Momentum Press is proud to bring to you Chemical Sensors: Simulation and Modeling Volume 1: Microstructural

Characterization and Modeling of Metal Oxides, edited by Ghenadii Korotcenkov. This is the frst of a new four-
volume comprehensive reference work that provides computer simulation and modeling techniques in various
felds of chemical sensing and the important applications for chemical sensing such as bulk and surface diffu-
sion, adsorption, surface reactions, sintering, conductivity, mass transport, and interphase interactions. In this
frst volume, you will fnd background and guidance on:
• Fundamentalsofelectrochemistryforgassensors
• Stabilizedzirconia-basedgassensors
• Ion-sensitivefeld-effecttransistor(ISFET)-basedchemicalsensors
• Microfuidicchipsasnewplatformsforelectrochemicalsensing
• Opticalandfberopticchemicalsensors
• Chemoluminscencechemicalsensingfornewapplicationsinwaterpollutioncontrol
Chemicalsensorsareintegraltotheautomationofmyriadindustrialprocessesandeverydaymonitoringof
such activities as public safety, engine performance, medical therapeutics, and many more. This four-volume
reference work covering simulation and modeling will serve as the perfect complement to Momentum Press’s
6-volume reference work, Chemical Sensors: Fundamentals of Sensing Materials and Chemical Sensors: Compre-
hensive Sensor Technologies, which present detailed information related to materials, technologies, construction,
andapplicationofvariousdevicesforchemicalsensing.Eachsimulationandmodelingvolumeinthepresent
series reviews modeling principles and approaches peculiar to specifc groups of materials and devices applied
for chemical sensing.
About the editor
Ghenadii KorotcenkovreceivedhisPh.D.inPhysicsandTechnologyofSemiconductorMaterialsandDe-
vicesin1976,andhisHabilitateDegree(Dr.Sci.)inPhysicsandMathematicsofSemiconductorsandDielec-
tricsin1990.Formanyyears,hewasaleaderoftheGasSensorGroup,andmanagerofvariousnationaland
internationalscientifcandengineeringprojectscarriedoutintheLaboratoryofMicro-andOptoelectronics,
TechnicalUniversityofMoldova.Currently,Dr.KorotcenkovisaresearchProfessorattheGwangjuInstitute
ofScienceandTechnology,RepublicofKorea.HisresearchhasincludedsignifcantworkonSchottkybarri-
ers,MOSstructures,nativeoxides,andphotoreceiversonthebaseofIII-Vscompounds.Hecontinueswith
research in various aspects of materials sciences and surface science, with a particular focus on nanostructured
metaloxidesandsolidstategassensordesign.Dr.Korotcenkovistheauthororeditorofelevenbooksandspe-
cial issues, eleven invited review papers, seventeen book chapters, and more than 190 peer-reviewed articles.
HisresearchactivitieshavebeenhonoredwiththeAwardoftheSupremeCouncilofScienceandAdvanced
TechnologyoftheRepublicofMoldova(2004)andThePrizeofthePresidentsoftheUkrainian,Belarusand
MoldovanAcademiesofSciences(2003),amongmanyothers.
ISBN: 978-1-60650-309-6
9 781606 503096
90000
www.momentumpress.net
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CHEMICAL SENSORS VoLuME 1: MICrostruCturAL CHArACtErIzAtIon
And ModELIng of MEtAL oxIdEs — Edited by ghenadii Korotcenkov, Ph.d., dr. sci.
A volume in the Sensors Technology SeriesEditedbyJoeWatson
Published by Momentum Press
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CONTENTS
Preface xiii
about the editor xvii
contributors xix
1 Microstructural characterization of tin dioxide thin filMs 1
J. Wang
Z. Jiao
M. H. Wu
C.-H. Shek
C. M. L. Wu
J. K. L. Lai
Z. W. Chen
1 Introduction 1
2 Growth and Nucleation of Thin Films 2
3 Multifractal Spectra of SEM Images of Thin Films 11
4 Microstructural Evolution of Nanocrystalline SnO
2
Thin Films 16
5 Concluding Remarks 24
6 Acknowledgments 24
References 24
2 Microstructural evolution by in-situ teM observations
and siMulations 29
Hiromi Nakano
Hidehiko Tanaka
1 Introduction 29
2 In-Situ TEM Observation Method 30
vi • contents
3 In-Situ Measurements of Phase Transitions of Metal Oxides 31
4 In-Situ Observation of Thermal Behavior of BaTiO
3
Grains 35
5 In-Situ Observation of Grain Growth of Metal Oxides 38
5.1 Grain Growth of Spherical Grains of BaTiO
3
38
5.2 Grain Growth of Faceted Grains of Ba
5
Nb
4
O
15
40
5.3 New Theory of Grain Growth and Sintering for
Simulation 42
6 Summary 45
7 Acknowledgments 45
References 46
3 raMan sPectroscoPy of oxide Materials 49
T. Pagnier
1 Introduction 49
2 Raman Spectroscopy Basics 50
2.1 The Raman Effect 50
2.2 Raman Spectrometers 53
2.3 Other Vibrational Spectroscopy Techniques 55
3 Structure Determination by Raman Spectroscopy 55
3.1 Basic Structural Characterization 55
3.2 Oxide Mixtures and Solid Solutions 59
4 The Nanostate: Nanopowders and Nanowires 59
4.1 SnO
2
Nanopowders 60
4.2 WO
3
Nanopowders 62
4.3 Other Oxides 63
4.4 Nanowires, Nanobelts, and Nanoribbons 63
4.5 Mixed Oxides 65
5 Synthesis of Nano-Objects 66
6 Interactions with Gaseous Species 67
7 Calculations of Raman Spectra 72
8 Conclusion 74
References 74
4 Microstructural and surface Modeling of sno
2
using
dft calculations 81
J. D. Prades
A. Cirera
G. Korotcenkov
B. K. Cho
contents • vii
1 Introduction 81
2 DFT-Based Approaches to Simulation and Modeling of
Structural Properties and Surface Chemistry of
Metal Oxides 83
2.1 Surface and Bulk Models 83
2.2 Bulk Stability 91
2.3 Surface Stability 95
2.4 Stability of Nanoparticles 104
2.5 Chemisorption 108
3 DFT Models and Results Related to SnO
2
Characterization 123
3.1 SnO and SnO
2
Bulk Properties 124
3.2 SnO
2
Surface Properties 127
3.3 Molecular Adsorption 137
3.4 Dopants and Their Role in Structural and Surface
Properties of the SnO
2
145
4 Conclusion 148
5 Acknowledgments 149
References 149
5 density functional theory Modeling of zno for gas
sensor aPPlications 163
M. J. S. Spencer
1 Introduction 163
2 Metal Oxides for Gas Sensing 164
2.1 ZnO for Gas Sensing 167
3 Theoretical Methods for Studying Gas–Sensor Reactions 169
3.1 Density Functional Theory 169
3.2 Theoretical Approach to Studying ZnO Surfaces 170
4 Examples of DFT Studies of Gas–ZnO Sensor Reactions 179
4.1 Nitrogen Oxides (NO, NO
2
, N
2
O) 180
4.2 Ethanol (CH
3
CH
2
OH) 198
5 Conclusions and Outlook 209
6 Acknowledgments 210
References 210
6 Modeling interactions of Metal oxide surfaces with water 217
L. Vlcek
P. Ganesh
A. Bandura
viii • contents
E. Mamontov
M. Predota
P. T. Cummings
D. J. Wesolowski
1 Introduction 217
2 Metal Oxide–Water Interactions and Their Study 219
2.1 General Oxide Properties and Surface Processes 220
2.2 Experimental Methods 223
2.3 Computer Simulations 224
2.4 Theoretical Models 228
3 Electronic Structure and Surface Reactions 229
3.1 TiO
2
229
3.2 SnO
2
233
3.3 ZnO 237
4 Thermodynamic and Structural Aspects of Adsorption 240
4.1 TiO
2
240
4.2 SnO
2
243
4.3 ZnO 245
5 Dynamics of Adsorbed Water 246
5.1 Fast Processes—Proton Motion 247
5.2 Slow Processes—Molecular Motion 248
6 Perspectives 251
7 Acknowledgments 252
References 252
7 density functional theory study of water dissociative
cheMisorPtion on Metal oxide surfaces 263
C. Zhou
H. Cheng
1 Introduction 263
2 Catalytic Water Dissociation on Metal Oxide Surfaces 265
2.1 Water Dissociative Chemisorption on Fe
3
O
4
(111) Surfaces 266
2.2 Water Dissociative Chemisorption on Rutile-TiO
2
(110)
Surfaces 275
2.3 Water Dissociative Chemisorption on
a-Al
2
O
3
(100) Surfaces 280
4 Summary 285
5 Acknowledgments 285
References 286
contents • ix
8 first-PrinciPles studies of hydrogen sPillover MechanisMs
on Metal oxides 293
L. Chen
M. Yang
H. Cheng
1 Introduction 293
2 General View of Spillover 294
2.1 Mechanism of Hydrogen Spillover on Metal Oxide 294
2.2 The Role of Noble Metals in the Spillover Effect 295
2.3 The Role of Spillover in Chemical Sensors 296
2.4 Experimental Confrmations of the Presence of
Spillover Effect 296
3 Computational Approach 297
4 Hydrogen Spillover in MoO
3
297
5 Hydrogen Spillover in Al
2
O
3
306
6 Hydrogen Spillover in WO
3
309
7 Summary 312
References 313
9 adsorPtion and diffusion of adatoMs and sMall clusters on
Metal oxide surfaces 317
R. Ferrando
A. Fortunelli
1 Introduction 317
2 Theoretical Methods and Concepts in Metal/Oxide Interaction 320
2.1 Theoretical Methods 320
2.2 Concepts in Metal/Oxide Interaction 322
3 Diffusion of Isolated Adatoms 324
3.1 Energy Barriers for Isolated Adatoms on Flat MgO(001) 324
3.2 Long Jumps in Adatom Diffusion 326
3.3 Diffusion in the Presence of Defects 329
4 Diffusion of Dimers, Trimers, and Tetramers 330
4.1 Dimers 330
4.2 Trimers 333
4.3 Tetramers 334
5 Adsorption and Diffusion on Exotic (Ultrathin) Oxide Substrates 338
5.1 Adsorption 341
5.2 Diffusion 347
5.3 Surface Nanopatterning and Template-Directed Assembly 350
x • contents
6 Conclusions 352
References 353
10 effect of size on the Phase stability of nanostructures 363
S. Li
Q. Jiang
1 Introduction and Motivation 363
2 Phase Stability and Structural Phase Transition 367
2.1 Crystals and Crystalline Structures 368
2.2 Factors Triggering Phase Transitions 369
2.3 Size Effect on Phase-Transition Pressure and
Temperature of Nanostructures 370
2.4 Research on the Thermodynamics of Solid Structural
Nanophase Transitions 370
2.5 Effect of Surface: Surface Energy and Surface Stress 371
2.6 Effect of Shape on Phase Stability 372
3 Theoretical Methods for Size-Dependent Phase Stability 372
3.1 Simulation Techniques 373
3.2 Thermodynamics 374
3.3 Applications: Case Studies 382
4 Concluding Remarks 389
References 390
11 segregation-induced grain-boundary electrical Potential
in ionic oxide Materials: siMulation aPProaches and
Pending challenges 397
R. L. González Romero
J. J. Meléndez Martínez
F. L. Cumbrera Hernández
D. Gómez García
1 Introduction: General Ideas About Segregation Effects in
Oxide Materials 397
2 Modeling of Segregation to the Grain Boundaries: Analytical
(or Continuum) Approach 398
3 Atomistic Approach: Molecular Dynamics Modeling 408
4 Mesoscopic Approach: Phase-Field Models 414
4.1 Topological Evolution of a Collective of Many Grains 415
4.2 Microstructural Evolution Coupled with Chemical
Segregation 417
contents • xi
5 Pending Problems and Future Prospects 418
6 Acknowledgments 419
References 419
index 425
xiii
PREFACE
This series, Chemical Sensors: Simulation and Modeling, is the perfect comple-
ment to Momentum Press’s six-volume reference series, Chemical Sensors:
Fundamentals of Sensing Materials and Chemical Sensors: Comprehensive Sensor
Technologies, which present detailed information about materials, technologies,
fabrication, and applications of various devices for chemical sensing. Chemical
