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Nanotechnology: The “Top-Down” and

“Bottom-Up” Approaches

Parvez Iqbal,1 Jon A. Preece,2 and Paula M. Mendes1


1
School of Chemical Engineering, The University of Birmingham, Birmingham, UK
2
School of Chemistry, The University of Birmingham, Birmingham, UK

every industry and every part of our lives and become the
1 Introduction 1 basis for remarkably powerful and inexpensive computers,
2 Nanofabrication 5 fundamentally new diagnostic and therapeutic technologies
3 Conclusion and Outlook 11 (see Supramolecular Nanoparticles for Molecular Diag-
nostics and Therapeutics, Nanotechnology) that could
Acknowledgments 12
enhance human health and longevity,2 advanced sensors3
References 12 for military applications and environmental protection, and
new zero-pollution transportation technology.4, 5
This article provides an overview of nanotechnology,
describing the origins of the field, present technology,
1 INTRODUCTION ongoing research, and future aspirations. In addition, the
two possible methodologies of fabrication—the top-down
Nanotechnology involves the study, imaging, measuring, and bottom-up approaches—are discussed, covering the
modeling, or manipulation of matter at scales falling in merits and drawbacks of each approach.
the range of 1–100 nanometers (nm). It is a highly mul-
tidisciplinary field, drawing from fields such as chem-
istry, materials science, colloidal science, applied physics, 1.1 Brief history of nanotechnology
engineering, and biology. In a relatively short span of
about 30 years of research, nanotechnology is already hav- Historically, the concept of nanotechnology was first pro-
ing an impact on society and several industrial sectors, posed by the Nobel laureate Richard Feynman, when he
and such impact will increasingly be felt as its prod- gave a now-famous talk called “There’s Plenty of Room at
ucts increase in number and become more commercial- the Bottom” at an American Physical Society meeting at
ized.1 Nanotechnology-based substances are now found Caltech in 1959.6 With this visionary talk, Feynman dis-
in a wide range of household products and products cussed both top-down and bottom-up possibilities of work-
intended for professional use, including sports gear, cosmet- ing at the molecular level, most of which are still relevant
ics, sunscreen lotions, food and food packaging material, today. Extrapolating from known physical laws, he argued
clothing, household appliances, electronic devices, disin- the possibility of molecular writing, seeing and rearranging
fectants, paints, furniture varnishes, building materials, and individual atoms, the prospect of designing molecules one
medicines. Nanotechnology is predicted to touch nearly atom at a time, and the challenges involved in developing
nanometer-scale devices. In his talk, Feynman made several
references to examples in nature such as cells, which “are
very tiny, but they are very active; they manufacture vari-
ous substances; they walk around; they wiggle; and they do

Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc195
2 Nanotechnology

all kinds of marvelous things—all on a very small scale.” and mapping nanoscale materials. The next leg of the stan-
Nonetheless, Feynman never used the term “Nanotechnol- dard story jumps us to 1986 with the development of
ogy” to describe this new scientific field. the AFM, which enabled mapping on nonconducting sur-
Several years later, in 1974, Professor Norio Taniguchi faces.12 In 1990, Don Eigler and Erhard Schweizer invented
coined the term “Nanotechnology” in order to define top- a technique for picking up individual atoms using the tip
down ultraprecision machining, describing the term as of an STM and depositing them in patterns onto a sur-
mainly consisting of the processing of separation, consol- face.13 They used the technique to position 35 individual
idation, and deformation of materials by one atom or a xenon atoms on a nickel metal surface to spell out their
molecule.7 Later, in the 1980s, Eric K. Drexler popu- corporate logo IBM, demonstrating how atoms could be
larized the word nanotechnology through his biologically moved and positioned. The technique has since been used
inspired bottom-up visions of building molecular machines, to create a variety of structures out of many different
the so-called “molecular assemblers,” which could guide atoms.
chemical reactions by positioning reactive molecules with In addition, the advances in supramolecular chem-
atomic precision.8, 9 However, Drexler’s sweeping visions istry, the constant pressure in device miniaturization in
and theories of “grey goo” have proved highly contro- the electronic industry, and the development of materials
versial,10 and nanotechnology as a scientific field was with nanoscale dimensions, such as fullerene,14 metallic
established in a way that diverged from Drexler’s origi- nanoparticles,15 graphene,16 carbon nanotubes (CNTs),17
nal vision of molecular manufacturing. Today, the goal for have contributed to the rapid growth of the field in the
nanotechnology research is not to immediately create syn- past 30 years.
thetic molecular assemblers but rather to understand the
unique properties of the nanoscale and use that knowl-
edge to create new, high-performance materials, devices, 1.2 Current research—nanotools,
and processes. nanostructured materials, and nanodevices
Although nanotechnology was first theorized by Feyn-
man,6 then coined by Taniguchi,7 and then later popularized Current research into nanotechnology may be divided into
by Drexler’s controversial vision of molecular manufactur- three broad categories: nanotools, nanostructured materials,
ing,8–10 a flurry of activity in the field was spurred by the and nanodevices. The various components of these cate-
invention of the scanning tunneling microscope (STM), the gories are schematically illustrated in Figure 1.
atomic force microscope (AFM), and the first manipula- Nanotools are a collection of methods and techniques
tion of atoms. In 1981, Gerd Binnig and Heinrich Rohrer employed to produce and evaluate nanostructured materials
developed the STM at IBM’s laboratories in Switzerland.11 and nanodevices. The fabrication of nanostructured mate-
This microscope enabled atomic scale characterization of rials has been led by the development of new synthetic
conducting surfaces and opened the possibility of imaging methods and major advances in supramolecular chemistry.

