Chemical Sensors Volume 2: Nanostructured Materials

CONTENTS
PREFACE TO CHEMICAL SENSORS: FUNDAMENTALS OF SENSING MATERIALS xi

PREFACE TO VOLUME 2: NANOSTRUCTURED MATERIALS xiii
ABOUT THE EDITOR xv
CONTRIBUTORS xvii
1 INTRODUCTION TO NANOMATERIALS AND NANOTECHNOLOGY 1

G. Korotcenkov
B. K. Cho
1 What Are Nanomaterials? 1
2 A Brief History of Nanotechnology 7
3 What Distinguishes Nanomaterials from Bulk Materials? 10
4 Nanomaterials Manufacturing 14
5 Nanotechnology and Its Possibilities 17
6 Nanotechnology: Future Trends 19
7 Acknowledgments 23
References 24
2 QUASI-ONE-DIMENSIONAL METAL OXIDE STRUCTURES: SYNTHESIS,

CHARACTERIZATION, AND APPLICATION AS CHEMICAL SENSORS 29
Pai-Chun Chang
Dongdong Li
Jia G. Lu
1 Introduction 29
2 Synthesis of Q1D Nanomaterials 30
v
vi  CONTENTS
2.1 Vapor-Phase Growth Methods 31

2.2 Solution-Phase Growth Methods 41
2.3 Template-Based Growth Methods 43
3 Electrical Transport Properties and Optical Characteristics 47
3.1 Nanowire Field-Effect Transistors and Electrical Properties 47
3.2 Photoluminescence Characteristics 52
4 Metal Oxide Nanowire Chemical Sensors 53
4.1 Sensor Device Fabrication 55
4.2 Mechanism of Nanowire Sensor Detection 56
4.3 Other Types of Q1D Structured Sensors 70
5 Summary and Future Outlook 72
References 73
3 CARBON NANOTUBES AND FULLERENES IN CHEMICAL SENSORS 87

G. P. Kotchey
A. Star
1 Introduction 87
1.1 History of Fullerenes and Carbon Nanotubes 87
1.2 Structure of Fullerenes 88
1.3 Structure of Carbon Nanotubes 88
2 Synthesis of Fullerenes and Carbon Nanotubes 89
2.1 Synthesis of Fullerenes 89
2.2 Synthesis of Carbon Nanotubes 90
3 Properties of Carbon Nanotubes 94
3.1 Physical/Mechanical Properties 94
3.2 Electronic Properties 94
3.3 Spectroscopic Properties 96
4 Chemical Modification and Functionalization of Carbon Nanotubes 98
4.1 Introduction 98
4.2 Noncovalent Functionalization 98
4.3 Covalent Functionalization 100
5 Solid-State Electrical Conductivity CNT Sensors 101
5.1 Nanotube FET for Gas-Sensing Applications 101
5.2 NO2 Detection Using Resistivity Measurements 102
5.3 Gas and Vapor Detection Using Functionalized CNTs 103
5.4 Chemicapacitors 105
CONTENTS  vii
5.5 Nanotube FETs for Detecting DNA Hybridization 108

5.6 Employing NTFETs for Protein Detection 110
5.7 Conductometric Glucose Biosensor 114
6 Raman Sensors 115
6.1 A Surface-Enhanced Raman Scattering (SERS)–Based pH Sensor 115
6.2 “Multicolored” Raman Probes for Biological Imaging and Detection 117
7 Optical Sensors 120
7.1 Employing SWNTs as Fluorophores for Long-Term Optical Glucose
Sensing 120
7.2 Employing Spectroscopic Properties of SWNTs to Detect DNA
Hybridization 122
8 Electrochemical Sensors 123
8.1 Employing Electrochemistry to Monitor DNA Hybridization 123
8.2 Electrochemical-Based Glucose Sensing 126
9 Field-Emission Sensors 128
9.1 A CNT-Based Triode Sensor That Employs the Field-Emission Effect to
Detect Gas Density 128
10 Electromechanical Resonators 130
10.1 Nanomechanical Nanotube Resonators for the Detection of
Evaporated Chromium Atoms 130
10.2 Surface Acoustic Wave (SAW) Devices That Employ Buckminsterfullerene
(C60) for the Detection of Toxic Organic Vapors 132
11 Outlook 133
References 135
4 SENSORS BASED ON MONOLAYER-CAPPED METALLIC NANOPARTICLES 141

U. Tisch
H. Haick
1 Introduction 141
2 Synthesis of MCNPs and Deposition of Solid MCNP Films 142
2.1 Synthesis of MCNPs 143
2.2 Surface Functionalization of Metal Nanoparticles 144
2.3 Methods of MCNP Film Deposition 145
3 Four Good Reasons to Use Monolayer-Capped Metallic Nanoparticles for
Chemical Sensing 147
3.1 Controllable Chemical Composition 147
viii  CONTENTS
3.2 Controllable Size and Shape 147

3.3 Controllable Nanoparticle Assembly 149
3.4 Biocompatibility 151
4 Chemical Sensors Based on MCNPs 151
4.1 Basic Principles 151
4.2 “Lock-and-Key” Sensor Versus “Electronic Nose” 152
4.3 The Role of the Number of Nanoparticles in Chemical Sensing 153
5 Categories of MCNP-Based Chemical Sensors 153
5.1 Optical Sensors 153
5.2 Chemiresistors 170
5.3 Electrochemical Sensors 180
5.4 Piezoelectric Sensors 185
6 Concluding Remarks 188
References 190
5 POROUS SEMICONDUCTORS: ADVANTAGES AND DISADVANTAGES FOR GAS

SENSOR APPLICATIONS 203
G. Korotcenkov
1 Introduction 203
2 Porous Semiconductors: Principles of Fabrication and Properties 205
2.1 Principles of Porous Silicon Fabrication 205
2.2 Properties of Porous Silicon 208
2.3 Techniques for Forming the Porous Silicon Layer 210
2.4 Porosification of Standard Semiconductors 220
3 Gas Sensors Based on Porous Semiconductors—Approaches and
Characteristics 226
3.1 Capacitance-Type Gas Sensors 226
3.2 Gas Sensors Employing Photoluminescence Quenching 232
3.3 Sensors Based on Optical Measurements 237
3.4 Conductometric-Type Gas Sensors 243
3.5 Gas Sensors Based on Schottky Barriers and Heterostructures 250
3.6 Gas Sensors Based on Measurement of Contact Potential Difference 257
3.7 Gas Sensors Based on Simultaneous Control of Several Parameters
of the Porous Material 258
3.8 Disadvantages of Porous Semiconductor Gas Sensors 259
CONTENTS  ix
3.9 Surface Modification of Porous Semiconductors to Improve

Gas-Sensing Characteristics 265
4 Advantages of Porous Silicon for Applications in Micromachining Sensor
Technology 269
5 Outlook 274
References 276
6 ORDERED MESOPOROUS FILMS AND MEMBRANES: SYNTHESIS, PROPERTIES, AND

APPLICATIONS IN GAS SENSORS 291
M. Tiemann
1 Introduction 291
2 Porosity in Resistive Gas Sensors 292
2.1 Categories of Porosity 292
2.2 Gas Diffusion in Porous Materials 293
2.3 Porous Films for Selective Gas Sensing 293
2.4 Other Porosity-Related Nanostructural Aspects 296
3 Synthesis Methods 297
3.1 Mesoporous Metal Oxides by Conventional Synthesis Methods 297
3.2 Mesoporous Materials by Supramolecular Structure Directors 299
3.3 Mesoporous Materials by Structure Replication 302
4 Summary 303
References 304
7 CHEMICAL SENSORS BASED ON ZEOLITES 311

R. Moos
K. Sahner
1 Introduction 311
2 Zeolites—Properties and Applications 312
3 Zeolites as an Auxiliary Phase in Chemical Sensors 316
3.1 Zeolites as Host Materials 316
3.2 Zeolites as Filters 319
3.3 Zeolites as Preconcentrators 321
3.4 Zeolites as Templates 321
x  CONTENTS
4 Zeolites as the Functional (Sensitive) Phase 322

4.1 Adsorptivity 322
4.2 Ionic Conductivity 323
4.3 Catalytic Activity 326
5 Conclusion 328
References 328
8 NANOCOMPOSITES: FROM FABRICATION TO CHEMICAL SENSOR APPLICATIONS 335

