs shown in the inset were taken
2 days after the reduction reaction was complete with (left) and without (right) ammonia [87]
different reducing agents (like NaBH4, N2H4, and HI) for different durations [83]. It
is observed that the bubbles appeared when GO films were immersed into NaBH4
and N2H4 solution, indicating that they reacted with GO to produce gases. The GO
films were broken down to small graphene debris after 16 h reaction. However,
immersion of GO films in HI acid solution hardly generated bubbles around them.
The films in the HI acid solution maintained their integrity very well even after a
long reaction time. Due to the advantage of HI reduction, Moon etal. [84] produced
HI-reduced GO films on a PET substrate (Fig.2.22b).
59
Fig. 2.22 a Optical photographs of reduction process by immersing a graphene oxide (GO) film
into different reducing agents for different durations at room temperature [83]. b Flexible GO
film (left) and HI-reduced GO thin films on a polyethylene terephthalate (PET) substrate [84].
(Reprinted with permission from [83, 84]. Copyright (2010) by Elsevier and Nature Publishing
Group)
Thanks to the extremely fast and efficient reduction abilities, the use of metal
and acid mixture for reduction of GO has gained much attention recently [151, 154].
The reduction is achieved by fast electron transfer between the metal and GO, and
the evolution of nascent hydrogen as the active reducing agent [159]. For example,
a mixture of aluminum powder (10mm) and hydrochloric acid produced rGO with
a C/O ratio of 18.6 and an electrical conductivity of 2100S/m [151]. The following
study shows that iron powder (10mm) in the presence of hydrochloric acid (Fe/
HCl) [152], zinc powder in hydrochloric acid (Zn/HCl) [153], solid zinc filings and
sulfuric acid (Zn/H2SO4) [154], tin(II) chloride in hydrochloric acid (Sn(II)/HCl)
[155], aluminum foil and hydrochloric acid (Al foil/HCl) [156], and magnesium in
hydrochloric acid (Mg/HCl) [157] were all effective reducing agents of GO, which
60
offered one of the shortest reaction times to obtain rGO. Metalalkaline, such as
aluminum or zinc metals in alkaline environments, was also shown to reduce GO
[156, 158]. For example, zinc powder in the presence of ammonia solution successfully reduced GO in 10min at room temperature [158]. Similarly, the reduction of
GO was also achieved with aluminum foil and zinc powder in sodium hydroxide
(Al foil/NaOH, Zn/NaOH) solution [156].
Apart from chemical reduction using various reducing agents, several other
strategies, including photocatalyst reduction, electrochemical reduction, and solvothermal reduction, have been explored recently [142]. Photocatalyst reduction is
based on the photochemical reactions with the assistance of a photocatalyst such as
TiO2 [160, 161]. It is proposed that charge separation occurs on the surface of TiO2
particles upon UV-irradiation. Because the holes are scavenged to produce ethoxy
radicals, the electrons accumulate within the TiO2 particles and interact with GO
sheets to reduce functional groups [162]. Electrochemical reduction is usually carried out in a normal electrochemical cell using an aqueous buffer solution at room
temperature without special chemical agents [163, 164]. The reduction of GO is
achieved mainly by the electron exchange between GO and electrodes, thus the use
of toxic reducing agents like hydrazine and producing byproducts can be avoided.
Solvothermal reduction is normally performed in a sealed container so that the temperature is maintained above solvents boiling point [165, 166]. Particularly in the
hydrothermal process, the overheated supercritical water plays the role of reducing
agent and the physiochemical properties can be controlled by pressure and temperature, offering a green chemistry alternative to organic solvents [165].
Thermal Reduction
Significant research has also been conducted for thermal reduction of GO into a
more pure form of graphene to restore the sp2 carbon structure and thus increase
the electrical conductivity [167]. It is found that the carriers traveling across rGO
thin films are scattered or trapped by sp3 carbon sites, defects, sheet junctions, and
other structural imperfections and impurities [64]. The large variation of electrical
conductivities can be explained by percolation transport. Mattevi etal. [167] investigated the role of residual oxygen and sp2 carbon fraction on electrical conductivities of thermally reduced GO. Figure2.23a shows the evolution of carbon bonds in
GO thin films as a function of annealing temperature in ultrahigh vacuum (UHV).
It is suggested that GO undergoes structural changes due to the loss of oxygen and
the carbon atoms in the basal plane may also rearrange.
Figure2.23b shows the plot of conductivities of rGO films as a function of sp2carbon fraction as well as the data for 100% sp2-bonded materials like graphene
and polycrystalline graphite for comparison. A high conductivity 1.25103Scm1
of polycrystalline graphite at a sp2 fraction of ~0.87 in reduced GO was estimated
by extrapolating the experimental data [64]. Even a minimum conductivity
~6103Scm1 was also suggested for a monolayer graphene [168], if the sp2 fraction were to increase above 0.9. The inset of Fig.2.23b shows the structural model
61
for the essential features of transport through an rGO sheet at different stages of reduction. Since the sp2 clusters are isolated by oxygen atoms (indicated by dots), the
GO film is insulating prior to reduction. As reduction restores sp2 carbon in GO, the
transport barrier between the clusters narrows, allowing small fraction of carriers to
hop or tunnel among sp2 sites. Upon further reduction of GO, better connectivity is
formed among the original sp2 domains by forming new, smaller sp2 clusters along
with concurrent formation of structural defects. Percolation among the sp2 clusters
dominates the transport at higher sp2 fractions. Percolation is found to occur at sp2
fraction of 0.6 from the fit and it is in reasonable agreement with the theoretical
threshold values for conduction among 2D disks [169].
Based on the above discussion, it is obvious that the heating temperature
significantly affects the reduction of GO [126, 170, 171]. Table2.6 presents thermal
reduction of GO carried out under different processing conditions, such as annealing temperature and atmosphere. It is shown that the C/O ratio was no more than
9 if the temperature was less than 500C, while the C/O ratio could be higher than
62
80
GO
500
Argon
5900
Hydrazine rGO 220
Argon
11,800
Hydrazine rGO 500
Argon
35,100
Solvothermal
1000
Helium
6.03
57,300
rGO
Hydrazine rGO 1000
Helium
6.36
66,700
GO
500
Argon
6.8
GO
1000
Argon
11.36
GO
500
Argon and
7.3
hydrogen
GO
1000
Argon and
12.4
hydrogen
8.9
GO
500
Ultrahigh
vacuum
GO
1050
Argon
10
GO
1100
Argon and
55,000
Hydrogen
Hydrazine rGO 400+1100
Argon
649
GO
1050
Hydrogen
2000
GO
1050
Argon
200
GO
1050
Vacuum
80
rGO
800
Ethylene
350
1000
Ultrahigh
1314
Aromatic
vacuum
moleculesfunctionalized
rGO
GO graphene oxide, rGO reduced graphene oxide
References
Chen etal. [180]
Chen etal. [180]
Chen etal. [180]
Chen etal. [180]
Dubin etal. [166]
Dubin etal. [166]
Yang etal. [79]
Yang etal. [79]
Yang etal. [79]
Yang etal. [79]
Yang etal. [79]
Schniepp etal. [69]
Mattevi etal. [167]
Wang etal. [144]
Wu etal. [177]
Wu etal. [177]
Wu etal. [177]
Lopez etal. [178]
Su etal. [179]
63
repair the defects in rGO sheets, Lopez etal. [178] exposed rGO to a carbon source,
such as ethylene, at an elevated temperature of 800C. The results showed that the
vacancies were partially repaired and the conductivity of the individual rGO sheet
reached up to 350S/m. Su etal. [179] discovered that rGO sheets functionalized
by aromatic molecules produced a highly graphitic material with a conductivity as
high as 1314S/cm after thermal annealing at 1000C, which is attributed to a similar defect-healing effect. Although reduction of GO at high annealing temperatures
is effective, there are also obvious drawbacks, such as large energy consumption,
critical treatment conditions, and inability to apply for substrates with a low melting
point, e.g., glass and polymer [142].
2.5.2Thermal Properties
The properties of phononsquanta of the crystal lattice vibrationsin graphene
have attracted much attention in the physics and engineering communities. It was
shown both theoretically and experimentally that transport properties of phonons,
i.e., energy dispersion and scattering rates, were substantially different in the quasi2D system, such as graphene, compared to basal planes in graphite or 3D bulk crystals. Because the carrier density of pristine graphene is relatively low, the electronic
contribution to thermal conductivity is negligible according to the Wiedemann
Franz law [181]. The thermal conductivity of graphene is dominated by transport
properties of phonon [182]. Acoustic phonons are the main heat carriers in graphene
near room temperature, whereas optical phonons are used for counting the number
of atomic planes in Raman experiments with FLG [183, 184].
Table2.7 compares the thermal conductivities of graphene in various forms and
CNTs. The theoretical thermal conductivity of suspended monolayer graphene is
about 6000Wm1K1 at room temperature according to the MD simulations based
on the GreenKubo approach, which is much higher than that of graphitic carbon
[185]. The thermal conductivities of graphene were measured using an optothermal Raman technique [186, 187], where a laser light was focused on a suspended
graphene sheet over a 3-m-wide trench, which was connected to heat sinks at its
ends to provide heat sources (Fig. 2.24a, b). Thermal conductivities were determined from the dependence of Raman G-peak frequency on the excitation laser
power and the independently measured G-peak temperature coefficient. The thermal
conductivity of monolayer graphene obtained thereby ranged from 4.84103 to
5.30103W/mK at room temperature.
Similar to the mechanical properties and electrical conductivities, the thermal
conductivities of GO or rGO are much lower than that of pristine graphene because
of the disorders arising from the residual oxygenated groups and the presence of
defects [199, 201]. The thermal conductivities of dielectrophoretically deposited
rGO sheets were measured using electrical four-point measurement method [158],
giving a range of very low values (0.142.87Wm1 K1). Indeed, these values are
in similar orders of magnitude estimated by the MD simulations: the thermal conductivity of GO with an O/C ratio of 0.5 was 8.9 W/mK, and it increased with
64
DZ
&
^
,
KZ
increasing the degree of reduction, reaching about 42W/mK when the O/C ratio
was 0.05, see Table2.7. The inverse relationship between the thermal conductivity
and the O/C ratio is attributed to the increase in phonon scattering with increasing
oxygenation [201]. It is also worth noting that GO showed an increasing thermal
conductivity in response to an external tensile stress, an entirely opposite trend to
those shown by other nanostructured materials, including pristine graphene.
The thermal conductivities of multilayer graphene and GO sheets were measured
using the thermal flash technique [159]. It was shown that the multilayer graphene
comprising 3045 layers had a thermal conductivity similar to bulk graphite,
whereas that of 3-layer GO was higher than that of bulk graphite. The enhancement in thermal conductivity of multilayer GO than graphite is attributed to the
intercalating oxygen atoms that introduced covalent bridges between the interlayers for interaction [200]. Due to the intrinsic properties of the individual graphene
sheets and the highly aligned structure of GO papers (GOPs) and graphene papers
(GPs), these flexible materials also show unique thermal properties [204]. Thermal
conductivities of GOPs and GOPs modified by divalent ions, Mg2+ and Ca2+, were
measured using a laser flash method. Their thermal conductivities were 3.91, 32.05,
and 61.38W/mK, respectively [205] (see Table2.7), indicating that the modification of GOP with these metal ions gave rise to significant enhancements in thermal
65
Table 2.7 Thermal conductivities of graphene, GO, rGO, graphene, and GO papers in comparison
with CNTs at room temperature
Material
Method
Thermal conductivity References
(W/mK)
Single-layer graphene Confocal micro48405300
Balandin etal. [186]
Raman spectroscopy
Suspended graphene
Confocal micro41004800
Ghosh etal. [188]
Raman spectroscopy
Suspended graphene
Thermal measurement 30005000
Seol etal. [189]
method
Thermal measurement 600
Seol etal. [189]
Graphene on SiO2
method
Few-layer graphene
Raman optothermal
~13002800
Ghosh etal. [190]
(24 layer)
Cai etal. [46]
Suspended graphene
Raman optothermal
~2500
Suspended graphene
Raman optothermal
15005000
Jauregui etal. [191]
Suspended graphene
Raman optothermal
600
Faugeras etal. [192]
Suspended graphene
Raman optothermal
1100
Murali etal. [193]
Nika etal. [194]
Graphene
Theory: valence force 20005000
field, Boltzmann
transport equation
Graphene
Theory: relaxation10005000
Nika etal. [195]
time approximation
Graphene
Theory: molecular
800010,000
Evans etal. [196]
dynamics, Tersoff
14002400
Lindsay etal. [197]
Graphene
Theory: Boltzmann
transport equation
Graphene
Theory: ballistic
~4000
Munoz etal. [198]
rGO
Electrical four-point
0.142.87
Schwamb etal. [199]
measurement
rGO
Thermal flash
21802275
Mahanta etal. [200]
technique
18776
Mahanta etal. [200]
GO
Thermal flash
technique
Graphene
Molecular dynamics
2188
Shen etal. [201]
simulation
rGO
Molecular dynamics
42a
Shen etal. [201]
simulation
Shen etal. [201]
GO
Molecular dynamics
8.9b
simulation
Graphene paper
Laser flash method
313
Wu etal. [202]
Graphene paper
Light flash system
178
Xiang etal. [203]
Graphene paper
Self-heating method
1434
Xin etal. [204]
GO paper
Laser flash method
3.91
Yu etal. [205]
Mg2+ modified GO
Laser flash method
32.05
Yu etal. [205]
paper
Laser flash method
61.38
Yu etal. [205]
Ca2+modified GO
paper
66
Method
Thermal conductivity
(W/mK)
~3000
References
conductivity. Several ameliorating mechanisms, including the intercalation of thermally conducting metal ions into the gallery and cross-linking between GO sheets
and metal ions thermally connecting the GO basal planes, were mainly responsible
for the reduction in thermal resistance along the intersheet galleries, and thus the
increase in thermal conductivity. GPs fabricated by vacuum filtration and hightemperature annealing showed a thermal conductivity of 313W/mK [202], which
is much high than GOPs. Xin etal. [204] demonstrated a facile approach to produce large area freestanding GPs through direct electrospray deposition of graphene
films and simple water exfoliation from highly hydrophilic aluminum substrates.
After mechanical press and high-temperature annealing, the highly aligned and
defect-free GPs displayed superior thermal properties with thermal conductivities
up to 1434W/mK.
Table2.7 also includes both the experimental and theoretical thermal conductivities for single-walled CNTs (SWCNTs) and multiwalled CNTs (MWCNTs). The
reported thermal conductivities of CNTs measured at room temperature are largely
scattered, ranging from ~1100 [209] to ~7000W/mK [182], with typical values
of MWCNTs and SWCNTs are ~3000 [206] and ~3500W/mK [207], respectively. Although CNTs possess similar thermal conductivities as graphene sheets, the
unique 2D structure makes graphene serve as an interconnect in 3D electronics
where graphene can simultaneously function as lateral heat spreaders [187, 213].
67
2.5.3Optical Properties
The high-frequency conductivity of Dirac fermions in graphene in the infrared to
visible range of the spectrum is constant and given by [214, 215]:
e2 / 2h.
(2.2)
For normal incidence light, the optical transmittance (T) and reflectance (R) are
given as follows:
T= (1+
R=
1
) 2 ,
2
1 2 2
T,
4
(2.3)
(2.4)
where
=
2 e2 / hc 1/ 137.
(2.5)
e is the electron charge, c the light speed, and h is the Plancks constant. Combining
Eqs.(2.3) and (2.5) yields the opacity of graphene:
(1 T ) 2.3%.
(2.6)
68
Fig. 2.25 Optical properties of graphene. a Optical image of a 50m aperture partially covered
by monolayer and bilayer graphene sheets [216]. b Transmittance spectrum of single-layer graphene (open circles). (Inset) Transmittance of white light as a function of number of graphene
layers [216]. c UVvis spectra of roll-to-roll layer-by-layer transferred graphene films on quartz
substrates [45]. d Optical image of graphene with one, two, three, and four layers [217]
temperature. A thicker film normally has a lower transparency because of the higher
degree of absorption of light (Fig.2.26e). The adsorption of small particles on the
quartz substrate surface may also be partly responsible for the darkening of rGO
films after the thermal treatment.
2.5.4Mechanical Properties
The mechanical properties of pristine graphene have been determined by nanoindentation under an AFM (Figs.2.27a, b), showing that the defect-free graphene had
a Youngs modulus of ~1.0 TPa and a fracture strength of 130 GPa [220]. Table2.8
presents the Youngs moduli of pristine graphene determined from a number of theoretical and experimental studies, which range from 0.9 to 1.1 TPa [221]. There are
69
t
Fig. 2.26 Characterization of optical properties of GO solution and GO films: digital images of
a GO and b rGO dispersions [171]; c UVVis spectra of GO and rGO dispersions [218]; d photograph of rGO films with different thicknesses (black scale bar is 1cm) obtained after thermal
treatment at 1100C [141]; and e optical transmittance spectra of the films in d with their thicknesses indicated [141]. GO graphene oxide, rGO reduced graphene oxide. (Reprinted with permission from [141, 171, 218]. Copyright (2008, 2010, 2011) by ACS, Elsevier and Wiley)
70
Armchair
dW
dW
Fig. 2.27 Mechanical properties of graphene sheets, graphene oxide (GO), and GO papers. a SEM
image of a graphene sheet spanning an array of circular holes (scale bar=3mm). b Schematic of
nanoindentation on suspended graphene [220]. c Graphene molecular model with chiral angles
between 0 and 30 [222]. d Youngs modulus of graphene with different chiral angles [222].
71
many parameters that affect the Youngs modulus of graphene, such as the chirality
[222], the presence of defects and wrinkles [223], and functionalization [226, 231].
Figure 2.27c shows the molecular model for graphene with chiral angles varying from 0 (zigzag) to 30 (armchair), showing that the Youngs modulus varied in
a narrow range from 1.086TPa for the zigzag configuration to 1.050TPa for the
armchair configuration (Figs. 2.27d). This observation agreed with the previous
proposal in that the elastic properties of graphene with a hexagonal structure should
be relatively independent of the loading direction and thus the Youngs modulus
should not be greatly affected by the chirality [222].
Mechanical properties of one to three layers of GO sheets were investigated
by AFM [234]. The measured Youngs modulus of a monolayer GO sheet was
207.6 GPa, which is much lower than the pristine graphene, due to the oxygenated
functional groups which adversely alter the perfect 2D structure of monolayer
graphene [220, 234]. To better understand the effects of defects and functionalization on mechanical properties of graphene sheets, molecular dynamics (MDs) and
molecular mechanics (MMs) simulations were performed to evaluate the Youngs
modulus, shear modulus, and wrinkling properties of pristine graphene and GO
sheets [223, 229, 235]. The simulation results show that the Youngs modulus was
dependent on the presence of StoneWales defects, degree of functionalization, and
the molecular structure of functional groups (Fig.2.27e). The presence of Stone
Wales defects caused the graphene sheet to wrinkle which affected only the initial
part of the stressstrain curves due to straightening of wrinkles, but a small number
of defects had only a negligible influence on Youngs modulus of graphene. The
shear modulus and critical wrinkling strain was also reduced once oxygen-containing functional groups were introduced (Fig.2.27f). It is found that the change in
the molecular structure of graphene sheet was associated with the binding energy
between the functional groups and GO. The altered structure of graphene sheets
caused their instability. Hydrogen [236] or methyl [237] groups showed similar
reduction in mechanical properties of graphene sheets.