sensors are integral to the automation of myriad industrial processes and every-
day monitoring of such activities as public safety, engine performance, medical
therapeutics, and many more.
Despite the large number of chemical sensors already on the market, selec-
tion and design of a suitable sensor for a new application is a diffcult task for
the design engineer. Careful selection of the sensing material, sensor platform,
technology of synthesis or deposition of sensitive materials, appropriate coatings
and membranes, and the sampling system is very important, because those deci-
sions can determine the specifcity, sensitivity, response time, and stability of the
fnal device. Selective functionalization of the sensor is also critical to achieving
the required operating parameters. Therefore, in designing a chemical sensor, de-
velopers have to answer the enormous questions related to properties of sensing
materials and their functioning in various environments. This four-volume com-
prehensive reference work analyzes approaches used for computer simulation and
modeling in various felds of chemical sensing and discusses various phenomena
important for chemical sensing, such as surface diffusion, adsorption, surface
reactions, sintering, conductivity, mass transport, interphase inter actions, etc.
In these volumes it is shown that theoretical modeling and simulation of the pro-
cesses, being a basic for chemical sensor operation, can provide considerable
assistance in choosing both optimal materials and optimal confgurations of
sensing elements for use in chemical sensors. The theoretical simulation and
model ing of sensing material behavior during interactions with gases and liquid
surroundings can promote understanding of the nature of effects responsible for
high effectiveness of chemical sensors operation as well. Nevertheless, we have to
understand that only very a few aspects of chemistry can be computed exactly.
xiv • preface
However, just as not all spectra are perfectly resolved, often a qualitative or ap-
proximate computation can give useful insight into the chemistry of studied phe-
nomena. For example, the modeling of surface-molecule interactions, which can
lead to changes in the basic properties of sensing materials, can show how these
steps are linked with the macroscopic parameters describing the sensor response.
Using quantum mechanics calculations, it is possible to determine parameters
of the energetic (electronic) levels of the surface, both inherent ones and those
introduced by adsorbed species, adsorption complexes, the precursor state, etc.
Statistical thermodynamics and kinetics can allow one to link those calculated
surface parameters with surface coverage of adsorbed species corresponding to
real experimental conditions (dependent on temperature, pressure, etc.). Finally,
phenomenological modeling can tie together theoretically calculated characteris-
tics with real sensor parameters. This modeling may include modeling of hot plat-
forms, modern approaches to the study of sensing effects, modeling of processes
responsible for chemical sensing, phenomenological modeling of operating char-
acteristics of chemical sensors, etc.. In addition, it is necessary to recognize that
in many cases researchers are in urgent need of theory, since many experimental
observations, particularly in such felds as optical and electron spectroscopy, can
hardly be interpreted correctly without applying detailed theoretical calculations.
Each modeling and simulation volume in the present series reviews model-
ing principles and approaches particular to specifc groups of materials and de-
vices applied for chemical sensing. Volume 1: Microstructural Characterization and
Modeling of Metal Oxides covers microstructural characterization using scanning
electron microscopy (SEM), transmission electron spectroscopy (TEM), Raman
spectroscopy, in-situ high-temperature SEM, and multiscale atomistic simulation
and modeling of metal oxides, including surface state, stability, and metal oxide
interactions with gas molecules, water, and metals. Volume 2: Conductometric-
Type Sensors covers phenomenological modeling and computational design of
conductometric chemical sensors based on nanostructured materials such as
metal oxides, carbon nanotubes, and graphenes. This volume includes an over-
view of the approaches used to quantitatively evaluate characteristics of sensitive
structures in which electric charge transport depends on the interaction between
the surfaces of the structures and chemical compounds in the surroundings.
Volume 3: Solid-State Devices covers phenomenological and molecular model-
ing of processes which control sensing characteristics and parameters of various
solid-state chemical sensors, including surface acoustic wave, metal-insulator-
semiconductor (MIS), microcantilever, thermoelectric-based devices, and sensor
arrays intended for “electronic nose” design. Modeling of nanomaterials and nano-
systems that show promise for solid-state chemical sensor design is analyzed as
well. Volume 4: Optical Sensors covers approaches used for modeling and simu-
lation of various types of optical sensors such as fber optic, surface plasmon
resonance, Fabry-Pérot interferometers, transmittance in the mid-infrared region,
preface • xv
luminescence-based devices, etc. Approaches used for design and optimization of
optical systems aimed for both remote gas sensing and gas analysis chambers for
the nondispersive infrared (NDIR) spectral range are discussed as well. A descrip-
tion of multiscale atomistic simulation of hierarchical nanostructured materials
for optical chemical sensing is also included in this volume.
I believe that this series will be of interest of all who work or plan to work in
the feld of chemical sensor design. The chapters in this series have been prepared
by well-known persons with high qualifcation in their felds and therefore should
be a signifcant and insightful source of valuable information for engineers and
researchers who are either entering these felds for the frst time, or who are al-
ready conducting research in these areas but wish to extend their knowledge in
the feld of chemical sensors and computational chemistry. This series will also be
interesting for university students, post-docs, and professors in material science,
analytical chemistry, computational chemistry, physics of semiconductor devices,
chemical engineering, etc. I believe that all of them will fnd useful information in
these volumes.
G. Korotcenkov
xvii
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 scientifc Gas Sensor Group and manager of
various national and international scientifc and engineering projects carried out
in the Laboratory of Micro- and Optoelectronics, Technical University of Moldova.
Currently, Dr. Korotcenkov is a research professor at the Gwangju Institute of
Science and Technology, Republic of Korea.
Specialists from the former Soviet Union know Dr. Korotcenkov’s research
results in the feld of 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
nanostructured metal oxides and solid-state gas
sensor design. Dr. Korotcenkov is the author or
editor of 11 books and special issues, 11 invited
review papers, 17 book chapters, and more than
190 peer-reviewed articles. He holds 18 patents,
and he has presented more than 200 reports at
national and international conferences.
Dr. Korotcenkov’s research activities have
been honored by an Award of the Supreme
Council of Science and Advanced Technology
of the Republic of Moldova (2004), The Prize of
the Presidents of the Ukrainian, Belarus, and
Moldovan Academies of Sciences (2003), Senior
Research Excellence Awards from the 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.
xix
Jian Wang (Chapter 1)
Shanghai Applied Radiation Institute
School of Environmental and Chemical Engineering
Shanghai University
Shanghai 200444, People’s Republic of China
Zheng Jiao (Chapter 1)
Shanghai Applied Radiation Institute and
Institute of Nanochemistry and Nanobiology
School of Environmental and Chemical Engineering
Shanghai University
Shanghai 200444, People’s Republic of China
Minghong Wu (Chapter 1)
Shanghai Applied Radiation Institute and
Institute of Nanochemistry and Nanobiology
School of Environmental and Chemical Engineering
Shanghai University
Shanghai 200444, People’s Republic of China
Chan-Hung Shek (Chapter 1)
Department of Physics and Materials Science
City University of Hong Kong
Kowloon Tong, Hong Kong
C. M. Lawrence Wu (Chapter 1)
Department of Physics and Materials Science
City University of Hong Kong
Kowloon Tong, Hong Kong
CONTRIBUTORS
xx • contributors
Joseph K. L. Lai (Chapter 1)
Department of Physics and Materials Science
City University of Hong Kong
Kowloon Tong, Hong Kong
Zhiwen Chen (Chapter 1)
Shanghai Applied Radiation Institute
School of Environmental and Chemical Engineering
Shanghai University
Shanghai 200444, People’s Republic of China
and
Department of Physics and Materials Science
City University of Hong Kong
Kowloon Tong, Hong Kong
Hiromi Nakano (Chapter 2)
Cooperative Research Facility Center
Toyohashi University of Technology
Tempaku, Toyohashi, Aichi 441-8580, Japan
Hidehiko Tanaka (Chapter 2)
National Institute for Materials Science
International Center for Materials Nanoarchitectonics
Tsukuba, Ibaraki 305-0044, Japan
Thierry Pagnier (Chapter 3)
Laboratoire d’Electrochimie et de Physicochimie des Matériaux et
Interfaces (LEPMI)
Grenoble Institute of Technology
38402 Saint-Martin-d’Hères, France
J. Daniel Prades (Chapter 4)
Departament d’Electrònica, MIND-IN2UB
Universitat de Barcelona
08028 Barcelona, Spain
Albert Cirera (Chapter 4)
Departament d’Electrònica, MIND-IN2UB
Universitat de Barcelona
08028 Barcelona, Spain
contributors • xxi
Ghenadii Korotcenkov (Chapter 4)
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, Republic of Moldova
Beongki Cho (Chapter 4)
Department of Material Science and Engineering and
Department of Nano Bio Materials and Electronics
Gwangju Institute of Science and Technology
Gwangju 500-712, Republic of Korea
Michelle J. S. Spencer (Chapter 5)
Department of Chemistry
La Trobe Institute for Molecular Science
La Trobe University Bundoora, Victoria 3086, Australia
and
Applied Physics, School of Applied Sciences
RMIT University
Victoria 3001, Australia
Lukas Vlcek (Chapter 6)
Chemical Sciences Division
Oak Ridge National Laboratory
Oak Ridge, Tennessee 37831, USA
Panchapakesan Ganesh (Chapter 6)
Center for Nanophase Materials Sciences