Rajesh
T. Ahuja
D. Kumar
1 Introduction 335
2 Types of Nanocomposites 337
3 General Approaches to Nanocomposite Fabrication 338
4 Metal Oxide–Based Nanocomposites 339
4.1 Synthesis 339
4.2 Properties 340
4.3 Application in Chemical Sensors 341
5 Polymer-Based Nanocomposites 344
5.1 Synthesis 344
5.2 Properties 346
6 Carbon Nanotube–Based Nanocomposites 349
6.1 Synthesis 350
6.2 Properties 352
7 Noble Metal–Based Nanocomposites 355
7.1 Synthesis 357
7.2 Properties 358
8 Outlook 361
9 Acknowledgment 361
References 362
INDEX 369
PREFACE TO
CHEMICAL SENSORS:
FUNDAMENTALS OF SENSING MATERIALS
Sensing materials play a key role in the successful implementation of chemical and biological sen-
sors. The multidimensional nature of the interactions between function and composition, preparation
method, and end-use conditions of sensing materials often makes their rational design for real-world
applications very challenging.
The world of sensing materials is very broad. Practically all well-known materials could be used for
the elaboration of chemical sensors. Therefore, in this series we have tried to include the widest pos-
sible number of materials for these purposes and to evaluate their real advantages and shortcomings.
Our main idea was to create a really useful “encyclopedia” or handbook of chemical sensing materials,
which could combine in compact editions the basic principles of chemical sensing, the main properties
of sensing materials, the particulars of their synthesis and deposition, and their present or potential ap-
plications in chemical sensors. Thus, most of the materials used in chemical sensors are considered in
the various chapters of these volumes.
It is necessary to note that, notwithstanding the wide interest and use of chemical sensors, at the
time the idea to develop these volumes was conceived, there was no recent comprehensive review or
any general summing up of the fundamentals of sensing materials The majority of books published in
the field of chemical sensors were dedicated mainly to analysis of particular types of devices. This three-
volume review series is therefore timely.
This series, Chemical Sensors: Fundamentals of Sensing Materials, offers the most recent advances
in all key aspects of development and applications of various materials for design of chemical sensors.
Regarding the division of this series into three parts, our choice was to devote the first volume to the
fundamentals of chemical sensing materials and processes and to devote the second and third volumes
to properties and applications of individual types of sensing materials. This explains why, in Volume 1:
General Approaches, we provide a brief description of chemical sensors, and then detailed discussion of
desired properties for sensing materials, followed by chapters devoted to methods of synthesis, deposi-
tion, and modification of sensing materials. The first volume also provides general background informa-
tion about processes that participate in chemical sensing. Thus the aim of this volume, although not ex-
haustive, is to provide basic knowledge about sensing materials, technologies used for their preparation,
and then a general overview of their application in the development of chemical sensors.
xi
xii  PREFACE TO CHEMICAL SENSORS: FUNDAMENTALS OF SENSING MATERIALS
Considering the importance of nanostructured materials for further development of chemical sen-
sors, we have selected and collected information about those materials in Volume 2: Nanostructured
Materials. In this volume, materials such as one-dimension metal oxide nanostructures, carbon nano-
tubes, fullerenes, metal nanoparticles, and nanoclusters are considered. Nanocomposites, porous semi-
conductors, ordered mesoporous materials, and zeolites also are among materials of this type.
Volume 3: Polymers and Other Materials, is a compilation of review chapters detailing applications
of chemical sensor materials such as polymers, calixarenes, biological and biomimetric systems, novel
semiconductor materials, and ionic conductors. Chemical sensors based on these materials comprise a
large part of the chemical sensors market.
Of course, not all materials are covered equally. In many cases, the level of detailed elaboration
was determined by their significance and interest shown in that class of materials for chemical sensor
design.
While the title of this series suggests that the work is aimed mainly at materials scientists, this is not
so. Many of those who should find this book useful will be “chemists,” “physicists,” or “engineers” who
are dealing with chemical sensors, analytical chemistry, metal oxides, polymers, and other materials and
devices. In fact, some readers may have only a superficial background in chemistry and physics. These
volumes are addressed to the rapidly growing number of active practitioners and those who are interested
in starting research in the field of materials for chemical sensors and biosensors, directors of industrial
and government research centers, laboratory supervisors and managers, students and lecturers.
We believe that this series will be of interest to readers because of its several innovative aspects. First,
it provides a detailed description and analysis of strategies for setting up successful processes for screen-
ing sensing materials for chemical sensors. Second, it summarizes the advances and the remaining chal-
lenges, and then goes on to suggest opportunities for research on chemical sensors based on polymeric,
inorganic, and biological sensing materials. Third, it provides insight into how to improve the efficiency
of chemical sensing through optimization of sensing material parameters, including composition, struc-
ture, electrophysical, chemical, electronic, and catalytic properties.
We express our gratitude to the contributing authors for their efforts in preparing their chapters.
We also express our gratitude to Momentum Press for giving us the opportunity to publish this series.
We especially thank Joel Stein at Momentum Press for his patience during the development of this
project and for encouraging us during the various stages of preparation.
Ghenadii Korotcenkov
PREFACE TO
VOLUME 2: NANOSTRUCTURED MATERIALS
Nanomaterials and nanotechnology are new fields of science and technology. Fundamentally, nanotech-
nology is about manipulating and making materials at the atomic and molecular levels. It is expected
that nanotechnology will change solid-state gas sensing dramatically and will probably gain importance
in all fields of sensor application over the next 10 to 20 years. Nanotechnology is still in its infancy, but
the field has been a hot area of research globally since a few years ago. It has been found that with reduc-
tion in size, novel electrical, mechanical, chemical, catalytic, and optical properties can be introduced.
As a result, it has been concluded that one-dimensional structures will be of benefit for developing new-
generation chemical sensors that can achieve high performance. Therefore, in the last decade, the study
of 1-D materials has become a primary focus in the field of chemical sensor design. Synthesis of new
nano objects and exploitation of their extraordinary properties is the goal and dream of many researchers
engaged in the field of sensor design. In addition, it has also been established that 1-D structures may
be ideal systems in which to study the nature of chemical sensing effects.
Although many people consider this a brand-new technology yielding cutting-edge applications for
consumer products, researchers have in fact been working in the field of catalysis and gas-sensing effects
for decades. What we call nanoparticle technology today actually began in the era of the 1950s–1980s,
and chemical catalysis and gas sensor research and development have been conducted at the nanoscale
ever since. Initially, research labs used the technology to increase the efficiency of heterogeneous catalysis
and to improve the sensitivity of solid-state gas sensors. Nanoclusters of metal catalysts and nanograins
of metal oxides with dimensions less than 10 nm were the main objects of research.
The recent development of advanced tools for characterizing materials at the nano- or subnanoscale
has provided scientists with new insights for understanding and improving existing devices and clues for
ways to design new nanostructured materials to make better catalysts and sensors. Recent research has
thus led to new types of prospective nanostructured materials.
It is obviously difficult to cover all aspects of a dynamic research area such as nanotechnology. Of
course, it is not possible to analyze in one volume every nanoparticulate matter and its role in the revolu-
tion of materials for chemical sensor applications. However, we have tried to cover this field more or less
completely. This book, together with Volume 1, includes as much as possible the recent advances and
breakthroughs in the area of nanomaterials for chemical sensors as achieved by research groups all over
the world. These contributions have led to the emergence of some general guidelines.
xiii
xiv  PREFACE TO VOLUME 2: NANOSTRUCTURED MATERIALS
This book includes eight chapters written by researchers who are at the forefront of their field,
which address the role of nanomaterials in chemical sensors. One-dimensional metal oxide structures,
carbon nanotubes, fullerenes, and metal nanoparticles are the objects of detailed analysis in the present
volume. Processing, properties, and applications of porous semiconductors, zeolites, nanocomposites
and ordered mesoporous materials are also discussed in this volume. A brief history of nanotechnology,
particulars of nanomaterial properties, specificity, and future trends in nanotechnology can be found in
this volume as well.
Ghenadii Korotcenkov
ABOUT THE EDITOR
Ghenadii Korotcenkov received his Ph.D. in Physics and Technology of Semiconductor Materials and
Devices in 1976, and his Habilitate Degree (Dr.Sci.) in Physics and Mathematics of Semiconductors
and Dielectrics in 1990. For a long time he was a leader of the scientific Gas Sensor Group and manager
of various national and international scientific and engineering projects carried out in the Laboratory of
Micro- and Optoelectronics, Technical University of Moldova. Currently, he is a research professor at
Gwangju Institute of Science and Technology, Gwangju, Republic of Korea.
Specialists from the former Soviet Union know G. Korotcenkov’s research results in the study of
Schottky barriers, MOS structures, native oxides, and photoreceivers based on Group III–V compounds
very well. His current research interests include materials science and surface science, focused on metal
oxides and solid-state gas sensor design. He is the author of five books and special publications, nine
invited review papers, several book chapters, and more than 180 peer-reviewed articles. He holds 16
patents. He has presented more than 200 reports at national and international conferences. His articles
are cited more than 150 times per year. His research activities have been honored by the Award of
the Supreme Council of Science and Advanced Technology of the Republic of Moldova (2004), The
Prize of the Presidents of Academies of Sciences of Ukraine, Belarus and Moldova (2003), the Senior
Research Excellence Award of Technical University of Moldova (2001, 2003, 2005), a Fellowship from
the International Research Exchange Board (1998), and the National Youth Prize of the Republic of
Moldova (1980), among others.
xv
CONTRIBUTORS
Tarushee Ahuja (Chapter 8)

Department of Applied Chemistry
Delhi College of Engineering
University of Delhi
Bawana Road
Delhi-110042, India
Pai-Chun Chang (Chapter 2)

Department of Physics
and Department of Electrical Engineering
University of Southern California
Los Angeles, California 90089-0484, USA
Beongki Cho (Chapter 1)

Department of Material Science and Engineering
and Department of Nanobio Materials and Electronics
Gwangju Institute of Science and Technology
Gwangju, 500-712, Republic of Korea
Hossam Haick (Chapter 4)

Department of Chemical Engineering
and Russell Berrie Nanotechnology Institute
Technion—Israel Institute of Technology
Haifa 32000, Israel
Ghenadii Korotcenkov (Chapters 1 and 5)