GO paper, which are a paper-like material made by flow directed or self-assembled GO sheets, is another useful GO-based material [238]. GO papers have many
potential applications, such as protective layers, chemical filters, supercapacitors,
adhesive layers, electronic or optoelectronic components, and molecular storage
[180, 238241]. The mechanical properties of GO papers have also been extensively studied, for example, tightly packed GO papers fabricated by vacuum filtration
showed an average elastic modulus of ~32 GPa [238]. Compare with those prepared
by vacuum filtration, the GO papers obtained at a liquid/air interface by evaporating
the hydrosol of GO showed a similar tensile strength but a slightly lower modulus
[241]. Chemical cross-linking by using divalent ions [239] or polyallylamine [240]
e Stressstrain curve of graphene sheets containing a row of StoneWales defects along with
morphological changes with increasing strain [223]. f Shear stressstrain curves for pristine graphene and GO sheets functionalized with carboxyl and hydroxyl groups [222]. g Tearing toughness of GO papers with different size groups [224]. h Cross-sectional SEM images and schematic
of self-assembly process of GO sheets with different sizes (S-GO in the left panel and UL-GO in
the right panel) [124]. SEM scanning electron microscope, S-GO small graphene oxide, UL-GO
ultralarge graphene oxide. (Reprinted with permission from [124, 220, 222, 223, 224]. Copyright
(2012, 2008, 2010, 2014) by ACS,Science Publishing Group and Elsevier)
72
Table 2.8 Youngs modulus of pristine graphene from representative experimental and theoretical
investigations. (Reprinted with permission from [221]. Copyright (2013) by RSC)
Method
E (TPa)a
Nanoindentation measurements [220]
1.02
Phonon dispersion measurements [225]
1.01
Ab initio computations [226]
1.05
Density functional theory [227]
1.05
First principles calculations [228]
1.01
MD and MM simulation [229]
1.051.09
Empirical force constant calculations [230]
1.13
Atomistic Monte Carlo simulations [231]
1.04
Continuum elasticity theory and tight-binding atomistic simulations [232]
0.92
Energetic model [233]
0.90
a
Because the Youngs modulus for a 2D sample is just force/length, elastic properties of graphene
in some references are reported in N/m, which are converted to TPa by taking effective thickness
as 0.34nm. MD molecular dynamics, MM molecular mechanics
b
&
73
'K
&
'K
Fig. 2.28 3D model snapshots of graphene oxide (GO) sheets a without water and c with intercalated water molecules; and 2D schematics of GO paper models with functional groups bonded
between adjacent GO sheets through hydrogen bonds b directly and d mediated by water molecules. e extrapolation of modulus values; and f plots of two different components of deformation
as a function of GO length. (Reprinted with permission from [124]. Copyright (2012) by ACS)
74
Fig. 2.29 AFM images of graphene, GO, and rGO. a Single layer graphene was first observed
by Geim et al. [8]. A few layer flake is shown, with optical contrast enhanced by an interference effect at a carefully chosen thickness of oxide [8]. b AFM image of single-layer graphene.
Notice the folded part of the film near the bottom, exhibiting a differential height of ~0.4nm [8].
cf Height c and e and corresponding phase d and f tapping mode AFM images of unreduced
c and d and chemically reduced e and f GO nanosheets deposited from aqueous dispersions onto
75
contact AFM mode [8]. The measured thicknesses of GO and rGO were 1.0 and
0.6nm, respectively (Fig.2.29cf) [244]. Besides imaging and thickness detection,
AFM was also used for the study of mechanical, frictional, electrical, magnetic,
and even elastic properties of graphene sheets and flakes [220]. Although the AFM
technique can successfully determine the surface morphology on a nanometer scale,
it is cumbersome for imaging large area graphene [14]. In addition, the samples
freshly cleaved HOPG. The images were recorded in the attractive regime of tip sample interaction. Superimposed onto each image is a line profile taken along the marked red line [244].
AFM atomic force microscopy, GO graphene oxide, rGO reduced graphene oxide, HOPG highly
ordered pyrolytic graphite
76
Fig. 2.31 a, b High-resolution transmission electron microscopy (TEM) images of solution cast
a monolayer and b bilayer graphene (scale bar 500nm). c Electron diffraction pattern of the sheet
in a, with the peaks labeled by MillerBravais indices. d, e Electron diffraction patterns taken from
the positions of the black d and white spots e, respectively, of the sheet shown in b, using the same
labels as in c. The graphene is clearly one layer thick in d and two layers thick in e. fh Diffracted
77
used for AFM characterization need to be deposited on a very flat substrate, such as
Si wafer, freshly cleaved mica, and quartz [245].
78
79
2.6.5Raman Spectroscopy
The Major features of the Raman spectra for graphite and graphene are the G band
at ~1584cm1 and the Gband at ~2700cm1 [257]. The positions and relative peak
heights of the G and Gbands indicate the number of graphene layers. As shown
in Fig.2.33ac, the location of the G peak for a single layer graphene is 35cm1
higher than that of bulk graphite, while the Gpeak shows a significant change in
both shape and intensity as the number of layers decreases. For bulk graphite, the G
band is comprised of two components. The low and high shift are roughly 1/4 and
1/2 of the G peak intensities, respectively. For a single-layer graphene, the Gband
shows a single sharp peak and the intensity is roughly four times the G peak.
The Raman spectroscopy is also an important tool to investigate the surface
chemistries of GO and rGO [76]. Because of the presence of isolated double bonds
that resonate at frequencies higher than that of the G-band of graphite, the G-band
peak of UL-GO was upshifted from 1581 to 1607 cm1, see Fig. 2.33d, f [258,
259]. The corresponding G-band after the thermal reduction (rUL-GO) occurred at
1590cm1, a reflection of the recovery of the hexagonal network of carbon atoms
containing defects. Due to the possibility of charge transfer reaction between the
(host) carbon in graphene and the (guest) chloride [260], the G-band of chemically
reduced C-rUL-GO at 1587cm1 was marginally downshifted. The high electronegativity of chloride species encouraged carbonchloride interactions that in turn
triggered charge transfer reactions and created holes in graphene. The G band is
Raman active for sp2-hybridized carbon-based material, while the D band is activated only if the defects participate in the double resonance Raman scattering near
K point of Brillouin zone [261]. Hence, the intensity ratio of ID/IG is often used for
estimating the sp2 domain size of graphite-based materials. The ID/IG ratio of rULGO was notably lower than UL-GO (Figs.2.33e), indicating that the thermal reduction process removed the functional groups and recovered the graphitic structure.
However, the ID/IG ratio increased after the chemical treatments that again altered
the graphene structure.
Besides the G and D bands, there are two other Raman bands, called 2D and
D+G at 26003000cm1 (Fig.2.33f), which are often ignored due to their weak
intensities compared to the D and G bands. The 2D band is Raman active for
crystalline graphitic materials and is sensitive to the band in the graphitic electronic structure, while the combination mode of D+G band is induced by disorder
[261]. These two bands were employed to distinguish the electronic conjugation of
UL-GO obtained at different stages of reduction and treatments. The intensity ratio
I2D/ID+G shown in Fig.2.33g was more sensitive to the change in electronic conjugation from UL-GO to rUL-GO than the ID/IG ratio (Figs.2.33e), as a reflection
of the recovery of graphitic electronic conjugation. The reduction of the I2D/ID+G
ratio corresponding to the modification from rUL-GO to C-rUL-GO indicates that
the newly doped functional groups, such as Cl, SOCl, and COOH, introduced
disorder again [76].
80
Fig. 2.33 Raman spectra of graphite, graphene, GO, and rGO. a Comparison of Raman spectra at
514nm for bulk graphite and graphene. Evolution of the spectra b at 514nm and c 633nm with
the number of layers [257]. d, f Raman spectra for NG, UL-GO, reduced rUL-GO, and chemically
doped, reduced C-rUL-GO. e, g The corresponding D/G and 2D/(D+G) intensity ratios [76]. GO
graphene oxide, rGO reduced graphene oxide, NG nano-graphene, UL-GO ultralarge graphene,
rUL-GO reduced ultralarge graphene oxide, C-rUL-GO carbon reduced ultralarge graphene oxide.
(Reprinted with permission from [76, 257]. Copyright (2011, 2006) by ACS and APS)
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81
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Chapter 3
3.1Introduction
Chemical vapor deposition (CVD)-grown graphene and graphene oxide (GO) have
been the main starting materials to produce graphene-based transparent conductors
(TCs) [1, 2]. For the CVD-grown graphene, the underlying substrates need to be
removed so that the graphene sheets can be transferred onto the device substrates.
Several strategies have been developed to transfer graphene sheets and they include
the etching and stamping method [3, 4], thermal release method [5], photoresist
method [6], roll-to-roll transfer method [7], and general method [8]. Another lowcost route to produce graphene-based TCs on a large scale is to synthesize GO
thin films and then reduce them. The ease of solution process of GO sheets due to
their high solubility in aqueous solutions has made it a more viable and favorable
approach [2]. Once a GO dispersion is produced, GO films can be formed on a
substrate using different deposition techniques, including electrophoretic deposition (EPD), spin coating, spray coating, dip coating, transfer printing, Langmuir
Blodgett (LB) assembly, rod coating, and inkjet coating [1].
95
96
Fig. 3.1 Etching method to transfer CVD-grown graphene. a Flow chart of the synthesis, etching, and transfer processes for the large-scale and patterned graphene films. b A centimeter-scale
graphene film grown on a Ni(300nm)/SiO2(300nm)/Si substrate. c A floating graphene film after
etching the nickel layers in 1M FeCl3 aqueous solution [3] RT Room temperature, HF Hydrofluoric acid, BOE Buffered oxide etchant. (Reprinted with permission from [3]. Copyright (2009) by
Nature Publishing Group)
Cu with nitric acid lead to the formation of H2 bubbles which cause cracking in the
graphene film. It is also found that HCl or HNO3 releases corrosive vapor and the
etching rate of copper is very slow. Since FeCl3 is able to etch the copper or nickel
without forming gaseous products or precipitates, it has been widely used recently [3].
Figure3.1a shows the typical etching transfer process by using FeCl3 (or acids). After
graphene was grown on nickel substrate, an aqueous FeCl3 solution was used as an
oxidizing etchant to remove the nickel layers. It is found that FeCl3 etches the nickel
layers effectively within a mild pH range without forming gaseous products or precipitates. The graphene film can be separated from the substrate within a few minutes.
97
Figure3.1b and c show the graphene film grown on nickel substrate before and after
FeCl3 etching, respectively. It is seen that the graphene film floating on the surface of
the solution is then ready to be transferred to any kind of substrates [3].
3.2.2Stamping Method
The stamping transfer is typically done by depositing a protective polymeric coating, such as polydimethylsiloxane (PDMS) [3], ploy(methylmethacrylate) (PMMA)
[14], or silicone [12], on top of the graphene thin film and removing the underlying
substrate. Figure3.2a shows a method of transferring graphene in wafer scale via
Fig. 3.2 Etching and stamping method to transfer CVD-grown graphene. a Transferring and patterning of graphene films grown on a metal/SiO2/Si wafer [9]. b Graphene transfer by polyethylene terephthalate (PET)/silicone [12]. (Reprinted with permission from [9, 12]. Copyright (2010,
2013) by ACS and Elsevier)
98
stamping method. The polymer supports such as soft PDMS stamps and thermal-release tapes are first attached to the graphene films grown on metal substrates. After
soaking in water with gentle ultrasonication for several minutes, the polymer support/graphene/metal layers are detached from SiO2 by water intervening between
metal and SiO2. The metal layers were then removed by soaking in FeCl3 solution.
The resulting graphene film on the polymer support is ready to be transferred onto
arbitrary substrates, such as poly(ethylene terephthalate) (PET) film or rubber substrate [9]. A two-layer structure consisting of PET and silicone was also developed
to transfer graphene grown by chemical vapor deposition onto various rigid and
flexible substrates through dispersive adhesion [12]. As shown in Fig.3.2b, three
essential steps, which include adhesion of the PET/silicone to the graphene/Cu,
etching of the Cu layer, and transferring of released graphene film, are involved in
the PET/silicone transfer process. The advantage of the two-layer structure is that
it only takes a few seconds to transfer graphene from PET/silicone to the target
substrates [12].
Kang et al. [4] modified the transfer technique by inking the stamp process,
enabling the transfer of single-layer graphene onto a Si/SiO2 substrate in a pattern
defined by the geometry of the PDMS stamp. As shown in Fig.3.3a, large-scale graphene was grown on Cu foil which was then laminated onto a microscale-patterned
PDMS stamp. The Cu foil was removed by etching with (NH4)2 S2O8 (ammonium
persulfate) solution, and the PDMS stamp was thoroughly rinsed with distilled (DI)
water. The raised features in the stamp were inked with graphene that has the
same pattern as the PDMS stamp, which was then transferred to the target substrate
by pressing and gently removing the PDMS mold. Figure3.3b shows the microscale
features of graphene on a SiO2 substrate, presenting graphene patterns over a large
area of 201000m, confirming the techniques capability to transfer large-area
patterns. The transfer mechanism is that the adhesion between the graphene and the
target substrate is higher than that of the PDMS/graphene interface [4, 15]. Graphene films with a variety of shapes were transferred onto different substrates using
the same technique, such as poly(4-vinylphenol) (PVP; Fig.3.3c, d).
To realize the transferring of graphene onto arbitrary substrates, a general method was developed to perform reliable transfer [8]. This general method relies on
a sacrificial self-releasing polymer layer placed between a conventional PDMS
elastomer stamp and the graphene film. As shown in Fig.3.4a, the general method
employs a polymer thin filmself-release layer (SRL)which is inserted between the elastomer stamp and the graphene sheet. The work of adhesion between
the SRL and the stamp has to be smaller than that between the graphene and the
destination substrate, making dry transfer of the release polymer/graphene bilayer
thermodynamically favorable. The SRL protects graphene from the contamination
by the low-molecular weight siloxane oligomers present in the PDMS stamp. After
patterning by oxygen plasma, a 0.21.0-mm thick SRL is spun-cast over the graphene and brought into conformal contact with the PDMS stamp, then the excess
graphene is removed by oxygen plasma. The Cu substrate is subsequently etched
99
Fig. 3.3 Inking elastomeric stamp method. a Schematics of the fabrication procedure for transferred micro-patterned graphene electrode-based organic field effect transistor using rubrene single-crystal semi-conductor. b An optical microscope image of patterned graphene electrodes on
a SiO2 layer fabricated by stamping method and a magnified view of patterned graphene in inset.
c An optical microscope image of graphene patterned electrode fabricated on PET/graphene/PVP
layer and the transparent PET/graphene/PVP/patterned graphene structure in inset. d A scanning
electron microscope (SEM) image of the hexagonal arrays of graphene electrodes micro-patterned
onto a SiO2 substrate. (Reprinted with permission from [4]. Copyright (2011) by Wiley)
off to transfer the polymer/graphene bilayer to the stamp. Through the graphene
face, the stamp is brought into contact with the destination substrate. After baking
for several minutes to enhance the conformal contact and adhesion, the stamp is
lifted off, leaving the release polymer/graphene bilayer on the destination substrate.
The SRL is then dissolved to obtain the graphene film transferred on the substrate.
Figure 3.4be shows the images of transferred graphene films onto SiO2/Si and
organic polymer substrates. The graphene films transferred using the SRL is largely
intact at the optical length (Fig.3.4b), while the film transferred without the SRL
is highly fragmented (Fig. 3.4c). The atomic force microscopy (AFM) image in
Fig.3.4d shows that the integrity of the graphene monolayer is preserved and no
cracks or contaminant residues are found. More importantly, the patterned graphene
films can be placed to align to features, allowing the integration of graphene into
more complex device structures. For example, millimeter-sized graphene pads were
transferred onto a polymer film while aligned with the underlying gold source
drain electrode array (Fig.3.4e).
100
Fig. 3.4 A general stamping method for transferring graphene. a Schematic of the SRL methodology in combination with a pick-and-place elastomer stamp. b, c Optical images of a centimeter-sized graphene film successfully transferred to a 300-nm thick SiO2/Si substrate b and failed
transfer when the SRL is not present c. d AFM images of graphene film on SiO2/Si at low and high
(inset) magnifications (inset z-scale is 3nm). e Digital camera image of pre-patterned graphene
films transferred to an organic semiconductor device structure. CVD chemical vapor deposition.
(Reprinted with permission from [8]. Copyright (2013) by Nature Publishing Group)
101
3.2.4Photoresist Method
Figure3.6a; presents the procedure employed to fabricate graphene device arrays
based on the photoresist method. Graphene is grown on a Cu- or Ni-coated Si wafer
substrate, which is used to fabricate a large-scale device array with a simple photolithography process [6]. The device consists of two large pads connected by a thin
strip. The photoresist covering the devices acts as a protective layer and oxygen
plasma etch is used to remove unwanted photoresist residue and graphene. After
the exposure to a continually refreshed etchant solution to remove Cu/Ni in the
unprotected areas and beneath the connecting photoresist/graphene strips, two large
pads of graphene/Cu laminate connected by a narrow channel of graphene can be
obtained. Figure3.6b, c shows the optical image of the fabricated device, indicating
that there exhibits a clear undercut around the edges of Cu/Ni as well as the intact
graphene channel. Figure3.6d provides the differential interface contrast image of
a long graphene channel, confirming that the surface of the device channel is very
clean without any visible residue underneath. The inset shows that the graphene
channel has a uniform Raman signature over a large area, further confirming the
high quality of the device channel.
102
103
Fig. 3.6 Fabrication of graphene device array. a Schematic of device fabrication procedure (see
main text for details). b Bright field optical image of a typical sample substrate after fabrication.
c Close-up bright field image of the same sample. Graphene connecting the copper pad is just
visible (boxed). Inset: Image of the device channel. d Differential interference contrast image of
a longer device. Upper inset: Raman spectra across the length of the graphene strip are highly
uniform. Lower inset: Bright field image of the sample. PR Photoresist, RIE Reactive ion etching.
(Reprinted with permission from [6]. Copyright (2009) by ACS)
104
Fig. 3.7 Roll-to-roll transfer of graphene films. a Schematic of the roll-based production of graphene films grown on a Cu foil. b Roll-to-roll transfer of graphene films from a thermal release
tape to a PET film at 120C. c A transparent large-area graphene film on a 35in. PET sheet. d An
assembled graphene/PET touch panel showing outstanding flexibility. e A graphene-based touch
screen panel connected to a computer with control software. f UVvis spectra of graphene films on
quartz substrates. The inset shows the UV spectra of graphene films with and without HNO3 doping. The corresponding optical images are shown in the right inset. g Sheet resistances of graphene
films transferred to a ploy (methylmethacrylate) (PMMA) substrate [7]
105
Spray coating
Spin coating
Electrophoretic
deposition
Method
Schematic figure
Partial aggregation of
GO sheets during drying
by heat
Uniformity cannot be
guaranteed
Randomly stacked GO
sheets, only applicable to
conductive substrates
Disadvantages
Advantages
Table 3.1 Fabrication methods of TCFs from GO. (Reprinted with permission from [1]. Copyright (2014) by Elsevier)
An etal. [23]
References
106
3 Fabrication of Graphene-Based Transparent Conducting Thin Films
LB assembly
Transfer printing
Dip coating
Schematic figure
Deposition of GO sheets
LbL, accurate control of
film thickness
Transfer of relatively
thick GO films with low
transparency
Randomly stacked GO
sheets
Disadvantages
Advantages
References
Schematic figure
Inkjet printing
Rod coating
Randomly stacked GO
sheets
High precision
Disadvantages
Advantages
References
108
3 Fabrication of Graphene-Based Transparent Conducting Thin Films
109
3.3.1Electrophoretic Deposition
The EPD technique includes a broad range of industrial processes where charged
particles in suspension move toward an electrode of opposite charge by an electric
field and deposit to form a compact film [39]. EPD is a versatile technique that can
be applied to solid powder particles with diameters ranging from micro- to nanometers, and requires a suitable medium for the formation of a stable suspension. It has
many advantages, including facile process, short processing time, cost effectiveness, and potential scaling up [40]. Due to the relatively high density, good chemical stability, and low conductivity, organic solvents such as alcohols and ketones are
commonly used. However, organic solvents are usually toxic and flammable, thus
an aqueous medium that is cheaper and environmental friendly is often used for the
deposition of sensitive materials [41].
The EDP technique was applied to fabricate a variety of GO-based thin films
[23, 42, 43]. When a direct current (DC) voltage is applied, GO sheets dispersed in
a suspension migrate toward the positive electrode and form a solid thin film. The
deposition rate is influenced by several processing parameters, such as the concentration of GO suspension, the applied DC voltage, and the conductivity of the
substrate. By modifying the deposition time, the film thickness can be controlled.
As shown in Fig. 3.8a, b, the color of the GO films changed from light to dark
brown with increasing thickness, especially after the reduction of GO using KOH
Fig. 3.8 EPD of GO films.
a, b Digital photographs
of GO a and rGO b films
deposited on ITO-coated
glass electrodes. c, d SEM
images of GO c and rGO
d films (the insets show
the corresponding optical
images). (Reprinted with
permission from. Copyright
(2009) by ACS)
110
and hydrazine. It is also found that wrinkling occurred along the boundaries between the individual GO sheets after reduction (Fig.3.8c, d).