Oak Ridge National Laboratory
Oak Ridge, Tennessee 37831, USA
Andrei Bandura (Chapter 6)
Department of Quantum Chemistry
The St. Petersburg State University
198504 Petrodvorets, Russia
Eugene Mamontov (Chapter 6)
Chemical & Engineering Materials Division
Oak Ridge National Laboratory
Oak Ridge, Tennessee 37831, USA
xxii • contributors
Milan Predota (Chapter 6)
Institute of Physics and Biophysics
University of South Bohemia
Ceske Budejovice, 37005 Czech Republic
P. T. Cummings (Chapter 6)
Department of Chemical and Biomolecular Engineering
Vanderbilt University
Nashville, Tennessee 37235, USA
and
Center for Nanophase Materials Sciences
Oak Ridge National Laboratory
Oak Ridge, Tennessee 37831, USA
D. J. Wesolowski (Chapter 6)
Chemical Sciences Division
Oak Ridge National Laboratory
Oak Ridge, Tennessee 37831, USA
Chenggang Zhou (Chapter 7)
Department of Chemistry
National University of Singapore
Singapore 117543
and
Faculty of Materials Science and Chemistry
China University of Geosciences Wuhan
Wuhan 430074, People’s Republic of China
Hansong Cheng (Chapter 7)
Department of Chemistry
National University of Singapore
Singapore 117543
Liang Chen (Chapter 8)
Ningbo Institute of Materials Technology and Engineering
Chinese Academy of Sciences
Ningbo 315201, People’s Republic of China
Ming Yang (Chapter 8)
Sustainable Energy Laboratory
China University of Geosciences
Wuhan 430074, People’s Republic of China
contributors • xxiii
Hansong Cheng (Chapter 8)
Department of Chemistry
National University of Singapore
Singapore 117543
Riccardo Ferrando (Chapter 9)
Dipartimento di Fisica
Università di Genova
16146 Genova, Italy
Alessandro Fortunelli (Chapter 9)
CNR-IPCF
Istituto per i Processi Chimico-Fisici del Consiglio Nazionale delle Ricerche
Pisa 56124, Italy
Shuang Li (Chapter 10)
USTC—CityU Joint Advanced Research Centre
Suzhou 215123, People’s Republic of China
and
Department of Physics and Materials Science
City University of Hong Kong
Hong Kong SAR, People’s Republic of China
Qing Jiang (Chapter 10)
Key Laboratory of Automobile Materials, Ministry of Education
and
School of Materials Science and Engineering
Jilin University
Changchun 130022, People’s Republic of China
Robert Luis González Romero (Chapter 11)
Departamento de Física de la Materia Condensada
Universidad de Sevilla
41080 Sevilla, Spain
Juan José Meléndez Martínez (Chapter 11)
Departamento de Física
Universidad de Extremadura
06006 Badajoz, Spain
Francisco Luis Cumbrera Hernández (Chapter 11)
Departamento de Física de la Materia Condensada
Universidad de Sevilla
41080 Sevilla, Spain
xxiv • contributors
Diego Gómez García (Chapter 11)
Departamento de Física de la Materia Condensada
Universidad de Sevilla
41080 Sevilla, Spain
1 DOI: 10.5643/9781606503119/ch1
Chapter 1
MICROSTRUCTURAL CHARACTERIZATION
OF TIN DIOXIDE THIN FILMS
J. Wang
Z. Jiao
M. h. Wu
C.-h. Shek
C. M. L. Wu
J. K. L. Lai
Z. W. Chen
1. IntroductIon
Semiconductor oxides are fundamental to the development of smart and functional
materials, devices, and systems (Wang 1998; Pan 2001; Chen 2006a). These oxides
have two unique structural features, mixed cation valences and an adjustable oxy­
gen defciency, which are the bases for creating and tuning many novel material
properties, from chemical to physical (Chen et al. 2004). Because of the increasing
importance of air pollution and the need to monitor concentration levels of gases
such as CO, CO
2
, NO
x
, O
3
, SO
2
, etc., the development of many kinds of sensors and
control systems has been jolted into action in recent years (Dai 2002; Ng 2003;
Wang 2003; Cheng 2004). Microstructure variations will inevitably change their
physical and chemical properties. Therefore, study of the microstructure of the
2 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
grains can help us to uncover certain nanoscale features and to explain the cor­
responding experimental results. With the continuous reduction of sizes and the
increased demands for performance of optical, electronic, and magnetic devices,
the control of thin-flm structures is becoming increasingly signifcant (Chen et
al. 2010).
Many materials have been reported to be usable for design of metal oxide sen­
sors. It has been established that materials in different structural states can be
used in these resistive­type gas sensors (Sberveglieri 1992; Korotcenkov 2008).
The surface conductance of a semiconducting oxide is affected by the concentra­
tion of ambient gases. Resistive gas sensors are based on this principle, and the
nature of the sensing mechanism is related to the electrical response of gas sen­
sors to reactive gases. The change in the sensor resistance provides an indication
of the gas concentration (Chen et al. 2006b). These sensors can be quite versa­
tile, as they may be used to detect oxygen, fammable gases, and common toxic
gases. Their mechanism of operation is complex, however, involving interactions
between gaseous molecules and defects on the surface and grain boundaries. In
practice, nanocrystalline and polycrystalline materials have found their greatest
application in solid­state gas sensors because of their small crystallite size, in­
expensive design technology, and stability of both structural and electrophysical
properties (Schierbaum 1992; Kohl 2001). Therefore, it is necessary to establish
the role of morphology and crystallographic structure in gas­sensing effects, and
the structural parameters of the oxides and the sensor response.
The main focus of this review is to explore the growth process and the micro­
structural characteristics of thin flms using tin oxides.
2. Growth and nucleatIon of thIn fIlms
The study of thin-flm growth has been characterized by the application of
surface­science methods to understand growth at the atomic level. Understanding
the physics of thin-flm nucleation and growth in synthesis processes is very im­
portant both theoretically and technologically (Chen et al. 2008). There has been
widespread interest in understanding the infuence of the nanometer size scale,
the surface and interface, and the nucleation and growth on the materials’ chemi­
cal and physical properties. Over the years, many thin-flm growth techniques
have been based on pulsed­beam deposition, such as pulsed laser deposition and
pulsed magnetron sputtering deposition. The pulsed laser deposition technique
stands out by its unique features, such as its extremely high instantaneous de­
position rate and the highly energetic ablated species, which permit the growth of
nanostructured thin flms that exhibit unprecedented properties (Hinnemann et
al. 2001). Therefore, investigation of the micro­ and nanostructure characteristics
of thin flms, by means of x-ray diffraction (XRD) and high-resolution transmission
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 3
electron microscopy (HRTEM), is an essential step toward a better understand­
ing of how the growth conditions infuence the thin-flm nanostructure, which, in
turn, determines the flm sensing performance (Chen 2003; Serventi 2003).
Pulsed laser deposition (PLD) is a growth technique in which photonic energy
is coupled to the bulk starting material via electronic processes (Nagano 1984;
Chrisey1994). The rationale for using PLD lies primarily in its pulsed nature, the
possibility of carrying out surface chemistry far from thermal equilibrium, and
under favorable conditions. Above a certain power density, signifcant material
removal occurs in the form of an ejected luminous plume. The threshold power
density needed to produce such a plume depends on the target material, its mor­
phology, and the laser pulse wavelength and duration, but might be of the order of
10–500 MW cm
−2
for ablation using ultraviolet (UV) excimer laser pulses of 10­ns
duration. Material from the plume is then allowed to recondense on a substrate,
where thin-flm growth occurs. The physical processes in PLD are highly complex
and interrelated. They depend on the laser pulse parameters and the properties of
the target material (Chrisey et al. 1994).
To investigate the scaling behavior of PLD, we consider a variant of the model.
In contrast to that model, the duration of a pulse is assumed to be zero (Combe et
al. 1998), and we neglect the transient enhancement of the mobility of freshly de­
posited atoms. However, the model is defned as a solid-on-solid growth model on
a square lattice of L × L sites with integer heights representing the confguration of
the adsorbed layer. This model is controlled by three parameters: the pulse inten­
sity I, the diffusion constant D, and the average fux density of incoming particles
F. In particular, the control parameters of PLD are the pulse intensity I, which is
the number of particles deposited in one pulse per unit area, and the diffusion­
to­deposition ratio D/F. The average deposition rate is given by F = I/Δt, where Δt
is the time interval between two pulses. The intensity is measured in monolayers
(ML), and D/F is dimensionless, as the lattice constant is set to unity (Hinnemann
2001; Chen 2011).
Figure 1.1 shows kinetic Monte Carlo simulations of pulsed laser deposition
(Figure 1.1a) and molecular-beam epitaxy (MBE) (Figure 1.1b) in the submono­
layer regime. It can be seen in Figure 1.1a that the surface morphology depends
sensitively on the pulse intensity.
In MBE, usually the surface is covered with many small islands, whereas for
PLD there are a few large islands spaced relatively far apart. However, if the power
density per pulse is reduced, we would expect PLD to produce the same island mor­
phology as MBE. This is indeed the case, although the two situations are not exactly
the same, as in PLD the deposition takes place at fxed times whereas in MBE it
is probabilistic and therefore the time intervals between two depositions have a
Poisson distribution. This difference only infuences the island morphology at high
D/F, while the fnite-size effect is setting in. For simulations presented here, only
the D/F ratio below the fnite-size region is considered in performing Monte Carlo
4 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
simulations (Chen et al. 1998). The nucleation density for various pulse intensi­
ties was investigated using a square lattice system of size 400 × 400 for Monte
Carlo simulation. The island distance is measured at 0.2 ML coverage, when the
island density reaches its maximum but coalescence has not yet set in. For small
densities, we recall the well-known power law for the island distance in MBE,