Department of Material Science and Engineering
Gwangju Institute of Science and Technology
Gwangju, 500-712, Republic of Korea
and
Technical University of Moldova
Chisinau, 2004, Moldova
xvii
xviii  CONTRIBUTORS
Gregg P. Kotchey (Chapter 3)

Department of Chemistry
University of Pittsburgh and the National Energy Technology Laboratory
Pittsburgh, Pennsylvania 15260, USA
Devendra Kumar (Chapter 8)

Department of Applied Chemistry
Delhi College of Engineering
University of Delhi
Bawana Road
Delhi 110042, India
Dongdong Li (Chapter 2)
Department of Physics and Department of Electrical Engineering
Jia Grace Lu (Chapter 2)

Department of Physics and Department of Electrical Engineering
Ralf Moos (Chapter 7)

Department of Functional Materials
University of Bayreuth
95440 Bayreuth, Germany
Rajesh (Chapter 8)
Liquid Crystal and Self Assembled Monolayer Section
National Physical Laboratory (CSIR)
Dr. K.S. Krishnan Marg
New Delhi 110012, India
Kathy Sahner (Chapter 7)

Functional Materials Laboratory
University of Bayreuth
95440 Bayreuth, Germany
Alexander Star (Chapter 3)

Department of Chemistry
University of Pittsburgh and the National Energy Technology Laboratory
Pittsburgh, Pennsylvania 15260, USA
CONTRIBUTORS  xix
Michael Tiemann (Chapter 6)

Department of Chemisty
Faculty of Science
University of Paderborn
Warburger Strasse 100
D-33098 Paderborn, Germany
Ulrike Tisch (Chapter 4)

Department of Chemical Engineering
Technion—Israel Institute of Technology
Haifa 32000, Israel
CHAPTER 1
INTRODUCTION TO NANOMATERIALS
AND NANOTECHNOLOGY
G. Korotcenkov
B. K. Cho
1. WHAT ARE NANOMATERIALS?

Recent scientific research has discovered an important role for nanotechnologies in fields such as informa-
tion technology, materials science, biology, medicine, engineering, electronics, physics, fiber-optic com-
munication networks, chemistry, computer simulations, aerospace technology, advanced materials tech-
nology, and chemical engineering (Feiner 2006; Wang et al. 2006; Mamalis 2007; Rickerby and Morrison
2007; Davenas et al. 2008; Meyer et al. 2009; Zhang and Webster 2009). As a result, a revolution of sorts
has occurred in the search for approaches to attaining needed properties of materials: We have reached an
era in which the control of physical, chemical, and biological properties of materials often takes place at
the molecular and supramolecular levels. Just a few years ago, this ability seemed unrealistic.
According to the International Union of Pure and Applied Chemistry (IUPAC), nanomaterials
are defined as materials having sizes smaller than 100 nanometers (1 nm = 10−9 m) along at least one
dimension (length, width, or height) (Wikipedia 2009). For comparison, Table 1.1 lists the dimensions
(sizes) of a number of well-known objects. In the range of crystallite sizes (<100 nm), and especially
in the range smaller than 10 nm, large differences in the properties of nanomaterials and nanoparticles
have been observed. For example, the exciton diameter in a semiconductor may be tens or hundreds of
nanometers, the distance between domain walls in a magnet may be hundreds of nanometers, etc. So,
nanostructures with characteristic size smaller than 10–100 nm can be considered as a special physical
state, because the properties of materials formed with the participation of nano-sized structural elements
1
2  CHEMICAL SENSORS: FUNDAMENTALS. VOLUME 2: NANOSTRUCTURED MATERIALS
Table 1.1. Characteristic dimensions of some commonplace objects
OBJECT SIZE
Resolution of electron microscope ~0.1 nm
Individual atom <0.2 nm
Simple gas molecules (N2, CO, O2, etc.) ~0.3 nm
Water molecule ~0.3 nm
Thickness of grapheme layer ~0.3–0.5 nm
Constants of crystallographic unit cells
Simple chemical elements 0.5–0.8 nm
Inorganic compounds 0.5–1.5 nm
Complex organic compounds 2–3 nm
Diameter of DNA double-helix molecule ~2.5 nm
NANOMATERIALS 1–100 nm
Wall thickness of carbon nanotubes ~2–12 nm
Nanoclusters, nanoparticles 1–10 nm
Nanocrystals 4–100 nm
Nanowires, nanotubes
Diameter 1–100 nm
Length 102 up to 106 nm
Magnetic domain ~hundreds nm
Smallest feature in an integrated circuit ~150–200 nm
Resolution of light microscope >200 nm
Quantum-dot transistor ~300 nm
Visible spectra ~400–800 nm
Diameter of biological cells ~(1–10) × 103 nm
Diameter of human hair ~(5–10) × 104 nm
Thickness of a book page ~105 nm
Pet flea ~106 nm
Head of a pin ~106 nm
are not identical to the properties of bulk substance (Rosei 2004; Schwarz et al. 2004; Roduner 2006;
Fahlman 2007). For instance, opaque substances may become transparent (copper); inert materials may
exhibit catalytic properties (gold); stable materials may become combustible (aluminum); insulators
may become conductors (silicon). Nanocrystallites of inorganic solids have been shown to exhibit size-
dependent properties, such as higher energy gaps and nonthermodynamic behavior (Alivisatos 1996a;
Murray et al. 2000; Schwarz et al. 2004). Therefore, by considering structure at the nanoscale as a physi-
cal variable, it is possible to greatly expand the range of performance of existing chemicals and materials.
Once it is possible to control feature size and shape, it is also possible to enhance material properties
and device functions beyond what are already established. For example, by creating nanometer-scale
structures, it is possible to control fundamental properties of materials such as their melting temperature
(Buffat and Borel 1976; Gulseren et al. 1995). It is known, for instance, that for grains smaller than
INTRODUCTION TO NANOMATERIALS AND NANOTECHNOLOGY  3
about 20–40 nm, the melting temperature of a crystal is inversely proportional to its effective radius (see
Figure 1.1). Usually, this effect is considered to be a consequence of the large fraction of atoms with low
coordination numbers that are present in solids with high surface-to-volume ratios.
There is also experimental verification of size-dependent thermal melting in thin one-dimensional
nanostructures, principally owing to the difficulty of fabricating free-standing rods or wires with dia-
meters smaller than 5–10 nm (Law et al. 2004). Photo-induced melting and fragmentation of metal
nanorods in solution have been studied in detail using femto- to nanosecond light pulses (Link et al.
1999, 2000). Also, a large melting-point depression was reported in the case of germanium nanowires
(10–100 nm in diameter) encased in carbon sheaths (Wu and Yang 2001). Transmission electron mi-
croscopy (TEM) has showed that the ends of sheathed Ge nanowires began to melt 280°C below the
bulk melting temperature of Ge. The same effect was also observed for CdS nanoparticles (Alivisatos
1996b).
The magnetic properties of solids can exhibit size dependence as a consequence of several effects,
including the influence of surfaces, the onset of carrier confinement, and the reduction of structure
size below that of a single magnetic domain (Law et al. 2004). It is possible to enhance or even induce
magnetic behavior by changing the dimensionality of a system. For example, the broken symmetry of a
surface can generate giant magnetic anisotropy energy in magnetic adatoms (Gambardella et al. 2003).
The study of electron transport in suspended chains of atoms (Rodrigues et al. 2003) suggests that cer-
tain nonmagnetic systems, such as Pd and Pt, become magnetic in such a geometry.
Other properties of nanomaterials, such as charge capacity and even their color, are also sensitive
to size and therefore can be changed even without changing the materials’ chemical composition (Rosei
2004; Schwarz et al. 2004). For example, gold is known to be a shiny, yellow noble metal that does not
tarnish, has a face-centered cubic structure, is nonmagnetic, and melts at 1336 K. However, a small sam-
ple of the same gold is quite different: 10-nm particles absorb green light and thus appear red (Eustis and
El-Sayed 2006). The melting temperature decreases dramatically as the size goes down (<5 nm) (Schmid
2001). Moreover, bulk gold ceases to be noble, and 2- to 3-nm nanoparticles are excellent catalysts (see
Figure 1.1. Size dependence of the melting points of (a) In and (b) Sn particles. (Reprinted with permis-
sion from Unruh et al. 1993 and Lai et al. 1996. Copyright 1993 and 1996 American Physical Society.)

4.0 Au/TiO2
0.3
3.0

2
3 0.2
2.0
0.1
1
1.0
2.0 3.0 4.0 5.0 6.0

Average cluster diameter, nm
Figure 1.2. Specific activity for CO conversion as a function of average Au cluster diameter on Au/
TiO2 at (1, 2) 300 K and (3) 350 K. The number of surface sites was computed using cluster morphol-
ogy determined by STM. Ptotal = 40 torr, CO/O2 = 1/5. [Data from (1) Valden et al. 1998a, (2) Valden
et al. 1998b, and (3) Haruta, 1997.]
Figure 1.2), which also exhibit considerable magnetism. At this size the particles are still metallic, but
smaller ones turn into insulators (Roduner 2006). As we can see from results presented in Figure 1.3, in
this range of cluster size we observe an increase of band gap. A metal-to-nonmetal transition is apparent
as the cluster size approaches ~4.0 nm in diameter (~400 atoms/cluster), the approximate size at which
onset of catalytic activity is observed for CO oxidation.

