Experimental and theoretical study on VO2-based

nanostructures for environmental applications

Zhengjie Zhang
A thesis in fulfilment of the requirements for the degree of

Doctor of Philosophy

Laboratory for Simulation and Modelling of Particulate Systems

School of Materials Science and Engineering

Faculty of Science

The University of New South Wales

March 2014
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Acknowledgements

I thank my supervisor A/Prof. Xuchuan Jiang for the financial support, constant

supervision of experimental design, result analysis and manuscript preparation. I

acknowledge his patience in every discussion that resulted in much of the material in

this thesis. I am also highly indebted to him for boosting my confidence and interest in

research. I also thank my co-supervisor, Prof. Aibing Yu, who is a great mentor for

building a career as a research scientist.

I would like to express my appreciation of the technical staff in the Electron Microscope

Unit and Solid State and Elemental Analysis Unit. I also thank my friends and

colleagues in the School of Materials Science and Engineering, especially Mr Yusuf

Kaneti, Mr. Haitao Fu, Mr Chuyang Chen, Dr. Jeffery Yue, Dr. Ruiping Zhou, Mr.

Changxing Li, Mr. Yongli Cui and Dr. Pramod Koshy, for their help in my PhD study

and life.

I thank Prof. Wen-Bin Jian and Dr. Shao-Chien Chiu from National Chiao Tung

University, Prof. Yanfeng Gao and Mr. Zhang Chen from Shanghai Institute of

Ceramics for their collaboration and helpful discussion in the experiment.

Most importantly, I want to acknowledge the loving support of my family. I cannot find

words to express my gratitude to my wife, who has given me a lot of encouragement

and support. My sister gives me the best example of love and hard work in my whole

life. I also thank my son, who has given me lots of happiness and passion in life.
List of Publications and Presentations

1. Synthesis of Porous FeVO4 Nanorods for Effective Detection of Volatile Organic

Compounds. Y. V. Kaneti, Z. J. Zhang, J. Yue, X. C. Jiang and A. B. Yu. Journal of
Nanoparticle Research (2013) 15:1948.
2. A Hydrothermal Approach to Low-dimensional Vanadium Dioxide Nanostructures
for Gas Sensing. Z. J. Zhang, A. B. Yu and X. C. Jiang. Chemeca #252, 2012.
3. Crystal plane-dependent gas-sensing properties of zinc oxide nanostructures:
experimental and theoretical studies Y.V. Kaneti, Z.J. Zhang, J. Yue, Q.
M.D.Zakaria, C.Y. Chen, X.C. Jiang and A. B Yu. Phys. Chem. Chem. Phys.,
2014,16, 11471-11480.
4. Hydrothermal synthesis of sodium vanadium oxide nanorods for gas sensing
application Z. J. Zhang, Y. V. Kaneti, X. C. Jiang and A. B. Yu. Sensors and
Actuators B: Chemical DOI: 10.1016/j.snb.2014.05.064.
5. Solvothermal synthesis of ZnO-decorated α-Fe2O3 nanorods with highly enhanced
gas-sensing performance toward n-butanol Y. V. Kaneti, Q. M.D.Zakaria, Z. J.
Zhang, C. Y. Chen, Q. M.D. Zakaria, J. Yue, X. C. Jiang and A. B. Yu. J. Mater.
Chem. A DOI: 10.1039/C4TA01837K
6. Hydrothermal Synthesis of Carbonaceous Nanotubes and Their Conversion to
Nanocables. C. Y. Chen, Z. J. Zhang, A. B. Yu and X. C. Jiang. (To submit).
7. Vanadium Dioxide Thin Films Prepared by Electrodeposition on Transparent
Conductive Substrate for Smart Window application. Z. J. Zhang, Y. V. Kaneti, X.
C. Jiang and A. B. Yu. (To submit).
8. The Electronic Structure and Optical Properties Investigation of Al, Ti and Cr
doped VO2 by First-principles Simulation. Z. J. Zhang, Y. V. Kaneti, X. C. Jiang
and A. B. Yu. (Drafting).
9. Novel Metal Vanadates Nanomaterials for Gas Sensing Application. ChinaNANO
5th-7th September, 2013. Beijing (oral presentation)
10. Hydrothermal Synthesis of Sodium Vanadium Oxide Nanoparticles for Gas
Sensing Application. 8th annual conference of the ARCCFN, 15-16 November,
2012 Sydney.
Abstract
Vanadium dioxide has shown great potential for many applications such as smart

window coatings, switches and sensors because of their unique thermochromic

properties. Many methods have been developed to prepare VO2 thin films/nanoparticles

to understand the phase transition mechanisms, however, there are still some limitations

in the synthesis of particles and films, due to difficulties in synthesizing crystalline

VO2(M/R) nanoparticles, high cost for film fabrication, complicated preparation

procedures and toxic precursors, and this has impeded the progress in

commercialization.

This thesis aims to study the preparation of vanadium dioxide nanoparticles and thin

films and their functional properties, using a combinatorial approach involving

experimental and computational aspects. A simple but efficient hydrothermal method

has been developed and used to synthesize vanadium oxide and sodium vanadium oxide

nanoparticles with promising potential in gas sensing. The thermochromic properties of

single VO2 nanoparticle have been measured using Ti/Au electrodes under a scanning

electron microscope assisted system. The electrodeposition and spin-coating methods

have been utilized to deposit VO2 thin films, and the thermochromic properties have

been measured under different conditions. In order to fundamentally understand the

metal-doped VO2 nanocompounds and the mechanisms governing the temperature-

related phase change, the computational simulation method ̶ density functional theory

(DFT) was employed to quantify the relationship between crystallographic and

electronic structure and functions. The findings in this thesis can be used to design and

construct unique nanostructures with unique properties promising for applicability as

smart window coatings and gas sensors.

Table of Contents

Table of Contents ......................................................................................... i

Caption of Figures ........................................................................................ i
Caption of Tables ....................................................................................... ix
List of Abbreviations................................................................................... x
Chapter 1. Introduction ........................................................................... 1
Chapter 2. Literature Review ................................................................. 4
2.1 Phase Transition ........................................................................................4
2.1.1 Transition between M1, M2 and R ............................................................. 5
2.1.2 Transition from B to A and R ..................................................................... 9
2.2 Synthesis and Modification of VO2 Nanoparticles ...................................9
2.2.1 Hydrothermal or Solvothermal ................................................................. 10
2.2.2 Thermolysis ............................................................................................... 14
2.2.3 Surface Modification ................................................................................. 15
2.3 Preparation and Modification of VO2 Thin Film ....................................17
2.3.1 Physical Vapour Deposition Method ........................................................ 18
2.3.2 Chemical Vapour Deposition Method ...................................................... 21
2.3.3 Sol-gel Method .......................................................................................... 23
2.3.4 Electrodeposition Method ......................................................................... 26
2.3.5 Doping Effect ............................................................................................ 28
2.3.6 Anti-reflection Coating ............................................................................. 32
2.3.7 Substrate Effect ......................................................................................... 34
2.4 Theoretical (DFT) Simulation of VO2 ....................................................37
2.4.1 Density Function Theory........................................................................... 37
2.4.2 Pure VO2 ................................................................................................... 39
2.4.3 Doped VO2 ............................................................................................... 41
2.5 Applications ............................................................................................45
2.5.1 Smart Window Coatings ........................................................................... 45
2.5.2 Lithium-ion Battery................................................................................... 48
 2.5.3 Sensor ........................................................................................................ 50
2.5.4 Switch........................................................................................................ 52
2.6 Summary .................................................................................................53
Chapter 3. Hydrothermal Synthesis of VO2 Nanoparticles for Gas
Sensing Performance ................................................................................ 55
3.1 Introduction .............................................................................................55
3.2 Synthesis of VO2(B) Nanoparticles ........................................................56
3.2.1 Experimental Section ................................................................................ 56
3.2.2 Structure and Morphology ........................................................................ 59
3.2.3 VO2-TiO2 nanocomposites ........................................................................ 67
3.3 Gas Sensing Properties ............................................................................69
3.4 Transformation to VO2(M1) ...................................................................72
3.5 Conclusions .............................................................................................73
Chapter 4. The Electrodeposition Method to Prepare VO2 Thin Films
for Smart Window Coatings .................................................................... 74
4.1 Introduction .............................................................................................74
4.2 VO2 Thin Films Prepared by the Electrodeposition Method ..................77
4.2.1 Experimental Section ................................................................................ 77
4.2.2 Fabrication of Pure VO2 thin film ............................................................. 80
4.2.3 Tungsten (W) Doped VO2 Thin Film........................................................ 90
4.3 Metal-to-semiconductor Transition Property ..........................................95
4.3.1 Experimental Section ................................................................................ 95
4.3.2 Results and Discussion.............................................................................. 97
4.4 Conclusions ...........................................................................................103
Chapter 5. Density Functional Theory (DFT) Simulation of Al, Cr
and Ti Doped VO2 ................................................................................... 104
5.1 Introduction ...........................................................................................104
5.2 Computational Details ...........................................................................107
5.3 Electronic and Optical Properties of Pure VO2 .....................................108
5.3.1 U Parameter Test ..................................................................................... 110
5.3.2 Cut-off Energy Test................................................................................. 110
5.3.3 Electronic and Optical Properties Investigation ...................................... 111
 5.4 Effect of Al Doping ...............................................................................113
5.5 Effect of Ti Doping ...............................................................................116
5.6 Effect of Cr Doping ...............................................................................118
5.7 Summarisation .......................................................................................120
5.8 Doping Effect on Phase Transition Temperature ..................................123
5.9 Conclusions ...........................................................................................124
Chapter 6. Hydrothermal Synthesis of Sodium Vanadium Oxide
Nanoparticles for Gas Sensing Application .......................................... 126
6.1 Introduction ...........................................................................................126
6.2 Experimental Section ............................................................................128
6.2.1 Chemicals ................................................................................................ 128
6.2.2 Synthesis Procedures ............................................................................... 129
6.2.3 Characterizations ..................................................................................... 129
6.2.4 Gas Sensing Measurements .................................................................... 130
6.2.5 Computational Details............................................................................. 131
6.3 Structure and Morphology ....................................................................131
6.4 Gas Sensing Performance .....................................................................137
6.5 Gas Sensing Mechanism .......................................................................140
6.6 Conclusions ...........................................................................................145
Chapter 7. Summary and Future Work ............................................ 147
7.1 Summary ...............................................................................................147
7.2 Future Work ..........................................................................................149
Chapter 8. References .......................................................................... 151
Caption of Figures