γ
µ( / )
D
l D F (1.1)
where the exponent γ depends on the dimensions of the surface, the island dimen­
sion, and the critical nucleus i*; that is, the smallest stable island contains i* + 1
atoms. For a two­dimensional surface, compact islands, and a critical nucleus of
i* = 1, one obtains γ = 1/6. One should note that here the islands are not compact
but fractal patterns, as can be seen in Figure 1.1. This is due to the fact that the
edge diffusion is not considered in the simulations. The exponent γ can be de­
termined from simulations if one monitors the number of nucleation events in a
layer
-
µ
2
( )
D
l as a function of D/F. However, for PLD with large densities, the island
distance obeys a different power law:

-
µ
v
D
l I (1.2)
figure 1.1. Kinetic Monte Carlo simulations of pulsed laser
deposition and molecular-beam epitaxy in the submonolayer
regime. (a) a simulated pLd-grown surface with D/F = 2 × 10
8

and I = 0.01 ML. (b) a simulated MBe-grown surface with D/F =
2 × 10
8
. The fgure shows typical confgurations after deposition
of 0.05 ML. (reproduced with permission from Chen et al. 2008.
Copyright 2008 taylor & Francis.)
1
Metal Oxide Characterization


Figure 1















MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 5
where γ γ = - = + /(1 2 ) 1/(2 )
f
v d and, more generally γ = + 1/(4 )
f
d if they have
the fractal dimension d
f
. In this regime the island distance is independent of the
parameter D/F, since the adatoms do not make use of their diffusion probabil­
ity. When they fnd an island, they attach to it in a much shorter time compared
with that of diffusion between two depositions. So, the two regimes described by
Eqs. (1.1) and (1.2) are separated by a crossover at a certain density, for which
the number of deposited atoms is of the same order of magnitude as the adatom
density. Since the average adatom density n in MBE scales as
γ - +
µ
1 2
( / ) n D F , the
critical density demonstrates the same scaling behavior:

γ - +
µ
1 2
( / )
c
I D F (1.3)
The qualitative difference between PLD and MBE for I > I
c
is shown in Figure 1.1.
There are many nucleations at an early stage, although the effective fux of incom­
ing particles is the same in both cases. The scaling behavior, namely, the fractal
dimension, is measured using the box­counting method. The fractal dimension
values for the PLD and MBE were decided to be 1.28 ± 0.03 and 1.62 ± 0.03, re­
spectively. Comparing the fractal dimension of PLD with MBE, we found that the
fractal dimension obtained by PLD is smaller than that of MBE (Chen et al. 2008).
A simple schematic diagram, shown in Figure 1.2, illustrates a key difference in
the nature of coalescence events between pulsed and continuous depositions,
although in a real system the same difference may unfold in a more complex
2
Metal Oxide Characterization


Figure 2




















figure 1.2. Schematic diagrams showing the difference
between the dynamics of coalescence in pulsed laser
deposition (pLd) and molecular-beam epitaxy (MBe).
(a) pLd (pulsed delivery): concurrent coalescence. (b)
MBe (continuous delivery): sequential coalescence.
(reproduced with permission from Chen et al. 2008.
Copyright 2008 taylor & Francis.)
6 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
way. Consider four droplets, A, B, C, and D, deposited/formed simultaneously,
for instance, in a pulsed process, or one after another (in the sequence A, B, C,
and then D) in the continuous process. As shown in Figure 1.2a (pulsed case),
the concurrent multiple droplet coalescence leads to a single large droplet. On the
other hand, the outcome in Figure 1.2b (continuous deposition case) shows that
the initial coalescence of A and B would produce a large droplet with no overlap
with the subsequently arriving/forming droplets C and D. Therefore, it is possible
to use a simple model to reveal the differences of coalescence dynamics between
pulsed laser deposition and molecular­beam epitaxy.
Figures 1.3a and 1.3b show XRD patterns of the cassiterite SnO
2
bulk and
the as­prepared SnO
2
thin flms, respectively. All refections can be indexed with
3
Metal Oxide Characterization


Figure 3




















figure 1.3. Xrd patterns of Sno
2
: (a) Sno
2
bulk material; (b) the as-prepared Sno
2
thin flm.
(reproduced with permission from Chen et al. 2005. Copyright 2005 elsevier.)
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 7
a tetragonal unit cell of SnO
2
, and the lattice parameters are close to a = 4.737 Å
and c = 3.185 (Zheng et al. 1996). XRD results showed that the average grain size
of the as­prepared nanocrystalline SnO
2
was about 12 nm. The crystallographic
planes identifed on the XRD patterns as presented in Figure 1.3b are typical of
a pure polycrystalline SnO
2
phase, in terms of peak positions and relative peak
intensities (ICDD, 1995). It is noted that a broad peak centered around 2h = 30°
was clearly visible in the XRD pattern of the PLD SnO
2
thin flms (see Figure 1.3b).
We believe that this broad peak is due to the presence of an amorphous SnO
phase. This was clearly demonstrated in previous work (Dolbec et al. 2002), where
PLD SnO
2
thin flms were grown under vacuum (laser infuence of ~4.6 J/cm
2
)
over a wide range of deposition temperatures (from room temperature to 600°C),
and the as-deposited flm consisted of both a polycrystalline SnO
2
phase and an
amorphous SnO (a-SnO) phase (Godbole 1990; Phillips 1996). The XRD signature
of a­SnO is a broad hump centered around 2h = 29.8°, which corresponds to the
most intense refection of the SnO phase (Chen et al. 2005a), in agreement with
the XRD patterns shown in Figure 1.3b. Moreover, for PLD SnO
2
thin flms as
thick of 4 mm (in our experiment), more than 98% of the XRD signal originates
from the flm, thereby eliminating any relevant consideration of a possible contri­
bution of the glass substrate to the broad component of the XRD pattern shown
in Figure 1.3b. The broad peak that characterizes glass is known to be centered
near 2h = 26°. The presence, therefore, of such an amorphous SnO phase in the
flms suggests that the growth conditions (i.e., under vacuum at room tempera­
ture) are in fact not appropriate for a complete crystallization of the pure SnO
2

phase. This conclusion accords with previous results (Dolbec et al. 2002), where
it was demonstrated that a suitable oxygen background pressure is a prerequisite
for the growth of pure polycrystalline SnO
2
phase.
To explain the nanostructures of metal oxide nanocrystallites, one should in­
vestigate a possible mechanism to explain the microstructural behavior. High-
resolution transmission electron microscopy (HRTEM) investigation of thin flms
that can be used as elements of conductance sensors can give useful information
about the local composition at dislocation cores. HRTEM images show that each
nanocrystallite is connected mainly with two or three neighbors through necks;
however, grain boundary contacts cannot be ignored. A more detailed analysis can
be made based on the highly magnifed HRTEM image in Figure 1.4. Figures 1.4a
and 1.4b show high­resolution transmission electron micrographs of as­ prepared
SnO
2
thin flms. Besides the amorphous SnO phase, several nanocrystallites are
clearly visible. In Figure 1.4a, the SnO
2
nanoparticle is clearly crystalline and
equiaxed (see the two white circles, A and B). However, nanocrystalline SnO
2

grains are often overlapped and connected with two or more neighbors through
necks (Figure 1.4a, white arrows). The overlapped parts display more edge dislo­
cations. In Figure 1.4b, besides the nanocrystallites A and B, it is found that the
nanocrystalline SnO
2
grains are overlapped and connected with four neighbors
8 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
through necks (see A, B, C, and D). The overlapped parts contain a high density
of extended defects, such as twin boundaries, exhibited in the neighborhood of
the white circle (Chen et al. 2005a). These results indicate that the thin flms are
composed of both polycrystalline SnO
2
and amorphous SnO phases. Since the
phenomenon of gas sensitivity is related to electron transport, the geometry and
nature of the contact areas between SnO
2
particles is especially important. The
grain­rotation process is directly related to the reduction of surface energy, which
is for the purpose of minimizing the area of high­energy faces (Moldovan et al.
2002). Figure 1.5 presents typical microstructural details of as­deposited tin­ oxide
thin flms, revealing that the as-deposited flms have been partially crystallized
even without heat treatment at high temperatures. The presence of crystalline
SnO
2
with a rutile structure was confrmed by selected-area electron-diffraction
pattern (SAED) analysis. The inset at the bottom left-hand corner displays the
SAED pattern taken from the flm, showing the polycrystalline diffraction patterns
of nanocrystallite which can be identifed as rutile SnO
2
structure. For instance,
one, two, three, and four diffraction rings in the inset at the bottom left­hand
corner have a lattice spacing of 2.369 Å, 2.119 Å, 1.498 Å, and 1.322Å, which
have been identifed to be the (200), (210), (210), and (202) refections of rutile-
type SnO
2
, which is a tetragonal phase with the space group P
42
/mnm and lattice
parameters a = 4.737 Å and c = 3.185 Å, respectively (Baur 1956; Von Allmen
1995; Chen 2005b). This low-magnifcation HRTEM image of the as-deposited thin
flm in Figure 1.5 shows randomly oriented particles, as well as several clusters
where the SnO
2
grains are overlapped and connected with two or three neighbors
through necks, formed by grains with the same crystallographic orientation (in­
dicated by white arrows). As can be seen in Figure 1.5, the presence of clusters is
quite common, suggesting the large­scale formation of such morphologies.
4
Metal Oxide Characterization


Figure 4

































figure 1.4. high-resolution transmission electron micrographs of as-prepared Sno
2
thin flms pre-
pared by the pLd method. (reproduced with permission from Chen et al. 2005. Copyright 2005
elsevier.)
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 9
Figure 1.6a shows that the grain cluster is composed of several primary nano­
crystallites without grain boundaries, which offers direct evidence that coalescence
occurs when two or more neighbor grains assume the same orientation, resulting
in a single nanocluster. Slight misorientations (indicated by the white arrows) are
visible in the image of a cluster composed of several primary SnO
2
nanocrystallites
(e.g., four nanocrystallites, indicated by one, two, three, and four regions), shown
in Figure 1.6a. These misorientations or defects originate from imperfect attach­
ment among several nanocrysallites, resulting in edge and screw dislocations.
A substantial driving force for the crystal rotation to achieve perfectly coherent
grain–grain boundaries is expected; however, some rotation may be metastable
and preserved by the formation of a coincident site array. Figure 1.6b shows the
initial stage of the grain­growth process. The white arrow in the circle indicates
the formation of necks between grains. An analysis of Figure 1.6b suggests that
5
Metal Oxide Characterization