1.5
Au/TiO2(110)
1.2
0.9
0.6
0.3
0.0
0.0. 2.0 4.0 6.0 8.0
Average cluster diameter, nm
Figure 1.3. Gold cluster band gap measured by scanning tunnel spectroscopy as a function of
particle size on Au/TiO2(110). (Adapted with permission from Chen and Goodman 2006. Copyright
2006 Elsevier.)
As has been established for carbon nanotubes, band gap also can be controlled through a change
of nanomaterial size (Robertson 2007). It was found that in the case of a semiconducting single-wale
nanotube (SWNT), its electrical band gap Eg varies roughly inversely with the diameter d and is given
in tight binding as
æ 2a ö
E g =  ççç ÷÷÷ (1.1)
èd ø
where  is the π-matrix element between adjacent carbon atoms and a is the C–C bond length. Given
that a sample of SWNTs contains a range of diameters, this variability of nanotube band gap adds com-
plexity to electronic design.
For semiconductor nanomaterials the situation is different. A detailed study of the effect of di-
mensionality on confinement in InP nanodots and nanowires (Yu et al. 2003) showed that the size
dependence of the band gap in wires is weaker than in dots by the amount expected from simple theory.
However, the absolute band-gap shifts in InP nanodots (ΔEg ≈ 1/d 1.35) and nanowires (ΔEg ≈ 1/d 1.45) did
not follow the particle-in-a-box prediction (i.e., 1/d 2) (Efros and Rosen 2000), demonstrating that ac-
curate treatment of confinement requires higher-order calculations to account for band structure (Law
et al. 2004).
As can be seen in Figures 1.4 and 1.5, the decrease of particle size is also accompanied by a strong
change of optical properties. In fact, we observe strong transformations in both absorption and photolu-
minescence spectra. The absorption energy of quantum dots is shifted to higher frequency with decreas-
ing diameter of the dots, with a dependence of 1/r 2. This is readily observed from the reflected colors of
quantum dots with varying diameters, shifting from blue to red with increasing size. With decreasing
Figure 1.4. UV/vis absorbance spectra of ZnO sols. Dashed lines show the procedure to determine
1/2 for a particle size of 27 Å. (Reprinted with permission from Meulenkamp 1998. Copyright 1998
American Chemical Society.)
Figure 1.5. Photoluminescence spectra of ZnS nanoparticles and ZnS clusters in zeolite Y (ZnS/Y).
For photoluminescence spectral measurement of ZnS nanoparticles, the excitation at exc = 280 nm
was used. (Reprinted with permission from Chen et al. 1997. Copyright 1997 American Institute of
Physics.)
size, the position of both surface plasmon adsorption and the fluorescence peak are shifted to shorter
wavelengths as well (see Figure 1.5). For the smallest of metallic nanoclusters, with dimensions ca. <2
nm, the surface plasmon absorption disappears. Since so few atoms comprise discrete nanoclusters of
this size, the spacing between adjacent energy levels becomes comparable to the thermal energy kT—
especially at lower temperatures and smaller nanocluster diameters (Fahlam 2007).
Mechanical properties are size-dependent as well. Many of the mechanical properties of nano-
materials are different from those of the bulk materials, including hardness, elastic modulus, fracture
toughness, scratch resistance, and fatigue strength, among others. One of the most familiar mechanical
phenomena involving size dependency is the Hall-Petch effect, which is characteristic of polycrystalline
solids (Law et al. 2004). The yield strength and hardness of a microstructured polycrystalline mate-
rial typically increase with decreasing grain size, owing to the progressively more effective disruption
of dislocation motion by grain boundaries. However, studies on solids composed of nanoscale grains
suggest that the Hall-Petch relation breaks down at a critical grain size, below which a material softens.
Atomistic modeling carried out by Schiotz and Jacobsen (2003) points to a transition from dislocation-
mediated yielding to grain boundary sliding at very small crystallite sizes as the primary explanation for
the anomalous maximum in the strength of metallic polycrystalline solids.
Phonon transport is expected to be greatly impeded in nanomaterials (i.e., d < Δ, where d is the
diameter and Δ is the phonon mean free path), due to increased boundary scattering and reduced
phonon group velocities stemming from phonon confinement (Law et al. 2004). Detailed models of
phonon heat conduction in cylindrical (Zou and Balandin 2001) and rectangular (Lu et al. 2003)
semiconducting nanowires predict a large decrease (>90%) in the lattice thermal conductivity of wires
that are tens of nanometers in diameter. Size-dependent thermal conductivity in nanostructures presents
a major hurdle in the drive toward miniaturization in the semiconductor industry. However, poor heat
transport is actually advantageous for thermoelectric materials.
These interesting phenomena occurring at this nanometer length scale are of interest to physicists,
chemists, biologists, electrical and mechanical engineers, and computer scientists, making research in
nanotechnology a frontier activity in materials science. The study of such nanomaterials creates great
opportunities for fundamental science in condensed-matter physics, solid-state chemistry, materials sci-
ence, electrical engineering, biology, and other disciplines. Nanoscience closes the gap between indi-
vidual atoms and bulk materials.
It is a mistake to think that nanomaterials are just ordinary materials in the form of nanopar-
ticles. As we will show in this volume, nanomaterials do not represent just one universal material; they
encompass a very wide range of different materials. Among nanomaterials are fullerenes (Chapter 3);
one-dimensional metal oxide structures (Chapter 2); metal and metal oxide nanoclusters and nanopar-
ticles (Chapter 4); and porous and mesoporous semiconductors and metal oxides (Chapters 5, 6, and
7). Among them are also included composites with components formed from nanomaterials (Chapter
8). The geometry of nanomaterials can be a variety of shapes (sphere, wire, rod, tube, ring, etc.) and is
dependent on the synthesis method (see Figure 1.6).
The basic composition of nanocomponents can be either organic (dendrimers, polymers, etc.),
inorganic (metals, metal oxides, metal hydroxides, etc.), carbon (carbon nanotubes, fullerenes, etc.), or
a combinations of these materials. In addition, more complex systems are possible if surface function-
alization is used to control surface charge and interactions (Rosei 2004; Suh et al. 2009). As follows
from the above-mentioned listing, many nanomaterials are not just separate particles; in many cases
they represent complicated microobjects, which are nanostructured on the surface or in the volume.
So, among nanomaterials we can find materials which have structured components with at least one
dimension, two dimensions, and three dimensions less than 100 nm. Materials that have one dimension
in the nanoscale (and are extended in the other two dimensions) are layers such as a thin films or sur-
face coatings. Materials that are nanoscale in two dimensions (and extended in one dimension) include
nanowires and nanotubes. Materials that are nanoscale in three dimensions are particles, for example,
precipitates, colloids, and quantum dots (tiny particles of semiconductor materials). Nanocrystalline
materials made up of nanometer-sized grains also fall into this category (properties of these kinds of
nanomaterials are discussed in Volume 1 of this series).
2. A BRIEF HISTORY OF NANOTECHNOLOGY
The term nanotechnology was first suggested in 1974 by N. Taniguchi. The first report about creation
of these new materials was published in 1985 (Kroto et al. 1985). In this report was announced the
discovery of a new type of carbon compound in nature—the fullerenes (C60). In 1996 the Nobel Prize
was awarded for this discovery. The first carbon nanotubes were created in 1991 (Iijima 1991). The
first National Nanotechnology Initiative was announced in the United States in 2000 (http://nano.
gov). Thus, one can see that we are at the beginning of a new era in materials science. However, the

Figure 1.6. ZnO nanostructures synthesized by thermal evaporation of solid powders: (a) nano-
combs; (b) tetraleg; (c) hexagonal disks; (d) nanopropellers; (f) nanospirals; (g) nanosprings; (h)
single-crystal nanoring; (i) combination of rods, bow, and ring. (Reprinted with permission from Wang
2005. Copyright 2005 Royal Society of Chemistry.)
publication of this book, as well as the appearance of many others (e.g., Nalwa 2004; Koehler and
Fritzsche 2004; Gogotsi 2006; Bhushan 2007; Hornyak et al. 2008) dedicated to various aspects of syn-
thesis, study, and application of nanomaterials in different fields means that even in such a short period
of time it has been possible to take a considerable step forward and obtain impressive results. According
to some forecasts, by the year 2015 the cost of nanotechnological production should exceed $1 billion
dollars (Kohler et al. 2005; Bhushan 2007).
Among other important discoveries in nanotechnology development, one can also note the inven-
tion of the scanning tunnel microscope (STM) in 1982 (Bennig and Rohrer 1982) and the scanning
atomic power microscope in 1986 (Bennig et al. 1986; Noble Prize in 1992). These new microscopes
allowed observation of the atomic-molecular structure of monocrystal surfaces in the nanometer size
range. It has also turned out that these new microscopes are useful not only in study of the atomic-mo-
lecular structure of substance (Adam et al 2006; Sugimoto et al., 2008); they have also found application
in the construction of nanostructures. The atom (molecule) manipulation used in this process is il-
lustrated schematically in Figure 1.7. In this process, the tip of the microscope is positioned above the
adsorbate (atom or molecule) and then brought to approach the surface (to a distance of 0.2–0.4 nm),
until a bond is formed between the tip and the adsorbate. The tip “feels” atoms as increases in current.
The bond between the atoms and the tip must be strong enough that the adsorbate follows the move-
ment of the tip parallel to the surface.
At present, three main parameters can be adjusted to manipule atoms/molecules on surfaces using
the STM:
• The electric field between the tip and the sample