Figure Caption Page

2-1 The unit cell of different phases of VO2 and the transition between 4
them (V, O atoms are shown in gray and red, respectively).
2-2 Images of the near-field scattering amplitude over the same 4-μm-by- 6
4-μm area obtained by s-SNIM operating at the infrared frequency ω
= 930 cm–1, which are displayed for representative temperatures in
the insulator-to-metal transition regime of VO2 to show percolation in
progress. The metallic regions (light blue, green, and red colors) give
higher scattering near-field amplitude compared with the insulating
phase (dark blue color).
2-3 (a) SEM images of the microfabricated push-to-pull (PTP) device. 7
When the device is pushed on the semicircle end (arrow at left), the
specimen gap (dashed rectangle) expands while staying in the field of
view of the electron microscope. (b) The linear force vs displacement
response of the PTP device without a nanowire spanning the
specimen gap, showing the inherent stiffness of the device. (c) The
uniaxial stress (along the cR direction) temperature phase diagram of
VO2. The arrow indicates the phase transition route under tensile
loading at room temperature. (d) A higher magnification SEM image
of the specimen gap of the PTP device with a VO2 nanowire fixed
across the gap by Pt welds. Two platinum dots were deposited on the
sample as indicated by two arrows in the middle of the nanowire for
directly measuring strain of the sample.
2-4 (a) Arrangement of vanadium ions in the phases involved in the MIT, 8
indicating their different vanadium chain periods and dimerization
(yellow). (b) Expected layout of the stress–temperature phase
diagram near the MST, showing the transition temperature Tc at zero
stress. (c) Experimental geometry, showing an electron micrograph
(right) of a VO2 nanobeam suspended across a slot of width L in a
silicon chip (left, optical micrograph) whose width is controlled by
pushing on the paddle and measured by deflection of a laser beam.
The yellow lines signify gold wire bonds. (d) Series of optical images
showing movement of the R–M1 and M1–M2 interfaces as L is
increased in roughly 100-nm steps at 64 °C.
2-5 TEM images (left), XRD patterns (middle) and DSC curves (right) of 12
samples prepared by the hydrothermal treatment at 260 °C for (a) 4 h,
(b) 16 h, (c) 18 h, and (d) 20 h, which shows the progress of
transition from VO2(B) to VO2(R).

Page i
2-6 Schematic illustration of the preparation of (VO(O)2(TOA)) 13
complexes, followed by the formation of alkyl amine capped
vanadium oxide NCs (left), and effect of steric ligands on the size of
vanadium oxide NCs (right). TEM images and corresponding SAED
patterns of the VO2 NC samples prepared from different vanadium
complex precursors: (a) VO(O2)2(TPA), (b)VO(O2)2(TOA), and (c)
VO(O2)2(CTA).
2-7 (a and b) Photographs of sample films at room temperature, (c) 16
optical transmittance spectra of sample films in UV-visible-near-IR
range, and (d) thermal hysteresis of sample films at a wavelength of
1500 nm.
2-8 Illustration of preparation process (left), HRTEM (middle) and 17
thermochromic properties of the films casting from VO2/TiO2
core/shell nanorods (right).
2-9 From left to right, scanning electron micrographs of nanoparticle and 20
thin film morphology, relative IR (λ= 980 nm) switching curves
through the structural phase transition; and x-ray diffraction θ/2θ vs
annealing time for pulsed laser deposited vanadium oxide films of
100 nm thickness fabricated at 450 °C in 250 mTorr of O2 to
crystallize them into VO2. From top to bottom 5, 10, 20, 40, and 80
min of annealing time. Notice the enhanced hysteresis, sharpness of
the transition and grain growth.
2-10 Schematic representation of the APCVD equipments. 21
2-11 SEM images for: (a) undoped VO2, (b) W-doped VO2 thin film 23
prepared by AACVD (left). Transmittance (a) and reflectance (b) IR
spectra for V0.9902W0.0098O2 thin film, above and below the transition
temperature (right).
2-12 SEM images and optical transmittance spectra of a PVP free film (a- 25
c) and a PVP-employing film (d-f) on fused-silica substrates.
2-13 Electrochemistry of V5+-TEA electrolyte at 80 °C on Pt coated quartz 27
(left). (a) Linear sweep voltammogram together with corresponding
mass changes. (b) Steady-state deposition rate dependence on the
applied potential obtained from mass vs time transients (black circles
and dashed lines) and steady state current density vs potential
dependence (green triangles and dotted line). Electrical transport
characterization of the annealed VO2 film (right). (a) Temperature
dependence of the normal to the film plane resistance showing the
MIT temperatures upon heating (red) and cooling (blue) measured at
0.5 K·min-1. Transition temperatures were determined from (b) a plot
of d(log(R))/dt vs T. (c) I-V characteristic of the VO2 film measured

Page ii
 at room temperature.
2-14 XAFS results for WxV1-xO2 (up). (a) The V K-edge EXAFS 29
oscillations and (b) their Fourier transforms for WxV1-xO2 samples,
along with the VO2 theoretical results of monoclinic (M1), rutile (R)
and monoclinic (M2) phases for references. (c) the WL3-edge
EXAFS oscillations and (d) their Fourier transforms, along with the
reference WO3 result, and the simulated curves for W-substituted
monoclinic and tetragonal VO2 phases. The bond distances as a
function of W concentration (bottom). The bond distances of the
nearest three shells of (a) V and (b) W as the center atom, based on
the XAFS fitting results of each sample with different W doping
concentration.
2-15 The phases, morphologies and phase transition behaviours of F-doped 31
VO2 nanopowders with different dopant concentrations (top). (a)
XRD patterns. (b) DSC curves. (c–e) TEM image, SAED pattern and
HRTEM of undoped and 2.93% F-doped VO2 nanopowders,
respectively. The optical and electrical properties of F-doped VO2
nanopowders with different dopant concentrations (bottom). (a) The
transmittance spectra of VO2-PU composite foils at 20 and 80 °C. (b)
The absorbance spectra of VO2-PU composite foils at 20 °C. (c) The
carrier density of VO2 nanopowders with different F doped
concentrations at different temperatures. (d) The resistivity of F-
doped VO2 nanopowders at different temperatures.
2-16 Luminous transmittance for normal incidence onto glass with an 33
antiflected VO2 coating, as indicated in the inset.
2-17 Spectral transmittance and reflectance at 20 and 80 °C for TiO2 (25 34
nm)/VO2 (50 nm)/TiO2 (25 nm) on SiO2 in comparison to VO2 (50
nm) on SiO2. Transmittance at 2000 nm as a function of temperature
for both films on SiO2.
2-18 Temperature dependence of resistivity for the VO2 films formed on 35
TiO2 (001) and TiO2 (110) Substrates (left). Phase transition
temperature vs lattice parameter c for the VO2 films deposited on
TiO2 (001) and TiO2 (110) substrates (right).
2-19 The electrical resistance plotted as a function of temperature for VO2 36
films grown on c- and r-sapphire substrates (left). The in-plane
arrangements and calculated misfits for monoclinic VO2 unit cells on
(a) c-sapphire and (b) r-sapphire, for (200) growth orientation of VO2
(right).
2-20 Molecular orbital diagram depicting the electronic structure of the 39
monoclinic and tetragonal phases of VO2. The left MO diagram
corresponds to the undistorted metallic phase of VO2, whereas the
diagram on the right shows the altered MO diagram upon transition to
Page iii
 the distorted insulating phase of VO2.
2-21 The calculated DOS of W-doped VO2(R) and VO2(M1) at the levels 42
of GGA + U (a & b) and HSE06 (c & d).
2-22 The calculated VO2 and F-doped VO2 structures and electronic 44
properties. The unit cell (a) with 4 V atoms and 8 O atoms and 2 *2 *
2 supercell (c). V atoms are shown in gray, F atom in blue and the O
atoms in brown and red. Band structure, total density of states and
partial density of states for V and O calculated for pure VO2 (b) and
F-doped VO2 with the F/(F + O) atom ratio 0.0156 (d).
2-23 (a) Digital photograph of the film; (b) temperature-dependent 48
transmittance spectra; (c) a hysteresis loop of a large-area (30*40
cm2) W-doped VO2 film; and (d) an image of model house (1,
temperature monitor; 2, VO2 glass; 3, temperature probe; 4, infrared
lamp; and 5,blank float glass).
2-24 (a, b) Charge/discharge curves of hierarchical vanadium oxide 50
nanowires at voltages of 2-4 and 1.75-4 V, respectively. (c, d)
Capacity vs cycle number, and Coulombic efficiency vs cycle
number of the ultralong hierarchical vanadium oxide nanowires.
2-25 (a) The design and principle of operation of VO2 NW MIT gas 51
sensor. PG and PL indicate heat fluxes dissipating in to the gas
environment and metal contacts correspondingly. (b) Realization of
the sensor using thin long nanowire with its ends immersed in the Ga-
In-Sn liquid microdroplets. The electrodes of the NIST μhp served as
the base for the liquid contacts. (c) Alternatively, wide microscopic
VO2 ribbons were employed when the imaging of the metal (M) and
insulator (I) domains dynamics was required. (d, e) The appearance
and evolution of the M domains (dark) with increasing the Joule heat
(optical images were taken with 1000× magnification, scale bars
correspond to 10 μm).
2-26 Schematic diagram of the sandwiched nanostrips (a, b) and SEM 53
image of a sample (c).
3-1 XRD patterns VO2(B) nanostructures using different reducing agents: 59
(a) citric acid, (b) ethanol and (c) ethylene glycol.
3-2 SEM images of VO2(B) nanostructures using different reducing 60
agents: (a) ethylene glycol, (b) ethanol and (c) citric acid.
3-3 XRD patterns of products obtained with different molar ratio between 61
V2O5 and citric acid: (a) 1:2, (b) 2:3, (c) 1:1, (d) 3:2 and (e) 2:1.
3-4 SEM images of products obtained with different molar ratio between 62
V2O5 and citric acid: (a) 2:1, (b) 3:2, (c) 1:1, (d) 2:3 and (e) 1:2.