Medicine and Information


health technology

Nanotools Nanodevices
Supramolecular chemistry
Nanomaterials Nanoelectronics
Food and Synthetic methods Nanoparticles Spintronics Transportation
nutrition Surface science Nanowires Nano-optoelectronics and aerospace
Nanolithography Fullerene Nanosensors
Analytic tools Graphene Drug delivery systems
Computer simulations Carbon nanotubes
Nanocomposites
Thin solid films
Biotechnology Nanopatterned surface Energy and
and agriculture Supramolecular systems environment

Textiles and National security


clothing and defense

Figure 1 Schematic illustration showing how nanotechnology and its nanotools, nanomaterials and nanodevices are impacting our
world.

Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc195
Nanotechnology: the “top-down” and “bottom-up” approaches 3

With advancements in synthetics methods, nanostructured <100 nm. Encompassed by this class of materials are nano-
materials with exquisite control over size, morphology, and particles, nanowires, nanorods, nanocapsules, nanofibers,
functionality have been achieved.18 Remarkable progress in nanotubes, nanocomposites, nanostructrured surfaces, and
the field of supramolecular chemistry has enabled the design thin solid films with nanoscale thickness.18 In many cases,
of molecular components to interact favorably with each the properties of such nanostructured materials can be very
other in such a way that they can self-assemble, through different from those of corresponding bulk materials, and
noncovalent interactions, into larger, well-defined entities desirable novel electrical, mechanical, chemical, optical,
on the nanoscale with tailored properties.19 Supramolecular magnetic, thermal, chemical, and/or biological properties
approaches have been successfully employed to construct, may be obtained. For instance, quantum effects can begin to
among other supramolecular systems, molecular devices dominate the behavior of matter at the nanoscale, affecting
and machines (see Photochemically Driven Molecular the optical, electrical, and magnetic properties of materi-
Devices and Machines, Nanotechnology), functional, bio- als.18 In tandem with their small size, nanostructured mate-
logically derived supramolecular systems (see Biologically rials may pass biological barriers, which are inaccessible to
Derived Supramolecular Materials, Nanotechnology), larger materials,24 or acquire superior chemical properties
polymeric nanomaterials (see Self-Assembled Nanopar- such as enhanced or new reactivities.25
ticles, Nanotechnology), supramolecular hybrid nanoma- Nanoparticles are one of the most prominent groups
terials (see Supramolecular Hybrid Nanomaterials as of nanostructured materials, and examples include carbon-
Prospective Sensing Platforms, Nanotechnology), and based nanoparticles such as fullerenes14 and metallic15
supramolecular nanoparticles (see Supramolecular Nanopar- (e.g., Au, Ag, Pt), semiconducting26 (e.g., CdSe, CdS,
ticles for Molecular Diagnostics and Therapeutics, Nan- ZnS, GaAs), magnetic27 (e.g., Fe3 O4 ), polymeric (see Self-
otechnology). Assembled Nanoparticles, Nanotechnology), and hybrid28
Furthermore, advances in surface science have led to the (e.g., core–shell) nanoparticles. Synthetic methods have
creation of techniques to fabricate nanoscale molecular- also been developed to achieve other morphologies such
assembly structures onto a variety of substrate surfaces, as nanowires, nanorods, nanocapsules, nanofibers, and nan-
including self-assembled monolayers (SAMs),20 Lang- otubes.18 Among the different nanotubes, CNTs, which
muir–Blodgett technique,21 and two-dimensional supra- were discovered in 1991,17 have received much atten-
molecular assembly (see Two-Dimensional Supramolecu- tion due to their unique physical/mechanical, electronic,
lar Chemistry, Nanotechnology). Many lithographic tech- chemical, optical, and other properties (see Advances in
niques have emerged for patterning surfaces with nanome- Supramolecular Chemistry of Carbon Nanotubes, Nan-
ter resolution (see Nanolithography, Nanotechnology). otechnology).
Photolithography, electron-beam lithography, soft lithog- Nanocomposites are a class of hybrid materials that have
raphy, nanoimprinting, colloidal lithography, and dip-pen at least one component with nanoscale dimensions, with
nanolithography are but a few examples of such tech- the most common involving polymers with either inor-
niques. Analytic tools, such as the AFM (see Atomic Force ganic nanoparticles (see Magnetically Responsive Self-
Microscopy Measurements of Supramolecular Interac- Assembled Composite Materials, Nanotechnology) or
tions, Nanotechnology), STM,11 and the near-field scan- CNTs.29 These materials can exhibit markedly enhanced
ning optical microscope,22 have provided revolutionary mechanical and other properties compared to conventional
improvements in our ability to investigate the structures composite and noncomposite materials. Nanopatterned sur-
and functions of nanostructured materials and nanodevices. faces (see Nanolithography, Nanotechnology) and thin
High-performance computer simulations based on advanced solid films, such as Langmuir–Blodgett films (LBFs),21
mathematical and physical modeling are at present a neces- SAMs,20 and two-dimensional supramolecular assemblies
sary tool in the development, design, and understanding of (see Two-Dimensional Supramolecular Chemistry, Nan-
nanoscopic systems.23 With these powerful contemporary otechnology), are two other groups of nanostructured mate-
tools—advanced synthetic methods, supramolecular chem- rials. SAMs and LBFs will be discussed in greater detail
istry, surface science, nanolithography, new or improved later in this article. An extreme limit of nanoscaling is
analytical techniques, and high-performance computer sim- monolayer graphene (see One-Dimensional Nanostruc-
ulations—many novel nanostructured materials and nan- tures of Molecular Graphenes, Nanotechnology), which
odevices have been constructed and characterized. The is only one atomic layer thin. Since its discovery in 2004, it
improvement of existing and the development of new nan- has attracted great interest because of its outstanding elec-
otools is an unrenounceable condition for further progress trical and mechanical properties.16 Undoubtedly, the main
in nanotechnology. driving force behind research and development in nanos-
Nanostructured materials can be defined as any material tructured materials is the expectation of accessing novel
that has structured components with at least one dimension and unique material properties and functionalities, with the

Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc195
4 Nanotechnology

potential to add great value to a wide range of everyday the development of ultracompact and power-efficient opto-
products. electronic devices such as photodetectors42 and lasers.43
Nanodevices are systems with nanostructured materials Nanowires have also been harnessed as building blocks
that carry out specific functions with either improved per- for the construction of nano-light emitting diodes (LEDs)
formance or new attributes. Recent years have witnessed with the ability of emitting in many different wavelengths
the emergence of new device paradigms based on nanos- depending on nanowire composition.44, 45 The conventional,
tructured materials, including nanoelectronic devices, nano- low efficient photovoltaic cells, which have restricted large-
optoelectronic devices, spintronic devices, nanosensors, and scale production of electrical energy, can be now replaced
drug and gene delivery systems. by nanosolar cells with much higher efficiencies and lower
Nanoelectronics (see Nanoelectronics, Nanotechnology) costs.46
have already revolutionized the semiconductor device Nanosensor devices incorporating nanostructured materi-
industry, in the form of integrated circuits with nanoscale als as sensing probes (see Supramolecular Hybrid Nano-
transistors that pack more and more functionality into com- materials as Prospective Sensing Platforms, Nanotech-
pact devices. Since the development of the first integrated nology) continue to advance toward commercialization for a
circuits over 60 years ago, the semiconductor industry has number of different applications, including, but not limited
seen the size of transistor devices decrease by a factor of 2 to, medical diagnostics, food safety, environmental protec-
in every 18 months,30 a trend that was first pointed out by tion, national security, and aerospace.3 While in the realm
Gordon Moore in the 1960s and is referred to as Moore’s of medicine nanosensors can detect the onset of disease, in
law.31 The miniaturization has primarily been achieved by the area of national security they could be used to detect
optimizing the photographic technique such as going from radioactive materials or biological warfare agents (such as
using visible light sources to UV and currently stands at anthrax and smallpox). The detection principle in nanosen-
22 nm; however, limits of the process are fast approaching, sors is based on measuring the physical and chemical prop-
where further miniaturization will no longer be possible erty changes, such as electrical, optical, magnetic, mass, and
with the current setup. Therefore, to continue the trend pH value, derived from the interaction of the target analyte
set by Moore’s law, fairly dramatic changes in the way with the nanodetection device. Today, numerous gas, chem-
transistors are designed and operate are required. Emerg- ical, and biosensors are being developed with substantially
ing nanoelectronic devices, such as Si nanowire field-effect smaller size, lower weight, more modest power require-
transistors (FETs),32 carbon-nanotube FETs,33 and graphene ments, greater sensitivity, better specificity, and, in some
nanoribbon FETs,34 are providing new opportunities for cases, with the ability to detect multiple analytes at the same
very-large-scale integration circuits in order to achieve con- time through high-density nanoarrays.47 In order to achieve
tinuing cost minimization and performance improvement, such powerful nanosensor capabilities, researchers have
while simultaneously enabling the extension of Moore’s been exploiting numerous nanostructured materials, includ-
law well into the next decade and beyond.35, 36 Another ing nanoparticles,24 CNTs,47 nanowires,48 , nanoscaled thin
extremely important area of research in nanoelectronics is films,49 and nanocantilevers.50 For instance, over the past
molecular electronics, which is the utilization of a single two decades, the evolution of fluorescent semiconductor
molecule or group of molecules as key active components nanoparticles known as quantum dots (QDs) has helped to
in electronic devices.37 Molecular electronic devices are usher in a new era in biomedical research and applications
expected to not only address the ultimate limits of possi- (i.e., as labels for the detection of DNA and immunosensing
ble miniaturization but also offer unlimited possibilities for of disease biomarkers, and to improve biomedical imaging).
technological development due to the potentially diverse The defining features of QDs are their exceptional pho-
electronic functions of the component molecules, which can tostability and size-dependent tunable photoluminescence.
be tailored by chemical design and synthesis.38 QDs emit different colors depending on their size, allowing
Advances in spintronics have already made their way into them to be used to color-code and track different cell pro-
magnetic hard discs, allowing for a huge increase in their cesses, thereby providing high-resolution cellular imaging,
storage capacity.39 In this rapidly growing field, researchers long-term observation of individual molecules, and their
are paving the way for spin computers, which will use movement within cells.24
the electron’s spin state to store and process vast amounts Liposomal drug delivery systems and delivery systems
of information more quickly while requiring less energy based on drug conjugates are two classes of nanotechnology
and generating less heat. Nanostructured materials, such as therapeutic products that are used in clinical practices.51
graphene40 and lithographically nanopatterned surfaces,41 Present research on nanotechnology-based drug and gene
are two promising candidates for use in spin computers. delivery systems is focused on achieving targeted delivery
Progresses in the synthesis of semiconducting nanostruc- of drugs to specific cells or tissues, improved delivery of
tures, such as nanowires and nanoparticles, are leading to poorly water-soluble drugs, multiple drug administration,

Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc195
Nanotechnology: the “top-down” and “bottom-up” approaches 5

monitoring drug delivery by combining therapeutic agents from infrared light as well, thus significantly increasing
with imaging biomarkers, and real-time read on the in vivo energy output.54 Wind, wave, and geothermal energy is
efficacy of a therapeutic agent.51, 52 Nanodevices are also also expected to be harnessed more effectively using new
expected to be developed for both diagnosis and therapy, nanostructured materials and stored or delivered more
and such theragnostic devices hold great promises in per- efficiently through nanotechnological advances in batteries
sonalized medicine (see Supramolecular Nanoparticles and hydrogen fuel cells.55 Nanotechnology is playing a
for Molecular Diagnostics and Therapeutics, Nanotech- major role in the development of hydrogen fuel cells, which
nology). is considered to be one of the most promising clean energy
Nanodevices are in some ways the most complicated conversion devices for a wide variety of power applications
nanotechnological systems. They require the understanding ranging from portable and stationary power supplies to
of fundamental phenomena, the synthesis of appropriate transportation.4, 5
nanostructured materials, the use of those materials to More recently, subfields of nanotechnology, such as
fabricate functioning devices, and the integration of these nanobiotechnology and nanomedicine, are contributing
devices into working systems. Nevertheless, significant toward the development of highly accurate and sensitive
progress is currently being reported, and development and early-stage diagnostic devices. For instance, biosensors and
availability of increasingly sophisticated nanodevices are molecular probes are capable of directly interacting with
greatly anticipated. the biological molecule and converting the interactions
into directly transduced or significantly amplified electrical
or electromagnetic signals.2, 56 Dramatic breakthroughs are
1.3 Possible applications of nanotechnology also expected in life sciences research that could contribute
to the treatment of a number of human diseases, including
The huge scope of nanotechnology is summed up in a cancer and neurodegenerative diseases, such as Alzheimer’s
quote from a report by the National Science Foundation and Parkinson’s. Therapeutic fields, such as gene and drug
in 1999,53 which quoted, nanoscience and technology will delivery, tissue engineering, and drug discovery, will also
change the nature of almost every human-made object in the benefit greatly from advances in nanobiotechnology and
21st century. The fascinating and often unrivaled properties nanomedicine.57, 58 For instance, one of the current chal-
of nanostructured materials and devices have been, and will lenges is developing multifunctional nanodevices that are
continue, to open new and sometimes unexpected fields of capable of targeting specific malignant cells, visualizing
application. Today, the widespread applications range from their location in the body, killing primarily the cancer cells,
information and communication technology, transportation with minimal side effects on the body’s normal cells and
and aerospace, energy and environment, national security tissues, and monitoring treatment effects in real time.59
and defence to healthcare and medicine, food and nutrition,
biotechnology and agriculture, textiles and clothing, and
many more (Figure 1). 2 NANOFABRICATION
Over the years, advances in the field of nanoelectronics,
Nanofabrication methods can be categorized into two
which deals with the miniaturization of electronic devices,
groups: the top-down and bottom-up approaches. The
have enabled the appearance of new products in a range
top-down approach revolves around fabrication via etch-
of areas, including consumer electronics (e.g., computers,
ing away bulk material to achieve the required smaller
mobile phones, televisions, etc.), the automotive industry,
structural architectures and this is generally achieved by
healthcare and environmental management.53 Nanoelec-
lithographic processes (see Nanolithography, Nanotech-
tronics are expected to have an impact in many areas of our
nology).60, 61 This process could be likened to sculpting
lives, as more and more functions are integrated into every-
a block of stone to the required image. In contrast, the
day products. For instance, nanoelectronic devices could
bottom-up approach involves the structures being crafted
be used to regulate energy use in buildings, while in cars
atom by atom or molecule by molecule through covalent
additional built-in electronics could allow for more assisted
or supramolecular interactions60–63 in a similar manner to
driving.
how a house is built brick by brick. Both approaches have
Renewable energy technologies are often regarded as
their merits and drawbacks, which will be discussed later.
clean or green energy since they are far less harmful to
the environment than conventional fossil fuel technologies.
Nanotechnology is offering a range of new opportunities, 2.1 Top-down approach
such as nanosolar cells that would be energy-intensive
and far less expensive to make,46 solar panels capable of Presently, the top-down approach is dominantly used in
tapping not only the visible light from the sun but also industry for the fabrication of many man-made materials,

Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc195
6 Nanotechnology

a prime example being the semiconductor industry,64, 65 hydrophilic–hydrophilic, and hydrophobic–hydrophobic


where features of metal oxide semiconductor field effect interactions), in nature has been a major inspiration toward
transistor (MOSFET) are imprinted onto a silica wafer the development of the bottom-up approach. In fact,
via a lithography-based procedure termed photolithogra- supramolecular chemistry provides an exciting tool that
phy.64, 65 The technique is based on a projection printing combines the concepts of self-assembly and molecular
system, which is done in a device called a stepper, where recognition for the fabrication of three-dimensional intel-
the features of the transistors are projected through a pho- ligent nanodevices. Similar to nature, artificial systems are
tomask onto a silicon wafer that has been prespinned with either responsive to external stimuli, such as electrical,
a photoresist (light-sensitive) material using UV light. If chemical/biochemical, temperature, and photons, or can
the photoresist is positive, the regions of the photoresist partake through intermolecular interactions with other iso-
that are exposed to UV light become soluble to a partic- lated components to form functional materials. There are
ular developing solvent and are washed away during the a number of two-dimensional and three-dimensional self-
developing step, leaving a pattern of raised features on the assemblies as shown in Figure 2, which can be utilized
wafer identical to the dark regions on the mask. Conversely, as the fundamentals for building novel nanotechnologi-
for a negative resist, the regions of the photoresist that are cal devices. The nanofabrication and applications of the
exposed to UV light become insoluble to a particular devel- three-dimensional self-assemblies in fields such as molec-
oping solvent and only the unexposed regions are washed ular diagnostics, therapy, and electronics are discussed
away during the developing step, leaving a pattern of raised in the articles to follow (see Self-Assembled Nanopar-
features on the wafer identical to the clear regions on the ticles, Magnetically Responsive Self-Assembled Com-
mask. For more details on the fabrication of MOSFET, refer posite Materials, Supramolecular Nanoparticles for
to article Nanolithography, Nanotechnology. Molecular Diagnostics and Therapeutics, Advances in
Supramolecular Chemistry of Carbon Nanotubes, Nan-
otechnology) and hence will not be discussed further in this
2.1.1 Limitations of the top-down approach
article.
Semiconductor technology is beginning to reach the lim-
its of miniaturization, with Intel announcing in May 2011 2.2.1 Two-dimensional thin solid films
another milestone as they demonstrated a production-ready
3D transistor technology for 22 nm called Tri-Gate. Cur- Self-assembly of well-ordered two-dimensional ultrathin
rently, the photolithography process uses 193 nm wave- films on conducting, semiconducting, and insulating sur-
length of light to pattern the wafers, but both technical faces provides a simple, cheap, and reproducible method of
and material limitations are envisaged to be approached obtaining nanoscale films with a wide variety of functional
as smaller features are to be obtained.60 For instance, groups, which can be chemically manipulated.23, 66–69 These
quantum effects and defects formed during the patterning surfaces are increasingly being utilized as foundations for
process (see Nanoelectronics, Nanotechnology) will play building nanodevices such as sensors and for electronic
more dominant roles as smaller features are fabricated.60 If applications.23, 66, 67 Three types of ultrathin films used for
smaller features are to be generated, new fluids, lens mate- such potential applications are LBFs,21, 70, 71 SAMs,20, 72 and
rials, and resist material with high index will be required two-dimensional supramolecular assemblies. The follow-
or a new generation of lithography techniques such as ing discussion excludes two-dimensional supramolecular
extreme UV lithography (EUVL), which uses light with assemblies since they are covered in great detail in arti-
wavelengths in the range 10–50 nm, needs to be introduced cle Two-Dimensional Supramolecular Chemistry, Nan-
(see Nanoelectronics, Nanotechnology). If smaller wave- otechnology.
lengths of light and hence higher energy photons are used,
it becomes deleterious to the materials used, such as the Langmuir–Blodgett films (LBFs)
focussing lenses, and resists layers.60 LBFs are the first practical example of ordered molecular
assemblies.21, 70, 71 The approach involves the transfer of
monolayers from a liquid–air interface, which is denoted
2.2 The bottom-up approach as a Langmuir film onto a solid substrate. The Langmuir
films are produced by amphiphiles, which are molecules
Scientists’ curiosity to understand and mimic how bio- that have a hydrophobic end and a hydrophilic end.70, 71 The
logical architectures are preprogrammed to self-assemble amphiphile molecule is deposited onto a water subphase
and self-organize into ordered, yet dynamic and functional, avoiding the formation of multilayers in the Langmuir film.
structures through supramolecular interactions (i.e., hydro- Initially, the distances between the molecules in the phase
gen bonding, van der Waals, electrostatic, π–π interactions, are large relative to the molecular dimensions and the film

Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc195
Nanotechnology: the “top-down” and “bottom-up” approaches 7

Self-assembly entities

Two-dimensional Three-dimensional
ultrathin films assemblies

Metallic, Micelles Vesicles


Self-assembled Langmuir–Blodgett semiconducting,
monolayers films magnetic, polymeric,
supramolecular and
hybrid nanoparticles

Carbon
Two-dimensional supramolecular assemblies Nanorods Fullerenes
nanotubes

Figure 2 Schematic representation of examples of two-dimensional and three-dimensional self-assemblies.