• The tunneling current of the electrons (increasing the current creates a bond between the tip and
the atom and therefore allows the atom to be moved)
• van der Waals or chemical forces that act between the tip and the sample and that can be adjusted
by varying the tip–sample separation
In working with single atoms or molecules, one distinguishes between lateral and vertical manipula-
tion. Lateral manipulation means that the particle is moved with the tip along the surface to the desired
position, without losing contact with the surface. Vertical manipulation means that the particle is picked
up by the tip and moved, on the tip, to the desired position. There it is dropped back to the surface.
While only the forces between tip and sample are important for reliable lateral manipulation, the electric
field and the tunneling current play important roles in vertical manipulation.
These techniques have made it possible to build up artificial nanostructures at the atomic scale. The
technical demands in using the STM in this way are high: It must be possible to control the tip position
in the range of fractions of an atom’s size. Also, stability against drift must be so high that it is possible
to work with a built-up artificial structure for days. Because of the thermal mobility of most adsorbates,
the STM has to work at low temperatures (down to 4 K).
In this volume we will not be discussing the opportunities to use these microscopes for the fabrication
of chemical sensors. However, since new technologies are being developed very quickly, we expect that in
the near future, technologies of self-organization (Scanlon and Aggeli 2008) and manipulation of nano-
structures will become an important part of the manufacture of nano- and micro-scale chemical sensors.

Tip Tip

Atom
(adsorbate)
Substrate

Figure 1.7. Operation and manipulation of atoms by STM.
3. WHAT DISTINGUISHES NANOMATERIALS FROM

BULK MATERIALS?
As we indicated earlier, while most microstructured materials have similar properties to the correspond-
ing bulk materials, the properties of materials with nanometer dimensions are significantly different
from those of atoms and bulk materials. Among the characteristics of nanomaterials that distinguish
them from bulk materials, it is important to note the following: (1) large fraction of surface atoms; (2)
high surface energy; (3) spatial confinement; (4) reduced numbers of imperfections that do not exist in
the corresponding bulk materials (Cao 2004).
The use of nanomaterials provides the following advantages. First, all nanomaterials consist of very
small particles. This is the first advantage of nanomaterials and nanotechnologies, promoting attainment
of superminiaturization. Because they are small, nanostructures can be packed very closely together. As
a result, on a given unit of area one can locate more functional nanodevices, which is very important for
nanoelectronics. Their high packing density has the potential to bring higher area and volume capacity
to information storage and higher speed to information processing (because electrons require much less
time to move between components). Thus, new electronic device concepts, smaller and faster circuits,
more sophisticated functions, and greatly reduced power consumption can all be achieved simultane-
ously by controlling nanostructure interactions and complexity.
Second, because of their small dimensions, nanomaterials have large specific surface areas, accelerat-
ing interactions between them and the environment in which they are located. For example, nanopar-
ticles with a radius of 2.5 nm and a density of 5 g cm–3 have a surface of 240 m2 g–1 when assuming a
ball-like shape. For comparison, a dense (compact) material with a weight of 1 g and the same density
has a surface area of 2 × 10−6 m2. Thus, nanoparticles have a much larger surface area per unit of mass
compared with larger particles. Because growth and catalytic chemical reactions occur at surfaces, this
means that materials in nanoparticle form will be much more reactive than the same mass of material
made up of larger particles.
A strong increase in the participation of surface atoms in the physical and chemical properties of
nanomaterials is another consequence of a decrease in particle size. It is known that the volume of an ob-
ject decreases as the third power of its linear dimensions, but the surface area decreases only as its second
power. Therefore, when materials are in the form of nanoparticles, their surface area-to-volume ratio,
i.e., the ratio between surface and bulk atoms, increases. This effect is especially strong when the sizes of
nanomaterials are comparable to the Debye length (Ogawa et al. 1982; Luth 1995). Simple calculations
show that a particle of size 30 nm has 5% of its atoms on its surface; at 10 nm, 20% of its atoms; and at
3 nm, 50% of its atoms (Royal Society 2004) (see Figure 1.8).
It is known that atoms on the surface of nanoparticles have unusual properties, and (relatively
speaking) there are a lot of them. These surface atoms make nanoparticles very different from just small
particles, because not all bonds of surface atoms with neighboring atoms are enabled. For atoms on
uneven surfaces, nonsaturation of the bonds is even higher. For this reason, corner atoms normally have
the highest affinity to form bonds to adsorbate molecules, followed by edge and in-plane surface atoms,
a fact that is of great importance for catalytic activity. Alternatively, because of their low stabilization
due to low coordination, edge and in particular corner atoms are often missing on single crystals, even
in thermodynamic equilibrium (Roduner 2006). Recently, size-dependent variation in oxidation state
Figure 1.8. Surface/volume ratio as a function of particle size. (Reprinted with permission from
Burda et al. 2005. Copyright 2005 American Chemical Society.)
and lattice parameter has been reported for cerium oxide nanoparticles (Deshpande et al. 2005) (see
Figure 1.9).
As a result of the changes that occur in particles with a decrease of particle size, nanomaterials
can have extremely high biological and chemical reactivity (Eustis and El-Sayed 2006). For example,
catalytically active nanomaterials allow accelerating either chemical or biochemical reactions by tens of
Figure 1.9. Semilog plot of lattice parameter as a function of particle size. (Reprinted with permis-
sion from Deshpande et al. 2005. Copyright 2005 American Institute of Physics.)
thousands, and even a million times. This attribute explains even 1 g of nanomaterial can be more effec-
tive than 1 ton of a similar but macro substance. As will be shown later, the high chemical and catalytic
activity of nanomaterials opens up fundamentally new opportunities for elaboration next-generation
chemical sensors.
Another aspect we must consider is that the free surface is a place of accumulation (sink) of crystal-
lographic defects. At small particles sizes, the surface concentration of such defects increases consider-
ably. Classical calculations of van Hardeveld and Hartog (1969) showed that the largest changes of pro-
portions between facets, edges, corners, and microdefects at the surface occur between 1 and 5 nm. As a
result, strong lattice distortion and even a change of lattice type can take place on the surface layer (see
Figure 1.10). In fact, due to accumulation of structural defects and chemical impurities on the surface,
we can observe purification of the bulk area of the nanoparticles.
An important specific characteristic of nanomaterial properties (we mean here polycrystalline ma-
terials with grain size less than 40 nm) is an increase of the role of interfaces with decrease of the size of
grains or crystallites in nanomaterials. Experimental research has shown that the state of grain boundaries
has a nonequilibrium character, conditioned by the presence of the high concentration of grain boundary
defects. This nonequilibrium is characterized by extra energy of the grain boundaries and by the presence
of long-range elastic stress (see Figure 1.10). At the same time, the grains have ordered crystallographic
structure, while the grain boundary defects act as a source of elastic strains. Nonequilibrium of the grain
boundaries initiates the occurrence of the lattice distortion, the change of interatomic distances, and the
appearance of sufficient displacement of atoms, right up to loss of an ordered state.
Another important factor peculiar to nanoparticles is their tendency to aggregation. The possibility
of migration (diffusion) of either atoms or groups of atoms along the surface and the boundaries, as well
Figure 1.10. Semilog plot of lattice strain as a function of particle size. (Reprinted with permission
from Deshpande et al. 2005. Copyright 2005 American Institute of Physics.)

CriticalMagneticSingleDomainSize
ExcitonDiffusionLengthinPolymers
PhononMeanFreePath
Exciton BohrRadius
DebyeScreeningLength
FermiWavelengthinMetals
0.1 1.0 10 100 1000