Figure 5






















figure 1.5. Low-magnifcation HRTEM image and SAED pattern of the SnO
2
particles prepared
by pulsed laser deposition at room temperature. arrows indicate the presence of clusters showing
that the Sno
2
grains are overlapped and connected with two or three neighbors through necks.
(reproduced with permission from Chen et al. 2005. Copyright 2005 Springer-Verlag.)
10 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
6
Metal Oxide Characterization


Figure 6
















figure 1.6. High-magnifcation HRTEM images of SnO
2
nano crystallites: (a) Sno
2
cluster com-
posed of several nanocrystallites; (b) the initial stage of the grain-growth process. (reproduced with
permission from Chen et al. 2005. Copyright 2005 Springer-Verlag.)
the frst step in the grain-growth process is the formation of necks. After this step,
a rotation may occur to decrease the angle of misorientation, changing the grains’
orientation. When the grains assume the same orientation, i.e., a coherent grain–
grain boundary, the grain boundary must migrate toward the smaller particle,
resulting in a single larger nanocrystallite. It can be seen that the SnO
2
particles
are well crystallized, but the grain interiors often appear to be free from defects.
Therefore, it is suggested that the formation processes of nucleation, grain rota­
tion, coalescence, and growth occur when two or more particles collide (Penn and
Banfeld 1998).
Figure 1.7 shows that the formation processes of nucleation, grain rotation,
coalescence, and growth, which occur when two or more particles collide, promote
attachment between particles. Figure 1.7a shows the nucleation process of SnO
2
nanocrystallites. Figure 1.7b displays the grain­rotation process after nucleation.
This process of attachment is followed by a process of rotation, which leads to a
low-energy confguration, thereby forming a coherent grain boundary and elimi­
nating the common grain boundary, resulting in a single larger nanocrystallite—
that is, the coalescence process (see Figure 1.7c). Figure 1.7d shows the growth
process of SnO
2
nanocrystallites (Lal et al. 1991).
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 11
3. multIfractal spectra of sem ImaGes of thIn fIlms
Since the middle of the 1980s, the relationships among the fractal formation of
thin flms, the annealing temperature, the annealing time, the thickness of flms,
the electron emission, etc., have been investigated thoroughly. The concept of
fractal geometry has proved useful in describing structures and processes in ex­
perimental systems (Musolino 1999; Hu 2002). In the past few years, multifrac­
tals have been found to have very important applications in electron microscopy.
The microstructure evolution of SnO
2
thin flms has been investigated using x-ray
diffraction, scanning electron microscopy (SEM), and atomic force microscopy,
and this formation of signifcant fractal features is rather unusual.
Multifractal spectra of SEM images are calculated by the box-counting method.
The images can be divided into many boxes of size (l × l), and we let e = l/L (L = 512,
ε < 1). P
ij
(ε) is the average deposition probability of the flm in box (i, j ). The height
distribution probability P
ij
(ε) is determined as
7
Metal Oxide Characterization


Figure 7



















figure 1.7. Schematic representation of the formation processes showing (a) nucleation, (b) grain
rotation, (c) coalescence, and (d) growth of nanoclusters in as-deposited thin flm. Arrows in (b)
illustrate the rotation between grains. (reproduced with permission from Chen et al. 2005. Copyright
2005 Springer-Verlag.)
12 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
ε =
å
( )
ij
ij
ij
h
P
h
(1.4)
where h
ij
is the average height of box (i, j ) of size e measured from the datum
planes corresponding to the Si (100) substrate surface. P
ij
(ε) can be described as
a multifractal as

α
ε ε ( )~
ij
P (1.5)

α
α
ε ε
- ( )
( ) ~
f
N
(1.6)
where a is the singularity of the subset of probabilities, N
α
(ε) is the number of
boxes of size ε with the same probability, and α ( ) f is the fractal dimension of the
a subset. The dependence of α ( ) f on a is the multifractal spectrum. For a random
multifractal, α ( ) f can be calculated by the partition function method using a com­
puter code (Huang 1989; Li 1995, 1996; Wang 1995; Chen 2001). The partition
function c
q
(a) is defned and expressed as a power law in terms of ε with an expo­
nent τ(q), where q is the moment order (–∞ < q < +∞):

τ
χ ε ε ε º =
å
( )
( ) ( )
q q
q ij
P (1.7)
τ(q) can be obtained from the slope of the ln c
q
(a)–ln ε curve. α ( ) f can be obtained
by performing Legendre transformation as follows:

[ ] τ
α =
( ) d q
dq
(1.8)
and
α α τ = - ( ) ( ) f q q (1.9)
In real calculations, the value of q cannot be infnite. One can take the maxi­
mum |q| when the a and α ( ) f approach to the saturated values with the increase of
q. The maximum |q| depends on the probability, and the narrower the probability
distribution, the larger the |q| were used. The width of the multifractal spectrum
is Δa, and the difference between the fractal dimensions of the maximum proba­
bility subset (a = a
min
) and the minimum one (a = a
max
) is [ ] ∆ ∆ α α = -
min max
( ) ( ) f f f f

(Wang 1995; Penn 1998).
Figure 1.8 presents SEM images of SnO
2
thin flms prepared on Si (100) substrate
at temperatures of (A) 300°C, (B) 350°C, (C) 400°C, and (D) 450°C, respectively. The
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 13
SEM observations indicated that all thin flms produced under different substrate
temperatures exhibited self­similar fractal patterns with increase in average frac­
tal size measurement on the fractal regions. It can be seen that the fractal patterns
have an open and loose structure with increasing substrate temperature. The
average sizes of the fractal patterns (or clusters) are about 0.307 mm (see Figure
1.8A), 0.906 mm (see Figure 1.8B), 1.202 mm (see Figure 1.8C), and 1.608 mm
(see Figure 1.8D). The average sizes of the fractal clusters for four thin flms were
estimated by measurement on the fractal regions. The measuring procedure was
as follows: for each SEM image, we chose 10 fractal patterns at random to get an
average value. The average sizes of the fractal patterns were obtained by averaging
the values of SEM images with different orientations. It was found that the aver­
age sizes of the fractal clusters increase with increasing substrate temperature
(Ohta and Honjo 1988).
Figure 1.9 shows the ln c
q
(a)–ln ε curves of the SnO
2
thin flm obtained at a Si
substrate temperature of 500°C. To display the ln c
q
(a)–ln ε curves clearly, only 13
ln c
q
(a)–ln ε curves with intervals of 40 |q| are plotted. The box sizes ε are taken
as 1/512, 1/256, 1/128, 1/64, 1/32, 1/16, 1/8, 1/4, 1/2, and 1. The correla­
tion coeffcients of the ln c
q
(a)–ln ε curves at q = ±280 are 1.0000. The linearity of
figure 1.8. SeM images of Sno
2
thin flms prepared on Si (100) substrate at temperatures of (A)
300°C, (B) 350°C, (C) 400°C, and (d) 450°C. (reproduced with permission from Chen et al. 2010.
Copyright 2010 american Chemical Society.)
8
Metal Oxide Characterization


Figure 8




























14 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
ln c
q
(a)–ln ε is very important for the multifractal, and its linear range is called the
scaling range. Regular multifractals have strict linearity in the ln c
q
(a)–ln ε plot at
all moments q, and this linearity can approach zero infnitely (ln ε → −∞). It can be
seen that the linearity of the ln c
q
(a)–ln ε curves is excellent at all q moments. It
is expected that the range will be wider if the number of pixels in the SEM images
is increased. The multifractal analysis can therefore be used to describe the SnO
2

thin flm deposition quantitatively.
Figure 1.10 shows the multifractal spectra α ( ) f of the SEM images. It can be
seen that the α ( ) f of the Si substrate hooks to the right, while those of the three
SnO
2
thin flms hook to the left. The plotted results indicate that the widths and the
shapes of the multifractal spectra are completely different. The width of the α ( ) f
of the Si substrate is smallest. The higher the substrate temperature, the wider
is the spectrum of α ( ) f , and the larger the a
max
. Table 1.1 shows the para meters
of the multifractal spectra of the specimens. It can be seen that Δa increases
with increasing substrate temperature, indicating that the height probability
became more nonuniform. Since ε < 1, a
min
presents the maximum probability
(
α
ε 
min
max
p )

and a
max
presents the maximin probability (
α
ε 
max
min
p ). Therefore,
the Δa can be used to describe the range of the probability due to
max min
/ . P P
∆α
ε
-

The larger the Δa, the wider is the probability distribution, and the larger the
9
Metal Oxide Characterization


Figure 9



























figure 1.9. ln c
q
(a)–ln e plots of Sno
2
thin flms obtained at a substrate temperature of 500
o
C.
(reproduced with permission from Chen et al. 2005. Copyright 2005 elsevier.)
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 15
10
Metal Oxide Characterization


Figure 10



























figure 1.10. Multifractal spectra f(a) of the substrate and three Sno
2
thin flms. (Reproduced with
permission from Chen et al. 2005. Copyright 2005 elsevier.)
difference between the highest and the lowest growth probabilities. It is found that
the Δf of the multifractal spectra of the SnO
2
thin flms are all greater than zero, and
increase as the Si substrate temperature increases, while the Δf of the multifractal
spectra of the substrate are less than zero. While α
min
( ) f represents the number
of the boxes of the same maximum probabilities
α
ε α ε ε
-
= 
min
( )
min min
( ) ( )
f
Np N and
α
max
( ) f refects the number of the minimum one
α
ε α ε ε
-
= 
max
( )
max max
( ) ( )
f
Np N , Δf
describes the ratio of the number of the maximum probability and that of the mini­
mum one:

ε ε ε
-
=
max min
( )/ ( )
f
Np Np . Consequently, Δf > 0 means that the chance
SubStrate temperature (°C) a
max
f(a
max
) a
min
f(a
min
) Da Df
Room temperature 2.043 2.169 2.033 1.590 0.010 –0.579
400 2.059 0.530 2.008 1.107 0.051 0.577
450 2.070 0.500 2.005 1.114 0.065 0.614
500 2.084 0.666 2.011 1.694 0.073 1.028
Source: Reproduced with permission from Chen et al. 2005. Copyright 2005
Elsevier.
table 1.1. parameters of the multifractal spectra of the specimens
16 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
of the height distribution of the deposits lying at the highest sites is greater than
that at the lowest sites, and vice versa.
In summary, the multifractal spectra α ( ) f show that the higher the substrate
temperature, the wider the spectrum, and the larger the ∆ ∆ α α = -
min max
[ ( ) ( )] f f f f .
The nonuniformity of the height distribution increases with increasing substrate
temperature, and the liquid droplets of SnO
2
thin flms are formed on previous
thin flms. These results show that the SEM images can be characterized by the
multifractal spectra. With an increase of substrate temperature, the higher long­
range temperature feld may promote new nuclei and subsequent growth, which
leads to the fractal growth of the fne branches and a lower fractal density. This
fractal structure may lead to improvement in the design of gas sensors for the
monitoring of environmental pollutants.
4. mIcrostructural evolutIon of nanocrystallIne sno
2

thIn fIlms
The low-dimensional systems such as thin flms demonstrate a variety of physical,
chemical, and functional properties which are different from their bulk counter­
parts (Chen et al. 2005c). The infuence of grain size on material properties is
especially remarkable for polycrystalline thin flms. In the past several years, the
interface and surface microstructure of nanomaterials have been extensively and
intensively investigated. Various types of interface structure models have also
been proposed for nanostructured materials, such as the gaslike model, order and
extended order models, etc. (Chopra 1993; Wang 1994). Commonly, the peculiar
properties of nanomaterials are explained in terms of the interface and surface
structures, while the effects from the microstructure of the grains are neglected.
As a matter of fact, for different preparation methods, the microstructure of nano­
materials can be nanocrystallite, nanoamorphous grain, or nanocluster agglomer­
ations with some crystalline features. Since the grains are the basic components
of nanomaterials, changes in their microstructure should inevitably change the
physical and chemical properties. Therefore, study of the microstructure of grains
can help us to discover the general structure of nanomaterials and explain the
corresponding properties.
Raman techniques can reveal local structural information of amorphous and
poorly crystallized samples. Usually, disordering induces spectral changes with
reference to the bulk crystal spectra and their vibrational state densities (Zhu et
al. 1987). Tin oxide gives rise to well-defned Raman spectra, and the dynamics
of rutile­like compounds have been extensively studied (Katiyar 1971; Gervais
1985). However, for nanocrystallites, the surface atoms represent a non-negligible
fraction of atoms and give rise to specifc spectral changes. The corresponding
frequencies of the optical modes have been calculated theoretically and measured
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 17
experimentally (Stao and Asari 1995). When the SnO
2
grain size is small, the
Raman spectrum is modifed, at least partially. Several authors have reported that
the existence of some Raman peaks is closely related to grain size (Xie et al. 1994).
Figures 1.11a, 1.11b, and 1.11c show x­ray diffraction patterns of commercial
SnO
2
bulks, and SnO
2
thin flms as-prepared and annealed at 300°C for 30 min,
respectively. Tin dioxide has a tetragonal rutile crystalline structure (known in its
mineral form as cassiterite) with point group
14
4h
D and space group P
42
/mnm (Wang
et al. 1994). The unit cell consists of two metal atoms and four oxygen atoms.
Each metal atom is situated amidst six oxygen atoms which approximately form
the corners of a regular octahedron. Oxygen atoms are surrounded by three tin
atoms which approximate the corners of an equilateral triangle.
The average grain sizes were calculated using the TEM micrograph and the
Scherrer formula λ β θ = / cos , D K

respectively, where D is the diameter of the
nanoparticles, K = 0.9, λ(Cu K
a
) = 1.5406 Å, and β is the full-width half- maximum
of the diffraction lines. Both results show that the average grain sizes of the
as­ prepared and the annealing SnO
2
nanoparticles are about 8 and 12 nm, re­
spectively. Figure 1.12 shows a TEM bright-feld image and the corresponding
selected-area electron diffraction (SAED) pattern (inset) of the as-prepared SnO
2

thin flm. The particle sizes observed in the micrographs are larger than those
estimated from XRD data, indicating signifcant agglomeration of the particles.
As seen in the TEM bright-feld image, there are many small particles of roughly
spherical shape. The contrast of the particles in different regions of the TEM im­
age indicates different densities, which may be related to the grain sizes. The
polycrystalline diffraction rings of SAED pattern (inset in Figure 1.12) also demon­
strate the characteristics of typical tetragonal SnO
2
thin flm (d
200
= 2.37 Å, d
210
=
2.12 Å, d
310
= 1.50 Å, and d
202
= 1.32 Å). The interplanar spacings in keeping with
those of the tetragonal rutile structure are shown in Table 1.2. These indicate that
the SnO
2
average grain size is smaller than that of the bulk material. The crystal­
lites close to the Bragg orientations are recognizable by their dark contrast. For
the tetragonal structure, the lattice parameters can be calculated by
=
+ +
2 2 2 2 2
1
[( )/ ] ( / )
hkl
d
h k a l c
(1.10)
where h, k, and l are all integers, (hkl ) is the lattice plane index, and a and c are
lattice constants. For a real crystal, the calculated values of a and c are the same
based on different crystal planes. However, the presence of a large number of
vacant lattice sites and local lattice disorders may lead to obvious reduction (or
even disappearance) of intensities in the XRD peaks of the some lattice planes
[e.g., the lattice planes (200), (220), (002), (310), etc., in Figure 1.11b]. Therefore,
these results imply destroyed periodicities in some crystal planes and a signif­
cant distortion of the rutile lattice. We have calculated the lattice parameters with
18 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
11

Metal Oxide Characterization


Figure 11








figure 1.11. X-ray diffraction patterns of Sno
2
thin flms: (a) commercial bulk SnO
2
; (b) as-prepared
Sno
2
thin flm; (c) annealed SnO
2
thin flm. (Reproduced with permission from Chen et al. 2004.
Copyright 2004 american physical Society.)
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 19
12


Metal Oxide Characterization


Figure 12





















figure 1.12. TEM bright-feld image of as-prepared nanocrystalline SnO
2
thin flm, showing the fne
grains of Sno
2
thin flms; selected-area electron diffraction (SAED) pattern (inset) corresponding to the
tetragonal rutile structure, showing the microstructural characteristics of the polycrystalline Sno
2
thin
flm. (Reproduced with permission from Chen et al. 2004. Copyright 2004 American Physical Society.)
mccarthy and Welton 1989, commercial bulk, aS-prepared thin film,
Sample d
hkl
(Å) d
hkl
(Å) d
hkl
(Å)
110 3.347 3.3608 3.3422
101 2.6427 2.6536 2.6347
200 2.369 2.3720 2.3660
111 2.3094
210 2.1189
211 1.7641 1.7667 1.7603
220 1.6750 1.6823 1.6738
002 1.5934 1.5964 1.5901
301 1.4984 1.4932
221 1.4829
112 1.4392
301 1.4155
Source: Reproduced with permission from Chen et al. 2004. Copyright 2004
American Physical Society.
table 1.2. relationships of interplanar spacing (d
hkl
) of index (hkl ) in the direct
lattice for different samples
20 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
different samples using Eq. (1.10). From Table 1.3, we can easily notice the rela­
tionship of the grain sizes to the change of lattice parameters. However, we found
that there is an increase in a and a decrease in c for the as­prepared SnO
2
thin
flms prepared by the PLD method. This implies that the as-prepared thin flms
may exhibit a large number of oxygen vacancies, vacancy clusters, and local lat­
tice disorder, which may lead to an increase in a and a decreases in c.
Figures 1.13a, 1.13b, and 1.13c show the room­temperature Raman spectra
of commercial SnO
2
bulk materials, as­prepared, and annealed at 300°C for 30­
min nanocrystalline SnO
2
thin flms, respectively. In general, SnO
2
with the rutile
structure belongs to the space group
14
4
,
h
D of which the normal lattice vibration at
the G point of the Brillouin zone is given as follows on the basis of group theory
(Traylor et al. 1971):

1 1 2 2 3 1 4 2 5 1 2
4 1 5
(1 ) (1 ) (1 ) (1 ) (1 ) (1 )
2 ( ) 3 ( )
g g g g g u
u u
A A B B E A
B E
Γ Γ Γ Γ Γ Γ Γ
Γ Γ
+ + + + - -
- +
= + + + + +
+ +

(1.11)
To investigate the characteristics of Raman spectra, Figure 1.14 depicts the
symmetries of the optic modes of the rutile structure for zero wave vector. Among
these vibrations, the symmetry A
2g
and B
1u
modes are optically inactive, while
symmetry A
2u
and E
u
modes are infrared active. The remaining optic modes, A
1g
,
B
1g
, B
2g
, and E
g
, are Raman active in frst order with the polarizability tensors
(Peercy and Morosin 1973):

α
æ ö
÷ ç
÷
ç
÷
ç
÷ =
ç
÷
ç
÷
ç ÷
÷ ç
è ø
1
0 0
( ) 0 0
0 0
g
a
A a
b

1
0 0
( ) 0 0
0 0 0
g
c
B c α
æ ö
÷ ç
÷
ç
÷
ç
÷ = -
ç
÷
ç
÷
ç ÷
÷ ç
è ø

(1.12)

2
0 0
( ) 0 0
0 0 0
g
f
B f α
æ ö
÷ ç
÷
ç
÷
ç
÷ =
ç
÷
ç
÷
ç ÷
÷ ç
è ø

0 0
( ) 0 0
0
g
d
E d
d d
α
æ ö
÷ ç
÷
ç
÷
ç
÷ =
ç
÷
ç
÷
ç ÷
÷ ç
è ø
mccarthy and
Sample Welton 1989 aS-prepared thin film commercial bulkS
a
110
4.733 4.753 4.727
a
110
4.738 4.744 4.732
Δa −0.005 0.009 −0.005
c
101­110
(Å) 3.186 3.198 3.173
c
101­200
(Å) 3.184 3.201 3.172
Δc 0.002 −0.003 0.001
Source: Reproduced with permission from Chen et al. 2004.
Copyright 2004 American Physical Society.
table 1.3. relationships of lattice parameters for different samples
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 21
13


Metal Oxide Characterization


Figure 13



figure 1.13. room-temperature raman spectra of (a) Sno
2
bulk material, (b) as-prepared nano-
crystalline Sno
2
thin flm, and (c) annealed SnO
2
thin flm. (Reproduced with permission from Chen
et al. 2004. Copyright 2004 american physical Society.)
22 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
figure 1.14. Symmetries of the optic modes of the tetragonal rutile structure for zero wave vector.
Labeling is in the notation of Mulliken (in parentheses, of Koster). doubly degenerate modes are
indicated by a ‘‘(2)’’ preceding the Mulliken symbol. (reproduced with permission from Chen et al.
2004. Copyright 2004 american physical Society.)
14