is disordered and known as two-dimensional gas phase. of layers formed depends on the number of immersions
The film is compressed to bring the molecules closer to and emersions. There are three possible multilayer struc-
each other. The area per molecule decreases and the surface tures that can be formed, which are X-, Y-, and Z-type
pressure increases when the distance between the molecules modes (Figure 3b). X and Z modes are formed only in the
approaches molecular dimensions. The profile between downstroke and upstroke, respectively, whereas Y mode is
the surface pressure against molecular area is known as formed both in the upstroke and downstroke and is the most
the pressure-area isotherm.70, 71 The pressure-area isotherm stable and commonly formed mode.
provides information on the stability of the monolayer In the Langmuir–Schaefer method, a flat substrate is
formed, at the liquid–air interface, the orientation of the placed horizontally onto a compressed monolayer on the
molecules in the two-dimensional system, phase transitions, liquid–air interface. When the substrate is lifted horizon-
and conformational transformation. tally and separated from the water subphase, the monolayer
There are two possible methods of transferring the mono- is transferred onto the substrate (Figure 4). The method is
layers from the liquid–air interface onto a solid sub- useful to transfer viscous films as well as monolayers of
strate. The most conventional method that is used is the lipids and proteins.73
vertical deposition of the substrate (Langmuir–Blodgett
method).70, 71 The second method is the horizontal depo- Self-assembled monolayers
sition of the substrate onto the Langmuir film, which is SAMs are two-dimensional quasi-ordered molecular assem-
known as the Langmuir–Schaefer method.70, 71 In the Lang- blies, which are formed via adsorption of molecules from
muir–Blodgett method, the monolayer is transferred onto solution. SAMs have been increasingly used over LBFs
the substrate, as the substrate is either emersed (retraction as they offer a number of advantages.20, 72 First and fore-
or upstroke) or immersed (dipping or downstroke) into the most, SAMs are more stable than the LBFs stemming
Langmuir film, as shown in Figure 3(a).70, 71 When the sub- from the molecules being chemisorbed onto the substrate,
strate surface is hydrophilic, the monolayer is transferred whereas in LBFs the molecules are physisorbed. Secondly,
as the substrate is retracted. However, if the substrate is SAMs provide more flexibility in the molecular design
hydrophobic the monolayer is transferred as the substrate of the molecules because the molecules that form LBFs
is immersed. The speed at which the substrate is dipped need to be amphiphiles, whereas in SAMs such a need is
and retracted is important for a quality film to be pro- not required. Hence, the surfaces of the monolayers are
duced. One of the unique benefits of LBFs is that mul- easily tunable, and a wide range of terminal functionali-
tilayers can be formed in a controlled manner. The number ties have been studied (e.g., carboxylic acid, amine, nitro,

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8 Nanotechnology

Substrate holder Barrier

Trough

(a)

Substrate Direction of the


barrier movement

(a) Hydrophilic substrate

X-type film

Hydrophobic– (b)
hydrophilic
interaction Raising of the
solid substrate

Y-type film

Hydrophilic–
hydrophilic
interaction

Z-type film (c)


Hydrophilic–
hydrophobic
Figure 4 Schematic representation of the Langmuir–Schaefer
interaction method. (a) Langmuir film, (b) the solid substrate is placed
horizontally on the Langmuir film, and (c) the solid substrate is
(b) lifted with a Langmuir–Schaefer film.
Figure 3 Schematic representation of (a) vertical deposition of
the Langmuir film onto the solid substrate and (b) possible
multifilms that can be formed by the vertical deposition process: Surface group or
X-type, Y-type, and Z-type. terminal group

hydroxyl, and methyl groups) and exploited to provide Backbone


control over surface properties such as wettability23, 67 and
Head group
adhesion.68, 69
The molecular structure of the adsorbate or surfactant
molecules can be divided into three components, head
group, backbone, and terminal group (Figure 5). The head Figure 5 Cartoon representation of the molecular structure of
group is the anchor, which binds the adsorbate to the an adsorbate and how they are typically tilted at an angle of θ in
substrate. The choice of head group depends on the the monolayer.
substrate used, as different groups have varied affinity for
particular substrates. The most common head groups are the surface such as wettability and corrosion. The terminal
thiols (SH) on gold and silanes on silica substrates.20, 72 The group also has an influence on the packing density in the
backbone takes a major role in the molecular ordering and SAM.71
the thermal stability of the SAM formed.70 The backbone
connects the head group with the terminal group and is Organosulfur-based SAMs Organosulfur-based SAMs
generally made out of an aliphatic chain and/or aromatic have been extensively studied and are well understood.
components. Each molecule in the SAM interacts with These types of molecules have shown to self-assemble on
neighboring molecules through the backbone. Depending a number of metal surfaces including Au, Ag, Cu, Pt, and
on the groups in the backbone, the molecules can interact Fe,74 the preferred surface being clean and hydrophilic. Au
by van der Waals or π–π interactions, leading to relative is the most commonly used for such type of SAMs, as
well-ordered molecular layers. The terminal group is the sulfur has a relative strong bond to Au. In addition, Au
surface group, which plays a crucial role in the properties of does not have a stable oxide, hence is easy to handle in

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DOI: 10.1002/9780470661345.smc195
Nanotechnology: the “top-down” and “bottom-up” approaches 9