The fabrication of TCs using large-area GO sheets via EPD was specifically
investigated [23, 44]. Reduced graphene oxide (rGO) was obtained using the intrinsic EPD process without the addition of chemical agents or high-temperature
treatments [18]. It is shown that the prepared GO films can be electrochemically
reduced by an explicit constant potential reduction step. During the EPD process,
the oxygen-containing functional groups of GO were substantially removed. The
final films showed improved electrical conductivities and low adhesion to the substrate for easy detachment. The conductivity of the rGO film was 1.43104Sm1,
which is much higher than the GO paper obtained by the filtration method, which
was 0.53103Sm1 [45]. Ishikawa etal. [44] deposited GO sheets obtained from
exfoliation of graphite oxide on a SiO2/Si substrate by an EPD process. The optimal
conditions with an EPD voltage of 10V for 5min resulted in a few layers of reduced
graphene with no wrinkles and reduction was confirmed by the XPS analysis. Its
sheet resistance was 4.59104/sq at a transmittance of 83.8%.
Although the technique enjoys a number of advantages in the preparation of thin
films, such as high deposition rate, good thickness controllability, and simplicity of
scaling up, its applicability is limited to only electrically conductive substrates, such
as ITO-coated glass, Cu, Ni, Al, stainless steel, and p-type Si. For the same reason,
it cannot be applied to flexible insulating plastic substrates. In addition, the stacking quality of GO sheets is rather difficult to control, making this method unable to
produce uniform deposition over a large surface area [1].
3.3.2Spin Coating
One of the most convenient and popular methods developed to deposit uniform
thin films on a flat substrate is spin coating. It involves the dropping of an excess
amount of solution on a substrate and rotating at a high speed to spread the fluid
over the entire substrate surface by a centrifugal force. The desired thickness of the
film can be controlled by rotating speed and the concentration of the GO solution.
GO films were deposited on quartz substrate and the deposition behaviors were
studied after different reduction processes [20]. Due to the fast dynamics of deposition by spin coating and the flexible nature of GO sheets, a significant degree of
disorder was noted from the measurement of film thickness. It is found that rGO
films reduced by hot hydrazine solution resulted in fragmentation and delamination of the films. Thermal annealing of GO films under nitrogen flow, argon flow,
and vacuum at temperatures ranging from 4001100C were also investigated. The
results indicate that a thermal graphitization procedure was most effective for reduction, producing films with sheet resistances as low as 1001000/sq with 80%
transmittance. Wu etal. [46] produced GO film via spin coating and used them as
transparent conductive anodes for an organic photovoltaic (OPV) cell. After reduction by a combination of hydrazine and high temperature annealing (4001100C),
111
Fig. 3.9 Spin coating of graphene oxide (GO) film. a Schematic of modified spin-coating technique. b AFM height image of a GO film. (Reprinted with permission from [47]. Copyright (2008)
by ACS)
the optical transmittance of the best films was higher than 80%, while the sheet
resistance varied from 5k/sq to 1M/sq. A modified spin coating technique [43]
was also devised as shown in Fig.3.9a. It is found that accelerated solution evaporation by blowing dry nitrogen while spin-casting resulted in continuous films with
GO sheets lying fairly flat on the surface (Fig.3.9b).
3.3.3Spray Coating
Spray coating is a type of painting technique where a spraying device based on forced
air is used to apply the coating material through air onto the substrate surface. The
method is fast, scalable, and facile to operate, and ideally suited to producing electrodes for liquid-crystal displays (LCDs) [26, 48], as well as conductive graphene
coatings on various substrates [49]. Once the graphene colloids are dried after the
deposition, they are not re-dispersible in water, resulting in a water resistant coating.
Due to the high aspect ratio of the graphene sheet, spray coating technique can
produce a continuous conducting network, which is thin and transparent. An rGO
coating was produced on a glass slide, achieving a sheet resistance of 2.0107/
sq with a transmittance higher than 96% [45]. GOhydrazine dispersions were also
spray deposited to produce large rGO films [21]. The GOhydrazine dispersion was
prepared by mixing GO dispersion with an excess amount of hydrazine monohydrate, as shown in Fig.3.10. Therefore, rGO dispersion was sprayed onto preheated
substrates to form rGO films with a sheet resistance of 2.2103/sq and a transmittance of 84%. Although the technique holds advantages of simple and fast process
and low cost, it is very difficult to avoid partial aggregation and crumpling or wrinkling of GO/rGO sheets generated during the coating process [1].
112
Fig. 3.10 Schematic of rGO film fabrication by spray deposition. (Reprinted with permission
from [26]. Copyright (2010) by Elsevier)
3.3.4Dip Coating
Dip coating involves three steps, that is, immersion of a substrate into a tank containing a coating material, removal of the substrate from the tank, and draining of
the coating material.
113
Fig. 3.11 Schematic illustration of layer-by-layer (LbL) assembly of an rGO film consisting
of alternate layers of negatively charged rGOCOO and positively charged rGONH3+. EDC
N-ethyl-N-(3-dimethyl aminopropyl)carbodiimide methiodide. (Reprinted with permission from
[27]. Copyright (2011) by RSC)
The coated substrate is then dried using forced air or by baking. By changing
the durations of these three steps, the thickness of the film can be easily controlled.
Graphene films of 10 nm thickness were obtained with a high transparency and
conductivity after coating with GO, followed by thermal reduction [50]. Pretreated
hydrophilic quartz substrates were immersed into a hot, aqueous GO dispersion to
coat GO films. Scrolled or folded GO sheets were observed arising from the film
fabrication, which is detrimental to transparency. Su etal. [51] reported the fabrication of rGO films by dip-coating the cleaned quartz substrates with large-size GO
sheets in a standard Piranha process, which were annealed at an elevated temperature in 20% H2/Ar. The obtained rGO films showed a sheet resistance of 188k/sq
with 98% transparency. A novel layer-by-layer (LbL) sequential assembly of positively and negatively charged rGO sheets was developed based on the dip-coating
method to avoid folding of graphene sheets during deposition [27]. As illustrated in
Fig.3.11, this approach employed the concept of electrostatic attraction between the
two oppositely charged suspensions of rGO sheets, which allowed the preparation
of multilayer rGO films with a tunable thickness, resistance, and transmittance by
controlling the number of bilayers.
114
3.3.6LangmuirBlodgett Method
The LB technique is a method to systematically control the interfacial molecular orientation and packing, making it possible to perform controllable fabrication
of laterally patterned structures on solid supports. This method is based on LbL
deposition of molecular-ordered domains formed at the airsolvent interface onto a
solid substrate without intermediate transfer processes. An LB trough (Fig.3.13a)
is usually used to perform the LbL assembly. The amphiphilic GO sheets floating
115
Fig. 3.12 Transfer-printing process of reduced graphene oxide (rGO) films. a Transfer-printing
process of rGO and the finished rGO films with different thicknesses [53]. b Schematic diagrams
(left) and the corresponding optical microscope images (right) depicting the PDMS-based soft
transfer-printing process of rGO [52]. (Reprinted with permission from [52]. Copyright (2009)
by Wiley)
on the surface of a given subphase (usually water) are compressed by moving the
two opposing barriers toward each other to increase the surface pressure and thus
the density of GO sheets. The surface pressure is a measure of the GO density on the
water surface, which in turn controls the quality of LB assemblies. Prior to deposition, a platinum plate is used to monitor the surface pressure during the compression and isothermal curves are recorded to identify the target pressure (Fig.3.13b)
[54]. The prepared substrate is immersed into the water and pulled out at a desired
speed once the desired surface pressure is reached, realizing uniform deposition of
a layer of GO sheets. The LB assembly method offers several unique advantages
over the other coating techniques: (i) the layered architecture of the films could be
accurately controlled by simply varying the LB assembly parameters, including
surface pressure and pulling speed of the substrate, (ii) the LbL deposition process
is amenable to assembling any combination of molecular carbon layers on a substrate, thus capable of tailoring the properties and structures of the films, (iii) the
assembly process is operative at room temperature with high throughputs, which
favors automation and mass production [1].
116
Pressure
measure plate
Dipper
Barriers
50 m
50 m
50 m
Fig. 3.13 LB assembly of GO films. a LB trough equipped with two movable Teflon barriers,
pressure measurement plate, and dipper for film transfer onto solid substrates [54]. b A typical
isothermal curve recorded during compressing of GO sheets prior to film transfer [54]. ch SEM
images of GO sheets deposited on a polyester slide by drop casting c. d, e Spin coating d and LB
assembly e [24]. f Close-packed monolayer GO sheets as the first layer. g, h Double layers with
a dilute top layer g, and double layers with a high-density top layer h prepared by LB assembly
[34]. (Reprinted with permission from [1]. Copyright (2014) by Elsevier)
117
relatively free of wrinkles or folds. It is also claimed that the LB method can produce a large-area flat monolayer GO with much higher surface coverage on the substrate with an accurately controlled thickness [55]. It is also possible to stack double
layers or multilayers of GO by sequential, LbL coating. As shown in Fig.3.13f, the
first layer is collected at close-packed density, which was either aged in air overnight or baked in an oven to enhance its adhesion to the substrate. Due to the repulsion from both their neighbors and those in the underlayer, the second layer of GO
tends to be wrinkled. Figure3.13g, h show the double layers of GO with low- and
high-packing density for the second layer, respectively. The heavy degree of folding
and wrinkling of the second layer with high-packing density (Fig.3.13h) suggests
strong repulsion between the two layers [34].
3.3.7Rod Coating
The rod coating method is a scalable technique for making solution-processed thin
films, and has been widely used in the coating industry to prepare liquid thin films
[36]. Coating is done using a Meyer rod which is a metal bar with a wire wrapped
around its surface. The wire is used to draw a solution over a substrate surface. A
wet film is left when the Meyer rod is rolled over the substrates, which is then dried
to obtain a solid film. The thickness of the final dry film can be controlled by the
diameter of the wire wrapped around the bar and the concentration of the fluid.
The preparation of the coating fluid is critically important because the coating fluid
should possess a low surface tension and carry sufficient coating material, that is,
GO sheets. Rod coating can be performed in a scalable way for roll-to-roll production in industry [56].
Wang etal. [36] demonstrated to fabricate a large-scale GO film on a PET substrate in a controllable manner using the rod-coating technique (Fig.3.14a). After
room-temperature reduction, highly flexible rGO films were used to assemble 4.5in. touch screens (Fig.3.14b). The thickness of GO films was controlled from a
single layer to tens of layers by adjusting the concentration of GO solution or the
diameter of the rod wire. The film thickness is shown to increase with increasing
GO concentration from 0.05 to 1mg/mL, see Fig.3.14cf. The GO films reduced
using hydrogen with the assistance of a small amount of a palladium (Pd) catalyst had a sheet resistance ranging 1.6820.1k/sq with a transmittance ranging
64.692.6%.
3.3.8Inkjet Printing
Inkjet printing is a process involving propelling droplets of ink onto papers, plastics,
or other substrates, and possesses many advantages, such as direct writing, additive
patterning, low cost, and scalability for large area manufacturing [57]. Kong etal.
[58] directly printed the rGO electrode onto flexible polymeric materials by inkjet
118
Fig. 3.14 Rod coating of rGO films. a Rod-coating setup. b A flexible touch screen fabricated
using an rGO/PET film as electrode. cf AFM images and height profiles of the GO films fabricated by rod coating with 0.2-mm-thick rod wires with different concentrations of GO dispersions,
0.05mg/mL c, 0.1mg/mL d, 0.2mg/mL e, 1mg/mL f. (Reprinted with permission from [36].
Copyright (2012) by Wiley)
References
119
Fig. 3.15 Inkjet-printed rGO films. a Digital images of the vials containing GO and rGO aqueous dispersions (TX-100=Triton-X100 surfactant). b Inkjet-printed GO film lifted from the PET
surface.c AFM image of rGO film obtained by reduction of the film in b with ascorbic acid.
(Reprinted with permission from [59]. Copyright (2010) by Wiley)
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Chapter 4
4.1Introduction
Transparent conductors (TCs) made from as-deposited reduced graphene oxide
(rGO) sheets significantly underperform those made from the chemical vapor deposition (CVD)-grown graphene in terms of optoelectrical properties because of (i)
the inherently inferior electrical conductivities of rGO, (ii) the remaining oxygenated functional groups, and (iii) the intersheet junctions with high contact resistance
between the rGO sheets [1]. To further improve the electrical conductivities of graphene or graphene oxide (GO)-based TCFs, several approaches have been taken,
such as chemical doping, hybridization, and using large-size GO sheets. Chemical
doping is an effective method to tailor the electrical properties of carbon materials, including graphite, carbon nanotube, and graphene [2]. There are two types of
chemical doping, that is, p-type and n-type, depending on the functions of the dopants used, as electron acceptor and donor, respectively. Doping is achieved either
through surface transfer doping or substitutional doping. Surface transfer doping
is usually performed by adsorption of strong electron-donating or electron-withdrawing chemical species. Substitutional doping is usually performed by replacing
the carbon atoms in the honeycomb lattice of graphene by atoms with a different
number of valence electrons, which would result in the disruption of the sp2 hybridization of carbon atoms [2]. Due to the reactions taking place in the surrounding
molecules, such as oxygen or water, the carbon materials doped by surface transfer
would not have long-term stability. Although the stability of chemical doping treatment needs to be further investigated, chemical doping is considerably simple and
high throughput. It is expected that doping treatment will be an efficient way to
produce graphene-based electronic devices with high performance.
The vast majority of GO or rGO sheets in current use for the fabrication of TCs
is very small, mostly with an area of hundreds of micrometer [26]. The small size
of graphene sheets results in high intersheet contact resistance between them due
to a large amount of intersheet junctions and the presence of oxygenated functional
groups on the edge. It was shown that small GO sheets with longer peripheries contained more carboxyl groups among different oxygenated groups than larger ones
Springer Science+Business Media New York 2015
Q. Zheng, J.-K. Kim, Graphene for Transparent Conductors,
DOI 10.1007/978-1-4939-2769-2_4
123
124
[7]. One of the most effective approaches to reduce the number of intersheet tunneling barriers is producing large-size graphene sheets. Another successful approach is
to bridge these intersheet junctions with 1D highly conducting nanofillers, such as
single-walled nanotubes (SWNTs), metal nanowire (NW), and nanogrids that can
facilitate the restoration of the inherent electrical conductivities while sacrificing
a little of the transparency of graphene. Apart from reducing the intersheet contact
resistance, the intercalation of conducting fillers between the GO layers may bring
about another important benefit by forming 3D conductive networks through the
film thickness [8].
4.2Chemical Doping
4.2.1Chemical Doping of Carbon Materials
Doping of Graphite Nanoplatelets
It is demonstrated that the Br2 vapor treatment enhanced the electrical conductivity
of graphite nanoplatelets (GNPs) by increasing the ionic component of Br functionalities [9]. The GNPs were prepared by thermal expansion of graphite intercalation
compounds (GIC) following by ultrasonication. The thickness and diameter of the
produced GNPs were estimated to be 4.5nm and 46m on average, respectively
[9]. GNPs were then exposed to Br2 vapor at room temperature in a closed desiccator for varying durations. The uptake of Br by GNP was evidenced by a weight
increase, through the increases in both intercalation complexes and covalent CBr
groups. Figure4.1a shows the changes in weight and Br atomic concentration as a
function of bromination duration. The weight increased rapidly with bromination
duration and then stabilized or decreased slightly after about 10h, which may be
caused by the dynamic process of absorption and desorption of Br atoms into graphite. Br was absorbed rapidly because of the ample availability of doping/reactive
sites in the GNPs for treatments below 10h. Further treatment did not induce additional absorption upon saturation of these sites, which can be attributed to gradual
changes in the nature and balance of the CBr bond types. Another evidence for Br
uptake was the increase in Br atomic concentration.
An effective way to measure the extent of intercalation is the (002) d-spacing of
graphite, which can be performed by X-ray diffraction (XRD) spectra. As shown in
Fig.4.1b, the peak corresponding to the 3h treatment differs in position and breadth
from those corresponding to the other bromination durations. Table4.1 shows that
with a 3h treatment the d-spacing exhibited a minimum while the width-at-half-maximum (WHM) of the peak showed a maximum. The disorder of graphite crystals
during the intercalation process was responsible for the broadened peak and low dspacing after the 3h treatment. Two possible types of bonds, that is, charge transfer
complexes and covalent bonds, were distinguished by time-of-flight secondary ion
mass spectrometry (ToF-SIMS) as shown in Fig.4.1c. The atomic bromine had two
125
Fig. 4.1 Chemical doping of graphite nanoplatelet (GNP). a Weight changes and Br atomic concentration determined by XPS as a function of bromination duration. b XRD spectra of brominated
graphite with different treatment durations. c ToF-SIMS spectra of brominated GNP. XPS X-ray
photoelectron spectroscopy. (Reprinted with permission from [9]. Copyright (2007) by Elsevier)
isotopic peaks at molar masses 79 and 81 with an intensity ratio of 50.5:49.5; Br2
showed a triplet at 158, 160, and 162 with a respective intensity ratio of about 1:2:1;
CBr exhibited a doublet at 91 and 93; and C2Br exhibited a doublet at 103 and 105 [9].
126
Table 4.1 XRD results with bromination duration. (Reprinted with permission from [9]. Copyright
(2007) by Elsevier)
Duration (h)
10
72
168
d-spacing ()
3.342
3.355
3.348
3.361
3.361
3.361
WHM ()
0.345
0.365
0.5
0.335
0.32
0.32
WHM width-at-half-maximum
h
,EK
d^K
127
Table 4.2 Sheet resistances of SWNT films with different numbers of layers measured before
and after chemical treatments. (Reprinted with permission from [13]. Copyright (2008) by Wiley)
Pristine (sq1)
SOCl2 (sq1)
SOBr2 (sq1)
One layer
5.0410
4.2310
4.02103
Two layers
456
322
298
Three layers
303
187
168
Four layers
184
76
56
tween CNTs via S atoms when SOBr2 was used, while SOCl2-induced conductivity
was mainly due to the formation of SWNT/SOCl2 charge-transfer complexes. In
contrast to SOCl2, SOBr2 is a relatively larger molecule, which may cause larger
binding energy between Br and SWNTs than that of Cl and SWNTs. Table4.2 compares the sheet resistances of the SWNT films before and after different chemical
treatments. It is noticed that the sheet resistance gradually decreased with increasing
number of layers, consistent with the fact that sheet resistance is determined by film
thickness.
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The charge transfer results in a shift of the Fermi level, leading to an increased carrier concentration and a decreased sheet resistance, see Fig.4.3a. It is also found
that the interlayer doping yielded better optoelectrical properties than the last-layer
doping (Fig.4.3b) due to the more efficient doping effect [15]. Besides the doping
effect, nitric acids can also clean the graphene film surface, leading to an improved
optical transparency (Fig.4.3c) [20].
Thionyl Chloride
Apart from nitric acids, halogenating agents have been popularly used to realize
charge transfer. For example, it was shown that the exposure to SOCl2 induced
functional groups on graphene surface, which acted as electron acceptors thus increasing the hole density in graphene [20]. The sheet resistance of the resulting graphene decreased by 5080% depending on the type of graphene [20]. The chlorine
decorated along the edges and the basal plane of graphene increased the number of
holes in the conjugated sp2 network. The p-type doping of graphene due to SOCl2
has been further confirmed by electronic structure calculations, which indicated a
Fermi level shift into the valence band and the results are shown in Fig.4.4df [11].
129
Fig. 4.4 SOCl2 doping of graphene. a Equilibrium structure of a SOCl2 molecule adsorbed on a
pyrene molecule, which represents a graphene or CNT segment. b Total change density of the system in a plane. c Different charge densities in the same plane, indicating regions of charge depletion and accumulation with respect to a superposition of neutral atoms. (Reprinted with permission
from [11]. Copyright (2005) by ACS)
An equilibrium structure of a SOCl2 molecule adsorbed on a pyrene molecule, representing a graphene or CNT fragment, is shown in Fig.4.4a. Figure4.4b shows the
corresponding charge distribution in SOCl2 that is adsorbed on pyrene. A net charge
transfer of about 0.1 electrons from pyrene to SOCl2 was observed according to the
calculation results. Figure4.4c displays the charge flow in the system, suggesting
that the largest charge accumulation occurred on oxygen and charge depletion was
uniform across pyrene [11].
To evaluate the doping effect of SOCl2 on thermally reduced GO films, the XPS
analysis was performed and the elemental compositions and the functionalities of
the GO films were identified at various stages [20]. Table4.3 presents the corresponding atomic concentrations of the elements at different stages including after
chemical oxidation, after thermal treatment, and after SOCl2 doping. After the thermal treatment, the C/O atomic ratio surged from 2.42 to 28.8, as a result of the recovery of the sp2-hybridized benzene rings. The C/O ratio was reduced to 5.0 along
with an increase in oxygen content to 15.3% after SOCl2 doping. The recovered
oxygen concentration was a reflection of the newly created species, such as SO2 or
SO3, which also gave rise to a relatively high concentration of sulfur at 1.96%. The
1.38% nitrogen and 4.04% chlorine originated from the doping agents of HNO3
and SOCl2, respectively.