Page iv
3-5 XRD pattern of the synthesized VO2(B) products. 63
3-6 SEM images of VO2 nanostructures obtained with different 65
surfactants and molar ratio: (a-c) VO(acac)2:CTAB =10:1, 1:1 and
1:10, respectively; (d-f) VO(acac)2:PVP=10:1, 1:1 and 1:10,
respectively; (g-i) VO(acac)2:AOT=10:1, 1:1 and 1:10, respectively.
3-7 TEM (a) and HRTEM (b) image of VO2(B) obtain at 180 °C for 24 h 66
with CTAB.
3-8 Schematic illustration of the formation process of the as-obtained 67
flower-like VO2(B) structures.
3-9 SEM images of VO2 particles (a) and VO2 particles coated with 0.1 67
ml (b), 0.3 ml (c) and 0.5 ml (d) TBT added into VO2 solution.
3-10 TEM images of TiO2 coated VO2 particles before and after boiling. 68
3-11 Energy Dispersive Spectroscopy images of the VO2 coated with 69
TiO2.
3-12 Real time sensing characteristics of VO2 nano-structure towards 70
ethanol, acetone, butanol and isopropanol.
3-13 Sensing responses versus vapor concentration of isopropanol, 71
acetone, butanol and ethanol.
3-14 XRD patterns of products obtained after annealing VO2(B) at 72
different conditions: (a) 500 °C 2 h, (b) 550 °C 3 h, (c) 700 °C 2 h
and (d) magnified XRD region between 25° and 30° (2θ).
3-15 SEM (a, b) and TEM (c, d) images of VO2(M) and VO2 (B), 72
respectively.
4-1 Schematic demonstration of the electrodeposition method to prepare 78
VO2 thin film.
4-2 Linear sweep voltammogram measured at a scan rate of 10 mV·s-1. 80
4-3 Deposition current densities j as a function of time t and voltages of 81
VO2 thin films deposited for 10 mins.
4-4 XRD patterns of VO2 thin film on FTO substrate annealed at 400 °C 82
for 2 h, 500 °C for 2 h and 500 °C for 3 h.
4-5 Raman shift (left) and real pictures (right) of VO2 thin films 83
deposited at -1.3 V for 10 mins before (a) and after (b) annealing.
4-6 XPS spectra of V2p peak and its fitting curves for V4+ and V5+ 84
ingredients.
4-7 SEM images of FTO substrate (a), VO2 thin films deposited at -1.3 V 85

Page v
 for 10 mins (b), the inset is the higher magnification of the VO2 film,
the cross section images of FTO substrate (c) and VO2/FTO double
layers (d).
4-8 Reflectance spectra for the VO2/FTO double-layered films deposited 86
at different voltages.
4-9 Transmittance spectra of films that were deposited at 600 °C for 10 87
min at -1.22 V (black line), -1.25 V (red line), -1.3 V (green line) and
-1.35 V (blue line). The solid and dashed lines present films
measured at 20 and 90 °C, respectively.
4-10 Temperature dependence of the optical transmittance at a fixed 89
wavelength (2000 nm) for VO2 film.
4-11 Schematic illustration of VO2 films (top) grown on FTO (bottom) 90
(010) and (100) planes.
4-12 XRD patterns of WO3 thin film on FTO substrate annealed at 500 °C 91
for 3 h.
4-13 Raman shift of VO2/WO3 thin film on FTO substrate annealed at 92
different temperature for 3 h.
4-14 XRD pattern of VO2/WO3 films obtained by annealing at 550 °C for 93
3h in comparison with VO2 films, WO3 films and FTO substrate.
4-15 XPS spectra of V 2p core level of VO2/WO3 films (a) and 93
compositional depth profile of films measured by XPS (b).
4-16 SEM images of films obtained by varying VO2 deposition time while 94
fixing deposition time 5 mins for WO3 films: (a) 0, (b) 10 mins, (c) V
15 mins, (d) 20 mins and (e) 25 mins.
4-17 Illustration and SEM image of the measurement device. 97
4-18 XRD pattern (a) and Raman shift (b) of VO2 films prepared by spin- 98
coating.
4-19 SEM images of films prepared by spin-coating for different times: (a) 99
1 time, (b) 5 times, (c) 10 times, (d) 15 times and (e) 20 times.
4-20 SEM images of VO2 films with different concentration of W doping: 100
(a) 0 %, (b) 0.5%, (c) 1%, (d) 1.5% and (e) 2%.
4-21 Raman shift of VO2 films with different concentration of W doping. 100
4-22 The original I–V characteristic of the particle (left) and simultaneous 101
temperature-dependent resistance measurements (right).
4-23 Ln(R) vs 1/T plot showing thermally activated behaviour of VO2. 102

Page vi
5-1 (a) Unit cell of VO2(R), (b) the projection of the rutile structure along 109
[001], showing two perpendicular orientations of the octahedral and
(c) projection along [010], vanadium atoms built chains parallel to the
c axis of the structure. (V atoms, grey and O atoms, red).
5-2 (a) Unti cell of VO2(M1), (b) the projection of the monoclinic 109
structure, (c) projection along [001], vanadium atoms forms zigzag
chains. (V atoms, grey and O atoms, red).
5-3 (a) Band structure of VO2(M1), (b) Total DOS plots of VO2(M1), (c) 112
PDOS plot of O 2p orbitals and (d) PDOS plots of V 3d orbitals.
5-4 Reflectivity spectra of pure VO2 in the infrared spectral range. 113
Subscripts P and V represent E // chain and E ⊥ chain, respectively.
5-5 Crystal structure of (a) pure VO2(M1), (b) Al doped VO2(M1), (c) 114
Pure VO2(R) and (d) Al doped VO2(R). Vanadium atoms are grey
and oxygen atoms red.
5-6 DOS plots of (a) Al-doped VO2(M1), (b) doped Al in VO2(M1), (c) 115
Al-doped VO2(R) and (d) doped Al in VO2(R).
5-7 Reflectivity spectra of Al-doped VO2 in the near infrared spectral 115
region.
5-8 Crystal structure of (a) pure VO2(M1) and (b) Ti-doped VO2(M1). 116
5-9 DOS plots of (a) Ti-doped VO2(M1), (b) doped Ti in VO2(M1), (c) 117
Ti-doped VO2(R) and (d) doped Ti in VO2(R).
5-10 Reflectivity spectra of Ti-doped VO2 in the near infrared spectral 118
region.
5-11 DOS plots of (a) Cr-doped VO2(M1), (b) doped Cr in VO2(M1), (c) 119
Cr-doped VO2(R) and (d) doped Cr in VO2(R).
5-12 Reflectivity spectra of Cr-doped VO2 in the near infrared spectral 120
region.
5-13 Crystal structure of (a) Al-doped, (b) Ti-doped and (c) Cr-doped 120
VO2(R).
6-1 Supercell structure of V2O5 (a) and Na1.08V3O8 (b). 127
6-2 Schematic illustration of the gas sensor device and the gas sensing 130
measurement equipment.
6-3 Photograph of the as-prepared product in deionized water. 132
6-4 XRD patterns of the as-prepared Na2V6O16·3H2O products: (a) 132
without thermal treatment, (b) with thermal treatment at 350 °C for 3
h, (c) with thermal treatment at 400 °C for 2 h, and (d) with thermal

Page vii
 treatment at 500 °C for 2 h.
6-5 SEM and TEM images of the as-prepared Na2V6O16·3H2O product: 133
(a) SEM image, (b) High magnification SEM image of the nanorings,
(c) TEM and (d) HRTEM images of the nanobelts.
6-6 TEM images of samples obtained from 0.02 M NaVO3 solution with 134
different molar ratio of NaVO3 to HCl: (a) 2:1, (b) 3:2, (c) 1:1 and (d)
2:3.
6-7 TEM images of samples obtained from 0.1 M NaVO3 solution with 135
different molar ratio of NaVO3 to HCl: (a) 2:1, (b) 3:2, (c) 1:1 and (d)
2:3.
6-8 SEM (left) and TEM (right) images of Na2V6O16·3H2O with thermal 136
treatment at 350 °C for 3 h.
6-9 Nitrogen adsorption–desorption isotherm of the as-prepared 137
Na2V6O16·3H2O product.
6-10 The sensitivity comparison between V2O5 and Na1.08V3O8 gas sensor 138
towards 100ppm ethanol as a function of temperature (a), the gas
sensitivity of sodium vanadium oxide based sensors with increasing
gas concentrations of ethanol (b), stability measurement of the
sodium vanadium oxide sensor (c) and the sensitivity toward four
gases as a function of operating temperature (d).
6-11 XPS spectra of the as-prepared Na1.08V3O8 nanorods (a) and XPS 142
spectra of V2p peak and its fitting curves for V4+ and V5+ ingredients
(b).
6-12 FT-IR curves of as-prepared Na1.08V3O8 nanorods and commercial 144
V2O5 powder.
6-13 Total DOS plots of methanol, ethanol and 1-butanol molecules. 145

Page viii
Caption of Tables

Table Caption Page

4-1 Summary of optical properties of the VO2/FTO double-layered 88

films deposited at different potentials.

4-2 Lattice parameters of FTO and VO2(R) and the mismatch between 90
them.

5-1 Effect of U parameter towards the lattice parameter. 110

5-2 Effect of cut off energy towards the lattice parameter. 111

5-3 Optimized structural parameters (in nm) of pure and metal-doped 121
VO2(R).

5-4 The optimized structural parameters of pure and metal-doped 122

VO2(M1).

6-1 Nanostructures obtained by controlling the synthesis conditions. 135

6-2 Comparison of the ethanol sensing performance of the Na1.08V3O8 139

nanorods with other sensing materials.