Adsorbates
physisorb

(a)
Adsorbates chemisorb
onto the substrate

Si Si Si
S S S
S O O O OO O Si O
S S S O Si Si O Si Si OO
S O (b)
O O O OO
Formation
(a) of islands
(b) van der Waals
interaction
Figure 6 Representation of the structures of (a) alkanethiolate
SAM on Au and (b) alkanesilane SAM on silica substrate, also
showing the cross-linking network between the molecules through (c)
Si–O–Si bonds.
Self-assembled monolayer
ambient conditions. Several different types of organosulfur
molecules have been shown to form well-ordered mono-
layers on Au: alkanethiol,20, 72 dialkyl disulfide,75 dialkyl (d)
sulfide,76 thioctic acid,77 and thiophene.78, 79 Alkanethiol-
Figure 7 Schematic representation of the deposition pro-
Au SAMs (Figure 6a) are the most studied and under-
cess of alkanethiol on Au. (a) Physisorption, (b) chemisorption,
stood. (c) formation of islands, and (d) formation of SAM.
The organosulfur-Au SAMs are generally deposited from
1 mM solution of the adsorbate molecule in an organic
organosilane-based SAMs is their susceptibility to hydrol-
solvent such as EtOH75, 76, 78 and CHCl3 .79 The deposition
ysis even in mild conditions.80, 81
process of alkanethiol-Au SAMs are well understood and is
thought to go through four stages. The first stage involves
the adsorbates physisorbing onto the surface (Figure 7a), Mixed SAMs Molecular level control over the density
followed by chemical bonds forming between the adsorbate and spatial distribution of functional groups on surfaces
and the substrate (Figure 7b). As the number of adsorbates is important in a wide variety of applications, and, in
bound to the substrate increases, the adsorbates reorganize particular, for biomedical applications. In many areas of
through van der Waals and other interactions to form islands medical and biological research, the functional groups
(Figure 7c), eventually leading to the formation of a well- mediate the immobilization of biomolecules to surfaces
ordered SAM (Figure 7d). The molecules in the SAM are and their efficient immobilization not only requires that
always slightly tilted from the normal of the substrate biomolecules preserve their activity after immobilization
(Figure 5) due to the optimization of the intermolecular but also that biomolecules are presented on the surface at an
interactions between the molecules (i.e., van der Waals optimal density and spatial distribution, such that efficient
interactions) and the trans conformation in alkyl chains in binding can occur between the immobilized biomolecules
the backbone. and target species in solution. At present, mixed SAMs
offer the best option for controlling the density and spatial
Organosilicon-based SAMs There are two types of distribution of the biomolecules on surfaces.
silicon-based adsorbates studied, alkyltrioxysilanes There have been a number of different approaches used
(R’Si(OR)3 )80 and alkyltrichlorosilanes (R’SiCl3 ).20 These for obtaining the mixed SAMs. The simplest approach is
are especially attractive for electronic applications because the formation of a monolayer via deposition of a substrate
the SAMs can be formed on silica or silicon wafers in a mixed solution that contains an active (containing the
(Si/SiO2 ). SAMs are formed on hydroxylated surfaces binding functional group) and inert surfactant (acts as the
(usually the native oxide). The SAM is afforded via a spacer to distribute the functional group in the first sur-
condensation reaction between the organosilane, hydrox- factant).82 This method is simple, but has some limitations
ylated surface and the neighboring silane,80 due to the such as the fact that the ratio of active surfactants in the
extensive cross-linking between the molecules (Figure 6b). monolayer is rarely identical to the ratio of active sur-
The organosilane-Si/SiO2 SAMs are thermally more sta- factants in the solution due to the preferential adsorption
ble than organosulfur-Au SAMs. The major drawback for of one of the components, thus affecting control over the

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DOI: 10.1002/9780470661345.smc195
10 Nanotechnology

density of the functional group on the mixed monolay- switch between bioinert and bioactive states, under an exter-
ers.83 Further, the formation of two-component monolayers nal thermal-, photo-, chemical/biochemical-, or electrical-
has been reported by some authors84–86 to lead to phase- induced stimulus, to trigger capture or release of biologi-
segregated mixed SAMs, that is, formation of two distinct cal entities.56 However, existing switchable SAM surfaces
local domains, each of which was mostly composed of one rely mostly on nonspecific interactions (i.e., hydropho-
constituent surfactant. In order to address some of these bic/hydrophilic and electrostatic) of the biomolecules with
issues, asymmetric dialkyl sulfide87 and dialkyl disulfide88 the active surface, thus lacking biospecificity and selec-
SAMs have been prepared, which consist of the active tivity and substantially limiting the application potential-
functional moiety on only one of the chains bound to ities of such surface systems. There are relatively few
the sulfur. Although this approach gives a more homo- reported examples in which specific biomolecular inter-
geneous monolayer compared to the mixed SAMs men- actions have been dynamically controlled in response to
tioned above, the spacing between the active molecules applied stimuli.90–92 Electro-switchable oligopeptide SAM
is restricted. Recently, Tokuhisa et al.89 proposed using surfaces have been successfully used to reversibly control
biomolecular interactions upon application of an electri-
dendrons as spacers. The dendrons were bound to lipoic
cal stimulus.92 In another example, a thermoresponsive
acid through an ester linkage.89 After the formation of the
oligo(ethylene glycol) derivative has been exploited to con-
monolayer, the dendrons were removed by hydrolysis under
trol the affinity binding between surface-tethered biotin
basic conditions and subsequently, a second surfactant was
groups and streptavidin.91 Albeit the progress and scien-
deposited onto the vacant areas to form a mixed monolayer.
tific advances in the field, exciting future developments
The spacing between the active sites was controlled by the
are ahead of us. One of the major challenges in the
size or generation of the dendron used. Novel approaches field of switchable biological surfaces today is the design
for molecular level control over the functional groups on of new and more versatile surfaces with tunable biospe-
surfaces will continue to aid in the development of more cific interactions. For a detailed discussion on the progress
advanced surface materials. made on stimuli-responsive surfaces, refer to the review by
Mendes.56