The convoluted XPS spectra given in Fig.4.5 provided further evidence of thermal reduction and SOCl2 doping treatment. The C1s signal consisted mainly of five
different chemically shifted components including: (i) C=C (sp2) in aromatic rings
at ~284.8eV, (ii) CC (sp3) in aromatic rings at ~285.6eV, (iii) CO (hydroxyl and
epoxy) at ~286.6eV, (iv) C=O (carbonyl) at 287.8eV, and (v) OC=O (carboxyl)
at ~290.3eV [21, 22]. The concentrations of the CO, C=O and OC=O groups
Table 4.3 Summary of elemental compositions of GO at different treatment stages. (Reprinted
with permission from [20]. Copyright (2011) by ACS)
Element (atom %)
Cl
C/O ratio
Ultralarge GO
(UL-GO)
66.14
27.32
2.69
2.42
Thermally reduced GO
94.43
3.28
0.75
0.16
28.79
SOCl2-doped rGO
76.88
15.37
1.38
1.96
4.04
5.00
UL-GO ultralarge graphene oxide, GO graphene oxide, rGO reduced graphene oxide
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were 15, 36, and 8%, which were drastically reduced to 9, 4, and 3%, respectively,
after the thermal treatment. SOCl2 doping induced a strong peak at 286.1eV attributed to CS [3], with about 15% signal composition. It is also worth noting that
the COOH group increased from 3 to about 10% after SOCl2 doping. Previous
theoretical [23] and experimental [24] studies reveal that proper carboxyl functionalization of CNT was beneficial to improving the electrical conductivity. As such,
the increase in COOH functional group possibly helped stabilize the p-doping owing to the electron-deficient property of doped CNT or graphene. It is suspected
that the sheet resistance may start to increase again if the COOH concentration is
too high because of the deterioration of the conjugation structure in graphene.
Thus, a proper control of the SOCl2 doping parameters, such as concentration and
immersion time, is of critical importance to achieve the highest possible electrical
conductivity.
Figure 4.6 shows the S 2p, N 1s, and Cl 2p spectra of the SOCl2-doped rGO film.
In the S 2p spectrum (Fig.4.6a), the peak at~169.5eV can be attributed to S with
an oxidation state VI (SO42) and SO covalent bonds [25]. An additional peak occurred at ~163.6eV, identical to that of an organic CS bond [26], indicating that
CSC bonds existed in the SOCl2-doped rGO film. The possibility of covalent
cross-linking between the rGO sheets through CSC bonds may also contribute to the enhanced electrical conductivity. In the N 1s spectrum (Fig.4.6b), the
components near 395405eV are attributed to the NO, CN groups that originated
mainly from the previous HNO3 treatment, confirming the attachment of N atoms
on graphene surface via covalent bonding. Although the treatment by HNO3 was
likely to introduce some defects on rGO, it appeared not to cause detrimental effect on the electrical properties of rGO films. This is because the dangling bonds or
defects formed by HNO3 are immediately passivated by OH or COOH groups.
Once OH or COOH groups are in contact with SOCl2, a nucleophilic substitution
by chloride takes place. The ionic bonds with Cl or SOCl groups can improve the
conductivity of the rGO films. The Cl 2p core level spectrum (Fig.4.6c) revealed
two nonequivalent chlorine sites from the 3/2 and 1/2 levels, which are separated
by 1.4 eV due to spinorbit coupling. The components are located at 202.0 and
200.4eV corresponding to covalent CCl bonds in the organic chlorocarbon compound [27]. The p-type doping associated with Cl led to the formation of charge
transfer complexes in the rGO sheets, resulting in a charge redistribution in the system that in turn increases the rGOs electrical conductivity [9]. In summary, SOCl2
doping introduced Cl or SOCl functional groups with a strong electronegativity
onto the rGO surface which served as electron acceptors to improve the electrical
conductivity.
SOBr2 doping also showed desired effects of enhanced electrical conductivity
and transparency of graphene films [17]. The mechanisms behind the improvemens
in these characteristics were identified by establishing the correlation with the surface chemistry of the thin films. In a typical process, the thermally reduced GO film
was subject to two additional processes: namely, (i) dipping in a HNO3 bath (70%)
for 3h and drying with gentle nitrogen flow; and (ii) dipping in a SOBr2 bath for 24
h and drying with gentle nitrogen flow. The deconvoluted C1s spectra taken before
132
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permission from [17]. Copyright (2011) by Elsevier)
and after thermal reduction were all essentially similar to those shown in Fig.4.5
because the materials and process employed were similar. Major differences arose
when the rGO films were subjected to additional treatments using HNO3 and SOBr2
and the corresponding XPS results are shown in Fig.4.7a and Table4.4.
The deconvoluted Br 3d spectrum in Fig.4.7b shows that there were two types of
CBr bonds, namely the charge-transfer complexes and the covalent bonds, similar
to the CCl bonds in thionyl chloride-doped rGO films. The intense Br 3d component at a core-level binding energy of ~70.1eV is typical of CBr covalent bonds,
whereas the less intense component with a lower binding energy of ~69.3eV is
assigned to ionic bromine [13]. These two different types of CBr bonds were confirmed by the ToF-SIMS analysis. The p-type doping associated with Br led to the
formation of charge transfer complexes in the rGO sheets, giving rise to enhanced
electrical conductivities of rGO films [9]. A nucleophilic substitution by bromide
takes place once OH or COOH groups are in contact with SOBr2. Then, the rGO
sheets form ionic bonds with Br or SOBr groups, further contributing to the conductivity of graphene films.
Figure4.8 shows the resulting sheet resistance values of the rGO films measured
at different stages. The sheet resistance of the rGO films changed from 104106 to
1002000/sq after the thermal treatment, which is about three orders of magnitude different. After the doping treatments, it was further reduced by about 2050%
to 501600/sq depending on the film thickness. To further explain the enhanced
Table 4.4 Elemental compositions of GO, thermally reduced GO, and SOBr2-doped rGO.
(Reprinted with permission from [17]. Copyright (2011) by Elsevier)
Element (atom %)
Br
GO
71.91
0.49
27.48
0.11
Thermally reduced GO
80.91
0.52
18.43
SOBr2-doped rGO
71.40
2.93
16.79
4.80
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electrical conductivities, the carrier type and sheet carrier concentrations at different stages were determined by a Hall measurement system using the Van der Pauw
method. The results are summarized in Table4.5, showing that the graphene films
remained as a positive carrier, that is, hole carrier, throughout the whole processes.
The sheet carrier concentration increased by about three orders of magnitude after
thermal treatment due to the removal of the oxygenated functional groups and the
graphitization; and it further increased by nearly 200% due to the chemical doping.
Auric Chloride
AuCl3 is also known to be an effective p-type chemical doping agent to reduce the
sheet resistance of graphene TCFs [14, 16]. The Raman spectroscopy of the AuCl3doped graphene indicates that AuIII was reduced to Au particles by charge transfer
from graphene to AuIII [16]. It is proposed that graphene was p-doped through the
following reactions when nitromethane is used as the solvent [16]:
2 graphene + 2AuCl3 2 graphene+ + AuCl2 (Au I ) + AuCl4 (Au III ) (4.2)
3 AuCl 2 2 Au 0 + AuCl 4 + 2 Cl
(4.3)
(4.4)
Table 4.5 Carrier type and sheet carrier concentration of graphene films at different stages.
(Reprinted with permission from [17]. Copyright (2011) by Elsevier)
Sample
38.7nm thick
+2.301011
+2.661014
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78.0nm thick
+7.111011
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+7.091014
135
Fig. 4.9 AuCl3 doping of graphene films. a The top steps indicate layer-by-layer (LbL) doping and
the bottom steps indicate the topmost layer doping. b Sheet resistance and transmittance of various samples as a function of the number of graphene layers. PET polyethylene terephthalate, ITO
indium tin oxide. (Reprinted with permission from [14]. Copyright (2010) by ACS)
136
the pristine single graphene sheet showed a large sheet resistance of 725/square
with a remarkable transmittance of 97.6% at 550nm. Regardless of the thickness,
the sheet resistance was greatly reduced by about 80% with AuCl3 doping (see filled
circle). It is also worth noting that the transmittance was slightly decreased compared with pristine graphene films due to the light scattering from the Au nanoparticles formed during the reduction reaction [14, 28]. The Au-doped graphene films
had at least a few folds higher electrical conductivities than those obtained after nitric acid treatment. However, the electrical conductivities of the AuCl3-doped films
were essentially similar regardless of whether the individual graphene layers were
doped or only the top layer of the multilayer graphene films was doped.
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4.3Hybridization
4.3.1Hybridization with CNTs
Another useful approach is to bridge the intersheet junctions between graphene or
rGO sheets with 1D highly conducting nanofillers, such as SWNTs, which facilitates the restoration of graphenes inherent electrical conductivity while sacrificing
a little of the transparency of graphene [30]. Apart from reducing the intersheet
contact resistance, the intercalation of CNTs may bring about another synergy of
forming 3D conductive networks through the film thickness [8, 31]. As such, the
development of graphene or rGO hybrids with CNTs is an attractive option that has
been devised for improving the optoelectrical properties of TCFs. These hybrid
films have been fabricated using several different techniques, such as the CVD
method [32], solution mixing [33, 34], self-assembly at the solventwater interface [35], LbL electrostatic self-assembly [3638], the bubble deposition method
(BDM) [39], and the LangmuirBlodgett (LB) technique [30]. The principles of
these techniques are summarized in Table 4.6 along with typical TCFs produced
based on the respective techniques. The corresponding optoelectrical performances
of these hybrid films are compared in Table4.7.
CVD Method
Kim et al. [32] proposed a facile methodology to form graphene/SWNT hybrid
films for use in high-performance TCs via the CVD growth method. As shown in
Table 4.6, SWNTs were first spin coated onto Cu foil, and graphene films were
subsequently synthesized on the SWNT/Cu foil using the CVD growth method to
decrease the contact resistance between graphene and SWNTs. The density and
alignment of precoated SWNTs were controlled by adjusting the spin-coating
speed, which is a crucial factor for achieving high-performance TCs. The obtained
graphene/SWNT hybrid films showed a notable sheet resistance of 300/sq with
96.4% transparency.
Freestanding transparent graphene/CNT paper was assembled via a solid-phase
layer-stacking approach [41]. This method has an advantage that the structural integrity and continuity of both components can be maintained and their intrinsic
electrical and mechanical properties can be preserved. As shown in Fig.4.11a, large
area CNT and graphene films were first grown by the CVD method. The CNT film
was then lifted from the substrate using a glass rod and gently placed on the graphene-coated copper foil. To secure a strong adhesion between graphene and CNTs,
ethanol was dropped onto the CNT film followed by drying. By etching the copper
away with a Fe(NO3)3 aqueous solution, freestanding graphene/CNTs hybrid films
were obtained which were rinsed with deionized water (Fig.4.11b). After drying,
the obtained graphene/CNTs composite films were found highly flexible, conductive, and transparent, with a sheet resistance of 735 /sq at 90% transmittance.
CVD method
Solution mixing
Table 4.6 Fabrication of graphene/CNT and rGO/CNT hybrid TCFs. (Reprinted with permission from [40]. Copyright (2014) by Elsevier)
Method
Schematics of synthesis process
Typical images
References
4.3 Hybridization
139
References
Electrostatic self-assembly
Typical images
Chen etal. [35]
Self-assembly at solventwater
interface
Method
140
4 Improvement of Electrical Conductivity and Transparency
Method
Typical images
References
Azevedo etal. [39]
4.3 Hybridization
141
LB assembly
Method
References
Zheng etal. [30]
142
4 Improvement of Electrical Conductivity and Transparency
Hydrazine solution,
95C for 1h
96.4
93
151
81
73
3.1
88.6
80
86
90
0.954
0.1
0.24
0.3
0.735
Rs (k/sq) T
CVD method
Reduction method
CVD method
Table 4.7 Comparison of optoelectrical properties of graphene/CNT and rGO/CNT hybrid TCFs
assembled via different approaches
0.21
0.034
0.36
3.2
16.0
10.0
4.7
34.0
DC / OP
Huang etal.
[34]
Li etal. [41]
Reference
4.3 Hybridization
143
Reduction method
0.56
86
Rs (k/sq) T
4.3
DC / OP
Zheng etal.
[30]
Azevedo etal.
[39]
Reference
GO graphene oxide, rGO reduced graphene oxide, CVD chemical vapor deposition, CNT carbon nanotubes, SWNT single-walled nanotubes, LB
LangmuirBlodgett
144
4 Improvement of Electrical Conductivity and Transparency
4.3 Hybridization
145
b
s
Ed
'
Fig. 4.11 Hybridization of chemical vapor deposition (CVD)-grown graphene and carbon nanotubes (CNT). a Schematic for the assembly of the graphene/CNT composite film. b Graphene/CNT
composite film floating on water surface. (Reprinted with permission from [41]. Copyright (2010)
by ACS)
Solution Mixing
Solution mixing of GO or rGO with CNTs before codeposition is another simple
method for producing rGO/CNT hybrid films [34]. Tung etal. [33] first produced a
hybrid layer of CNT and rGO via a solution mixing method, which is facile, inexpensive, scalable, and compatible with flexible substrates. As schematically shown
in Table4.6, SWNTs were refluxed in a mixture of nitric acid and sulfuric acid to
activate the surface with oxygen functionalities and most of the SWNTs were terminated with hydroxyl and carboxylic moieties. GO powers were then mixed with
functionalized SWNTs and dispersed directly in anhydrous hydrazine followed by
stirring for 1day. A uniform dark-gray suspension was formed upon the reduction
of GO and functionalized SWNTs. rGO/SWNT dispersions were deposited onto
substrates by spin-coating and subsequently heated to 150C to remove excess solvent. The obtained hybrid film presented a sheet resistance of 240 /sq at 86%
transmittance after chemical doping. Using a similar process, Huang etal. [34] directly dispersed dry powders of GO and SWNTs in anhydrous hydrazine to produce
hybrid suspensions of rGO and SWNTs. rGO/SWNT films were produced by a spin
146
coating method. For the film formed with one and five layers, the sheet resistance
reached as low as 954 and 254/sq, respectively. However, increasing the number
of spin-cast layers meant thicker films with increasingly reduced optical transmittance from 88.8 to 58.7%.
Self-Assembly at SolventWater Interface
Since GO sheets are amphiphilic in nature, they can form thin films at organic solventwater interfaces based on a self-assembly process [43, 44]. Chen etal. [35]
presented an ethanol-assisted self-assembly method for the quick formation of GO/
CNT composite thin films with tunable composition, transmittance, and surface
resistivity at pentanewater interface. As shown in Table4.6, ethanol serves as a
nonsolvent when it is injected into the aqueous solution containing GO or carboxylic acid functionalized SWNTs. The injected nonsolvent (ethanol) has a significant
influence on the stability of GO in water, providing a driving force to allow GO or
SWNTs to aggregate at the waterpentane interface. GO/SWCNT (SWCN Singlewalled carbon nanotubes) composite thin films were produced based on the selfassembly process at the waterpentane interface. Reduced GO/SWCNT composite
films had a much lower surface resistivity of 3.1k/sq at 73% transmittance than
the neat rGO thin films, 8.3k/sq at 72% transmittance.
Electrostatic Self-Assembly
The LbL electrostatic self-assembly is a versatile fabrication method of hybrid thin
films by repeated, sequential immersion of a substrate into aqueous solutions of
complementarily functionalized materials, that is, positively or negatively charged
GO sheets or CNTs. Hong etal. [38] reported that rGO/CNTs hybrid films were
prepared by integrating rGO-COO with MWNT-NH3+via the LbL assembly. A
significant increase in electrical conductivity was achieved by incorporating CNT
layers onto the rGO layers, with a sheet resistance of 8 k/sq at 81% transparency. In a similar study, Yu etal. [36] reported the preparation of positively charged
rGO sheets after hydrazine reduction and using polyethyleneimine (PEI) as the
stabilizer (Fig.4.12a). The PEI-modified rGO sheets were employed for sequential self-assembly along with negatively charged acid-oxidized Multi-walled carbon nanotube (MWNT) to form hybrid carbon films with interconnected carbon
structures and well-defined nanoscale pores (Fig. 4.12bc). The similar strategy
was employed to fabricate large, uniform, and durable rGO/MWNT hybrid double
layers (Fig.4.12d), [37] showing that the adsorption of MWNTs onto rGO films
considerably decreased the sheet resistance of the films without much compromising the transparency.
4.3 Hybridization
147
Fig. 4.12 Electrostatically self-assembled reduced graphene oxide (rGO)/CNT hybrid films.
a Illustration of deposition of positively charged PEI functionalized rGO and negatively charged
MWNTs on a silicon wafer or ITO-coated glass substrate. [36] SEM images of b the first rGO
layer and c the first bilayer deposited on a silicon substrate [36]. d Fabrication of rGO/MWNT
hybrid layer on a substrate [37]. (Reprinted with permission from [36, 37]. Copyright (2010, 2009)
by ACS)
The BDM
The BDM is another simple method to precisely order and deposit GO films onto
any substrates [39]. The BDM is based on the confinement of nano-objects in the
core of water bubbles. The core thickness decreases under drainage and change the
interference phenomena and the film color. There are mainly four major steps for
the BDM process (Table4.6): (i) formation of bubbles using GO or GO/CNT hybrid
solution in a closed chamber, (ii) start of water drainage, (iii) deposition of films on
the substrate, and (iv) fast evaporation of the residual water after the busting of the
bubbles. The BDM can produce densely packed monolayer to multilayer GO sheets
as well as GO/CNT composite thin films in ambient conditions. However, it should
be noted that this method is incompatible with large-scale production and is only
suitable for fundamental studies.
148
LB Assembly
It is well known that the LB assembly technique is the most sophisticated and accurately controllable among all available techniques to fabricate GO/CNT hybrid
films, where amphiphilic ultralarge graphene oxide (UL-GO) and functionalized
SWNTs are consecutively deposited via an LbL manner [30]. The deposition of
SWNT layers is a crucial part of the whole process, thus the fabrication of COOHfunctionalized SWNTs needs special attention. Due to the strong van der Waals
forces between SWNTs, they are highly insoluble and aggregated, making pristine
SWNTs unsuitable for the LB assembly. The conventional solution is to apply noncovalent functionalization, including wrapping SWNTs with a variety of surfactant
or polymers, such as poly(m-phenylene vinylene-co-2,5-dioctyloxy-pphenylene
vinylene) (PmPV) [45] or poly(2,5-dioctyloxy-1,4-phenylene-alt-2,5-thienylene)
(POPT) [46], to avoid the formation of insoluble bundles. However, these additives
are insulating and difficult to be completely eliminated after the film formation,
which is harmful to electrical conductivity of the films due to the additional contact resistance between them [13]. In the absence of surfactant treatment, SWNTs
can also be dispersed using special solvents [47], such as N-methyl-2-pyrrolidone
(NMP) [48], N,N-Dimethylform (DMF) [49], o-dichlorobenzene (DCB) [50], and
dichloroethane (DCE) [45], but they are unsuitable for the LB assembly because
of their high boiling points [4850] or toxic nature [45, 50]. Hence, carboxylic
moieties were introduced non-uniformly along the SWNTs length, making them
amphiphilic and ready for the LB assembly.
The XPS results of the COOH functionalized SWNTs shown in Fig.4.13a confirmed COOH functional groups upon sulfuric acid and nitric acid (typically 3: 1
volume ratio) treatments [30]. Typically, the COOH functionalized SWNTs were
dispersed in a 1:3 water/methanol solution before spreading. The surface pressure
area isotherm curves in Fig. 4.13b shows the changes in slope due to the phase
transitions of the SWNT monolayer from gas to condensed liquid and to a solid
state at~2 and~10mN/m, respectively. There were also small shifts of the gasliquid and liquidsolid phase transition points toward a smaller area with increasing
the cycles probably because of the loss of a small amount of material from the
monolayer after each cycle [43]. The COOH functionalization was effective in
dispersing the bundles into individual SWNTs (Fig.4.13c). Alternate monolayers
of GO and SWNTs were deposited on the substrate one after another by carefully
controlling the surface pressure.