6-3 Comparison of V-O bonds between V2O5 and Na1.08V3O8. 143

Page ix
List of Abbreviations

SMT Semiconductor-metal Transition

DFT Density Functional Theory
NIR Near Infrared
AOT Sodium bis(2-ethylhexyl) Sulfosuccinate
CTAB Cetyltrimethylammonium Bromide
PVP Polyvinylpyrrolidone
PVD Physical Vapour Deposition
CVD Chemical Vapour Deposition
APCVD Atmospheric Pressure Chemical Vapour Deposition
Aerosol-assisted Pressure Chemical Vapour
AACVD
Deposition
FTO Fluorine Doped Tin Oxide
AR Anti-reflection
LDA Local Density Approximation
GGA Generalized Gradient Approximation
PVDF Poly (vinylidene fluoride)
FIB Focused Ion Beam
SCE Saturated Calomel Electrode
FTIR Fourier transform Infrared
XPS X-ray Photoelectron Spectroscopy
TEA Triethanolamine
BET Brunauer-Emmett-Teller
HCl Hydrochloric Acid
DOS Density of State
PDOS Partial Density of States
EDS Energy Dispersive Spectroscopy
EG Ethylene Glycol
HRTEM High Resolution Transmission Electron Microscope
MD Molecular Dynamics
PLD Pulsed Laser Deposition

Page x
SEM Scanning Electron Microscopy
TEM Transmission Electron Microscopy

Page xi
Chapter 1. Introduction

Vanadium is mainly used to produce special steel alloys such as high speed tool steels.

The most important compound of vanadium is vanadium pentoxide, and this is

generally used as a catalyst for the production of sulphuric acid. Additionally, V2O5 is

used as a gas sensing material and shows good performance in detecting several gases.

Metal vanadates show similar properties to V2O5; however, there have been very few

studies on using these materials as gas sensing materials.

Of the other oxides of vanadium, vanadium dioxide (VO2) has been widely studied due

to the potential for semiconductor-metal transition (SMT). There has been increasing

research on VO2 with regard to electronic aspects such as phase transition mechanisms,

strain/pressure induced phase transitions and device fabrication, and chemical aspects

such as VO2 nanoparticles/thin films. Smart window coating is a particularly attractive

application for VO2, due to current environmental and energy problems.

Many methods have been used to synthesize VO2 thin films,1-3 such as chemical vapour

deposition (CVD), physical vapour deposition (PVD) and sol-gel method. Despite some

success in this area, there still exist several challenges with regard to the synthesis. For

instance, there has been few reported works on the effect of different surfactants on

controlling the morphology of the particles. Moreover, the use of VO2 for smart

windows is still in its infancy due to the existence of several issues such as: (1) low

visible transmittance; (2) low near infrared switching efficiency; (3) high transition

temperature; (4) unfavourable colour and (5) poor durability and stability of the films.

Page 1
This thesis aims to find suitable solutions to the problems, by achieving the following

objectives:

(1) To develop a simple but efficient method for the synthesis of VO2 nanoparticles;

(2) To develop the electrodeposition method for the preparation of VO2 thin film and

characterize optical properties;

(3) To investigate the gas sensing properties of vanadium oxides; and

(4) To fundamentally understand the electronic structure of VO2 and doping systems by

utilizing theoretical simulation methods (e.g., density functional theory, DFT).

These research objectives will be mainly demonstrated in the following chapters:

Chapter 3 discusses the development of a hydrothermal method which has been used to

produce relatively uniform VO2(B) nanorods with the addition of a surfactant. The

synthesis conditions have been analysed systematically and the gas sensing properties of

the VO2(B) have been measured. In addition, the electronic properties of single VO2(M1)

nanoparticles have been measured using a microscopic device.

Chapter 4 provides details about the fabrication of VO2 thin films by electrodeposition

method at room temperature. The thermochromic property measurement showed that a

combination of good thermochromic properties and relatively low emissivity has been

achieved, which shows that it has great potentials for industrial smart window

application.

Beyond physical experiments, Density-Functional Theory (DFT) simulation for

vanadium oxide becomes a hot research field focusing on the metal doped VO2 and its

phase transitions subject to temperatures.

Page 2
Chapter 5 presents the DFT simulation that can be used to study the electronic structure

and optical properties of low-valence metal doped VO2. The doped metals can hybridize

with the V 3d orbitals or O 2p orbitals to impact the band gap width, thereby changing

the optical properties of the material.

Chapter 6 aims to investigate the synthesis and gas sensing properties of sodium

vanadate. It is found that Na1.08V3O8 nanorods exhibited a good sensitivity towards

alcohol(s), and acetone at the optimized operating temperature. The as-prepared

Na1.08V3O8 nanorods displayed a higher sensitivity towards ethanol than pure V2O5

nanobelts and metal oxide coated/doped V2O5 nanobelts. The DFT simulation was used

to fundamentally understand the sensing performance towards alcohol.

Overall, this thesis aims to study the preparation of vanadium dioxide nanoparticles and

thin films and their functional properties with a combinatorial approach involving

experimental and computational aspects. Although the commercialization of VO2 for

smart window application is not achieved yet, this study will deepen researcher‟s

understanding of this particular interesting material, and contribute to commercialize the

smart window application.

Page 3
Chapter 2. Literature Review

2.1 Phase Transition

There are several main phases reported for VO2, such as B, A, R, M1 and M2. The

phase transitions between these phases are quite interesting and attract researchers‟

attention significantly. Figure 2-1 shows the unit cell of several common polymorphs of

VO2. VO2(R) has the Rutile structure, vanadium atoms are at the centre of regular

oxygen octahedra with two long bonds (0.196nm) and four relatively short bonds

(0.192nm). VO2(B) is a monoclinic structure and the parameters of the unite cell are: a=

12.030 Å, b= 3.693 Å, c= 6.42 Å and β= 106.6 °. The cell parameters of the room

temperature phase VO2(M1) are: a= 5.753 Å, b= 4.526 Å, c= 5.383 Å, β= 122.6 °, Z=

4.4 The cell parameters of the room temperature phase VO2(M2) are a= 9.083 Å, b=

5.763 Å, c= 4.532 Å, β= 90.3 °, Z= 8.5

Fig. 2-1 The unit cell of different phases of VO2 and the transition between them (V, O atoms

are shown in gray and red, respectively).

Page 4
2.1.1 Transition between M1, M2 and R

The transition between R and M1 is particularly attractive due to the reversible

transition and relatively low transition temperature (68 °C). When the temperature is

above Tc, with the existence of rutile structure, the vanadium atoms align in the linearly

chains along c-axis and nearest V4+–V4+ distance is 0.288 nm, and the extra electron

could be shared by all of the V atoms in the same chains. However, monoclinic

VO2(M1) has two different V–V distances of 0.266 and 0.313 nm, forming zigzag-type

chains. The extra electron is localized in the zigzag-type direction, giving

semiconductor behaviour of M1. The parameters relationship between R and M are as

follows: aM= 2cR , bM= aR , cM= bR -cR .

As a strongly correlated material, VO2 has been an interesting system of research for the

metal-semiconductor transition (MST). Two different mechanisms have been proposed

for the phase transition of VO2. Peierls lattice distortion types has been suggested to

explain the transition of VO2, which means that the transition was caused mainly by the

strong electron-lattice coupling. Wentzcovitch and his colleges performed density

functional theory to study the electronic and structural properties of VO2.6 The band

theory finds that a monoclinic distorted ground state is in good agreement with

experiment and an almost open gap to charge excitations, which suggest VO2 may be

more band-like than correlated. However, recent work by Kim and co-workers shows

the importance of electron-electron correlations, which means that the Mott-Hubbard

distortion type may be more reasonable.7,8 They have illustrated that the phase transition

of VO2 can be caused by hole doping either through photoassisted hole excitation or by

the application of an electric field without the need for a structural phase transition.

Qazilbash et al. directly image nanoscale metallic puddles appeared at the onset of the

Page 5
insulator-to-metal transition by scanning near-field infrared microscopy.9 Moreover, in

combination with far-field infrared spectroscopy, the data reveal the Mott transition

with divergent quasi-particle mass in the metallic puddles.

Fig. 2-2 Images of the near-field scattering amplitude over the same 4-μm-by-4-μm area

obtained by s-SNIM operating at the infrared frequency ω = 930 cm–1, which are displayed for

representative temperatures in the insulator-to-metal transition regime of VO2 to show

percolation in progress. The metallic regions (light blue, green, and red colors) give higher

scattering near-field amplitude compared with the insulating phase (dark blue color).9

The phase transition of VO2 can be further complicated by the discovery of monoclinic

M2 phase, which was observed to exist after doping10 and applying strain11-12. The

Page 6
elastic properties and structural phase transitions of individual VO2 nanowires have

been studied.12 They utilized an in situ push-to-pull microelectromechanical device to

realize quantitative tensile analysis in a transmission electron microscope and a

synchrotron X-ray microdiffraction beamline. A plateau in the stress-strain curve

signifies superelasticity of the nanowire arising from the M1-M2 structural phase

transition. The transition was induced and controlled by uniaxial tension.

Fig. 2-3 (a) SEM image of the microfabricated push-to-pull (PTP) device. When the device is

pushed on the semicircle end (arrow at left), the specimen gap (dashed rectangle) expands while

staying in the field of view of the electron microscope. (b) The linear force vs displacement

response of the PTP device without a nanowire spanning the specimen gap, showing the

inherent stiffness of the device. (c) The uniaxial stress (along the cR direction) temperature

phase diagram of VO2. The arrow indicates the phase transition route under tensile loading at

room temperature. (d) A higher magnification SEM image of the specimen gap of the PTP

device with a VO2 nanowire fixed across the gap by Pt welds. Two platinum dots were

deposited on the sample as indicated by two arrows in the middle of the nanowire for directly

measuring strain of the sample.12

Page 7
Recently, Park et al. investigated the tensile stress–temperature phase diagram of

vanadium dioxide with a micromechanical device and single-crystal nanobeams.13 Their

experiment presents a surprising and interesting fact: the metal–semiconductor phase

transition of VO2 is in fact a triple point (M1, M2 and R) can coexist. The experiment

also determines the entropy differences between the various phases, which provide

significant information to a complete understanding of the phase transition.

Fig. 2-4 (a) Arrangement of vanadium ions in the phases involved in the MIT, indicating their

different vanadium chain periods and dimerization (yellow). (b) Expected layout of the stress–

temperature phase diagram near the MST, showing the transition temperature Tc at zero stress.