Metal Oxide Characterization


Figure 14





MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 23
It can be seen from Figure 1.13b that the Raman intensity is strongest for the
mode A
1g
at 636.3 cm
−1
, followed by the mode B
2g
at 780.9 cm
−1
and the mode E
g

at 474.1 cm
−1
. The data for the A
1g
, B
2g
, and E
g
modes are in agreement with those
observed in the previous report (Diéguez et al. 2001). Thus, the Raman spectra
show the typical features of the rutile phase for the as­prepared SnO
2
thin flm.
However, the variation of the mode B
1g
could not be measured in the present
experiment. The mode B
1g
appears quite often with smaller nanoparticles, but is
diffcult to locate due to its very low intensity with respect to the other modes [e.g.,
0.001I (A
1g
)] and the existence of the low­frequency bands (Peercy and Morosin
1973). The remarkable aspect of the Raman spectrum for the as­prepared SnO
2

thin flm (see Figure 1.13b) is the appearance of a new Raman peak at about
516.1 cm
−1
. This new Raman peak has not been observed in previous reports. To
explore whether this new Raman peak comes from the nanocrystalline SnO
2
, the
as­prepared SnO
2
thin flm was annealed at 300°C for 30 min. Figure 1.13c shows
the Raman spectrum of the nanocrystalline SnO
2
thin flm annealed at 300°C for
30 min. The remarkable aspect of the Raman spectrum is that this new Raman
peak disappears in annealing SnO
2
thin flm. This result agrees well with the
theoretical predication of the vibrational modes in the high­frequency region of
542–486 cm
−1
that have been investigated by Diéguez et al. (2001). In theory, this
vibrational mode can be attributed to disorder activation of the Raman forbidden
mode (Abello et al. 1998).

The appearance of this new peak indicates that it arises
either as a consequence of reduced particle dimensions (when prepared by PLD
techniques) or due to the conversion from amorphous to crystalline material.
It is known that, in a disordered crystal, there is a correlation between pre­
venting atoms from vibrating in phase and preventing their displacement by im­
perfections modifying the space symmetry. Changes in the local symmetry of the
crystal produce changes in some of the components of the polarizability tensor,
even the normally forbidden vibration modes—i.e., due to the loss in long­range
order, all phonons are optically possible and the Raman spectrum should re­
semble the phonon density of the states. In an intermediate case, a shift of the
classical modes accompanied by broadening and the appearance of some SnO
2

forbidden modes should be observed. This is indeed what occurs with modes
A
1g
, B
2g
, E
g
, and A
2u
. However, the band at 516.1 cm
−1
cannot ft any of the SnO
2

Raman forbidden modes. The appearance of this new mode as a consequence of
the coupling between modes also cannot explain the high contribution of this
band observed in the spectrum of the smaller nanoparticles. Furthermore, it is
well known that nanometer­sized crystalline materials have a crystalline compo­
nent forming the crystallite nucleus and an interfacial component consisting of
all the atoms situated at the grain boundaries between particles or at their sur­
faces. The latter usually have several atomic layers in which atoms are slightly
displaced from the exact position that would be suggested by the crystalline
structure of the material.
24 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
5. concludInG remarks
This chapter has introduced in detail the current state of synthesis, characteriza­
tion, and microstructure of tin oxides. It has been clearly shown that tin oxide
nanocrystals are a promising strategic material for fabricating unexpected nano­
structures with controllable size and morphology and adjustable properties. With
recent advances in the feld of metal oxide nanofabrication techniques, smart arti-
fcial tin oxide nanocrystals should be drawing more attention and fnding many
uses in a variety of applications, including optics, electronics, solar cells, and
sensing. Some of these properties are tunable based on the adjustment of the re­
lated fabrication processes and the structural parameters of the nanostructures.
Due to these interesting and tunable properties, some fabricated nanostructures
are close to being incorporated into micro/nanodevices. Some challenges still
remain, however, in clarifying the intricate aspects of these thin flms and the
applications of SnO
2
thin flms.
6. acknowledGments
The work described in this chapter was fnancially supported by the Shanghai
Pujiang Program (Project Number 10PJ1404100), China, Key Innovation Fund of
Shanghai Municipal Education Commission (Project Number 10ZZ64), National
Natural Science Foundation of China (Project Numbers 11074161 and 20871081,
Key Project Number 40830744), Science and Technology Commission of Shanghai
Municipality (Project Numbers 10JC1405400, 09530501200, and 09XD1401800),
and Shanghai Leading Academic Discipline Project (Project Number S30109). This
work was also supported by a grant from the City University of Hong Kong (Project
Number 7002657).
references
Abello L., Bochu B., Gaskov A., Koudryavtseva S., Lucazeau G., and Roumyantseva M.
(1998) Structural characterization of nanocrystalline SnO
2
by X-ray and raman spec­
troscopy. J. Solid State Chem. 135, 78–85.
Baur W.H. (1956) Uber die verfeinerung der kristallstrukturbestimmung einiger Vertreter
des Rutiltyps: TiO
2
, SnO
2
, GeO
2
und MgF
2
. Acta Crystallogr. 9, 515–520.
Diéguez A., Romano-Rodríguez A., Vilà, A., and Morante J.R. (2001) The complete
Raman spectrum of nanometric SnO
2
particles. J. Appl. Phys. 90, 1550–1557; DOI:
10.1063/1.1385573.
Chen Z.W., Zhang S.Y., Tan S., Hou J.G., and Zhang Y.H. (1998) Fractal formation and
tunneling effects on the conductivity of Au/a-Ge bilayer flms. Thin Solid Films 322,
194–197; DOI: 10.1016/S0040­6090(97)00907­3.
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 25
Chen Z.W., Wang X.P., Tan S., Zhang S.Y., Hou J.G., and Wu Z.Q. (2001) Multifractal be­
havior of crystallization on Au/Ge bilayer flms. Phys. Rev. B 63, 165413­1­3­5; DOI:
10.1103/PhysRevB.63.165413.
Chen Z.W., Lai J.K.L., Shek C.H., and Chen H.D. (2003) Synthesis and structural charac­
terization of rutile SnO
2
nanocrystals. J. Mater. Res. 18, 1289–1292; DOI: 10.1557/
JMR.2003.0176.
Chen Z.W., Lai J.K.L., and Shek C.H. (2004) Insights into microstructural evolution from
nanocrystalline SnO
2
thin flms prepared by pulsed laser deposition. Phys. Rev. B 70,
165314­1­7; DOI: 10.1103/PhysRevB.70.165314.
Chen Z.W., Lai J.K.L., and Shek C.H. (2005a) High-resolution transmission electron
microscopy investigation of nanostructures in SnO
2
thin flms prepared by pulsed laser
deposition. J. Solid State Chem. 178, 892–896; DOI: 10.1016/j.jssc.2005.01.013.
Chen Z.W., Lai J.K.L., Shek C.H., and Chen H.D. (2005b) Nucleation and growth of SnO
2