The scanning electron microscope (SEM; Fig. 4.14b) images suggest partially wrinkled edges when the GO sheets were squeezed toward each other during
compression and pullout. The transmission electron microscope (TEM) image and
the corresponding selected area electron diffraction (SAED) pattern (Fig. 4.14c)
confirmed the primarily amorphous nature of the GO sheets [17]. Due to the amphiphilic GO and SWNT surfaces, strong bonds were formed though interactions
and van der Waals forces when the SWNT layer was deposited on the GO layer
[51]. The SWCNTs functioned as conductive bridges connecting the separate GO
sheets.
4.3 Hybridization
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Fig. 4.14 Fabrication of GO/SWNT hybrid films via an LB assembly process: schematic a,
SEM b, and TEM c images of a monolayer of GO; schematic d, SEM e, and TEM f images for
one bilayer GO/SWNT hybrid film, with SWNTs bridging GO sheets; schematic g, and SEM h, i
images of four bilayers GO/SWNT hybrid film. (Reprinted with permission from [30]. Copyright
(2012) by RSC)
The typical surface morphologies of the GO/SWNT hybrid thin films with four
bilayers are shown in Figs.4.14h, 4.14i and 4.15a. Figure4.15b shows the mean
surface roughness values of the hybrid films as a function of number of bilayers before and after thermal treatment. As the film thickness increased, the surface roughness presented a generally increasing trend. Because of the deposition of porous
SWNT monolayer and flat GO layer, there were sudden surges and drops in roughness. Due to the graphitization effect, the thermal reduction generally decreased
the surface roughness with less significant drops and surges. The compaction of
the films resulting from the removal of oxygenated functional groups and graphitization during annealing were mainly responsible for the reduction in roughness.
After thermal treatment, the 30-nm-thick hybrid films had a surface roughness of
~10nm, which is far lower than those prepared by other coating techniques, typi-
4.3 Hybridization
151
cally ~35nm for the hybrid films with a similar thickness [34]. The GO/SWNT hybrid films without additional doping treatments delivered excellent sheet resistance
ranging 180560/sq with an optical transmittance ranging 7786% depending on
the number of hybrid layers.
152
ZnO Nanorods/NWs
Choi etal. [60] fabricated a heterogeneous 3D nanostructure consisting of 1D ZnO
nanorods grown epitaxially on a 2D graphene electrode with no damage using a low
temperature solution growth. As shown in Fig.4.16, a large-scale graphene film was
grown on a Ni-coated SiO2/Si wafer by a CVD method. Then, the transparent graphene film was transferred to a flexible polyethylene naphthalate (PEN) substrate.
After ZnO nanorods were grown on the graphene sheet, a rollable graphene-based
transparent nanogenerator was integrated. A flexible TCF material composed of
vertically aligned ZnO NWs grown on rGO-PDMS substrates was also reported
[61]. The rGO films were obtained by spin coating of GO dispersion on a Si/SiO2
substrate and annealing at a high temperature. After peeling them from the silicon
substrate in a hydrogen floride (HF) solution, the rGO films were transferred to
PDMS substrates. ZnO NWs were hydrothermally grown on the rGO film with a
uniform structure even in highly deformed states, showing a typical metalsemiconductor ohmic contact without a contact barrier.
Silver NWs
Because Ag NW networks had a relatively low sheet resistance lower than 80/
sq at a transmittance of ~90%, Ag NWs were combined together with graphene
to form a high-performance TCF [62]. CVD grown graphene, rGO and GO were
employed to improve the optoelectrical properties and stabilities of the hybrid TCFs
with varied successes. The optoelectrical properties of graphene/Ag NWs hybrid
TCFs assembled with different approaches are compared in Table4.8.
It was found that Ag-NWs could decrease the resistance of CVD grown graphene
films [63]. Ag NWs were spin coated on glass and SiO2/Si substrates for integration with graphene, as shown in Fig.4.17a. The CVD grown graphene was then
transferred onto the Ag-NW films using the dry transfer technique. The sheet resistance of the resulting graphene/Ag-NW films was comparable to the intrinsic Rs of
perfect graphene, namely~30 /sq for graphene/SiO2 system [63, 64]. In another
study, rGO was hybridized with Au nanoparticles (NPs) in the presence of Ag-NWs
to improve the conductivity without adversely affecting the transparency [65]. The
fabrication process involved spin coating of Ag-NW solution on the substrate and
covered by a GO/Au-NPs coating, followed by reduction using a hydrazine vapor
to prepare hybrid films (Fig.4.17b). The resulting rGO/Au-NP films had a sheet resistance of 28.6k/sq, while the final rGO/Au-NP/Ag-NW hybrid films showed a
much lower sheet resistance of 26/sq at a transparency of 83%. It is believed that
the presence of Ag-NWs had an extra benefit of minimizing the junction resistance
between the rGO platelets, even at sub-percolation concentrations, similar to the
bridging effect seen in GO/SWNT hybrid TCFs [30].
4.3 Hybridization
153
Bar coating
Spin coating
Spin coating
Bar or spray
coating
Spin coating
Spin coating
Spin coating
Spin coating
14
13
48
27
86
24.8
26
86
1460
33
16
34.4
30.4
32.5
225
24
22
Rs (/sq)
88
71.9
91.2
80
80
92
83
85
91
94
91.1
92.8
71.2
81.5
91.3
91
88
T (%)
204.0
80.9
83.3
59.1
18.6
178.5
44
74.3
25.9
4.1
181.8
246.9
143.9
33.5
53.9
18.0
162.7
129.8
DC / OP
CVD chemical vapor deposition, GO graphene oxide, rGO reduced graphene oxide, NW nanowire, LB LangmuirBlodgett
LB assembly
GO
GO
Spray coating
GO
LB assembly
Spin coating
GO
GO
Spin coating
Gold-decorated rGO
Dip coating
Spin coating
Gold-decorated rGO
Transfer printing
Spin coating
Gold-decorated rGO
Drop casting
Spin coating
Spin coating
Spin coating
Spin coating
Spin coating
Drop casting
Deposition method
of Ag NWs layer
Graphene layer
Table 4.8 Comparison of optoelectrical properties of Ag NW/graphene hybrid TCFs assembled with different approaches
Xu etal. [62]
Reference
154
4 Improvement of Electrical Conductivity and Transparency
4.3 Hybridization
155
Fig. 4.17 Ag nanowire (NW)/graphene hybrids for TCFs. a Schematic illustration of Ag NW/graphene films fabrication [63]. b Schematic of reduced graphene oxide (rGO)/Au nanoparticle (NP)/
Ag NW hybrid film preparation [65]. c Schematic of the fabrication process of the 2D AgNW/
rGO hybrid nanomaterials prepared through a two-step reduction process by sodium borohydride
(NaBH4) and ethylene glycol [66]. d Schematic illustration of the fabrication of a Ag NW/GO network on a glass substrate at room temperature [67]. (Reprinted with permission from [63, 6567].
Copyright (2012, 2013, 2014) by ACS and Elsevier)
156
Fig. 4.18 Reduced graphene oxide (rGO)/Cu nanowire (NW) hybrid films for TCs. a Schematic
of preparation of rGO/Cu NW hybrid films. b Photographs of GO aqueous dispersion and Cu NWs
dispersed in IPA. c rGO (top) and Cu NW (bottom) films on glass substrates. d PMMA/rGO film
delaminated from the glass substrate in NaOH aqueous solution. e Photograph of rGO/Cu NW
films on a glass substrate after the PMMA layer was removed. f Sheet resistance versus transmittance of the neat Cu NW and rGO/Cu NW hybrid films. g, h SEM images of individual rGO platelets g and rGO/Cu NW film h. (Reprinted with permission from [52]. Copyright (2013) by ACS)
4.3 Hybridization
157
bridge two or more disconnected Cu NWs separated by any distance smaller than
the lateral size of the platelet (Fig.4.18g), leading to higher electrical conductivities
of the hybrid films (Fig.4.18h).
Fig. 4.19 a Schematic and b SEM image of graphene/metal nanogrids hybrid TCFs. c Image of
a hybrid electrode on the PET substrate bent around a cylinder of d=1cm. d Sheet resistance of
hybrid electrodes as a function of bending cycle. (Reprinted with permission from [77]. Copyright
(2011) by ACS)
158
tances of the hybrid films increased by 2030% after the initial 50 bending cycles,
originating from the graphene film itself (Fig. 4.19d). It is worth noting that the
sheet resistance stabilized even up to 500 bending cycles because the weak areas on
the graphene did not survive during the initial bending and changed their forms to
stabilize upon further cycles [77].
4.4Using UL-GO
Although mechanical cleavage of graphite could prepare high-quality graphene
with a millimeter size, the yield of this method is extremely low, being unsuitable
for mass production [78]. Alternatively, graphitization of Si-terminated SiC (0001)
in an argon atmosphere could produce monolayer graphene films with a domain
size of several tens of micrometers [79]. However, the graphene obtained thereby
was difficult to transfer to other substrates and the yield was very low. The CVD
technique has been extensively explored to grow extremely large-area graphene on
Ni films or Cu foils [8082]. However, the CVD method usually requires specific
substrate materials, which have to be removed chemically after the growth of graphene. The high cost of single crystal substrates and the ultrahigh vacuum conditions necessary to be maintained for the CVD growth significantly limit the use of
the method for large-scale applications [81].
Because GO sheets are hydrophilic and produce stable and homogeneous colloidal suspensions in aqueous and various polar organic solvents, they are easy to be
processed to produce TCs on a substrate [83]. However, these GO sheets are usually
small, mostly with an area in the order of 100m2 [35]. Due to a large amount
of intersheet junctions, the small-size GO sheets result in high intersheet contact
resistance even after reduction [1]. Thus, efficient synthesis and assembly of largearea GO sheets are essential to improving the optoelectrical properties of GO-based
TCs. Different deposition techniques have been used to prepare TCs using UL-GO
sheets, and a summary is presented along with their optoelectrical properties, as
shown in Table4.9.
159
Table 4.9 Comparison of optoelectrical properties of UL/GO-based TCFs assembled with different approaches
Size of
UL-GO
(m)
Deposition
method of
UL-GO
Reduction method
Rs (k/
sq)
DC / OP
Reference
~20
Solution
casting
Thermal annealing,
600C in argon for
3h
0.52
63
1.4
Bae etal.
[84]
~20
Solution
casting
Thermal annealing,
600C in argon for
3h
3.110
90
1.1
Bae etal.
[84]
19.1
79
0.079
Zhao etal.
[1]
1005
98
0.018
Su etal.
[85]
413
98.1
0.047
Su etal.
[85]
98
0.099
Su etal.
[85]
Up to
~20100
Up to
~1000
Up to ~200 LB
assembly
Thermal annealing,
1100C in argon,
0.5h
0.5
90
6.97
Zheng
etal. [20]
Up to ~200 LB
assembly
HI solution (57%),
90C, 10min
1.1
91
3.55
Lin etal.
[86]
PMMA (HEFG/PMMA) film was transferred to a PET film. HEFG on PET (HEFG/
PET; Fig. 20d) was obtained once PMMA was removed in acetone. The optical
transmittances of the HEFG/PET TCFs were in the range of 6390% with sheet
resistances of 0.523.11k/sq. It should be noticed that the edge of the HEFG film
was much thicker than the central part due to the nonuniform evaporation during
the solution casting process.
160
Fig. 4.20 Solution casting of edge-selective functionalization of graphite (EFG) for the production of large-area uniform graphene films. (Reprinted with permission from [84]. Copyright (2011)
by ACS)
the TCF made from sample I (~7000 m2 in area) had a sheet resistance of ~840/
sq while the TCF made from sample II (~10003000m2 in area) and sample III (
~100300m2 in area) had sheet resistance of ~5.6 and ~19.1/sq, respectively.
Because three types of TCFs were reduced under the same condition, it is believed
that the lower sheet resistance of sample I was mainly due to the increase in average sheet area and consequent decrease in the number of intersheet tunneling barriers in a continuous rGO film [1]. A similar trend was also found by Su etal. [85].
As shown in Table4.9, the sheet resistance of the TCF prepared from the UL-GO
sheets with typical sizes approximately a millimeter after 1h sonication was significantly lower than those prepared from the sample ll GO (S-GO) sheets with typical
lateral sizes ~15m after 6h sonication and those from the L-GO with typical
sizes 20100m after 2h sonication.
161
Fig. 4.21 TCFs produced from UL-GO sheets. a, b Optical images of GO films produced by dip
coating a before and b after HI acid reduction. c Sheet resistance and transmittance at 550nm of
TCFs assembled with GO sheets with different sizes. (Reprinted with permission from [1]. Copyright (2010) by ACS)
162
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Fig. 4.22 Isothermal curves of the UL-GO. a Surface pressure vs. area plot showing the corresponding four stages (ad) of the formation of GO monolayers in LB assembly. b Isotherm plots
of two sequential compression/expansion cycles, showing essentially overlapped two curves over
the whole area, except at the early stage of compression. (Reprinted with permission from [20].
Copyright (2011) by ACS)
163
Control of GO Structure
It was found that the GO structure in the TC films can be controlled by varying the
LB assembly parameters such as surface pressure and pulling speed [20, 87]. Several unique microscopic morphologies, such as wrinkles, folds and overlaps, were
observed as a result of the interactions between the neighboring GO sheets when
they were brought together side by side during the LB assembly. The wrinkles,
folds, and overlaps are undesirable as they reduce the optical transparency of the
GO films [88]. For S-GO, the rigid S-GO sheets collected from the LB assembly
were free of wrinkles, while other deposition methods, such as drop-casting, spincoating, and spraying, usually produced wrinkled sheets [89]. The packing density increased continuously as the surface compression increased from (a) isolated
S-GO sheets, to (b) close-packed S-GO sheets, (c) over-packed GO sheets with
folded edges, and (d) over-packed S-GO sheets with folded edges and overlapping
on top of another (Fig.4.23) [44].
UL-GO sheets tend to be softer and more flexible than S-GO sheets due to the
large sizes ranging from a few tens to ~200m, presenting microscopic morphologies distinct from those observed in S-GO sheets depending on the pressure applied (Fig.4.24). With increasing the surface pressure or the packing density, the
typical features varied from: (a) isolated UL-GO sheets, (b) close-packed UL-GO
sheets, (c) overlapped UL-GO sheets with some wrinkles, to (d) overlapped ULGO sheets with extensive wrinkles. It is worth noting that at a high surface pressure
the UL-GO sheets tended to wrinkle while the S-GO sheets were more susceptible
to overlapping. For example, the UL-GO films collected at a low surface pressure
(0 to ~10mN/m) consisted of dilute, well isolated, flat individual UL-GO sheets
(Fig.4.24a, b). The UL-GO sheets were forced to squeeze each other with increasing the surface compression beyond the close-packed region, leading to overlapping
and buckling. Figure4.24c, d shows typical graphene oxide wrinkles (GOWs) with
different degrees of wrinkling. The hydrogen bonds present between the carboxylic
acid edge groups encouraged the interactions between UL-GO edges, preventing
them from sliding and producing wrinkled UL-GO. Due to the irregularly shaped
polyhedrons with polydisperse sizes of UL-GO sheets, they would squeeze each
other from random directions, resulting in random wrinkling orientations. In view
of the fact that these wrinkles tended to be aligned along the contact lines of neighboring sheets, the source of wrinkling was confirmed to be caused by buckling
developed under in-plane compression.
Different pulling speeds were found an important parameter in controlling the
degree of wrinkling. A much higher degree of wrinkling was observed at a high pulling speed of 1.0mm/min for UL-GO films, designating it concentrated GOWs
(CGOWs), see Fig.4.24e, f. The LB transfer of flat GO sheets is a self-assembly
process whose quality depends on the evaporation of water molecules trapped between the UL-GO sheets and substrate. Wrinkle-free S-GO films could be produced
(Fig.4.23) because the S-GO allowed water to evaporate easily. However, the relatively larger size of UL-GO often entrapped the water droplets between the UL-GO
sheets and the capillary force induced by water evaporation caused wrinkling of the
164
Fig. 4.23 SEM images of S-GO sheets collected on a Si substrate at different stages of surface
pressure. The packaging density increases from a isolated S-GO sheets, to b close-packed S-GO
sheets, c over-packed S-GO sheets with folded edges, and d over-packed S-GO sheets with overlapping. e and f Over-packed S-GO sheets at a high magnification. (Reprinted with permission
from [20]. Copyright (2011) by ACS)
165
Fig. 4.24 ad SEM images of UL-GO sheets collected on a Si substrate at different stages of surface pressure at a pulling speed of 0.1mm/min. The packaging density increases from a isolated
UL-GO sheets, to b close-packed UL-GO sheets, c overlapped UL-GO sheets with some wrinkles,
and d overlapped UL-GO sheets with extensive wrinkles. e, f SEM images of UL-GO sheets at
stage d of the surface pressure curve at a pulling speed of 1.0mm/min: concentrated GO wrinkles
(CGOWs): taken at e low and f high magnifications. (Reprinted with permission from [20]. Copyright (2011) by ACS)
166
Fig. 4.25 Schematics for the generation of concentrated graphene oxide wrinkles (CGOWs) due
to capillary forces. UL-GO ultralarge graphene oxide. (Reprinted with permission from [20].
Copyright (2011) by ACS)
sheets [90, 91]. In particular, if a high pulling speed were to be applied, there would
be too short a time for the UL-GO sheets to relax into a flat state and transfer onto
the substrate. Due to the capillary force and gravity (Fig.4.25), the trapped water
caused wrinkling during the transfer process. This explains why the UL-GO sheets
assembled at a high pulling speed and a high surface pressure became CGOWs after
transfer.
It is reported that GO nanoribbons can be produced by plasma etching of GOWs
[92]. By accurate control of the plasma etching conditions, single- or double-layer
GO nanoribbons were obtained so that the top layers of GOWs acted as the sacrificial layers. The method of producing GOWs by LB assembly offers a facile
and environment-friendly approach to prepare large-size GOs with controllable
amounts of wrinkles on their surface.
Other than using a fast pulling speed, the compression of the films can also cause
wrinkling even before deposition. Another way of controlling the GO structure in
167
Fig. 4.26 a Schematic of the formation of carbon nanoscroll (CNS)-like structures and the loose
dense pattern during the LB process. bd TEM b, optical microscope image c, and AFM image d
of CNS-like structures transferred onto a glass substrate. (Reprinted with permission from [87].
Copyright (2010) by Elsevier)
the LB assembly was proposed by Gao etal. [87]. It is found that the LB method
is a highly efficient fabrication approach for producing carbon nanoscrolls (CNSs)
using functionalized GO sheets (Fig.4.26a). The CNSs had a tubular structure without caps at its ends (Fig.4.26b) and aligned parallel to the moving barriers of the
LB equipment, exhibiting a loose-dense pattern during the LB compression process
(Fig.4.26cd). A possible formation mechanism of the CNS-like structure is that the
scrolling of a GO sheet is determined by the competition between the free energy
and the elastic energy [93]. The overlapping of GO sheets decreases the free energy
while the bending increases the elastic energy. It follows then that stable CNSs can
be spontaneously formed when the van der Waals energy gain overweighs the bending energy. When moving the barriers, the functionalized GO sheets are bent due
to the compression force. Once a close-packed monolayer is formed, the edge of
GO sheets starts to scroll upon further compression. Thus, the CNS-like structure is
formed near the barriers, which expands into the center of the trough. The CNS-like
structure and bundles pack closely and align parallel to the moving barriers with the
progress of the assembly. The simultaneous formation of the CNS-like structure and
the collapse of CNS monolayer result in the loosedense pattern.
Because CNS, GOWs, and CGOWs have no caps at their ends, it may be easier
to encapsulate functional molecules or nanomaterials in the internal cavities of GOs
than in CNTs [94, 95]. In addition, the interlayer distance of the wrinkles can also
be tailored to better accommodate the intercalants of various sizes [87]. The UL-GO
sheets with high-density wrinkles, such as CNS, GOWs, and CGOWs, are considered promising candidates for many applications, including hydrogen storage,
supercapacitors, biosensors, and nanomechanical devices. Table4.10 summarizes
168
Table 4.10 Various GO structures obtained at different pulling speeds and surface pressures [20, 87]
Type of GO
Pulling speed
(mm/min)
Surface pressure
(mN/m)
Structure
Potential applications
S-GO
0.11.0
Any
Flat GO
Nanoelectronic devices
UL-GO
0.1
015
Flat GO
UL-GO
0.1
>20
GOWs
Fabrication of GO
nanoribbons
UL-GO
1.0
>20
CGOWs
Functionalized
GO
0.11.0
~50
CNSs
GO graphene oxide, UL-GO ultralarge graphene oxide, GOWs graphene oxide wrinkles, CGOWs
concentrated graphene oxide wrinkles, CNSs carbon nanoscrolls
various GO structures that can be obtained by varying pulling speeds and surface
pressures, along with their potential applications.