(c) Experimental geometry, showing an electron micrograph (right) of a VO2 nanobeam

suspended across a slot of width L in a silicon chip (left, optical micrograph) whose width is

controlled by pushing on the paddle and measured by deflection of a laser beam. The yellow

lines signify gold wire bonds. (d) Series of optical images showing movement of the R–M1 and

M1–M2 interfaces as L is increased in roughly 100-nm steps at 64 °C.13

Page 8
2.1.2 Transition from B to A and R

Due to the shear structure, VO2(B) possesses more deformed oxygen octahedra with

vanadium atoms being no longer in the centre. B is the common phase of the final

products synthesized by hydrothermal at relatively low temperature. Further increasing

the reaction temperature, it will transform to A, which is also a metastable phase of VO2.

Oka and his co-workers investigated the structural phase transition of B to A. They

believe the transition from B to A corresponds to the change in the structural units. The

change is accomplished by the shift of oxygen vacancies along with the rearrangement

of vanadium atoms.14

The R can be obtained by annealing the B in protective atmosphere as well. Tsang et al.

successfully synthesized VO2(B) particles by a simple chemical method first and B

begins to transform irreversibly to the thermodynamically more stable R at around

350 °C.15 Similar to the above research, VO2(R) nanobelts were prepared by the

irreversible transformation of VO2(B) nanobelts at the elevated temperature.16 The as-

obtained VO2(R) nanobelts have a monoclinic structure with a length of 350–600 nm, a

wideness of 100–150 nm and a thickness of 20–30 nm. Due to the reversible phase

transition between M and R, the final products after annealing are usually the M phase.

2.2 Synthesis and Modification of VO2 Nanoparticles

In experiment, many methods have been used to synthesize VO2 nanostructures (e.g.,

rods, wires, sheets and belts), including vapour transport, thermolysis and hydrothermal

synthesis. Due to the various applications of VO2, it is important to synthesize the small

homogeneous nanoparticles, which are easy to be assembled into useful device. The

Page 9
hydrothermal and thermolysis methods are the two common methods to synthesize the

VO2 nanoparticles.

2.2.1 Hydrothermal or Solvothermal

Hydrothermal method is the most efficient method to synthesize the VO2(M1)

nanoparticles. In a typical procedure, all the reactants (slurry or solution) were added

into the autoclave, and then the autoclave was sealed and maintained at different

temperature for different time. After the hydrothermal treatment, the autoclave was

cooled to room temperature. Finally, the resulting precipitates were collected and

washed with distilled water or organic resolution several times and dried in air or

vacuum.

This method is a part of solution processing and it can be described as super heated

aqueous solution processing.17 The product of the hydrothermal method is usually in

nano dimension. As the size is reduced to the nanometer range, the materials exhibit

different and interesting chemical and physical properties: increased surface area,

enhanced diffusivity, higher specific heat and electrical resistivity compared to the

conventional bulk materials due to a nano-size effect. These properties may be

beneficial to the future commercialization of VO2, especially for the smart window

application.

Different phases of VO2 nanostructures can be synthesized by this method and neither

sophisticated techniques nor catalysts are required. However, the high pressure is

necessary. In addition to the high pressure, the autoclave is always maintained in the

Page 10
range of 180 °C to 260 °C for many hours or even days, which is quite energy

consuming.

The growth of vanadium dioxide with various morphologies has been widely studied.

Different morphologies of VO2 nanostructures have been synthesized with

hydrothermal or solvothermal method, such as naobelts18-20 nanorods21-24, nanowires25-

28
and nanorings29. In most experimetns, the V5+ oxide or salts are utilized as the

vanadium source and different kinds of reducing agent has been investigated, such as

oxalic acid30-34, N2H4.H2O35, glucose36-37, Polyvinylpyrrolidone (PVP)38 and ethylene

glycol25,27. For example, Wu et al. reported a controlled oxidation reaction to realize the

direct solution-based synthesis of monoclinic VO2(M1) nanoparticles at 200 °C for 36

h.39 The adopted V3+ precursors-V(OH)2NH2 was chosen as the vanadium source and

HNO3 provides the acid conditions and appropriate oxidizing ability. However, the

synthesized nanobelts are still quite large with diameter sizes ranging from 30 nm to

120 nm and lengths up to 400–800 nm.

Due to the existence of various phases of VO2, temperature is one of the key factors to

determine the final phase of VO2. In general, when the reaction temperature is below

180 °C, the main products by hydrothermal method are the metastable VO2(B)

nanoparticles. VO2(R) nanoparticles can only be obtained in the range of 220-260 °C

using the V5+ oxide or salts as the vanadium source. The phase transition between

VO2(B) and VO2(R) under hydrothermal condition has been explored by Dai et al.40

Nanobumps were first formed on the VO2(B) nanorods and then gradually grew bigger

until the VO2(B) totally turned into the VO2(M1). The strong size effect of VO2(M1)

Page 11
has also been investigated and the phase transition temperature was reduced to less than

68 °C if the particle size is less than 13 nm.

Fig. 2-5 TEM images (left), XRD patterns (middle) and DSC curves (right) of samples prepared

by the hydrothermal treatment at 260 °C for (a) 4 h, (b) 16 h, (c) 18 h, and (d) 20 h, which

shows the progress of transition from VO2(B) to VO2(R).40

Many papers have been published on the synthesis of VO2(M1) by hydrothermal

method and different morphologies have been synthesized. However, most of the

Page 12
products are in one-dimension due to the layered structure of the VO2 crystal, it is still

difficult to synthesize the uniform nanospheres with size smaller than 100 nm.

Solvothermal method has been adopted to prepare small size VO2 nanoparticles.

Nguyen et al. developed a new solvo-hydrothermal method for the synthesis of uniform

vanadium oxide nanocrystals (NCs) with various sizes and shapes in aliphatic

amine/toluene/water.41 Monodisperse vanadium dioxide NCs with various sizes and

shapes, such as nanospheres, nanocubes, nanorices, and nanorods, can be achieved at

relatively low temperature (180 °C) compared with the hydrothermal method (220 –

260 °C). However, the complicated vanadium precursors were prepared from an ion

exchange reaction in the water-toluene mixture. An easy and effective solvothermal

method needs to be developed in order to synthesize the VO2(M1) nanoparticles with

small size (few nonometrers) in large scale for real industrial application in the future.

Fig. 2-6 Schematic illustration of the preparation of (VO(O)2(TOA)) complexes, followed by

the formation of alkyl amine capped vanadium oxide NCs (left), and effect of steric ligands on

the size of vanadium oxide NCs (right). TEM images and corresponding SAED patterns of the

VO2 NC samples prepared from different vanadium complex precursors: (a) VO(O2)2(TPA),

(b)VO(O2)2(TOA), and (c) VO(O2)2(CTA).41

Page 13
Different elements doping can also be easily achieved by hydrothermal method. For

instance, Sb-doped VO2 nanoparticles has been obtained with relatively uniform size

and high crystallinity.42 As a result of Sb3+ doping, the particles became smaller and

similar results have been obtained by Bi3+ and Ti3+ doping. The extra repulsion force

induced by dopant-resultant defects has been proposed as the reason for modification of

particle sizes. Although the relatively uniform nanoparticles have been successfully

synthesized, the transition temperature for these Sb-doped VO2 nanoparticles is in the

range of 62-65 °C, which is far from the desired temperature (25- 30 °C).

Due to the relatively easy operation and promising potential to enlarge to industry scale,

the hydrothermal method seems to be the best method to make the VO2 commercialized.

However, the synthesized VO2 nanoparticles are not quite stable in the air and further

surface modification is needed. Moreover, the synthesized products were just

nanoparticles, more research in regard to assembling the particles into the films needs to

be carried out. New problems need to be solved when making films by these

nanoparticles, such as the diffusion of Na+ and the adhesion between the foil and glass.

2.2.2 Thermolysis

Due to the disadvantages of the hydrothermal method, thermolysis method has been

developed in order to synthesize the VO2(M1) by a simple and easy to scale up method.

A vanadium precursor, usually V4+ compound, is annealed in nitrogen or argon

atmosphere to directly obtain the VO2(M1) particles. Compared to the hydrothermal/

solvothermal method, this process can easily be integrated into commercial production

lines with a short cycle period and simple operation.

Page 14
Zheng and his co-workers reported a new and simple method to prepare a fine vanadium

dioxide powder by thermolysis of a precursor.43 The (NH4)5[(VO)6(CO3)4(OH)9]•10H2O

was synthesized and used as the precursor by a quite critical condition. The precursor

was then heated in a silica tube at a rate 5 °C·min-1 in a flow of nitrogen gas. Different

phases of VO2 could be obtained by controlling the annealing temperature and time.

When the precursor was heated at 450 °C for 30 mins, the phase transition temperature

was about 71 °C.

In order to synthesize the W-doped VO2, Peng et al. mixed the

(NH4)5[(VO)6(CO3)4(OH)9]•10H2O precursor with WPTA at low temperature.44 After

annealing at high temperature, W-doped VO2 powders have been successfully obtained.

DSC curves showed the phase transition temperature was 67.15 °C for pure VO2

powders, while after doping with tungsten, the temperature decreased to 26.46 °C.

Though the products of thermolysis method are powders and this method can be easily

integrated into commercial production lines with a short cycle period and simple

operation, the complex of synthesizing the precursor and the critical condition,

especially the relatively high temperature and nitrogen atmosphere, inhibit its wide

application.

2.2.3 Surface Modification

The valence state of V in VO2 is 4+, which can be easily oxidised to 5+, thus surface

modification is significant to increase the chemical stability. After coating with other

metal oxides, such as TiO245-46 and SiO247-48, the stability of the VO2 nanoparticles can

be enhanced with a reasonable transmittance in the visible region. For example, coating

the VO2 nanoparticles with a thin SiO2 shell significantly improved their stability.47 The
Page 15
silica shell increased the anti-oxidation and anti-acid abilities of the VO2 nanoparticles

and made further modification of the silica layer with the silane coupler easier, and the

silane coupler could facilitate the preparation of the VO2@SiO2/PU composite film.