nanocrystallites prepared by pulsed laser deposition. Appl. Phys. A 81, 959–962.
Chen Z.W., Kai J.K.L., and Shek C.H. (2005c) Multifractal spectra of scanning electron
microscope images of SnO
2
thin flms prepared by pulsed laser deposition. Phys. Lett. A
345, 218–223; DOI: 10.1016/j.physleta.2005.05.104.
Chen Z.W., Lai J.K.L., and Shek C.H. (2006a) Quantum dot formation and dynamic scaling
behavior of SnO
2
nanocrystals induced by pulsed delivery. Appl. Phys. Lett. 88, 033115­
1­4; DOI: 10.1063/1.2162689.
Chen Z.W., Lai J.K.L., and Shek C.H. (2006b) Facile strategy and mechanism for orthor­
hombic SnO
2
thin flms. Appl. Phys. Lett. 89, 231902­1­3; DOI: 10.1063/1.2399352.
Chen Z.W., Wu C.M.L., Shek C.H., Lai J.K.L., Jiao Z., and Wu M.H. (2008) Pulsed laser
ablation for tin dioxide: Nucleation, growth, and microstructures. Crit. Rev. Solid State
Mater. Sci. 33, 197–209; DOI: 10.1080/10408430802415006.
Chen Z.W., Pan D.Y., Zhao B., Ding G.J., Jiao Z., Wu M.H., Shek C.H., Wu C.M.L., and
Lai. J.K.L. (2010) Insight on fractal assessment strategies for tin dioxide thin flms. ACS
Nano 4, 1202–1208; DOI: 10.1021/nn901635f.
Chen Z.W., Jiao Z., Wu M.H., Shek C.H., Wu C.M.L., and Lai J.K.L. (2011) Microstructural
evolution of oxides and semiconductor thin flms. Prog. Mater. Sci. 56, 901–1029; DOI:
10.1016/j.pmatsci.2011.02.001.
Cheng B., Russell J.M., Shi W.S., Zhang L., and Samulski E.T. (2004) Large-scale, solution-
phase growth of single­crystalline SnO
2
nanorods. J. Am. Chem. Soc. 126, 5972–5973;
DOI: 10.1021/ja0493244.
Chopra K.L., Major S., and Pandya D.K. (1993) Transparent conductors—A status review.
Thin Solid Films 102, 1–46; DOI: 10.1016/0040­6090(83)90256­0.
Chrisey D.B. and Hubler G.K. (1994) Pulsed Laser Deposition of Thin Films. Wiley, New York.
Combe N. and Jensen P. (1998) Changing thin-flm growth by modulating the incident fux.
Phys. Rev. B 57, 15553–15560; DOI: 10.1103/PhysRevB.57.15553.
Dai Z.R., Gole J.L., Stout J.D., and Wang Z.L. (2002) Tin oxide nanowires, nanoribbons,
and nanotubes. J. Phys. Chem. B 106, 1274–1279; DOI: 10.1021/jp013214r.
Dolbec R., El Khakani M.A., Serventi A.M., Trudeau M., and Saint-Jacques R.G. (2002)
Microstructure and physical properties of nanostructured tin oxide thin flms grown
by means of pulsed laser deposition. Thin Solid Films 419, 230–236; DOI: 10.1016/
S0040­6090(02)00769­1.
26 • CheMiCaL SenSorS – SiMULation and ModeLinG: VoLUMe 1
Gervais F. and Kress W. (1985) Ab initio phonon dispersion curves of Si. Phys. Rev. B 31,
4089–4091; DOI: 10.1103/PhysRevB.31.4089.
Godbole V.P., Vispute R.D., Chaudhari S.M., Kanetkar S.M., and Ogale S.B. (1990)
Dependence of the properties of laser deposited tin oxide flms on process variables.
J. Mater. Res. 5, 372–377; DOI: 10.1557/JMR.1990.0372.
Hinnemann B., Hinrichsen H., and Wolf D.E. (2001) Unusual scaling for pulsed laser depo­
sition. Phys. Rev. Lett. 87, 135701­1–1­4; DOI: 10.1103/PhysRevLett.87.135701.
Hu M., Noda S., and Komiyama H. (2002) A new insight into the growth mode of metals on
TiO
2
(110). Surf. Sci. 513, 530–538; DOI: 10.1016/S0039­6028(02)01856­3.
Huang L.J., Liu B.X., Ding, J.R., and Li, H.D. (1989) Multifractal characteristics of
magnetic-microsphere aggregates in thin flms. Phys. Rev. B 40, 858–861; DOI:
10.1103/PhysRevB.40.858.
Joint Committee for Powder Diffraction Standards (JCPDS) Data Card. (1995) International
Center of Diffraction Data, Swarthmore, PA, 72­1147.
Katiyar R.S., Dawson P., Hargreave M.M., and Wilkinson G.R. (1971) Dynamics of the
rutile structure. III. Lattice dynamics, infrared and Raman spectra of SnO
2
. J. Phys. C:
Solid State Phys. 4, 2421–2431; DOI: 10.1088/0022­3719/4/15/027.
Kohl D. (2001) Function and applications of gas sensors. J. Phys. D: Appl. Phys. 34, R125–
R149; DOI: 10.1088/0022­3727/34/19/201.
Korotcenkov G. (2008) The role of morphology and crystallographic structure of metal oxi­
des in response of conductometric­type gas sensors. Mater. Sci. Eng. R 61, 1–39; DOI:
10.1016/j.mser.2008.02.001.
Lal R., Grover R., Vispute R.D., Viswanathan R., Godbole V.P. and Ogale S.B. (1991) Sensor
activity in pulsed laser deposited and ion implanted tin oxide thin flms. Thin Solid Films
206, 88–93; DOI: 10.1016/0040-6090(91)90398-H.
Li H., Ding Z.J., and Wu Z.Q. (1995) Multifractal behavior of the distribution of secondary-
electron­emission sites on solid surfaces. Phys. Rev. B 51, 13554–13559; DOI: 10.1103/
PhysRevB.51.13554.
Li H., Ding Z.J., and Wu Z.Q. (1996) Multifractal analysis of the spatial distribution of
secondary­electron emission sites. Phys. Rev. B 53, 16631–16636; DOI: 10.1103/
PhysRevB.53.16631.
McCarthy G. and Welton J. (1989) X-ray diffraction data for SnO
2
. An illustration of the
new powder data evaluation methods. Powder Diffr. 4, 156–159.
Moldovan D., Yamakov V., Wolf D., and Phillport S.R. (2002) Scaling behavior of grain­
rotation­induced grain growth. Phys. Rev. Lett. 89, 206101­1­4; DOI: 10.1103/
PhysRevLett.89.206101.
Musolino V., Dal Corso A., and Selloni A. (1999) Initial stages of growth of copper on
MgO(100): A frst principles study. Phys. Rev. Lett. 83, 2761–2764; DOI: 10.1103/
PhysRevLett.83.2761.
Nagano M. (1984) Growth of SnO
2
whiskers by VLS mechanism. J. Cryst. Growth 66, 377–
379; DOI: 10.1016/0022­0248(84)90221­5.
Ng H.T., Li J., Smith M.K., Nguyen P., Cassell A., Han J., and Meyyappan M. (2003) Growth
of epitaxial nanowires at the junctions of nanowalls. Science 300, 1249; DOI: 10.1126/
science.1082542.
Ohta S. and Honjo H. (1988) Growth probability distribution in irregular fractal-like
MiCroStrUCtUraL CharaCteriZation oF tin dioXide thin FiLMS • 27
crystal growth of ammonium chloride. Phys. Rev. Lett. 60, 611–614; DOI: 10.1103/
PhysRevLett.60.611.
Pan Z.W., Dai Z.R., and Wang Z.L. (2001) Nanobelts of semiconducting oxides. Science
291, 1947–1949; DOI: 10.1126/science.1058120.
Peercy P.S. and Morosin B. (1973) Pressure and temperature dependences of the Raman­
active phonons in SnO
2
. Phys. Rev. B 7, 2779–2786; DOI: 10.1103/PhysRevB.7.2779.
Penn R.L. and Banfeld J.F. (1998) Imperfect oriented attachment: Dislocation generation in
defect­free nanocrystals. Science 281, 969–971; DOI: 10.1126/science.281.5379.969.
Phillips H.M., Li Y., Bi Z., and Zhang B. (1996) Reactive pulsed laser deposition and laser
induced crystallization of SnO
2
transparent conducting thin flms. Appl. Phys. A 63,
347–351; DOI: 10.1007/BF01567325.
Sato T. and Asari T. (1995) Temperature dependence of the linewidth of the frst-order
Raman spectrum for SnO
2
crystal. Jpn. J. Appl. Phys. 64, 1193–1199; DOI: 10.1143/
JPSJ.64.1193.
Sberveglieri G. (ed.) (1992) Gas Sensors—Principles Operation and Development. Kluwer
Academic Publishers, Dordrecht, The Netherlands.
Schierbaum K.D. and Weimar U. (1992) Comparison of ceramic, thick-flm and thin-
flm chemical sensors based upon SnO
2
. Sens. Actuators B 7, 709–716; DOI:
10.1016/0925-4005(92)80390-J.
Serventi A.M., Dolbec R., El Khakani M.A., Saint-Jacques R.G., and Rickerby D.G. (2003)
High-resolution transmission electron microscopy investigation of the nanostructure of
undoped and Pt­doped nanocrystalline pulsed laser deposited SnO
2
thin flms. J Phys.
Chem Solids 64, 2097–2103; DOI: 10.1016/S0022­3697(03)00262­2.
Traylor J.G., Smith, H.G., Nicklow R.M., and Wilkinson M.K. (1971) Lattice dynamics of
rutile. Phys. Rev. B 3, 3457–3472; DOI: 10.1103/PhysRevB.3.3457.
Von Allmen M. and Blatter A. (1995) Laser-Beam Interactions with Materials. Springer­
Verlag, New York.
Wang D.Z., Wen S.L., Chen J., Zhang S.Y., and Li F.Q. (1994) Microstructure of SnO
2.
Phys.
Rev. B 49, 14282–14285; DOI: 10.1103/PhysRevB.49.14282.
Wang B., Wang Y., and Wu Z.Q. (1995) Multifractal behavior of solid-on-solid growth. Solid
State Commun. 96, 69–72; DOI: 10.1016/0038­1098(95)00383­5.
Wang Z.L. and Kang Z. C. (1998) Functional and Smart Materials: Structural Evolution and
Structure Analysis. Plenum Press, New York.
Wang Z.L. (2003) Nanobelts, nanowires, and nanodiskettes of semiconducting oxides—From
materials to nanodevices. Adv. Mater. 15, 432–436; DOI: 10.1002/adma.200390100.
Willmott P.R. and Huber J.R. (2000) Pulsed laser vaporization and deposition. Rev. Mod.
Phys. 72, 315–328; DOI: 10.1103/RevModPhys.72.315.
Xie C., Zhang L., and Mo C. (1994) Characterization of Raman spectra in nano-SnO
2
solids.
Phys. Status Solidi A 141, K59–K61; DOI: 10.1002/pssa.2211410138.
Zheng J.G., Pan X.Q., Schweizer M., Weimar U., Göpel W., and Rühle M. (1996)
Dislocations in nanocrystalline SnO
2
thin flms. Phils. Mag. Lett. 73, 93–100; DOI:
10.1080/095008396180885.
Zhu X., Birringer R., Herr U., and Gleiter H. (1987) X-ray diffraction studies of the structure
of nanometer­sized crystalline materials. Phys. Rev. B 35, 9085–9090; DOI: 10.1103/
PhysRevB.35.9085.
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Momentum Press is proud to bring to you Chemical Sensors: Simulation and Modeling Volume 1: Microstructural
Characterization and Modeling of Metal Oxides, edited by Ghenadii Korotcenkov. This is the frst of a new four-
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andapplicationofvariousdevicesforchemicalsensing.Eachsimulationandmodelingvolumeinthepresent
series reviews modeling principles and approaches peculiar to specifc groups of materials and devices applied
for chemical sensing.
About the editor
Ghenadii KorotcenkovreceivedhisPh.D.inPhysicsandTechnologyofSemiconductorMaterialsandDe-
vicesin1976,andhisHabilitateDegree(Dr.Sci.)inPhysicsandMathematicsofSemiconductorsandDielec-
tricsin1990.Formanyyears,hewasaleaderoftheGasSensorGroup,andmanagerofvariousnationaland
internationalscientifcandengineeringprojectscarriedoutintheLaboratoryofMicro-andOptoelectronics,
TechnicalUniversityofMoldova.Currently,Dr.KorotcenkovisaresearchProfessorattheGwangjuInstitute
ofScienceandTechnology,RepublicofKorea.HisresearchhasincludedsignifcantworkonSchottkybarri-
ers,MOSstructures,nativeoxides,andphotoreceiversonthebaseofIII-Vscompounds.Hecontinueswith
research in various aspects of materials sciences and surface science, with a particular focus on nanostructured
metaloxidesandsolidstategassensordesign.Dr.Korotcenkovistheauthororeditorofelevenbooksandspe-
cial issues, eleven invited review papers, seventeen book chapters, and more than 190 peer-reviewed articles.
HisresearchactivitieshavebeenhonoredwiththeAwardoftheSupremeCouncilofScienceandAdvanced
TechnologyoftheRepublicofMoldova(2004)andThePrizeofthePresidentsoftheUkrainian,Belarusand
MoldovanAcademiesofSciences(2003),amongmanyothers.
ISBN: 978-1-60650-309-6
9 781606 503096
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www.momentumpress.net
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CHEMICAL SENSORS VoLuME 1: MICrostruCturAL CHArACtErIzAtIon
And ModELIng of MEtAL oxIdEs — Edited by ghenadii Korotcenkov, Ph.d., dr. sci.
A volume in the Sensors Technology SeriesEditedbyJoeWatson
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