Surface Morphology
The electrostatic repulsion between the ionized carboxylic and phenol hydroxyl
groups facilitate the formation of GO colloidal solution in water [96]. When the
second GO layer is deposited on top of the first layer, these two layers are likely
to experience both electrostatic repulsion and van der Waals attraction. It should
be noted that the scaling law of van der Waals potential versus separation depends
on the geometry of the interaction bodies [43]. When the GO sheets are brought
together in a face-to-face manner, they can be treated as two parallel plane and their
van der Waals potential then scales with (1/d2), where d is the distance between the
two GO sheets. Besides van der Waals force, the residual -conjugated domains
can also contribute to the attraction between the GO sheets. These attractive forces
dominate and lead to successful LbL deposition of GO sheets. However, the electrostatic repulsion that GO sheets experience from both their neighbors and those
already deposited can cause wrinkling. Since the substrate is no longer flat due to
the presence of GO sheets deposited previously, wrinkling becomes serious when
depositing a large number of layers [43].
Figure 4.27 shows the typical surface morphologies of as prepared UL-GO and
rUL-GO films after thermal treatment on a quartz substrate. The corresponding arithmetical mean roughness, root mean square roughness, and peak-to-peak roughness values are summarized in Fig. 4.28ac, while the thicknesses of the deposited UL-GO films measured using atomic force microscopy (AFM) are plotted in
Fig.4.28d. It is noted that the surface roughness of both films increased consistently
169
Fig. 4.27 AFM images of UL-GO films consisting of two layers a, b and eight layers c, d of
monolayer GO sheets taken before a, c and after thermal treatment b, d. (Reprinted with permission from [20]. Copyright (2011) by ACS)
with increasing the number of GO layers. Instead of a linear increase, the parabolic
increase may indicate that the wrinkles have been accumulated after the deposition of each GO layer deteriorating the flatness of the films. The surface roughness
was consistently reduced after the thermal treatment which removed oxygenated
functional groups and graphitization of the films [17, 97]. Although the wrinkles
and defects cannot be completely removed after thermal treatment, the surface
roughness of the films produced by LB assembly was much lower than the films
produced by other techniques. It is interesting to note that the average thickness of
the films made from one layer of UL-GO was ~1.9nm, which is about 50% larger
than the literature value [98, 99]. This observation is not surprising because the
corresponding roughness of the film was about 1nm due to wrinkling of UL-GO
sheets [20].
The effects of substrate material on UL-GO film morphology and surface roughness were also investigated [86]. To study the morphology of UL-GO on a soft substrate, such as PET, the substrate surface needs to be made hydrophilic for proper
wetting to take place by water and efficient deposition of UL-GO. One effective way
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to modify the PET surface is using oxygen plasma, for enhanced hydrophilicity of
PET. Figure4.29a shows the contact angles and the AFM images of the PET substrate
surfaces obtained at different stages. It is found that the oxygen plasma treatment enhanced the hydrophilicity of the PET substrate, reducing the contact angle from 69
to 22. The oxidation effect during the oxygen plasma treatment process endowed
the PET surface with moieties of polar groups, which in turn reduced the C/O ratio
while increasing the surface energy. Once a UL-GO layer was deposited on the PET
substrate, the contact angle increased notably from 22 to 74.5, due mainly to the
amphiphilic GO sheets that had both hydrophilic groups (COOH, OH, and C=O)
and hydrophobic (CC, CH) groups. The contact angle increased to 103.2 after HI
reduction due to the removal of the oxygenated groups, and dropped back to 83.5
after the chemical doping with HNO3 and SOCl2 introducing of new functionalities.
Figure4.29b summarizes the corresponding thickness and mean roughness values of the UL-GO films on the PET substrate. Similar to UL-GO films on the quartz
substrate, the average thickness of the film increased with increasing the number
of GO layers. It is worth noting that the initially very high roughness of the film
rapidly decreased with the increasing number of layers due possibly to the flattened
PET substrate surface on the microscopic scale. From the AFM images shown in
Fig.4.29a, it is seen that the sharp peaks were removed by the deformation caused
by the attractive forces between the hydrophilic PET surface and the amphiphilic
UL-GO sheets. The larger the number of UL-GO layers, the larger the deformation
and the more flattening of the sharp peaks, which helped mitigate the overall surface roughness [86].
171
172
Fig. 4.30 Optoelectrical properties of LB assembled ultralarge graphene oxide (UL-GO) films.
a Comparison of optical and electrical properties between UL-GO films of different numbers of
layers taken at different stages of treatment (transmittance measured at 550nm wavelength). b
Sheet resistance at different stages. c Sheet resistance and transmittance measured at 550nm for
transparent conductors consisting of rS-GO, rUL-GO, and C-rUL-GO. (Reprinted with permission
from [20]. Copyright (2011) by ACS)
nificantly deteriorated after the thermal treatment due to the reduction of GO and
the adsorption of impurity particles on the other side of quartz substrates, while part
of the lost transparency was restored after the chemical treatments [17]. However,
the removal of these impurities after acid treatment contributed to the improvement
of transparency. There appeared to be a strong interaction between the rUL-GO and
quartz substrate after thermal treatment arising from the graphitization effect of the
high-temperature annealing. After the thermal treatment, the sheet resistance of the
rUL-GO films was in the range of 277605/sq for film thickness 3.718.5nm
(Fig.4.30b). The sheet resistance was further reduced by 3050% to 197459/sq
after the chemical treatments.
To evaluate whether these properties remained stable, which is critical for practical applications [15], the sheet resistance of the chemically doped, reduced ultralarge graphene oxide (C-rUL-GO) film was measured after 4 months of exposure
to ambient air (Fig.4.30b). It was found that the sheet resistance increased by about
1030% after exposure depending on the film thickness. The loss of ameliorating
chloride functional groups I was mainly responsible for the degradation of the elec-
References
173
trical conductivity. Because the acyl chloride groups were reactive with water, it was
likely that the functional groups doped on the graphene film may have reacted with
moisture present in air during ageing. Employing a protective coating could reduce
the possibility of decomposition and thus retain the improved electrical conductivity [29]. The sheet resistance values are compared between the films made from
GO sheets of two different sizes using the same processing conditions, as shown in
Fig.4.30c. The rUL-GO sheets showed a much lower sheet resistance than the rSGO sheets, by a remarkable one order of magnitude, for a given transmittance of the
films. The reduced number of intersheet tunneling barriers in a continuous rUL-GO
film because of the large area of GO sheets was responsible for this observation [1].
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Chapter 5
5.1Introduction
As graphene has several potential advantages over indium tin oxide (ITO) including
weight, robustness , flexibility, chemical stability, and cost, many applications, such
as touch panels, displays, solar cells, organic light-emitting diode, transistors and
other new areas, have been demonstrated [1]. Although the application of graphene
for transparent conductors (TCs) is still in its early stage and the performances of
some devices presented in this book are in a preoptimized state, the unique functional characteristics can make graphene a strong candidate to replace the currently
commercially dominant TC materials [2]. These devices, with their functional,
structural, and mechanical requirements, where graphene has been considered to
apply are discussed in this chapter.
5.2Touch Screen
A touch screen is an electronic visual display that detects the presence and location
of a touch [2]. A variety of touch-screen technologies, such as resistive, surface
acoustic wave, capacitive, surface capacitance, projected capacitance, has been developed [3]. The most commonly used touch screens are the resistive and capacitive
types, which require a sheet resistance of ~3001500 /sq at a transparency of
~8690% [4]. Graphene has several advantages including flexibility, wear resistance, chemical durability, and low toxicity (Fig. 5.1ab) compared to the traditional ITO. Based on the successful fabrication of graphene films, with outstanding
sheet resistance and transparency, and a large size of tens of centimeters, Bae etal.
[5] incorporated them into touch-screen panel devices (Fig.5.1b). It is revealed that
the touch-screen display made from graphene outperformed that of ITO in terms
of the applied strain. The former touch screen could handle twice as much strain as
conventional ITO-based devices (Fig.5.1c) [5]. The graphene-based panel resisted
up to 6% strain, which is limited mainly by the silver electrode and not by graphene
itself, while the ITO-based touch panel easily broke at just 23% strain.
Springer Science+Business Media New York 2015
Q. Zheng, J.-K. Kim, Graphene for Transparent Conductors,
DOI 10.1007/978-1-4939-2769-2_5
179
180
Fig. 5.1 a Structure of graphene-based resistive-type touch screen [6]. b Image of flexible touch
screen based on graphene films. c Electromechanical properties of graphene-based touch-screen
devices compared with ITO/PET electrodes in tension. The inset shows the resistance change with
compressive and tensile strains applied to the upper and lower graphene/PET panels, respectively [5]
5.3Displays
181
5.3Displays
Nearly 1.7billion display device panels are produced annually [4] as major components for mobile phones, televisions, laptops, desktops, machine interfaces, monitors, etc. Transparent electrodes have critical functions in display devices, such as
liquid crystal displays (LCD) and light-emitting diode (LED) [4] and the functions
in these displace devices are discussed as follows.
5.3.2Light-Emitting Diodes
LEDs have received great interests as they can be used in many areas such as flashlights, traffic signals, and text and video displays [7]. It is expected that both the
LED TV and LED backlights market will grow steadily in the future. ITO has been
the dominant material for LED applications. However, the price fluctuations and
its ceramic nature have greatly limited the future development. Novel TCF material with outstanding optoelectrical and mechanical properties is urgently needed
182
Fig. 5.2 a Schematic diagram of the structure of an
LCD with typical layer thicknesses in brackets: 1 glass
(1mm), 2 graphene, 3 Cr/Au
contact surrounding graphene
flake (5nm Cr+50nm Au),
4 alignment layer (PVA;
40nm), 5 liquid crystal
(20m), 6 alignment layer
(40nm), 7 ITO (150nm), 8
glass (1mm). The graphene flake is surrounded
by a nontransparent Cr/Au
contact. Optical micrographs
of an LCD using green light
(505nm, fwhm 23nm) with
different voltages applied
across the cell: b V= 8 Vrms, c
V= 13 Vrms, d V= 22 Vrms, and
e V=100 Vrms. Overall image
width is 30m. The central
hexagonal window is covered
by graphene, surrounded by
the opaque Cr/Au electrode.
f An optical micrograph (in
reflection, using white light)
of a graphene flake on the
surface of a 1-mm-thick glass
slide. The contrast is in the
order of 6%. Overall image
width is 10m. g The same
image but in a transmission
mode. The flake is practically
invisible. h Control device
with no graphene in the opening of the Cr/Au contacts
with V=100 Vrms applied
across the cell. i Light transmission through the LCD as
a function of voltage applied
across the cell, normalized to
the maximum transmission.
(Reprinted with permission
from [8]. Copyright (2008)
by ACS)
5.3 Displays
183
Fig. 5.3 a Processes of batch fabrication of GaN-based LEDs with patterned MLG electrodes; b
schematic cross-sectional view of GaN-based LED structure with a transparent MLG electrode;
and cf optical micrographs of GaN LEDs with transparent MLG electrodes. c Large-area patterned multiple LED devices and d an individual LED. e LED with tip probes attached before
applying the input current and f after applying an input current of 100A [9]
to replace ITO in LED devices. It was recently demonstrated that patterned multilayer graphene (MLG) could be used for a large-scale fabrication of GaN LEDs [9].
Figure5.3a shows the fabrication process of the LED devices with MLG electrodes
where the chemical vapor deposition (CVD)-synthesized graphene film was used
as a top anode for GaN LEDs. Figure 5.3b shows the schematic cross-sectional
view of the LED, which consists of an MLG anode, an active luminescent layer (pGaN/multiple quantum wells (MQW)/n-GaN), a Cr/Au cathode, undoped GaN, and
the sapphire substrate. Figure5.3cd presents large-scale, batch-processed multiple
devices with patterned MLG electrodes. The optical micrographs of an MLG electrode LED before (Fig.5.3e) and after (Fig.5.3f) applying an input current show
that blue light emission is clearly visible even at a low input current of 100A [9].
Graphene thin films were used as transparent electrodes for organic light-emitting
diodes (OLEDs) [10]. It is shown that the electrical and optical performance of a
small molecule OLED on graphene was similar to that of control devices on an
ITO, although there were marked differences in total thickness of the optical stack.
It is believed that graphene is a viable alternative to ITO [10, 11], while further
184
5.4Solar Cells
Many kinds of graphene-based solar cells, including dye-sensitized solar cells [12],
organic bulk-heterojunction (BHJ) photovoltaic cells [13], hybrid ZnO/poly(3-hexylthiophene) (P3HT) solar cells [14], Si Schottky junction solar cells [15], and InGaN
pin solar cells [16], have been developed recently [7]. One important advantage
of graphene-based solar cell is that graphene can be used for flexible photovoltaic
device applications. Arco etal. [17] demonstrated a feasible, scalable, and an effective method to employ CVD-grown graphene as a highly transparent, continuous,
and flexible electrode for organic photovoltaic (OPV) cells. As shown in Fig.5.4a,
graphene films were synthesized by CVD and transferred to transparent substrates.
The TCFs were then evaluated in organic solar cell heterojunctions (TCE/poly-3,4ethylenedioxythiophene:poly styrenesulfonate (PEDOT:PSS)/copper phthalocyanine/fullerene/bathocuproine/aluminum). The key to success was the continuous
nature of the CVD graphene films. The comparison study shows that graphene offers
comparable performance with ITO. Graphene solar cells demonstrated an outstanding capability to operate under bending conditions up to 138, whereas the ITObased devices displayed cracks and irreversible failure with 60 bending [17].
A major challenge to successful implementation in these applications is the
difficulty to effectively separate photogenerated electronhole pairs and transfer
the separated charge carriers to the electrodes [7]. Graphene-based materials have
shown controllable surface and interfacial properties as well as tailored work functions via functionalization during synthesis and/or posttreatment [7, 18, 19]. Because the potential created by the different work functions helps to separate the
exciton pairs, it is important to facilitate better transport of charge carriers to each
electrode, which can be achieved by an additional functional layer [19]. Choe etal.
[13] reported the application of MLG films grown by the CVD method to OVP
cells. Figure5.4b shows the device structure of a photovoltaic cell with graphene as
a transparent and conducting electrode. The cross-sectional transverse electromagnetic mode (TEM) image of the photovoltaic cell (Fig. 5.4c) presents distinctive
interfaces formed between the layers of the individual components. It is shown that
the optimized cell structure with an inserted TiOX layer enhanced the power conversion efficiency up to 2.580.45% (Fig.5.4de).
5.5Transistors
Since graphene has rapidly evolved from the exclusive domain of condensed-matter
physicists to explore by pioneers in a variety of scientific and engineering communities, graphene-based transistors have attracted much interest [20]. It is well known
that graphene is now considered as an option for post-silicon electronics. Due to
5.5Transistors
185
Fig. 5.4 a Implementation of continuous, highly flexible, and transparent graphene films obtained
by CVD as transparent conductive electrodes (TCE) in OVP cells [17]. b Schematic diagram of
photovoltaic device structure with MLG electrodes and a hole-blocking TiOX layer. c TEM crosssectional image of a photovoltaic device. The insets show HRTEM images near the TiOX layer
(top) and near the MLG films (bottom). d JV curves of photovoltaic devices with 1000C-grown
MLG electrodes (circles) and with ITO electrodes (diamonds). The curves without TiOX layer
(filled symbols) are compared to the ones with TiOX layer (open symbols). e PCEs for grapheneelectrode photovoltaic devices in comparison with those for the ITO-electrode photovoltaic
devices with and without TiOX layers (pristine) [13] PCE Power conversion efficiency. (Reprinted
with permission from [13, 17]. Copyright (2010) by Elsevier and ACS)
186
Fig. 5.5 a Schematic illustration of the fabrication of OFETs with patterned graphene electrodes. b
Transfer characteristics of pentacene-based OFETs with graphene and Ag electrodes. c Transfer characteristics of pentacene-based OFETs with graphene and Cu electrodes [21]. d Schematic illustration
of the approach to fabricate patterned graphene electrodes [25]. e Structure of the CuPc monolayer
transistor device with metal electrodes protected by a 50nm layer of silicon dioxide [23]. f OM and
5.6Other Applications
187
5.6Other Applications
5.6.1Electromagnetic Interference (EMI) Shielding
Electromagnetic interference (EMI) or radiofrequency interference (RFI) refers
to the disturbance that affects an electrical circuit due to either electromagnetic
induction or electromagnetic radiation emitted from an external source, like radio
and TV stations, cell phones, or electric power transmission lines. Shielding can be
achieved by reflection and absorption of electromagnetic radiation to shield against
the penetration of the radiation energy [26]. Due to the high demand for sophisticated electronic devices and rapid growth of radio frequency (RF) radiation sources,
EMI shielding in electronic devices has become a serious concern in modern society [26, 27]. In addition, EMI shielding is essential to protect the environment
AFM images of a representative device. The average thickness of a monolayer graphene is ~0.8nm,
and the gap size between the graphene ends is ~100nm. Inset is the height profile across the nanogap
[24]. (Reprinted with permission from [21, 23, 24, 25]. Copyright (2008, 2010, 2009) by Wiley)
188
and human body. Due to the light weight, resistance to corrosion, flexibility, and
processing advantages, electrically conducting composites have become popular to
replace conventional metal-based EMI shielding materials [28, 29]. Graphene is an
excellent choice for high-performance EMI shielding in the form of either sheets
[26], papers [3032], polymer-based composites, or coatings [3336] because of
its high conductivity, saturation velocity, flexibility, and mechanical strength [37].
Monolayer graphene prepared by the CVD method was found able to serve as an
ultrathin, transparent, weightless, and flexible EMI shield [26]. The measurement
setup for the EMI shielding effectiveness (SE) of monolayer graphene is shown in
Fig.5.6ab. The results show that the monolayer CVD graphene has an average SE
value of 2.27 dB, corresponding to ~40% shielding of incident waves (Fig.5.6c),
while the defective graphene provided almost no shielding effect (Fig. 5.6d). It
is suggested that manufacturing an ultrathin, transparent, weightless, and flexible
EMI shield by a single or a few atomic layers of graphene would be tremendously
important for portable electronic devices, transparent electronics and displays, automobiles, and EM field isolation in 3D ICs [26]. It was also demonstrated that
patterned graphene/insulator stacks could be used as tunable far-infrared notch filters (Fig. 5.6ef), which could lead to the development of transparent mid- and
far-infrared photonic devices such as detectors, modulators, and three-dimensional
metal material systems [37].
Freestanding graphene papers also show excellent and specific EMI SE [3032].
Gupta etal. [31] demonstrated that MnO2 decorated graphene nanoribbons (GNRs)
in paper form possessed outstanding microwave shielding properties. MnO2 in
GNRs effectively enhanced the electronic polarization, interfacial polarization,
and anisotropy energy in the presence of microwaves. A maximum SE of 57dB
in the Ku band, that is, 1218GHz, was achieved for a 3.0-mm-thick sample. By
using nickel pellet as a catalyst template during the CVD synthesis, Zhang etal.
[32] developed a polymer-free process for synthesis of three-dimensional graphene
structures and graphene papers. The obtained graphene papers with thickness below
100m already showed excellent EMI SE. For example, the graphene paper with
thickness of 50m showed 60dB EMI SE.
Recently, efforts have also been made for the development of high-performance
EMI shielding graphene/polymer nanocomposite materials [3336]. For example,
Chen etal. [36] developed a graphene/poly(dimethyl siloxane) (PDMS) foam composite. As shown in Fig. 5.7ab, the fabricated graphene/PDMS foam composite
is lightweight, flexible, and highly porous. The results show that its SE is as high
as 30dB in the 30MHz1.5GHz frequency range and 20dB in the X-band frequency range. Kims group [35] in HKUST further found that self-aligned rGO/
epoxy nanocomposites (Fig.5.7c) with highly anisotropic mechanical and electrical properties present high-performance EMI shielding with a remarkable shielding efficiency of 38dB. It is proposed that the relatively high shielding efficiency
is associated with two unique features of the composites: namely, (i) the aligned
rGO sheets contributed positively to shield the electromagnetic waves that emanate
through the thickness direction (Fig.5.7d), and (ii) the capability of absorbing the
5.6Other Applications
189
Fig. 5.6 Schematic drawings of the measurement setup for the electromagnetic interference shielding effectiveness of graphene. a Waveguide measurement system (frequency range: 2.27GHz)
with two waveguide-to-coaxial adapters and a vector network analyzer. b Measurement setup
using a horn antenna, a TEM cell, and a vector network analyzer. The SE, absorbance loss (AL),
and reflectance loss (RL) of c a monolayer graphene, and d defective graphene [26]. e Extinction in transmission, 1-T/T0, using a single layer of unpatterned graphene in the far-infrared and
terahertz wavelength range for undoped graphene on quartz without (gray squares) and with (red
squares) the polymer buffer layer underneath, and for doped graphene on quartz with the polymer
buffer layer (green squares). Solid lines are corresponding fitted curves. Inset: schematic of the
measurement. f Fitted Drude weight and scattering width as a function of graphene layer number
in the stacked devices [37]
190
incidental electromagnetic waves by polarization in the electric field due to the high
charge storage capacities of the rGO/epoxy composites [35].