Furthermore, the performance of the VO2 foils was further improved. Integrated visible

transparency and solar modulation ability values of >41% and 15.5% were observed,

respectively.

Fig. 2-7 (a and b) Photographs of sample films at room temperature, (c) optical transmittance

spectra of sample films in UV-visible-near-IR range, and (d) thermal hysteresis of sample films

at a wavelength of 1500 nm.47

The surface modification may also be beneficial to lower the transition temperature, as

reported by Li et al..46 Similar to the VO2 thin films deposited on the TiO2 (001)49, the

strain in the interface has an important effect on the phase transition when core/shell has

been applied. The misfit-induced interfacial strain along the cR axis leads to the increase

Page 16
of transition temperatures, especially on the cooling procedure of the heating− cooling

cycle, which reduces the transition hysteresis loop width (from 23.5 to 12.0 °C).

Fig. 2-8 Illustration of preparation process (left), HRTEM (middle) and thermochromic

properties of the films casting from VO2/TiO2 core/shell nanorods (right).45

Currently, the surface engineering by modification of VO2 nanoparticles mainly focuses

on TiO2 and SiO2. Other oxides or metals may also be beneficial for the properties

improvement, such as the colour of the film, the magnetic property and the reflectivity.

More research needs to be carried out in this area. Another issue is that the coating

method involves two steps which will increase the cost of the products when prepared

in large scale. One pot synthesis of the core shell structure could make the VO2 more

appealing for different applications, especially the smart windows.

2.3 Preparation and Modification of VO2 Thin Film

Although the VO2 bulk material has been widely investigated, it is the VO2 thin film

that has the practical application. The single crystals of VO2 do not generally survive

the stress generated by the phase transition while thin films survive repeated cycling.50
Page 17
The magnitude of resistance switching has been observed to be within 102- 105 fold for

films, especially in the infrared (IR) region due to the reversible SMT. Many different

methods have been developed to synthesize the VO2 thin films. They mainly include:

physical vapour deposition (PVD), chemical vapour deposition (CVD), sol-gel spin or

dip coating and newly reported electrodeposition method. Many methods have been

reported on preparing the VO2 thin films, however, it is still challenging to prepare the

VO2 thin films on the normal flat glass, especially in large scale.

2.3.1 Physical Vapour Deposition Method

Physical vapour deposition (PVD) is a physical coating method, used to deposit thin

films by the condensation of a vaporized form of the material onto various surfaces. It

involves two main procedures: (1) removing atoms or molecules from a target under

reduced pressure conditions; (2) react with any seed gases present in the deposition

chamber to form a thin film of the desired compound by condensing onto a substrate.3

There are many different ways to energetically remove atoms from a metal target and

most have been used to prepare vanadium (IV) oxide thin films. These include laser

ablation, rf magnetron sputtering, dc magnetron sputtering, and ion beam sputtering.3

Sputtering deposition utilized a glow plasma discharge to bombard the material

sputtering some away as a vapour. Much work has been done to synthesize VO2 thin

films by sputtering deposition.51-54 Chen et al. have synthesized the nanostructured

vanadium dioxide thin films, based on the silicon and silica substrates with a 300 nm

thickness of Si3N4 buffer layer.55 The semiconductor-to-metal phase transition of

vanadium dioxide thin films has been lowered to 35 °C. The low-temperature phase

transition is also accompanied by a significant change in the thin film‟s infrared

Page 18
transmission property. Ruzmetov et al. have synthesized high-quality VO2 films,

sputtering from a VO2 target instead of the conventional V target.56 They investigated in

depth how the synthesis conditions affect MST parameters derived from temperature

dependence of electrical resistance. The MST parameters can be greatly improved by

the thickness of the films, while no lateral size dependence is observed in VO2 devices

scaled down to 20 µm. They also reported that a wider hysteresis loop indicates smaller

average grain size while a sharper transition may be due to the narrower size

distribution of the grains.

Pulsed laser deposition (PLD) utilizes a high power laser to ablate material from the

target into a vapour and this method has been widely used to prepare vanadium

dioxide.57-59 Due to the accurate control of the film thickness and composition, this

method has been investigated for the preparation of VO2 thin films. Choi et al. grew

VO2 film on a sapphire (0001) substrate using pulsed laser deposition method.60 They

demonstrated that the transport and optical properties near the MST region are strongly

influenced by the connectivity of the metallic domains. Pauli et al. ablated the vanadium

metal target in the presence of a pulsed N2O reactive gas source, films were then grown

on Si (001) and Al2O3 (0001) substrates.61 Films grown at room temperature and on Si

(001) are amorphous and very flat, and only crystallize into the VO2 phase upon thermal

annealing in a background of O2. In contrast, ultrathin layers of VO2 grown on Al2O3

form twinned, elongated, rodlike islands oriented along the three equivalent in-plane

crystallographic axes of the Al2O3 (0001) surface.

The transition temperature and sharpness of the transition have also been investigated

by thermal oxidation of VO2 film prepared by PLD method.62 The width and shape of

Page 19
the hysteresis cycle are thus determined by the competing effects of crystallinity and

grain size. The high quality crystalline samples will normally lead to sharp peaks while

poor quality crystalline VO2 will produce broader and more diffuse diffraction peaks.

Moreover, the hysteresis width narrows in the smaller granular film because the phase

transition can easily occur in this highly defective structure. Overall, the competing

effects of crystallinity and grain size determine the width and shape of the hysteresis

cycle.

Fig. 2-9 From left to right, scanning electron micrographs of nanoparticle and thin film

morphology, relative IR (λ= 980 nm) switching curves through the structural phase transition;

and x-ray diffraction θ/2θ vs annealing time for pulsed laser deposited vanadium oxide films of

100 nm thickness fabricated at 450 °C in 250 mTorr of O2 to crystallize them into VO2. From

top to bottom 5, 10, 20, 40, and 80 min of annealing time. Notice the enhanced hysteresis,

sharpness of the transition and grain growth.62

Page 20
PVD has been widely studied to prepare vanadium dioxide thin films and to explore

different substrate effects on the thin film synthesis due to its accuracy in controlling the

thickness. The composition of thin film can be also controlled by the quantity of

material removed from the target and the quantity of reactive gas present in the

deposition chamber.3 This method may have advantages in device preparation. However,

the apparatus of PVD experiment is quite expensive and the productivity is low,

exhibiting little potential for large scale application.

2.3.2 Chemical Vapour Deposition Method

The development of CVD method for VO2 thin film preparation has been significantly

attractive because of the atmospheric pressure chemical vapour deposition (APCVD)

method developed by Manning et al..63 This process has the advantage of being easily

integrated into float-glass production lines and has fast deposition rates. Compared to

the traditional CVD, the APCVD experiment in the reaction chamber is at or near

atmospheric pressure.

Fig. 2-10 Schematic representation of the APCVD equipments.64

Page 21
Manning and Parkin synthesized VO2 thin films doped with up to 3 atom% tungsten on

glass substrates from the APCVD reaction of VOCl3, H2O and WCl6.63 Contrary to the

W+6 in VO2 nanostructures by hydrothermal method, the XPS studies indicated the

tungsten was present as W4+ by APCVD. They also suggested that incorporation of

tungsten caused a reduction in the VO2 thermochromic switching temperature of 19 °C

per W atom%. Thus the APCVD could reduce the phase transition to a range of 5-55 °C,

which includes the ideal temperature of 25-30 °C. Moreover, the APCVD is easily

integrated into the float-glass production process sufficiently fast to be suitable for

float-glass production lines, which shows that APCVD is the ideal technique for

forming VO2 coatings on glass. A lot of work has been done to apply this method to

prepare the VO2 films by this group.65-67

Most recently, aerosol-assisted (AA) CVD has been reported for deposition of VO2 on

glass.68-69 In this technique, the precursor (vanadium (III) acetylacetonate and vanadyl

(IV) acetylacetonate) is dispersed in a solvent and an aerosol of the solution is generated

ultrasonically. The precursor is transported to the substrate through the aerosol droplets

by a carrier gas.70 Films with niobium content up to 3.7% were prepared by AACVD

method and the doping of 2 atom% Nb by this method can decrease the phase transition

by 15 °C. The thermochromic properties have also been measured and no particularly

interesting finding has been reported.

Both of the APCVD and AACVD have obvious advantages for industrial process,

whereas, the expensive equipment is necessary for CVD process and the cost is

relatively high compared with the following mentioned sol-gel spin or dip coating.

Page 22
Fig. 2-11 SEM images for: (a) undoped VO2, (b) W-doped VO2 thin film prepared by AACVD

(left). Transmittance (a) and reflectance (b) IR spectra for V 0.9902W0.0098O2 thin film, above and

below the transition temperature (right).68

2.3.3 Sol-gel Method

Different to PVD and CVD methods, expensive equipment is unnecessary for the sol-

gel spin or dip coating method. It is the easiest way to prepare the VO2 films. This

method usually involves three steps: (1) forming the precursor solutions, such as metal

alkoxides, VOCl2 and V2O5 solution; (2) spin coat or dip coat the films on substrates; (3)

thermal annealing for the as-synthesized film. Due to its simplistic nature, it has been

applied to prepare VO2 nano thin films widely.71-77 Guzman et al. described the sol-gel

spin coating method to prepare the VO2 films.78 Vanadium alkoxide molecular

precursors are deposited onto a fused silica substrate by the spin coating technique. The

amorphous thin film was then obtained at room temperature when the precursor heated

at 450 °C under a reducing atmosphere (Ar-H2). The annealed film exhibited a good

optical transparency.
Page 23
Zhang et al. synthesized the high quality vanadium dioxide thermochromic thin films by

sol-gel spin coating method.72 By varying the film thickness, they got the films with

ultrahigh visible transmittance values of 75.2% and 75.7% for the M and S states,

respectively. The phase transition temperature could be lowered to 42.7 °C by annealing

the film at 440 °C, which still needs to be reduced to the room temperature. Although

the thermochromic results are better than others, the integral value of the films still

needs to be improved for practical smart windows. Furthermore, the vanadium

oxyacetylacetone precursor dissolved in methanol is not suitable for large scale

applications.