Characteristic Length, nm
Figure 1.11. A few characteristic length scales for condensed systems at 300 K. (Data from Law et
al. 2004.)
as the presence of attractive forces between them, often leads to processes of self-organization into vari-
ous cluster structures. This effect has already been used for creation of ordered nanostructures in optics
and electronics.
One more important aspect of nanomaterial properties is connected with the fact that, during
transport processes (diffusion, electro- and thermal conductivity, etc.), there are certain effective lengths
of free path of a carrier of this transport (Le ), such as phonon and electron mean free paths, the Debye
length, and the exciton diffusion length for certain polymers (see Figure 1.11). While proceeding to sizes
smaller than Le, transport speed starts to depend on both the size and the shape of the nanomaterial;
generally, the transport speed increases sharply. For example, in some cases the length of the electron free
path can be considered as Le. As can be seen in Figure 1.11, chemically synthesized nanowires 5–100 nm
in diameter allow experimental access to a rich spectrum of mesoscopic phenomena.
Nanomaterials are unique because these substance exist in a specific “nanosize” state. The prin-
cipal characteristics of nanomaterials are conditioned by not only by their small the size, but also by
the appearance of new quantum mechanical effects in a dominating role at the interface (Esaki 1991;
Gimzewski and Welland 1995; Serena and Garcia 1997; Ciraci et al. 2001). Those quantum size effects
occur at a critical size, which is commensurate with the so-called correlative radius of one or another
physical phenomena, for example, with the length of the free path of electrons or photons, the length
of coherence in a superconductor, sizes of magnetic domains, and so on. As a rule, quantum size effects
appear in materials with crystallite sizes in the nanorange D < 10 nm. As a result, in nanomaterials with
characteristic size, one can expect the appearance of effects which cannot be observed in bulk materials.
In particular, quantum effects may appear in the form of an oscillating change of electric properties—
for example, conductivity—or the appearance of new energetic states for electrons (see Figure 1.12). At
nanoscale dimensions the normally collective electronic properties of the solid become severely distort-
ed, and the electrons at this length scale tend to follow the ‘‘particle-in-a-box’’ model, so that they often
require higher-order calculations to account for band structure (Law et al. 2004). The electronic states
are more like those found in localized molecular bonds than in macroscopic solids. The main implica-
tion of this confinement is a change in the system total energy, and hence the overall thermodynamic
stability. These effects thus create conditions for the elaboration of chemical sensors based on entirely
new principles.
Absence of point defects is another characteristic property of some nanomaterials, such as nano-
tubes. For example, because of the absence of point defects, individual carbonic nanotubes have strength
that exceeds the strength of the best steel. At the same time, they are much lighter in weight than steel,
such that nanotubes may be 6 times lighter in weight and 50–100 times stronger than steel.
4. NANOMATERIALS MANUFACTURING
The synthesis, characterization, and processing of nanostructured materials are part of an emerging and
rapidly growing field (Hullmann 2006). As we will show, a variety of dry and wet technologies can be em-
ployed in the manufacture of nanomaterials (Edelstein and Cammarata 1998; Knauth and Schoonman
2002; Cao 2004; Rao et al. 2004; Grimsdale and Müllen 2005; Bochenkov and Sergeev 2005; Lu et
al. 2006; Bhushan 2007; Weber et al., 2008). As shown in Figures 1.13 and 1.14, there are two ap-
proaches to nanomaterial manufacturing. Using top-down methods, manufacturers selectively modify
the starting material, much as an artist creates a sculpture from a slab of marble. Top-down manufactur-
ing, perfected by the semiconductor industry over the last 30 years, involves precision engineering and
lithography to grind or cut bulk materials into tiny pieces and to etch or print nanoscale patterns onto
them. Photolithography and electron-beam lithography are examples of top-down approaches that are
used extensively in the semiconductor industry to fabricate electronic integrated circuits. The top-down
Size
Figure 1.12. Schematic of electron-level transforma-

tion, starting from discrete levels of atoms forming
a molecule having bonding and antibonding levels
to “bulk crystal” with continuous bands. (Reprinted
with permission from Alivisatos 1997. Copyright 1997
Elsevier.)
Nanomaterials manufacturing

Bottom-up approach Top-down approach
Chemical Self- Positional Lithography Cutting, etching,

synthesis assembly assembly (el.; photo) grinding

Particle, Crystals, Experimental Electronic Precision
clusters, films, atomic or devices chip engineered

molecules tubes molecular devices masks surfaces
Figure 1.13. Technological approaches used for nanomaterial manufacturing.
approach limits the dimensions of devices to what is technically achievable using lithography, however.
At present, lithographic techniques can create device features as narrow as 130 nm, and the industry
sees the road ahead pretty well drawn up for line widths down to ~50 nm. This continued progress does
not come without a price, however; the cost of new fabrications is growing extremely quickly, at a pace
that may limit continued progress simply because devices and circuits may become too expensive to be
economically viable (Samuelson 2003).
Using the bottom-up method, fabricators seek to build larger and more complex systems based
on small functional building blocks. This approach is based on using growth methods such as atom by
atom, layer by layer, or molecule by molecule (Harry et al. 2006). Bottom-up manufacturing assembles
“Top-down” “Bottom-up”
Nanomaterials Molecular
precursors (<<1 nm)
•
• •
• • •• ••
• ••• ••
•
• • • •
••
••
Ball-milling,
Chemical synthesis
Lithography/etching
Figure 1.14. Comparison of “top-down” and “bottom-up” approaches to nanomaterials preparation

(synthesis).
nanostructures from scratch through conventional chemical synthesis, self-assembly (harnessing natural
physical or chemical bonding to assemble structures, like crystal formation), and positional assembly
(in which atoms or groups are manipulated individually into a structure) (Dowling 2004). Presently,
atoms, molecules, clusters, and nanoparticles can be used as functional building blocks for fabricating
advanced and totally new phases of condensed matter on the nanometer length scale. There is only one
requirement to these blocks: They must have the ability to self-assemble spontaneously when a chemical
or physical trigger is applied. There are many organic and inorganic materials which have self-assembly
properties that can be exploited by properly devised design features to build structures with controlled
configurations (Smith et al. 2006; Scanlon and Aggeli 2008). One examples of this approach is shown
in Figure 1.15.
The assembly of components into functional devices is amenable to diverse approaches, from micro-
fabrication techniques to self-assembled chemical methods. The optimal size of the unit components
that participate in self-assembly depends on the particular property to be engineered: By altering the
dimensions of the building blocks and controlling their surface geometry, chemistry, and assembly, it is
possible to tailor functionalities in unprecedented ways (Rosei 2004). In the case of devices comprising
a single molecule or processed from a single crystal (e.g., single polymers, certain microfabricated struc-
tures, grafted polymeric structures, or precipitated particulates), assembly is often not an issue. However,
integration of multiple, individually microfabricated components is periodically necessary and may at
times drive the need for assembly, even for silicon- and other semiconductor-based devices. Indeed, for
semiconductor and polymeric devices, standard top-down techniques can sometimes be employed in
concert with bottom-up device assembly methods to achieve better and/or more efficient device con-
struction approaches, and in some instances this combination of approaches may be the only feasible

Figure 1.15. Example of self-assembly of colopymer blocks containing hydrophobic and hydrophilic
parts. (Idea from Smith et al. 2006.)
way to create a device. Furthermore, many hybrid nanodevices contain multiple, chemically diverse
components that must be precisely assembled to sustain their functional, cooperative contributions to
device performance (Smith et al. 2006).
In addition to various chemical methods of synthesis, in the frame of the bottom-up approach a va-
riety of vacuum deposition and nonequilibrium plasma chemistry techniques are used to produce nano-
structured films, layered nanocomposites, and nanotubes. Atomically controlled structures are produced
using molecular-beam epitaxy and organometallic vapor-phase epitaxy. Various wet chemical routes are
used for synthesis of one-dimensional structures and nanosize powders.
Although bottom-up processes are less developed and understood, they hold great promise for the
future. These new techniques allow us to mimic nature and self-assemble nanowire materials and devices
at extremely downscaled dimensions, making it as easy to fabricate a 5-nm as a 200-nm nanoelectronic
device (Samuelson 2003). There is, however, a significant obstacle along this path to device fabrica-
tion—namely, that the requirement for self-assembly is very different from that for device utilization.
Self-assembly requires mobility, whereas device utilization requires stability. More detailed discussion of
this problem has been given by Harry et al. (2006).
5. NANOTECHNOLOGY AND ITS POSSIBILITIES
Nanotechnology is a brainchild of modern fundamental science. It is a very complicated professional