5.6.2Functional Glasses
Most functional glass products would not have the desired functional properties
without proper coatings. The unique properties of graphene offer the opportunities for improving functionalities of glass. Nowadays, graphene/glass defoggers
(Fig. 5.8a) are fabricated, revealing that the graphene-based heating system has
a better heating efficiency in term of temperature vs. power density than any
other existing heating systems [38]. Figure5.8b shows the assembly process of a
graphene/glass defogger. The results show that the graphene/glass defoggers had
(with different power densities). d Saturated temperature vs. electrical power density of graphene
and Cr thin-film defoggers. e Schematics of direct scattering, trappingdesorption process of ambient gases and thermal energy transfer between molecules and electrode surface for graphene and
Cr thin-film defoggers [38]. f Schematic diagram of extremely rapid growth process on glass substrates at a low temperature without using metal catalyst. g Optical images of graphene-like carbon
based films with different thicknesses obtained for different growing periods [40]
5.6Other Applications
191
Fig. 5.8 a Schematic of heat transfer in a graphene defogger, showing substrates and expected temperature profile over the cross-section. b Layer-by-layer (LbL) transfer process of graphene on to
glass substrate. c Temperature profile of two defoggers reaching the similar saturated temperature
192
shorter response times and higher saturated temperatures than Cr/glass defoggers
(Fig.5.8cd), which can be explained by the competition between direct scattering
and trappingdesorption of ambient gases (Fig.5.8e) [39]. Because the adsorption
energies of ambient gases like O2, N2, and H2O in graphene are relatively low, the
thermal accommodation coefficient is also low. The novel interfacial property opens
a new possibility for a variety of flexible and transparent heating systems, such as
outdoor displays and vehicle front-window defrosters and defoggers [38]. It is also
reported that transparent and conductive graphene-like carbon films were deposited
on a glass substrate at a low temperature by a fast and noncatalytic growth method,
see Fig.5.8f, g [40]. The fabrication process is extremely rapid and performed on a
2in. wide scale dielectric substrate at a relatively low temperature (<550C) without using a metal catalyst, so that the damaging and expensive transfer processes of
graphene-based films could be avoided, making it compatible with current fabrication technologies [40].
5.6.3Transparent Loudspeakers
Since the invention of loudspeaker more than a century ago, many kinds of loudspeakers have been proposed and commercialized [41]. The next generation display
devices require transparent and flexible loudspeakers for new audio environments.
Because graphene is electrically conducting and has a low mass density, it is an
ideal building material for small, efficient, high-quality broad-band audio speakers
[42, 43]. Xu etal. fabricated graphene-based loudspeakers by transferring the graphene film on the PVDF piezoelectric film [44], demonstrating that the graphenebased loudspeaker could be a practical magnet-free loudspeaker by simply applying an audio frequency field through it. Compared with the commercial thin-film
speakers, graphene-based film loudspeakers can generate sound with a wide frequency range, a high sound pressure level (SPL) and low total harmonic distortion
(THD), and has much less power consumption [44]. Especially, it is transparent
and superior to those made from commercial films such as aluminum-based films.
Figure5.9a shows the structure and the sound generation mechanism of a graphenebased PVDF thin-film speaker. Once a time variable voltage is applied to the graphene electrodes, an audio frequency vibration on the PVDF piezoelectric film is
produced by the attractive and repulsive forces between the internal charges as the
external field varies. A photograph of the graphene-film loudspeaker is shown in
Fig.5.9b. This kind of transparent and flexible film loudspeakers has wide potential
applications, especially in transparent and flexible devices [44].
5.6.4Transparent Heaters
Due to a wide range of applications including outdoor displays, vehicle window
defrosters, heating retaining windows, and other heating systems, transparent and
5.6Other Applications
193
Fig. 5.9 a Schematic illustration of the structure and function. b Photograph of a graphene-based
thin-film loudspeaker connected to the sound source and amplifier. (Reprinted with permission
from [44]. Copyright (2013) by AIP)
flexible film heaters have attracted growing interest [45, 46]. Although ITO has
been widely used to prepare transparent heating films, the drawbacks of ITO,
including limited availability of indium, intolerance to acid or base and fragility under mechanical bending, limit its future applications [12]. The exceptional
optoelectrical and thermal properties of graphene offer many advantages for producing transparent heaters [47]. It is suggested that the CVD-grown large-scale
graphene films could be used for the fabrication of transparent heaters [45, 47]. As
illustrated in Fig.5.10a, graphene films were placed on a polyethylene terephthalate
(PET) substrate and the copper layer was used to enhance the contact with graphene
at the edges. Figure5.10bc shows the fabricated graphene-based heater, indicating
the highly transparent and flexible nature. The time-dependent temperature results
194
Fig. 5.10 a A schematic structure of a transparent, flexible graphene heater combined with a plastic substrate and Cu electrodes. b An optical image of the assembled graphene-based heater showing its outstanding flexibility. c An infrared picture of the assembled graphene-based heater while
applying an input voltage under bending conditions. d Temperature profiles of graphene-based
heaters with two different doping agents and an ITO-based heater measured using an infrared scanner. e Mechanical stability test results of the graphene-based heater. (Reprinted with permission
from [47]. Copyright (2011) by ACS)
(Fig. 5.10d) show that the graphene-based heater had a faster heating rate and a
more homogeneous temperature distribution than the ITO-based heater. Due to the
flexibility of graphene-based heater (Fig.5.10e), it can be used on a curved window
surface or a rollable screen [47].
5.6.5Transparent Actuators
Transparent flexible electronics, especially those having excellent mechanical actuating capabilities have received much interest [10, 48]. Transparent soft actuators
can also satisfy our daily lives with artificial intelligence devices [48]. Although
much progress has been made in developing soft actuators, the realization of high
transparency in soft actuators is hampered by the actuator component materials [49].
Kim etal. [50] proposed a transparent, stretchable graphene-based actuator consisting of a dielectric elastomer substrate and multiple stacked graphene electrodes.
Figure5.11a depicts the working principle of the proposed actuator. The designed
FLG-driven actuator captured by the digital single lens reflex (DSLR) camera in the states of voltage e OFF and f ON. The manuscript images through the FLG-driven actuator is compared in
g and h, each corresponding to the voltage OFF and ON, respectively [51]
5.6Other Applications
195
Fig. 5.11 a Operating principle of graphene-based actuator. b Displacement of the actuator based
on three-layer graphene electrodes. The actuator is maintained for 10s per single voltage level from
0.3 to 3.0kV as a sine wave of frequency 0.5Hz. c Performance of the actuator when the input
voltage is applied from 0 to 3kV [50]. d Preparation of FLG-driven actuator. eh Photographs of
196
graphene-based actuator was able to generate the motion along the thickness direction while it has outstanding durability and robustness. At a frequency of 0.5Hz
in a button-like motion, the high displacement of 1050 m was achieved for a
100-m-thick graphen-based actuator (Fig.5.11bc). In addition, it is shown that
the graphene-based actuator could still work well even under 25% stretching while
preserving its electrical and mechanical properties. It is suggested that the graphene-based actuator could be used for functional touch-screen panel devices [50].
Hwang etal. [51] also fabricated a transparent dielectric elastomer actuator driven
by few-layer-graphene (FLG) electrode. The silicone elastomer substrate was sandwiched between the two layers of FLG electrodes to form the transparent actuator,
see Fig.5.11d. The FLG-driven actuator had an optical transparency of over 57% at
a wavenumber of 600nm, and produced bending displacement performance ranging from 29 to 946 m as functions of frequency and voltage, demonstrating its
application feasibility in variable focus lens and opto-electro-mechanical devices,
see Fig.5.11eh [51].
5.6.6Transparent Sensors
Sensors are essential components of many electronic and optoelectronic devices, and
if these sensors are made transparent, they could lead to the development of skinlike multifunctional sensors [52]. Due to the excellent stretchability and transparency, graphene is an excellent candidate to realize a new class of human-interface devices [53, 54]. Bae etal. [54] demonstrated a graphene-based strain sensor that was
capable of monitoring the motion of body parts. As shown in Fig.5.12a, graphenebased transparent strain sensors were fabricated on a flexible plastic or stretchable
rubber substrate using reactive ion etching and stamping techniques. Figure5.12b
shows a rosette gauge of graphene fabricated on a thinner PDMS substrate. The
graphene strain sensor had high transparencies of 7580% over wavelengths ranging 400700nm, see Fig.5.12c. A motorized tensile machine (Fig.5.12d) was used
to apply an uniaxial tensile strain to a thin-film material so that the piezoresistive
properties of the graphene strain sensors were investigated in tension. The presence
of a strong van der Waals force between graphene and the PDMS substrate allowed
the same strain level in graphene as in the PDMS film. The measurement results
(Fig.5.12e) indicate a nonmonotonic resistance change against tensile strain up to
7.1%, attributed to the presence of defects, disorders, and micro-cracks in graphene
[54]. It is also demonstrated that the transparent rosette gauge on a stretchable and
wearable hand glove was able to detect the bending motion of a finger.
Graphene woven fabrics (GWFs) were utilized to design highly sensitive strain
sensors for human motion monitoring [52]. GWFs were obtained by atmosphericpressure CVD growth on crisscross copper meshes, as shown in Fig.5.13a. After
the copper meshes were etched away in FeCl3/HCl solution, GWFs were transferred
to a composite film consisting of a medical tape and PDMS. The GWF/PDMS/tape
was dried and connected to silver wires with silver paste on both ends to obtain
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197
Fig. 5.12 a Schematic representation of various steps in fabrication process; b transparent graphene strain sensor; c transmittance spectrum for wavelength ranging 400700nm and Raman
spectrum of graphene film (inset); d graphene strain sensor fixed in motion controller under
stretching test, and the initial distance (~0%) and final distance (~7.1%) between the two fixed
points (inset), and e variation of resistance with respect to stretching up to ~7.1% of graphene
strain sensor. (Reprinted with permission from [54]. Copyright (2013) by Elsevier)
the final GWF strain sensor. The assembled transparent sensor exhibited relatively
good sensitivity to follow human skin deformation (Fig.5.13b). Its relative resistance change could be 10 times at 2% strain or 104 times at 8% strain, and also
could be 0.07 time at 2% strain depending on deformation strain which was formed
by the motions, and these values are large enough for ordinary instruments to detect
the motion signals (Fig.5.13c). Weak motions were chosen to test the resistance
change, including hand clenching, phonation, expression change, blink, breath, and
198
Fig. 5.13 Transparent graphene strain sensors for human motion monitoring: a schematic illustrations of fabrication procedure of a human motion sensor based on GWF/PDMS/medical tape film;
b images of GWF/PDMS/tape at various positions; and c relative change of resistance between 0
and 2% strain. (Reprinted with permission from [55]. Copyright (2014) by Wiley)
pulse. Due to the distinctive features of high sensitivity and reversible extensibility,
the transparent GWF-based piezoresistive sensors can find wide potential applications, such as robotics, fatigue detection, and body monitoring [55].
5.6.7Transparent Supercapacitors
The high specific surface area, excellent chemical stability, and outstanding electrical conductivities make graphene an ideal material for the next generation energy
storage devices [56]. Stretchable and transparent supercapacitors with highly stable
performance can open up new possibilities for multifunctional applications of electronics in various energy, biomedical, and wearable optoelectronic systems [57].
However, most of the existing electrodes are either brittle (e.g., ITO), or with poor
transparency (e.g., conducting polymers) [57]. Graphene films that are optically
5.6Other Applications
199
200
graphene films produced by vacuum filtration had high optical transparencies and
homogeneous morphology, see Figs.5.14ac. For the film of~25nm in thickness,
a specific capacitance of 135F/g was obtained at a transmittance of ~70%. Transparent and stretchable graphene-based supercapacitors were also developed by
Chen etal. [57] where wrinkled graphene (WE) films were stretched to avoid the
reduction in electrical conductivity. As shown in Fig.5.14dg, highly transparent
(up to 60% at 550nm) and stretchable multilayer WE sheets were transferred onto
a polydimethylsiloxane (PDMS) substrate. The WE films were used as both the
current collector and active electrodes, which showed high transparency of 57%
and flexibility of up to 40% strain. Even after the films were stretched to 40%
strain, their capacitancevoltage (CV) profiles and charge/discharge performance
(Fig.5.14h) as well as the specific capacitance (Fig.5.14i) were almost unchanged.
The mechanical cycleability was also measured by stretch/unloading tests of 40%
strain for over 100 cycles (Fig.5.14jk). Both the CV curves and charge/discharge
characteristics remained almost unchanged, confirming highly stretchable and mechanically durable graphene-based transparent supercapacitors [57].
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Chapter 6
205
206
Table 6.1 Comparison of optoelectrical properties of graphene- and graphene oxide (GO)-based
TCFs collected from representative references. (Reprinted with permission from [2]. Copyright
(2014) by Elsevier)
Fabrication
method/film
type
Comments
CVD
Ni substrate
1000
T (%) DC / OP References
90
3.48
Ni substrate
280
80
5.70
Ni substrate
1350
91
2.89
Cu substrate
350
90
9.96
Li etal. [8]
Cu substrate
200
85
11.1
1.5105
92
0.03
Li etal. [10]
4.0106
95
0.0018
4.59104 83.8
0.044
Rs (/sq)
High temperature
annealing
6848
82
0.27
Chemical reduction
3.0104
80
0.05
Chemical reduction
+ high temperature
annealing
3500
85
0.64
Chemical reduction
+ high temperature
annealing
1.0105
65
0.008
Chemical reduction
+ high temperature
annealing
7.0104
65
0.011
Graphite, exfoliated in
sodium cholate solution
2000
75
0.61
High temperature
annealing
1000
80
1.60
High temperature
annealing
800
82
2.26
Wu etal. [20]
High temperature
annealing
5000
80
0.32
Wu etal. [21]
High temperature
annealing
1750
70
0.55
Spray coating
5000
90
0.697
Dip coating
Chemical reduction
1000
85
2.23
Spin coating
87
0.23
High temperature
annealing
1800
70
0.54
High temperature
annealing
8000
70
0.12
95
0.0007
Chemical reduction
Chemical reduction
+ high temperature
annealing
1.110
11106
207
Comments
Doped rGO
Rs (/sq)
T (%) DC / OP References
9900
93.7
0.58
2104
65
0.04
1600
82
1.13
840
78
1.70
3110
90
1.12
intercalation, thermal
shock exfoliation,
chemical oxidation and
thermal reduction
500
90
6.97
300
96.4
34.0
Kim et al.[33]
Reduced by hydrazine
vapor and doped by
SOCl2
Hybridization
with CNTs
Electrostatic
self-assembly
Solution mixing
Hybridization
with NWs or
nanogrids
2.8105
90
0.01
8000
81
0.21
954
87
3.17
100
80
15.97
240
86
10.03
Self-assembly at water
interface
8300
72
0.13
LB technique
560
86
4.30
26
83
74.25
Kholmanov etal.
[40]
16
91.1
246.9
Xu et al.[41]
20
90
174.24
Zheng et al.[39]
CNT carbon nanotube, CVD chemical vapor deposition, DMF N, N-Dimethylform, EPD
electrophoretic deposition, GO graphene oxide, HI hydrogen iodine, LB LangmuirBlodgett,
NWs nanowires, rGO reduced graphene oxide, SWNT single-walled carbon nanotubes
with halogen elements [36], the complex and expensive transfer process of graphene limits their large scale applications. For example, the CVD method usually
requires specific substrate materials, such as copper and nickel, which have to be
etched away after the graphene growth. The high cost of the metal substrates, the
ultrahigh vacuum conditions necessary for the CVD growth, and the extra steps
208
required for graphene transfer to the target substrates significantly restrict the wide
application of the CVD method [4]. In particular for the next generation flexible
electrodes and circuits, the CVD-grown graphene needs roll-to-roll transfer equipment [5], making it highly dependent on initial infrastructural investments. In addition, several other challenges must be overcome before the industrial application of
CVD grown graphene is realized. These challenges include (i) growth of graphene
with large and controllable grain sizes, such as single-grain graphene with wafer
scale size; (ii) CVD growth of graphene with controllable number of layers; (iii)
reduction of the synthesis cost by low temperature growth or direct growth on any
metal substrates without posttransfer processes; and (iv) developing easy, reliable,
and scalable transfer processes.
Facile and inexpensive methods for fabricating graphene-based TCFs are highly
desirable to achieve the standard quality to replace ITO. Since graphene oxide (GO)
dispersions are easy to be obtained and deposited on a substrate in a controllable
manner, GO can provide a practical route toward the low-cost and scalable production of TCFs with tunable optoelectrical properties. GO-based TCFs are known to
be cheaper and easier to scale up than the CVD-grown graphene, and are thus appealing for applications where cost reduction is essential. Although many studies
have been dedicated to the development of GO-based TCFs, their applications in
real products are still in their infant stage. This is because the assessment of competition on the materials/manufacturing costs and relative functional performance
between the TCFs produced using different materials and techniques are ongoing.
There is still large room for improvements in the two major functional criteria.
This book offers an overview of the research and development expended thus
far on the synthesis and property measurements of GO-based TCFs with particular
emphasis on the principles of different techniques devised for GO synthesis and deposition, as well as their influences on the corresponding optoelectrical properties
of TCFs. To produce GO-based TCFs, GO or rGO sheets have been deposited via
several well-established techniques, including spin or spray coating, transfer printing, dip coating, electrophoretic deposition, and LB assembly, followed by further
chemical reduction and/or thermal annealing. When comparing these approaches,
the LB assembly is found to be the only technique that can realize layer-by-layer
(LbL) deposition of GO sheets, ensuring accurate control of the film thickness
upon repeated depositions. The optoelectrical properties of the final products can
be optimized by varying the deposition parameters, such as surface pressure and
pulling speed.
A few strategies have been successfully adopted as the postdeposition treatments
to improve the optoelectrical properties of graphene or rGO films, and thus to fully
exploit their fascinating properties. These strategies include: (i) doping with acids,
especially diluted nitric acid; (ii) doping with nitrogen or halogenating agents, such
as SOBr2, SOCl2 and AuCl3 solutions; (iii) use of large size GO sheets; (iv) hybridization with carbon nanotube (CNTs), metal nanowires (NWs), or nanogrids. Notable examples with high conductivity ratios based on the techniques include the use
of large-size GO sheets with a conductivity ratio of 7.0 [32], GO/CNT hybrid TCFs
prepared by solution mixing with a conductivity ratio of 16.0 [36], CVD grown
209
graphene/CNT hybrid film with a conductivity ratio of 34.0, rGO or graphene hybridized with Ag NWs with a conductivity ratio of 246.9 [41], and graphene hybridized with nanogrids with a conductivity ratio of 174.2 [42]. It should also be noted
that apart from using large-size GOs and hybridizing with CNTs, metal NWs like
Ag NWs or Cu NWs, or nanogrids that function as bridges between the isolated GO
sheets, the conductivity of graphene-based TCFs can be further improved though
simple doping treatments by immersing the TCFs into halogenating agents, like
AuCl3, SOCl2, or SOBr2.
After the reduction of GO films, additional treatments have been applied separately or in a series of two or more processes. For example, it is found that the
acid treatment helped remove the impurities present on graphene films as well as
substrate surfaces, while the dopant functional groups arising from the halogenating agents and nitrogen increased the carrier densities in rGO films. It is also found
that the TCFs made from ultralarge graphene oxide (UL-GO) sheets showed a much
lower sheet resistance than that of small size GO sheets, by one to two orders of
magnitude for a given transmittance of the film. Due to the increase in sheet area
of GO from several to thousands of m2, the reduction in the number of inter-sheet
tunneling barriers in a continuous rGO film was responsible for this observation.