The vanadium valency in sol-gel for spin or dip coating is usually 5+ and reductive

atmosphere is necessary to obtain the VO2 thin films. In order to reduce the cost and

make the procedure more compatible with the industrial line, a polymer-assisted

deposition method was reported by Gao‟s group.79 The VOCl2 was utilized as the

vanadium source and PVP was added into the solution to increase the viscosity. The

synthesised films were characterized by different techniques and were confirmed to be

VO2(M). Achievable NIR switch efficiency has been reported compared to the films

prepared by using precursor without any PVP. The mechanism of the film forming was

also discussed. The negatively charged carbonyl groups of PVP will interact with the

positively charged amine groups of other molecules, such as VO22+ in this case.

Different doping has also been reported by this method, such as Ti and W.80,79

Nanocomposites have also been reported by using this method.81 However, due to the

existence of PVP, it is difficult to control the composition of final thin film. In addition,

the precursor-VOCl2 is highly toxic, which will create environment or health issues.

Page 24
Fig. 2-12 SEM images and optical transmittance spectra of a PVP free film (a-c) and a PVP-

employing film (d-f) on fused-silica substrates.79

To conclude, sol-gel spin or dip coating is the most convenient way to prepare the

vanadium dioxide films and it can produce films with complete coverage of the

substrate and even thickness. However, it is not suitable for integrating into the

industrial float-glass process due to the extraction of the Na+ into the VO2 films during

the annealing process. Moreover, it is also an offline process, which will increase the

difficulty to produce the smart windows. Although the spin coating method has been

Page 25
commercialized in the semi-conductor industry, it is not an appropriate method for the

smart window application.

2.3.4 Electrodeposition Method

For VO2 thin film preparation, the electrodeposition method is a newly developed

method with few papers reported. It is a green method of preparing VO2 thin film and

has many advantages, such as low cost, industrial applicability and higher deposition

rates. The main disadvantage is that conductive substrate is necessary for this method.

Transparent conductive films with low emissivity, such as fluorine doped tin oxide

(FTO), is the ideal substrate to prepare VO2 thin films for the smart windows

application. Because of the low emissivity of the FTO substrate, the fabricated smart

windows can not only control the heat passing through the window in summer, but also

prevent the heat escaping the room in winter. Therefore, the energy saving effect may

be improved all together.

Cezar et al. first reported the electrodepositions of VO2 thin film with 0.15 M

VOSO4·xH2O solution as the electrolyte.82 After deposition at −0.75 V for 30 mins and

vacuum annealing at 500 °C for 270 min, VO2 thin films grown on Si substrates with a

few nanometers thickness have been obtained. In order to increase the thickness of the

VO2 films, Koza et al. reported an electrodeposition method for VO2 thin films based on

V5+ reduction with triethanolamine as the complexing agent. VO2 films of

approximately 140 nm can be deposited on Pt-coated glass at 80 °C.83 The annealed

film is nanocrystalline and dense, with an average grain size of 66 ± 7 nm and

roughness of 10 ± 1 nm. Recently, Minch et al. has reported the cathodic deposition of

VO2 from VOSO4 with a mixture of ethanol with water (10 vol%) as the electrolyte.84
Page 26
As the VOSO4 is not soluble in ethanol, sufficient amount of water is needed in this

approach for the base generation for the forming of VO(OH)2 form VO2+ at the interface.

Fig. 2-13 Electrochemistry of V5+-TEA electrolyte at 80 °C on Pt coated quartz (left). (a) Linear

sweep voltammogram together with corresponding mass changes. (b) Steady-state deposition

rate dependence on the applied potential obtained from mass vs time transients (black circles

and dashed lines) and steady state current density vs potential dependence (green triangles and

dotted line). Electrical transport characterization of the annealed VO2 film (right). (a)

Temperature dependence of the normal to the film plane resistance showing the MIT

temperatures upon heating (red) and cooling (blue) measured at 0.5 K·min -1. Transition

temperatures were determined from (b) a plot of d(log(R))/dt vs T. (c) I-V characteristic of the

VO2 film measured at room temperature.83

The electrochemical method, which is pretty compatible with industrial production line

and allows deposition on substrates with complex geometry, does not attract the

attention they deserve. More research needs to be carried out to investigate the potential

of this method to synthesize the VO2 thin films for different applications.
Page 27
2.3.5 Doping Effect

Since Granqvist proposed thermochromic VO2 films as smart window coatings, many

experimental efforts have been undertaken to realize the smart window application.85

For particular application, such as the smart window, the high phase transition

temperature needs to be lowered and doping is the most effective way. Doping with

other elements can vary the V–V distances. Usually, high-valent metals can introduce

extra electrons into the VO2 systems and is favourable for decreasing the temperature.

Instead, the low-valent metal doping will increase the transition temperature. Many

elements in the period table have been investigated, such as W68,86-87, Mo88-91, Nb89,92,

Fe93, Mg54, Ti75,80,94, Sn95, F96-99 and Cr100-101.

W and Mo seem to be the most effective metals to lower the transition temperature. W-

doped VO2 thin films have been prepared by many different methods introduced above.

Due to the accurate control of the composition for the films, PVD method has been

successfully applied to dope W into the VO2 films.87,98,102 The transition temperature

can be lowered with the efficiency around 20 K per atom concentration W doping.98

Despite the PVD method, other method can dope W into the VO2 as well, such as sol-

gel method75 and AACVD68. In order to understand the atomic structure evolutions of

W dopant, more detailed research has been carried out with the advanced synchrotron

radiation X-ray absorption spectroscopy technology by Tan et al..103 With the

combination of X-ray absorption fine structure (XAFS) spectroscopy and DFT

simulation, they discover that the isolated W dopant possesses an intrinsically

symmetric tetragonal-like structure, driving the de-twisting of the nearby asymmetric

monoclinic VO2 lattice towards R phase.

Page 28
Fig. 2-14 XAFS results for WxV1-xO2 (up). (a) The V K-edge EXAFS oscillations and (b) their

Fourier transforms for WxV1-xO2 samples, along with the VO2 theoretical results of monoclinic

(M1), rutile (R) and monoclinic (M2) phases for references. (c) theWL3-edge EXAFS

oscillations and (d) their Fourier transforms, along with the reference WO 3 result, and the

simulated curves for W-substituted monoclinic and tetragonal VO2 phases. The bond distances

as a function of W concentration (bottom). The bond distances of the nearest three shells of (a)

V and (b) W as the centre atom, based on the XAFS fitting results of each sample with different

W doping concentration.103

For non-metal doping, F has been widely researched due to the unique property to

enhance the luminous transmittance for VO2 films. Burkhardt et al. deposited the

thermochromic F-doped VO2 films by reactive sputtering.98 With optical measurements

Page 29
and photoelectron spectrometry (XPS, UPS) analysis, they reported that F-doped films

were not suited for smart window coating due to the poor switching behaviour at room

temperature because F doping can cause the strong distortion of the VO2 host lattice.

However, F-doped VO2 films prepared by AACVD method exhibited an increase in the

visible transmittance whilst retaining the thermochromic properties96. Recently, Dai et

al. prepared the F-doped VO2 glass foils by casting the nanoparticles, which were

obtained by hydrothermal method.104 The 2.93% F-doped VO2 foil showed an increased

solar-heat shielding ability (35.1%) and a modified comfortable colour, while still

maintaining a good solar modulation ability (10.7%) and an appropriate visible

transmittance (48.7 %).

Since single element doping cannot obtain the ideal VO2 thin film, which exhibits low

phase transition temperature and high luminous transmittance. For example, tungsten

doping does not change the colour of the VO2 films and doping with F, sufficient phase

transition temperatures are not achieved without heavily sacrificing the switching of the

energy transmittance. Co-doping has been investigated in order to combine the positive

impacts of each element doping on the layer performance.74,97,105-106

Combining the advantages of W and F doping, W and F co-doped VO2 thin films were

prepared by RF sputtering by Burkhardt et al.97 They found clear evidence for an

interaction of fluorine and tungsten in VO2 thin film in the switching behaviour at the

semiconductor-to-metal phase transition. Both W and F doping could destabilise the

semiconducting phase, and consequently lower the semiconductor–metal transition

temperature. However, the transition temperature of co-doped layers is slightly higher

Page 30
Fig. 2-15 The phases, morphologies and phase transition behaviours of F-doped VO2

nanopowders with different dopant concentrations (top). (a) XRD patterns. (b) DSC curves. (c–e)

TEM image, SAED pattern and HRTEM of undoped and 2.93% F-doped VO2 nanopowders,

respectively. The optical and electrical properties of F-doped VO2 nanopowders with different

dopant concentrations (bottom). (a) The transmittance spectra of VO2-PU composite foils at 20

and 80 °C. (b) The absorbance spectra of VO2-PU composite foils at 20 °C. (c) The carrier

density of VO2 nanopowders with different F doped concentrations at different temperatures. (d)

The resistivity of F-doped VO2 nanopowders at different temperatures.104

Page 31
would be expected if the two effects of single-element doping are just simply added.

That can be explained by the fact than some of the F atoms become inoperative in co-

doped VO2 thin films. Mo and W co-doped VO2 thin films have also been prepared by

sol-gel method.74 The Mo-W codoping introduces a smoother surface and a smaller

grain size of VO2 film. The transition temperature lowering effect of the codoped VO2

films is not the superposition of the respective influence of each single ion doping.

Moreover, the Tc of codoped films is lower than that of single Mo doped VO2 film at

the same doping level of 1.6 atom%.

2.3.6 Anti-reflection Coating

Despite the high phase transition temperature, the low luminous transmittance is another

disadvantage for the smart window application. Usually, the visible transmittance of the

windows for commercial building should not be lower than 60%.67 Due to the strong

inner band and inter band absorptions in the short-wavelength range,107 the visible

transmittance of the VO2 films is not high enough for real application, in particular for

the smart window application. Except for the F doping, anti-reflection coating is another

effective way to enhance the transmittance in the visible region, although it will increase

the cost of the smart windows.