area, uniting the efforts of professionally qualified chemists, physicists, mathematicians, materials sci-
entists, physicians, computer scientists, and so on. Nanotechnology in general comprehension is not
“a technology” but “a set of technologies,” yielding a set of technical breakthroughs that will seep into
many different markets. For example, in the world of nanotechnology one can identify three broad
branches: nanomaterials, nanodevices, and nanotools (Kohler et al. 2005). Nanotools include fabrica-
tion techniques, analysis and metrology instruments, and software for nanotechnology research and
development.
There is no doubt that a nanotechnology will require extensive human investment for many long
years ahead. Nanotechnology will be a strategic branch of science and engineering in the coming decades,
which will fundamentally restructure the technologies used in manufacturing, medicine, defense, energy
production, environmental management, transportation, communications, computing, and education.
Already, recent achievements in nanotechnology testify to the opportunities to create new generations
of functional materials (Rosei 2004). For example, metallic/magnetic nanoparticles and quantum dots
may be used in quantum electronics for storing individual bits of information or as biological transport
for targeted drug delivery, providing enhanced drug efficacy and reduced toxicity. Iron, cobalt, or iron
oxide nanoparticles and several other magnetic nanoparticles and alloys are also promising candidates
for application in the medical treatment of cancer, magnetic storage, and magnetic resonance spectros-
copy. Engineering better medicine represents a grand challenge that will allow us to diagnose diseases
at an early stage and provide optimal treatment to individual patients. Many of the applications in this
area may not be realized for 10 years or more (owing partly to the rigorous testing and validation regimes
that will be required). In the much longer term, the development of nanoelectronic systems that can
detect and process information may lead to the development of an artificial retina or cochlea (Dowling
2004). Of course, achievement of this objective will require additional advances in nanosensors and
nanodevices, genomics, and bioinformatics (Bailey et al. 2004).
Nanoelectronic devices based on new nanomaterials systems and new device structures will con-
tribute to the development of a next generation of nanophotonics as well as micro- and nanoelectronics
(Samuelson 2003; Harry et al. 2006; Robertson 2007). For example, because of their high electronic
mobility, structural flexibility, and capability of being tuned from p-type to n-type conductivity by the
application of a gate voltage, grapheme and carbon nanotubes are considered a potential breakthrough
in terms of carbon-based nanoelectronics. We need to note that single-electron transistors (Tans et al.
1997; Postma et al. 2001) and field-effect transistors (Tans et al. 1998; Martel et al. 1998; Keren et al.
2003) based on single-wall carbon nanotubes have already been designed. Prototype simple logic circuits
of carbon nanotubes have already been demonstrated (Rueckes et al. 2000; Bachtold et al. 2001; Collins
et al. 2001; Derycke et al. 2001). Further, nanotechnology was also expanded extensively to other fields
of interest due to the novel properties of nanomaterials discovered and to be discovered. For example,
nanowires have started to be used in nanophotonics, laser, solar cells, resonators, and high-sensitivity
sensors. Quantum dots and the electrons that can be trapped in their discrete energy levels are of great
interest for quantum information processing. The spin state of these trapped electrons could act as carri-
ers of quantum information or “qubits” (Robledo et al. 2008). Nanoparticles are remarkable candidates
for application in functional coatings, energy storage, and as catalysts (Eustis and El-Sayed 2006). For
example, recently synthesized TiSi2 nanobelts show excellent results during photosplitting of H2O into
H2 and O2 upon the absorption of visible light. Therefore, nanomaterials such as TiSi2 nanonets might
be attractive for energy-harvesting applications such as H2 production from solar energy. Nanostructured
thin films can be used in light-emitting devices, high-efficiency displays, and photovoltaics (Law et al.
2004; Kim et al. 2008). The nanorods in solar cells function as additional light absorbers and charge-
separation interfaces. Lasers and light-emitting diodes (LED) from both quantum dots and quantum
wires are very promising for the future of optoelectronics as well.
Carbon nanohorns provide a unique combination of strength, electrical conductivity, high surface
area, and open gas paths, making them an ideal next-generation electrode for various fuel-cell applica-
tions. Carbon nanotubes are also being considered as a possible material for the storage of hydrogen
(Atkinson et al. 2001; Zandonella 2001), and they make excellent tips for scanning probe microscopes.
Silicon nanoparticles have been shown to dramatically expand the storage capacity of lithium-ion batter-
ies without degrading the silicon during the expansion/contraction cycle that occurs as power is charged
and discharged. Zinc, zinc oxide, and silver nanoparticles can be used as antimicrobial, antibacterial,
antibiotic, and antifungal agents when incorporated in coatings, fibers, polymers, first-aid bandages,
plastics, soap, and textiles. Tungsten oxide nanoparticles are being used in dental imaging because they
are sufficiently radioopaque (impervious to radiation) for high-quality x-ray resolution. Nanocrystalline
zinc selenide, zinc sulfide, cadmium sulfide, and lead telluride are candidates for the next generation
of light-emitting phosphors. Fluorescent nanoparticles are being used by biologists to stain and label
cellular components (Bailey et al. 2004). By changing the size of the quantum dot, the color emitted
can be controlled. With a single light source, one can see the entire range of visible colors, an advantage
over traditional organic dyes. Nanosized titanium dioxide and zinc oxide are currently used in some sun-
screens, because they absorb and reflect UV rays and yet are transparent to visible light, and so they are
more appealing to consumers (Dowling 2004). Nickel–metal hydride batteries made of nanocrystalline
nickel and metal hydrides are envisioned to require less frequent recharging and to last longer because of
their large grain boundary (surface) area (Royal Society 2004). Nanotechnology may offer non–energy-
intensive solutions to water desalination and purification. About one-sixth of the world’s population
does not have sufficient access to water, and over one-third of the people today suffer from poor sanita-
tion due to unavailability of water. In fact, more deaths are caused by the lack of clean water than by
wars. Nanoporous membranes or fibers can be designed to filter out salt, pollutants, and bacteria from
sea water, recycled water, or any available water source.
These are only a few of the fastest-developing nanotechnologies; numerous other potential applica-
tions of nanomaterials have already been or will be discovered. The new concepts of nanotechnology
are so broad and pervasive that they may be expected to influence science and technology in ways that
are currently unpredictable. For example, over the last decade, nanomaterials have been highlighted as
promising candidates for application in regenerative medicine to replace traditional tissue engineering
materials. Unique properties of nanomaterials have helped to improve the growth of various tissues over
what is achievable today. Zhang and Webster (2009) have shown that nanomaterials can be used for
bone, cartilage, vascular, neural, and bladder tissue engineering applications as well.
6. NANOTECHNOLOGY: FUTURE TRENDS
As we have shown, nanotechnology has already produced great achievements in design of new func-
tional materials and devices. We anticipate even greater progress in the future. However, we have to
admit that every next step will require greater combined efforts by thousands of highly skilled scientists
and engineers, and greater financial investments in expensive fundamental research. This fundamental
research must answer a huge number of questions, including the following:
• Is there a sharp boundary between the bulk state of a substance and the nanocrystalline state?
How fast does the transformation occur, and at what stage of atomic association is the formation
of one or another property of bulk crystals completed? Is there some critical grain or particle size
below which the properties that are characteristic of nanocrystal become apparent and above
which the properties of bulk material occur?
• What new and novel quantum properties will be enabled by nanostructures, especially at room
temperature?
• How will the use of nanomaterials influence human health? Do nanomaterials bioaccumulate?
What is the fate, transport, and transformation of nanosized materials after they enter the
environment? What is the danger of exposure via skin absorption, ingestion, or inhalation
(Fahlam 2007)?
The greater specific surface area of nanoparticles may lead to increased rates of absorption
through the skin, lungs, or digestive tract and may cause unwanted effects to the lungs as well
as other organs. However, the particles must be absorbed in sufficient quantities in order to
pose health risks (Lauterwasser 2007). As of now, in the realm of occupational health, much
is unknown about the ways in which people may be exposed to nanomaterials during their
manufacture and use in the workplace, and the potential health implications of such exposure.
Therefore, estimation of the potential health risks associated with these new materials requires
understanding of the mechanisms of ill health, identification of some property or metric of the
material which relates exposure to the material to health risk, and some method for measuring
exposure in relation to that metric (Royal Society 2004; Borm et al. 2006; Weyer, et al. 2009;
Zhang and Webster 2009). We suspect that the environmental and health hazards of nanomate-
rials will prove no more serious or difficult to manage than those of existing particulate sources
such as diesel exhaust or asbestos. However, ignoring or dismissing outright the concerns of the
public in this or any other area of emerging technology is socially irresponsible, unbalanced sci-
ence (Law et al. 2004).
• Why do nanocomponents show increased catalytic activity in specific reactions in a narrow range
of sizes?
For example, the gold has maximum catalytic activity to CO low-temperature oxidation at
a particle size of ~3 nm (Valden et al. 1998). The highest ethanol selectivity of Rh-based cata-
lyst during ethanol synthesis by CO2 hydrogenation was obtained when the size of Rh particles
was about 2.5 nm (Kusama et al. 1997). High selectivity of catalytic activity is also typical for
nanoparticles of such well-known catalysts as palladium, platinum, nickel, and cobalt (see Figure
1.16) (Bezemer et al. 2006; Villani et al. 2006; Weber et al. 2006; Zhou and Lee 2008; Hoxha et
al. 2009).
Such high sensitivity of catalytic activity to the sizes of small particles shows the importance
of developing specific methods and techniques suitable for synthesis and deposition of nano-
particles accurate to several atoms or several decades of atoms. A very narrow distribution of
nanoparticle sizes is necessary not only for heterogeneous catalysis but also for chemical sensor
Figure 1.16. Influence of cobalt particle size on activity in the Fischer-Tropsch reaction normalized
to the cobalt loading (220°C). (Reprinted with permission from Bezemer et al. 2006. Copyright 2006
Americal Chemical Society.)
elaboration. As is known, the incorporation of catalytically active additives to the gas-sensing

matrix is one of the main approaches to improving their exploitation parameters (see Volume 1
of this series).
• How can we communicate signals from the nanoscale to the macroscopic world? (Fahlam 2007).
• How can stabilization of the size and shape of nanoparticles, which have a tendency to agglomer-
ate and coalesce, be attained (Born et al. 2006)?
Considering these yet-unanswered questions, one can conclude that in spite of the progress that
has been achieved, nanotechnologies and nanomaterials cannot resolve all our problems; and their de-
velopment will take time even under the conditions of the “nanotechnology race” that is now occurring
all over the world. For example, early publications included some sensational results and conclusions.
Primarily, these concerned potential opportunities to change radically the properties of substances and
materials by transition to the nanostate. Hopes were very high. Many published articles included such
phrases as “the astonishing new science that will transform the world,” or “nanotechnology will change
the future of your business.” It was expected that, by determining the novel properties of materials and
systems at the nano scale, nanotechnology could affect the production of virtually every human-made
object—everything from automobiles and tires to computer circuits, to advanced medicines and tissue
replacement—and lead to the invention of objects yet to be imagined. However, accurate research has
shown that many results testifying to unusual properties of nanomaterials were connected not with the
decrease of the particle sizes, but with large amounts of impurities such as oxygen, nitrogen, hydrogen,
as well as with large areas of interface, and the structure’s nonequilibrium. In addition, it turned out
that, in producing devices from nanomaterials, it is very difficult to keep grain size small and attain the
desired effect.
Difficulties in manipulation of nanosized objects also appeared. For example, to fabricate the struc-
tures shown in Figure 1.17, we need to cut, separate, select, put, and fix nanowires on a certain place
and then make electrical contact with an electrode. For these procedures it is necessary to elaborate