Besides employing large size GO sheets, producing pure rGO sheets with a minimal
number of defects is another efficient approach for improving the optoelectrical
properties of TCFs. The purpose of avoiding defects is to eliminate any noncarbon
atoms that may disrupt the perfect hexagonal pattern of graphene, which is essential
for establishing solid conducting networks in rGO.
Hybridizing rGO sheets with highly conducting 1D materials, such as CNTs,
metal nanowires, or nanogrids is shown to be another particularly attractive option to improve the optoelectrical properties. The conducting 1D nanofillers or
nanogrids can bridge isolated rGO sheets, where the extended conjugated network
structure serve as fast electronic conducting channels. However, there are still some
challenges in the process and use of these hybrid thin films. For example, weak
bonds are formed between GO and CNTs because CNTs are usually physisorbed
onto the hydrophilic surface of GO sheets, resulting in high contact resistance at the
junctions. After high temperature reduction, the bonds between GO and CNTs can
be even more deteriorated, necessitating the functionalization of these nanocarbons
to allow covalent bonds to form between them, as proposed by molecular dynamics
(MD) simulations [43, 44]. The rGO hybrids with metal nanowires and nanogrids
also have potential issues that need to be addressed, such as high contact resistance,
poor environmental stability, lack of scalable fabrication and uniformity, and electrical shorts due to the large aspect ratios of these hybrid fillers.
In summary, doped metal oxides, such as ITO and fluorine tin oxide (FTO) ,
have well served for over 60 years for TCF applications. However, these materials suffer from several drawbacks including brittleness, lack of chemical stability,
and high manufacturing cost. Emerged over the last 20 years, conducting polymers
have potential to solve the issues inherent to doped metal oxides. Unfortunately,
however, conducting polymers suffer from poor environmental stability and noticeable color. CNTs have shown excellent potential for commercial use in TCF
210
applications, but the similar challenges, including the unacceptably large surface
roughness and high cost, still exist. Metallic NWs and nanogrids also possess high
electrical conductivities, however, the large film apertures require the combination
with another more continuous, transparent electrode material.
With about 10 years of short history of the discovery of graphene, extensive
and in-depth research efforts have been directed toward understanding the characteristics and properties of graphene and its derivatives. Thanks to these strenuous
efforts, graphene is now finding a number of useful applications as sensors and
actuators, additives and free-standing electrode materials for energy conversion
and storage devices, conducting and strong nanofillers to reinforce composites, and
especially TCFs for various optoelectronic devices, like touch screens, liquid crystal displays (LCDs), organic photovoltaics (OPV) cells, and organic light emitting
diodes (OLEDs). It is proven that graphene is an attractive alternative to currently
dominant ITO for TCF applications. CVD grown graphene films show excellent
electrical conductivity, but they cannot be produced in sufficient quantities. GO
based TCFs have more defects and possess lower electrical conductivity, but they
are capable of mass production with low cost. Nevertheless, many challenges are
still ahead, such as the relatively low conductivity, before full-scale industrial applications of these materials are realized. If these desirable attributes are not to be
compromised with others weaknesses, producing large-size GO sheets from natural graphene flakes and reduction to defect-free or near defect-free rGO sheets to
achieve recovery of their inherent electrical conductivities are among the ongoing issues that need to be addressed. The relatively little understanding of their
long-term functional durability to sustain the desired optoelectrical properties and
structural stability under different service environments is another challenging issue
that has seldom received attention. As the existing synthesis methods are becoming
matured, future research efforts should also focus on developing novel processing
technologies that were previously inconceivable and exploiting exciting properties
of graphene-based TCFs in new applications, especially for a revolutionary new
breed of transparent and flexible electronics [2].
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Index
Symbols
-conjugated domains, 168
A
Abrasion resistance, 4
Absorbance loss (AL), 189
Absorption
and desorption, 124
of electromagnetic radiation, 187
optical
of polymers, 9
AB stacking, 105
Accumulation, 114, 129
charge, 129
Active electrodes, 200
Acyl chloride, 126, 172
Adsorption energy, 190
Aluminum-doped zinc oxide (AZO), 7, 8
Ammonium persulfate, 98, 153
Amorphous substrates, 7
Amphiphilic
GO sheets, 115, 146, 170
UL-GO, 148
Anhydrous hydrazine, 145
Anisotropy energy, 188
Aqueous solution, 95, 96, 138, 146, 156
Arithmetical mean roughness, 168
Aromatic ring, 14, 129
Ascorbic acid, 119
Aspect ratio, 17, 18, 111, 209
Atomic concentration, 124, 129
Atomic force microscopy (AFM), 101
Audio frequency field, 192
B
Bending energy, 167
Bending motion, 196
Binary compounds, 7
Binding energy, 127, 133
Biosensors, 167, 168
Body monitoring, 197
Boiling point, 148
Bromination, 124, 125
Bromination duration, 124, 125
Bubble deposition method (BDM), 138, 147
Buckling, 163
Bulk-heterojunction (BHJ), 184
C
Capacitance-voltage (CV), 200
Capacitive type, 179
Capillary force, 163, 166
Carbonaceous byproducts (CB), 19
Carbon nanoscrolls (CNSs), 167
Carbon nanotubes (CNTs), 4, 18, 19
chemical structure of, 127
doping of, 126
hybridization with, 138, 146, 208, 209
Carboxyl groups, 123
Carrier concentration, 127, 128, 134
Carrier type, 134
Catalyst template, 188
Catalytic activity, 105
Cathode ray tubes (CRT), 4
Cellulose/ester membrane, 114
Centrifugal force, 110
Charge accumulation, 129
215
216
Charge distribution, 129
Charged particles, 109
Charge flow, 129
Charge redistribution, 131
Charge-transfer complex, 127, 133
Chemical doping, 123, 145, 170
n-type, 123
of carbon materials, 124
of graphene, 127
p-type, 123
treatment, 20, 126
Chemical durability, 4, 179
Chemically doped, reduced ultra-large
graphene oxide (C-rUL-GO), 172
Chemical reduction, 208
Chemical vapor deposition (CVD), 19, 158
Chlorocarbon compound, 131
Chlorosulfonic acid (CSA), 19
Close-packed, 116, 117, 149, 161, 163, 165,
167
Coating density, 153
Coating fluid, 117
Cold cathode fluorescent lamp (CCFL), 2
Compression force, 167
Computer monitors, 4
Concentrated graphene oxide wrinkles
(CGOW), 164167
Conducting nanofillers, 124, 138
Conducting paths, 126
Conductive networks, 124, 138
Contact angle, 170
Contact barrier, 152
Contaminant residues, 99
Contrast ratio, 181
Copper nanowire (Cu NW), 17, 18, 151, 156,
157, 209
Copper phthalocyanine (CuPc), 187
Core level spectrum, 131
Corrosion devices, 15
Corrosive vapor, 96
Covalent bonding, 131
Covalent functionalization, 19
Cracking, 96
Cu foils, 158
Current collector, 200
Current leakage, 9
Curved window surface, 194
D
DC to optical conductivity ratio, 19, 205
Decomposition, 136, 173
Defect, 209
structural, 9
Defogger, 190, 192
Cr/glass, 190
Index
Degree of absorption, 171
Degree of polymerization, 14
Degree of wrinkling, 163
Deionized (DI), 138
Density, 161
and alignment, 138
of GO sheets, 115
Deposition rate, 109, 110
Deposition time, 109
Desorption
of Br atoms into graphite, 124
Detector, 188
Dichloroethane (DCE), 19, 148
Diethylene glycol (DEG), 15
Digital single lens reflex (DSLR), 196
Dimethyl sufoxide (DMSO), 15
Dip coating, 95, 105, 112, 113, 156, 158, 205,
208
of UL-GO, 159, 161
Direct current (DC), 109
Disorder, 110, 196
Dispersive adhesion, 98
Doping effect, 128
of SOCl2, 129
Driving force, 146
Drop casting, 116
and spin coating, 117
Dry transfer, 98, 152, 156
Durability, 1, 4
long-term functional, 210
E
Edge-selective functionalization, 208
Elastic energy, 167
Electrical conductivity, 5, 9, 14, 19, 131, 136,
138, 148, 151, 173, 210
and optical transmittance, 171
and optical transparency, 6
and transmittance, 136
and transparency of graphene films, 131
of graphite nanoplatelets, 124
of PPy thin films, 14
of the CNT TCFs, 126
Electric field, 109, 181, 190
Electrochemical properties, 18
Electrochromic mirrors, 2, 4
Electromagnetic interference shielding, 189
Electron
acceptor, 123, 128, 131
beam evaporation, 6
donor, 123
scattering, 17
Electronegativity, 131
Electronic polarization, 188
Electronic structure, 128
Index
Electrophoretic deposition, 95, 105, 109, 110,
205, 208
Electrostatic repulsion, 161, 168
Electrostatic self-assembly, 138, 146
Energy efficiency, 1
Energy storage, 198
Epitaxial growth, 19
Equilibrium structure, 129
Etchant solution, 101
Etching bath, 95
Etching method, 95, 97
Etching rate, 96
F
Face-to-face manner, 168
Fatigue detection, 197
Feature resolution, 114
Fermi level, 128
Few-layer-graphene (FLG), 196
Field effect transistors, 168
Flat panel display (FDP), 2
Flexibility, 9, 103, 114, 153, 157, 181, 188,
194, 200
Flexible
EMI, 188
film heaters, 193
GO sheets, 110
polyethylene naphthalate (PEN), 152
polymeric materials, 118
steel or plastic substrates, 1
substrates, 145
TCFs, 4
touch screen-based graphene films, 180
Fluorine tin oxide (FTO), 209
Fluoroalkyl trichlorosilane (FTS), 9, 13
Free energy, 167
Front electrodes, 1
Fullerene, 19, 184
Functional glasses, 190
Functional groups, 10, 123, 134, 148, 169,
173, 209
Functionalization, 209
G
Gaseous product, 96
Glass slide, 111, 182, 200
Grain boundaries, 105
Grain size, 105, 208
Graphene, 4, 19, 20, 95
Graphene nanoribbons (GNR), 188
Graphene oxide wrinkles (GOW), 163, 166
Graphene patterns, 98, 100102
Graphene woven fabrics (GWFs), 196
Graphite intercalation compounds (GIC), 124
217
Graphite nanoplatelet (GNP), 124
Graphitic materials, 127
Graphitization, 110, 134, 150, 169, 172
Gravity, 166
H
Halogenating agents, 127, 128, 208, 209
Harmonic distortion, 192
Heating rate, 193
Height profile, 118, 187
Highly ordered pyrolytic graphite (HOPG),
101
High temperature annealing, 6, 110, 172
Human interface devices, 196
Human motion monitoring, 196, 197
Human skin deformation, 196
Hybridization, 205, 208
Hydrazine, 110
Hydrocarbon gas, 105
Hydrogen bonds, 105, 163
Hydrogen floride (HF), 152
Hydrogen storage, 167, 168
Hydrophilic, 158, 170, 209
Hydrophobic, 14, 170
Hydroxyl groups, 168
I
Impedance of free space, 20
Indium-doped cadmium-oxide (ICO), 7
Indium-free oxides, 8
Indium tin oxide (ITO), 4, 5
Industry applications, 19
Infrared heat lamp, 118
Infrared scanner, 194
Ink droplets, 118
Inkjet printing, 105, 117
In-plane compression, 163
Input voltage, 194, 195
Insulator
stacks, 188
Intelligence devices, 194
Intensity ratio, 125
Interfacial polarization, 188
Interlayer distance, 105, 167
Intermediate transfer processes, 115
Intersheet junctions, 123, 124, 158
Invisible security circuits, 4
Ion diffusion, 9
Ionic bond, 131, 133
Ionic bromine, 133
Ionic liquid, 15
Isopropanol (IPA), 15
Isothermal curve, 115, 116, 162
Isotopic peaks, 125
218
L
Laboratory ovens, 4
Langmuir-Blodgett (L-B), 114
Large-scale manufacturing, 9
Lateral size, 160
Layer-by-layer (LbL), 113, 114
Layered architecture, 115
L-B trough, 115, 116
Light emitting diode (LED), 181
Light scattering, 136
Liquid/air interface, 159
Liquid crystal display (LCD), 1, 181
Liquid phase exfoliation, 118
Low-emissivity glass windows, 1
M
Machine interface, 181
Magnetron sputtering (MS), 8
Mass density, 192
Mass production, 116, 158, 210
Mechanical bending, 118, 193
Mechanical cleavage, 158
Mechanical properties, 9, 183, 194
Medical tape, 196, 198
Memory devices, 15
Metal nanogrids, 9, 17, 157
Metal nanowires, 17, 20, 209
Meyer rod, 117
Micro-cracks, 196
Mild heat, 103
Modulator, 188
Molar mass, 125
Molecular beam epitaxy, 6
Molecular orientation, 114
Molecular structure, 9
Motion signals, 197
Multi-component oxides, 7, 8
Multifunctional sensors, 196
Multi-layer graphene (MLG), 183
Multiple quantum wells (MQW), 183
Multi-walled carbon nanotube (MWCNT), 9
N
Nanocomposites, 188, 190
Nanogenerator, 152
Nanomechanical devices, 167
Nanoparticles (NPs), 6, 136
Nanorods, 152
Nanowires (NWs), 9
Near-infrared region, 9
Negatively charged
MWNTs, 147
rGO sheets, 113, 146
Index
Neutral atoms, 129
Nitric acid, 96, 127, 128, 136, 208
Nitrogen flow, 110, 126, 131
N-Methyl-2-pyrrolidone (NMP), 148
Non-covalent functionalization, 18, 19, 148
Nonpolar environments, 9
Nonsolvent, 146
Nucleophilic substitution, 131, 133
O
O-dichlorobenzene (DCB), 148
Opacity f, 181
Optical microscope, 99, 181
Optical reflectance, 6
Optical transmittance, 6, 19, 111, 146, 151,
153, 159
and electrical conductivity, 171
Optoelectronic devices, 1, 4, 6, 9, 210
Organic light emitting diodes (OLEDs), 1, 4,
15, 183
Organic photovoltaics (OPVs), 4
Organic solvents, 109, 158
Outdoor displays, 192
Overlapped, 162, 163, 165
Oxidizing agent, 15
Oxidizing etchant, 96
Oxygenated groups, 123, 170
Oxygen-containing functional groups, 110
P
Packing density, 117, 163
Patterned structures, 114
Peak to peak roughness, 168, 170
Percolation, 153
Permeation rate, 114
Phase transition, 148, 161
Photolithography, 100, 102
Photons, 17
Photoresist method, 95, 101
Photovoltaic cell, 184, 185
Piezoelectric
film, 192
Piezoresistive sensors, 197
Planar graphene, 187, 199
Plasma display panel (PDP), 2
Plasma etching, 102, 166, 187
Plasma wavelength, 1, 2
Plastic substrates, 1, 9, 110
Platinum plate, 115
Polar groups, 170
Polar molecules, 9
Poly(2,5-dioctyloxy-1,4-phenylene-alt-2,5thienylene) (POPT), 148
Index
Poly(3,4-ethylenedioxythiophene) (PEDOT),
9, 12, 15
Poly(4-vinylphenol) (PVP), 98
Polyaniline (PANI), 9, 12, 14
Polydimethylsiloxane (PDMS), 97, 198, 200
Polyethyleneimine (PEI), 146
Polyethylene terephthalate (PET), 98
Poly(methyl methacrylate) (PMMA), 97
Poly(m-phenylene vinylene-co-2,5dioctyloxy-pphenylene vinylene)
(PmPV), 148
Poly(para-phenylene vinylene) (PPV), 9, 10,
12
Polypyrrole (PPy), 9, 12, 14
Polystyrene sulfonate) (PSS), 15, 184
Polythiophene (PT), 9, 12
Positively charged, 113, 146, 147
Post-transfer process, 95
Precipitate, 96
Printable
electronics, 4
Processability, 10
Processing condition, 11, 173
Projected capacitance, 179
Pulling speed, 115, 163166, 168, 208
Pulsed laser deposition (PLD), 6, 8
Pyrene, 129
Q
Quartz substrates, 104, 113
R
Radiation energy, 187
Radio frequency interference (RFI), 6
Radio frequency (RF), 6
Raman spectroscopy, 134
Reactive ion etching, 196
Rear-projection (RP), 2
Rechargeable batteries, 15
Reflectance loss (RL), 189
Resistive-type touch screen, 179
Robotics, 197
Robustness, 179, 194
Rod coating, 95, 105, 117
Rollable screen, 194
Roll-to-roll transfer, 95, 103, 105, 208
Roll-up displays, 4
Root mean square roughness, 168
Rotating speed, 110
S
Scaling law, 168
Schottky junction, 184
219
Screen printing, 6
Secondary doping, 15
Self-assembly, 9
Self-polymerization, 9
Self-release layer (SRL), 100
Semiconductor, 185
Sensitivity, 196
Sensors, 1, 196, 210
Sheet resistance, 2, 4, 6, 17, 19, 20, 110, 113,
118, 128, 134, 136, 146
Shielding effectiveness (SE), 189
Silicon dioxide, 187
Silicone, 97, 98, 196
Silver nanowire (Ag NW), 208, 209
Single crystal, 158
Single-walled carbon nanotube (SWCNT), 18
Small graphene oxide (S-GO), 160, 161, 163,
164
Smart windows, 2, 9
Sodium cholate (SC), 19
Sodium dodecyl benzene sulfonate (SDBS),
19
Sodium dodecyl sulfate (SDS), 19, 126
Soft pressure, 103
Soft transfer printing, 114, 115
Solar cell, 1, 4, 9, 15, 184
Solar spectrum, 1
Sol-gel techniques, 6
Solid solution, 5
Solid supports, 114
Solubility, 15, 105
Solvent-water interface, 138, 146
Sound pressure level (SPL), 192
Source-drain electrode, 99
sp2 hybridization, 123
sp3 hybridization, 129
Specific capacitance, 199, 200
Spin coating, 205, 208
Spinorbit coupling, 131
Spray coating, 19, 95, 105, 111, 205, 208
Stability, 8, 10, 123, 136, 137, 151
Stamping method, 95, 98, 99
Strain boundaries, 17
Strain level, 196
Strain sensor, 196, 197
Substitutional doping, 123, 127
Sulfuric acid, 15, 18, 145, 148
Supercapacitors, 167, 198, 199, 200
Surface acoustic wave, 179
Surface capacitance, 179
Surface coverage, 105, 117
Surface morphology, 105, 118, 168
Surface pressure, 115, 148, 149, 161, 163,
165, 208
220
Surface pressure-area isotherm, 148, 161
Surface roughness, 6, 150, 151, 168, 169, 210
Surface tension, 117
Surface transfer doping, 123, 127
Surfactants, 18, 19
T
Teflon barriers, 116
Television tubes, 4
Temperature distribution, 193
Tensile strain, 181, 196, 199
Thermal reduction, 150
Thermal release method, 95, 101
Thermal releasing tapes, 101
Thermal stability, 1, 2
Thionyl bromide (SOBr2), 19, 126, 127, 131,
133, 208
Thionyl chloride (SOCl2), 19
Time-of-flight secondary ion mass
spectrometry (ToF-SIMS), 124
Titanium nitride, 1
Total harmonic distortion (THD), 192
Touch screen, 1, 179, 210
Toxicity, 7, 9, 179
Transfer printing, 19, 105, 114, 205, 208
of GO films, 114
Transistor, 179, 184, 187
Transparent actuators, 194
Transparent conducting oxides (TCOs), 5, 7, 9
Transparent conducting polymers, 9
Transparent conductive films (TCFs), 1, 4, 20,
138, 153
Transparent conductors (TCs), 2
Transparent heaters, 193
Transparent loudspeakers, 192
Index
Transparent sensors, 196
Transparent supercapacitors, 198200
Triton X-100, 19
U
Ultralarge graphene oxide (UL-GO), 159, 163,
172
Ultrasonication, 124
Uniaxial tensile strain, 196
V
Vacuum arc plasma deposition (VAPE), 8
Vacuum filtration, 114, 198
Valence band, 128
Van der Pauw method, 134
van der Waals force, 105, 148, 168, 196
Visible range, 6, 9
Vitamin C, 118
W
Water-pentane interface, 146
Water resistant coating, 111
Wearable optoelectronic systems, 198
Wear resistance, 179
Width-at-half-maximum (WHM), 124
Work function, 184, 185
Work of adhesion, 98
Wrinkled graphene, 199, 200
Wrinkles, 105, 117
X
Xerographic copiers, 4
X-ray diffraction (XRD), 124