Switchable SAMs Recently, there has been an increas- 2.2.2 Hybrid approach: Combination of the
ing activity in fabricating stimuli-responsive SAM surfaces, top-down and bottom-up approaches
where the surface properties are manipulated through exter- Currently, a significant challenge in nanotechnology is
nal stimulus providing an on and off switch for regulat- to spatially self-organize self-assembled nanoscale compo-
ing the immobilization of biological and chemical partic- nents (such as nanoparticles, CNTs, proteins, cells, organic
ulates (Figure 8).56 Such SAM surfaces potentially pro- molecules, polymers, etc.) onto surfaces to fabricate func-
vide a wide range of applications to many areas in sci- tional nanostructured systems for electronic, optoelectronic,
ence and technology, especially in the life sciences. These or sensing applications.93, 94 Precise control over the rel-
SAM surfaces enable modulation of biomolecule activ- ative position and orientation of the nanocomponents is
ity, protein immobilization, and cell adhesion at the liq- frequently required in such systems to obtain useful prop-
uid–solid interface for applications including biofouling, erties. Moreover, the integration and the stability of inter-
cell culture, regenerative medicine, and tissue engineer- faces to these nanostructures from the micron-length and
ing.56 This field is in its infancy and early examples of macroscopic scales are key to the success of future appli-
switchable biological SAM surfaces include surfaces that cations.

Stimulus

Chemical / Biochemical
Thermal
Electric
Optical

Inactive surface Active surface

Figure 8 Schematic representation depicting the range of stimuli and how they can be used to modulate the binding of particulates
on stimuli responsive-based self-assembled monolayers.

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DOI: 10.1002/9780470661345.smc195
Nanotechnology: the “top-down” and “bottom-up” approaches 11

Nanostructuring surfaces of macroscopic materials by creating nanostructured materials with high degrees of
top-down nanolithography techniques, and subsequently control, and is being actively pursued by a number of
building into the third dimension utilizing bottom-up groups within the scientific and engineering communi-
self-organization of self-assembled nanoentities, is an ties.93–97
attractive approach for creating such a bridge between
macroscopic systems and the nanoscale dimensions that
many modern technologies demand. With this in mind, 3 CONCLUSION AND OUTLOOK
different hybrid top-down and bottom-up fabrication appr-
oaches have been investigated to create three-dimensional Nanotechnology is going to play an increasingly important
nanostructured surfaces.93, 95, 96 Several strategies rely on role in a number of sectors, addressing important issues
the formation of an ultrathin film (e.g., SAMs) on the sur- such as health, energy, environment, transportation, water,
face material of interest, followed by chemical transforma- food, and security. For instance, in medicine, nanotech-
tion/damage on the film caused by a lithographic technique nology has a role to play in developing novel, highly
(see Nanolithography, Nanotechnology), and finally the accurate and sensitive early-stage diagnostic devices, as
immobilization of nanoscale components on the modified well as providing novel methodologies for the treatment
surfaces through either covalent or supramolecular inter- of chronic (such as diabetes) or life threatening diseases
actions to form functionalized three-dimensional nanos- such as cancer through gene therapy or drug delivery.
tructures. SAMs are attractive ultrathin organic films for Both the top-down, which relies on dimensional reduction
patterning high-resolution features on a number of tech- through selective etching and various nanoimprinting tech-
nologically relevant surface substrates. The attraction of niques, and bottom-up methods, which assemble atoms or
these systems as ultrathin resists is driven primarily because molecules into nanostructured materials, in several cases
SAMs eliminate depth of focus, transparency issues and through use of supramolecular chemistry, are at the heart
can be prepared with a discrete number of well-defined of such developments. As a result of the numerous fun-
chemical functional groups to permit further nanoscale damental breakthroughs made in the past three decades,
materials attachment. Currently, patterning SAMs can be neither the top-down nor the bottom-up approach is superior
achieved by several different types of lithographic tech- at the moment; each has its advantages and disadvantages
niques, which include (i) stamping or moulding methods, (Table 1).
that is, soft lithography,64 (ii) scanning probe lithogra- The top-down nanofabrication has been used with obvi-
phy (SPL)-based techniques such as dip-pen nanolithogra- ous success by the semiconductor industry for several
phy,98, 99 nanografting,100, 101 and nanoshaving,102 and (iii) decades now, with physicists and engineers manipulating
radiative techniques that include ultraviolet/visible (UV/vis) progressively smaller pieces of matter by photolithogra-
light, X-rays, and electron-beam. Generation of three- phy and related techniques, but the top-down approach
dimensional nanostructures by self-organization of vari- is quickly reaching its physical and economic limits. On
ous self-assembled nanoscale components onto nanopat- the other hand, the bottom-up nanofabrication offers ulti-
terned SAM surface templates has also been demon- mate limits of miniaturization, opens virtually unlimited
strated.93, 95–97 The integration of the top-down and bottom- possibilities concerning the design and construction of func-
up methodologies is representing a new paradigm for tional nanostructured materials, and has the potential to be

Table 1 Summary of the merits and drawbacks for the top-down and bottom-up approaches.

Top-down approach Bottom-up approach

Advantages Already well understood and have established techniques Self-assembly provides a simple, fast, and low-cost
method for producing nanostructured materials
Provides control and precision when patterning the surfaces Offer ultimate limits of miniaturization
through lithography
Procedures reproducible Opportunities open to the fabrication of a wider range
of functional nanostructured materials by chemical
synthesis
Disadvantages More sensitive to defects as features become smaller At present, the mastery of self-assembly is limited
to fairly simple nanostructured materials, not being
able, for example, to create integrated devices
Tighter tolerance as features become smaller
More expensive as compared to the self-assembly methods

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DOI: 10.1002/9780470661345.smc195
12 Nanotechnology

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Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc195
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Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc195

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