Figure 1.17. SEM micrographs of structure for transport measurements of ZnO nanowires. (Reprinted
with permission from Heo et al. 2004. Copyright 2004 Elsevier.)
fundamentally new technological and measuring equipment (Mamalis 2007). Nor will nanotechnol-
ogies be incorporated into products and devices without the development of scalable, cost-effective
manufacturing techniques that retain and preserve the properties of the nanoscale material in the final
product. For example, researchers over the past few years have demonstrated electronic devices that are
faster and smaller but that are quite often characterized by fundamentally different (and possibly better)
operational characteristics than existing technologies (Samuelson 2003). However, existing technologies
follow well-established manufacturing paradigms known as a “top-down” approach, while nanoscience
is typically based on a bottom-up approach. Herein lies the primary challenge in the development of
nanotechnology: A chemically fabricated transistor, no matter how good it is, cannot just be slipped
into the next generation of microprocessors. Such a transistor would not be compatible with top-down
manufacturing (Heath 1999).
Another outstanding scientific challenge that needs to be addressed urgently is the integration
and interfacing problem (Law et al. 2004). The ability to create high-density arrays is not enough:
How to address individual elements in a high-density array and how to achieve precise layer-to-layer
registration for vertical integration are just two of the many challenges still ahead. Equally important is
precise control of the size uniformity, dimensionality, growth direction, and dopant distribution within
semiconductor nanostructures, as these structural parameters will ultimately dictate the functionality
of the nanostructures. In particular, the physical significance of the dopant distribution and the inter-
facial junction, and their implications in device operation and performance, will likely require careful
reexamination and/or redefinition at the nanometer-length scale. Lastly, accurate theoretical simulations
appropriate to the above-mentioned mesoscopic regime are becoming feasible with the enhanced com-
puting power available and should assist our understanding of many of these size- and dimensionality-
controlled phenomena (Law et al. 2004).
Moreover, potential products and applications will not be realized unless there is a market for them
(Royal Society 2004). Therefore, nobody can predict the time when the potential of nanotechnology
will be realized completely. It is really difficult to give a detailed time scale, because most of elaborations
are at such an early stage of development. However, the whole promise of nanoscience is that it will
eventually produce a bottom-up manufacturing paradigm for the inexpensive fabrication of electronic
devices, sensors, motors, etc. Such a paradigm may allow for the fabrication of mesoscopically complex,
atomically precise, true three-dimensional architectures (Heath 1999).
Thus, admitting that the technologies falling under the umbrella term “nanotechnology” have the
chance to transform many aspects of our lives, we have to evaluate sensibly the opportunities in nano-
materials and nanotechnologies. We also should not have big expectations for their use. Perhaps some
applications may never be realized, whereas unanticipated scientific breakthroughs may lead rapidly to
developments not foreseen at the time of our study. Perhaps opportunities for nanotechnology in the
development of materials and technologies will have concrete limitations. For example, a nano level of
structure exists in any material, but in most of them, nanosize does not play a role in the development
of functional properties. Therefore, it is useless to turn to nanosizes in such materials.
In many ways, the future of nanotechnology will depend on the ability to engineer two- and three-
dimensional systems constructed from complex components such as macromolecules, biomolecules,
nanostructured solids, etc. No doubt the principles on which these systems are built should be based
on the principles of self-assembly or positional assemby (CRN 2005), and not on technologies based
on manipulation of individual atoms (Oyabu et al. 2003). There are several possible approaches to such
molecular manufacturing (Merrill and Sun 2009). A particularly promising nanofabrication strategy
is the use of surface chemistry to direct the assembly of one-dimensional nanostructures onto litho-
graphically patterned substrates (Law et al. 2004). By modifying the surfaces of the nanowires and the
substrate with self-assembled monolayers (SAMs), it is possible to control the attractive and repulsive
interactions that dictate where and how nanowires attach to the substrate and to each other. These inter-
actions can be of a van der Waals, hydrophobic/hydrophilic, electrostatic, or covalent nature. Mallouk
and colleagues have demonstrated the selective adhesion of thick gold nanowires to appropriately func-
tionalized gold surfaces using both electrostatic and covalent linkages in solution (Martin et al. 2002).
However, it is necessary to note that most of the possibilities discussed in numerous papers, especially
popular ones, have never been studied. Naturally, elaboration of such technologies is not a momentary
process; it is a long and complex one, which would give results only after fundamental research.
People are often not able to be patient in awaiting realization of their hopes. However, all scientific
revolutions, even with great names, are made step by step. Therefore, in spite of the fact that nanoscale
materials are already incorporated into hundreds of consumer products, including food, packaging, cos-
metics, clothing, and paint, we have to admit that to come to a real industrial-scale realization of the so-
called nano-revolution, it is necessary to wait a little. For example, Thompson and Parthasarthy (2006)
have recently considered the question of introducing nanomaterials into logic and memory devices and
suggest that 20 years may be needed to develop the necessary processes to do this economically. This
estimate was based on the time to introduce low-k dielectrics and Cu interconnects.
However, it is necessary to add that all we have said above does not apply to the field of chemical
sensors. The results presented in this series and in numerous reviews (Comini 2006; Agu et al. 2008;
Comini et al. 2008; Kauffman and Star 2008; Korotcenkov 2008; Liu 2008; Weber et al. 2008; Xiao
and Li 2008) clearly testify that the use of nanomaterials and nanotechnologies in chemical sensors
design is progressing well and has already produced considerable improvement in desired parameters.
Therefore, the development of nanomaterials and nanostructures with novel functionalities and innova-
tive properties for high-performance chemical sensing is the most promising current trend in solid-state
sensing technology. As will be shown in following chapters, nanotechnology has already reached a fairly
mature stage in nanomaterials processing, including synthesis, functionalization, and hybridization with
sensing nanodevices, to fabricate chemical sensors and sensor arrays with high sensitivity and high speci-
ficity. Nanomaterials in chemical sensors present new possibilities for controlling the properties of signal
transducers, new signal transduction technologies, new matrices for immobilization of biomolecules,
redox mediators, markers, indicators, etc., and lower detection limits.
7. ACKNOWLEDGMENTS
This work was supported by the World Class University (WCU) Program at the Gwangju Institute
of Science and Technology (GIST) through a grant (Project No. R31-20008-000-10026-0), by the
Ministry of Science and Technology (MEST) of the Korean Government, and by the Korean Science
and Engineering Foundation (KOSEF) (Grant No. 2009-0078928). G. Korotcenkov and B. K. Cho are
grateful also to the Korean BK21 Program for support of their scientific research.
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Chemical Sensors Volume 2: Nanostructured Materials

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Chemical Sensors Volume 2: Nanostructured Materials

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CONTENTS

PREFACE TO CHEMICAL SENSORS: FUNDAMENTALS OF SENSING MATERIALS xi

1 INTRODUCTION TO NANOMATERIALS AND NANOTECHNOLOGY 1

2 QUASI-ONE-DIMENSIONAL METAL OXIDE STRUCTURES: SYNTHESIS,

2.1 Vapor-Phase Growth Methods 31

3 CARBON NANOTUBES AND FULLERENES IN CHEMICAL SENSORS 87

5.5 Nanotube FETs for Detecting DNA Hybridization 108

4 SENSORS BASED ON MONOLAYER-CAPPED METALLIC NANOPARTICLES 141

3.2 Controllable Size and Shape 147

5 POROUS SEMICONDUCTORS: ADVANTAGES AND DISADVANTAGES FOR GAS

3.9 Surface Modiﬁcation of Porous Semiconductors to Improve

6 ORDERED MESOPOROUS FILMS AND MEMBRANES: SYNTHESIS, PROPERTIES, AND

7 CHEMICAL SENSORS BASED ON ZEOLITES 311

4 Zeolites as the Functional (Sensitive) Phase 322

8 NANOCOMPOSITES: FROM FABRICATION TO CHEMICAL SENSOR APPLICATIONS 335

Tarushee Ahuja (Chapter 8)

Pai-Chun Chang (Chapter 2)

Beongki Cho (Chapter 1)

Hossam Haick (Chapter 4)

Ghenadii Korotcenkov (Chapters 1 and 5)

Gregg P. Kotchey (Chapter 3)

Devendra Kumar (Chapter 8)

Jia Grace Lu (Chapter 2)

Ralf Moos (Chapter 7)

Kathy Sahner (Chapter 7)

Alexander Star (Chapter 3)

Michael Tiemann (Chapter 6)

Ulrike Tisch (Chapter 4)

1. WHAT ARE NANOMATERIALS?

Table 1.1. Characteristic dimensions of some commonplace objects

2.0 3.0 4.0 5.0 6.0

2. A BRIEF HISTORY OF NANOTECHNOLOGY

• The electric ﬁeld between the tip and the sample

3. WHAT DISTINGUISHES NANOMATERIALS FROM

0.1 1.0 10 100 1000

Figure 1.12. Schematic of electron-level transforma-

Bottom-up approach Top-down approach

Chemical Self- Positional Lithography Cutting, etching,

Figure 1.13. Technological approaches used for nanomaterial manufacturing.

Figure 1.14. Comparison of “top-down” and “bottom-up” approaches to nanomaterials preparation

5. NANOTECHNOLOGY AND ITS POSSIBILITIES

Nanotechnology is a brainchild of modern fundamental science. It is a very complicated professional

6. NANOTECHNOLOGY: FUTURE TRENDS

elaboration. As is known, the incorporation of catalytically active additives to the gas-sensing

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