Babulanam et al. carried out a theoretical study of the AR coatings on VO2.85 Fig. 2-16

shows the calculated results, the first maximum in Tlum, corresponding to the effect of a

quarter-wavelength antiflection coating, yields Tlum ≈ 0.54 at dAR ≈ 65 nm for ƐAR = 4

and Tlum ≈ 0.48 at dAR ≈ 95 nm for ƐAR = 2, compared to the original value Tlum ≈ 0.34

for the uncoated VO2. They concluded that the luminous transmittance could be

Page 32
significantly increased by the use of a high-refractive-index antireflection coating of

suitable thickness.

Fig. 2-16 Luminous transmittance for normal incidence onto glass with an antiflected VO2

coating, as indicated in the inset.

TiO2 is the widely researched material for the VO2 anti-reflection coating layer. Jin et al.

prepared a TiO2 (25 nm)/VO2 (50 nm)/TiO2 (25 nm) structure by magnetron sputtering,

which exhibited quite good optical properties.108 A maximum increase in luminous

transmittance by 86% (from 30.9% to 57.6%) has been achieved with the double-layer

AR design. ZrO2 has also been utilized as the AR coating.109 With 56 nm ZrO2 coating,

an improvement of luminous transmittance from 32.3% to 50.5% was reported for the

semiconductor phase with similarity also for the metallic one.

Page 33
Fig. 2-17 Spectral transmittance and reflectance at 20 and 80 °C for TiO2 (25 nm)/VO2 (50

nm)/TiO2 (25 nm) on SiO2 in comparison to VO2 (50 nm) on SiO2. Transmittance at 2000 nm as

a function of temperature for both films on SiO2.108

2.3.7 Substrate Effect

Together with the phase transition, sharp changes in electrical resistivity and infrared

transmission make VO2 useful for potential applications. However, the phase transition

is too high and there has been a continuing effort to modify the transition temperature of

VO2 by applying pressure or doping it with elements.89 Besides this, the stress along the

c axis induced by the lattice mismatch between the film and substrate can effectively

change the temperature as well.

Due to the same crystal group of TiO2 and VO2(R), TiO2 with different plane is an ideal

substrate to investigate the effect of uniaxial stress along the c axis on SMT transition of

VO2. Thin films grown on TiO2 (001) and (110) substrates has been prepared by PLD

method.49 Theoretically, the lattice parameters of VO2 are smaller than those of TiO2.
Page 34
On one hand, the c-axis length of films grown on TiO2 (001) should decrease resulting

in an in-plane tensile stress at the interface (lattice mismatch: 0.86%), on the other hand,

the c-axis length will increase for a VO2 film grown on TiO2 (110) (mismatch: 3.6%).

As a result of the change of c in the c-axis length, a decrease or an increase in

temperature is predicted. Confirmed by the XRD and temperature dependent resistivity

results, a massive reduction in the transition temperature from 341 K for a single crystal

to 300 K has been observed in the film on TiO2 (001), while the temperature rose to 369

K in the film on TiO2 (110). The correlation between Tc and the c-axis length has been

suggested, which may be important to elucidate the mechanism of the MST transition in

VO2.

Fig. 2-18 Temperature dependence of resistivity for the VO2 films formed on TiO2 (001) and

TiO2 (110) Substrates (left). Phase transition temperature vs lattice parameter c for the VO2

films deposited on TiO2 (001) and TiO2 (110) substrates (right).49

Similarly, a comparative study of epitaxial growth of VO2 thin films on c-cut (0001)

and r-cut (1102) sapphire substrates has been reported.110 The semiconductor to metal

transition SMT characteristics of these films have also been investigated and correlated

with their structural details. The SMT temperature for VO2 films on c-sapphire was
Page 35
72.6 °C, close to the bulk value of 68.0 °C. The substantial decrease in transition

temperature to 60.3 °C for VO2 films on r-sapphire has been caused by the compressive

strain along (002) direction of VO2.

Fig. 2-19 The electrical resistance plotted as a function of temperature for VO 2 films grown on

c- and r-sapphire substrates (left). The in-plane arrangements and calculated misfits for

monoclinic VO2 unit cells on (a) c-sapphire and (b) r-sapphire, for (200) growth orientation of

VO2 (right).110

MgF2, another material having the same isostructural structure with VO2(R), has been

utilized as a substrate for the fabrication of epitaxial VO2 films.111 By x-ray diffraction

(XRD) and Raman scattering measurements, the effects of epitaxial strain on the crystal

lattice have been confirmed. As a result of the shorter V–V distance and the reduced

twisting angle of the V–V dimer, the transition temperature in the strained film is lower

caused by in-plane tensile strain. A siginificant reduction in the transition temperature

from 341 K for a single crystal to 318 K has been observed in the film deposited at

420 °C. The substrate effect to lower the phase transition may be a good way to

commercialize the VO2 without sacrificing the optical properties compared to the

Page 36
doping method. Therefore, further investigation of this area is useful to produce some

VO2 devices for different applications.

2.4 Theoretical (DFT) Simulation of VO2

2.4.1 Density Function Theory

Density functional theory (DFT) is a computational quantum mechanical modelling

method used in physics, chemistry and materials science to describe properties of

condensed matter systems, which include not only standard bulk materials but also

complex materials such as molecules, proteins, interfaces and nanoparticles. The main

principle of DFT is that the properties of a many-electron system can be determined by

using functionals, which is the spatially dependent electron density in DFT. Its

significance is to reduce the 3N degrees of freedom of the N-body system to only three

spatial coordinates through its particle density. DFT simulation is based on the well

known Hohenberg-Kohn theories,112 which claims that all properties of a system can be

considered to be unique functionals of its ground state density. Together with the Born-

Oppenheimer approximation113 and Kohn-Sham equations114, practical accurate DFT

calculations have been accessible via approximations for the exchange-correlation (XC)

potential, which describes the effects of the Pauli principle and the Coulomb potential

beyond a pure electrostatic interaction of the electrons. Because it is difficult to

calculate the exact XC potential (by solving the many-body problem exactly), a general

approximation is the local density approximation (LDA) which locally substitutes the

XC energy density of an inhomogeneous system by that of a homogeneous electron gas

evaluated at the local density.

Page 37
LDA uses only the electron density, n(r), at spatial point r to determine the exchange-

correlation energy density at that point. The exchange-correlation energy density is

considered to be a uniform electron gas of the same density. The exchange part of the

functional is defined as the exact expression derived for a uniform electron gas.114 The

difference among versions of LDA is their representation of correlation.

GGA adds the gradient of the density, |∇ n(r)|, as an independent variable. The gradient

introduces non-locality into the description of exchange and correlation. GGA

functionals have evolved in two main directions. One is sometimes called „parameter

free‟, where the new parameters are obtained from known expansion coefficients and

other exact theoretical conditions. The other is empirical, with parameters determined

from fits to experimental data or accurately calculated atomic and molecular

properties.115

It is generally understood that the main reason of inaccuracy in DFT for d and f

electrons is the correlated nature. A widely used method for making an improvement in

the description of d and f electrons is the DFT+U method, in which an “on-site”

potential is added to introduce intra-atomic interactions between the strongly correlated

electrons. The value of U is different from element to element, and one study has

suggested that it is transferable between different oxidation states of a given element.116

U is usually determined empirically, to fit some specific physical property, most often

the crystal lattice parameters or the band gap between the occupied and unoccupied

states.117-118 The main problem with this approach is that no two properties are

described well by the same value of U, and therefore, a value is chosen to minimizes the

average error in several properties.

Page 38
2.4.2 Pure VO2

In 1971, Goodenou constructed a schematic energy band diagram for both the metallic

and the insulating phase of VO2.119 Similar to some transitional metal oxides, the

octahedral crystal field splitting V 3d band into lower t2g and higher eg levels. Moreover,

the t2g states, which are located near the Fermi energy, are divided into a d state, which

is directed along the rutile c axis, and the remaining π∗ states. In the VO2(M1), further

dimerization of V atoms makes the d‖‖ band split into two parts. The lower d‖‖ band is

completely filled while the π∗ band is empty. eg1 is involved with the band gap between

O2p orbital and π∗, and eg2 is associated with the band gap between the lower d‖‖ and p∗

band. He suggested that the metal-insulator transition results mainly from the increased

p–d overlap as a result of the antiferroelectric distortion of the VO6 octahedra. It can

lower and raise the bonding and antibonding π and π∗ levels, respectively. The d states

would be split as a consequence of the symmetry change.120 Different to the electron-

lattice interaction theory, Zylbersztejn and Mott suggested that the metal-insulator and

structural transition was due to the presence of strong electron-electron correlations

especially in the d band.121

Fig. 2-20 Molecular orbital diagram depicting the electronic structure of the monoclinic and

tetragonal phases of VO2.119,122

Page 39
Density Functional Theory (DFT) simulations have been carried out for the VO2 using

many different functions. Eyert et al. calculated the electronic structure for different

phase of VO2 with local density approximation (LDA).120 He found that in the M1

phase splitting of the d‖‖ band due to metal-metal dimerization and upshift of the π∗

bands due to increased p–d overlap lead to an effective separation of both types of

bands. However, the simulation leads to an incomplete opening of the optical band gap

due to the shortcomings of the LDA. In order to resolve this contradiction within the

band approach, the LSDA + U formalism of correction for correlation effects was

carried out.123 The L(S) DA + U approach predicted much more dramatic changes in the

orbital occupations; however, unfortunately it did not give the metallic solution for the

R phase. Because the DFT-LDA calculations fail to yield the opening of the band gap:

the top of the bonding d‖‖ band is found to overlap slightly with the bottom of the π∗

band. Various LDA + DMFT methods have been applied to investigate the MST.124-125

Both the metallic r and the insulating monoclinic phase can be correctly captured by this

method. Another method that can correctly describe the semiconductor property is the

GW approcoach.126 Recently, the hybrid functional have been utilized to calculate both

rutile and monoclinic VO2, which is well capable of generating an insulating gap in the

single-particle spectrum of both the M1 and M2 phases and of properly describing the

antiferromagnetic ordering on the Heisenberg chains of the latter.127 However, Ricardo

et al. argued that the HSE hybrid functional description is not correct to describe

VO2.128 They reported that the HSE functional fails in the description of both the

electronic structure and the energetics of the transition of VO2. The results of the

simulation give a magnetic ground state for the M1 phase, a nonmetallic ground state

for the R phase, and an R-M1 energy difference in significant disagreement with the

experimental latent heat.

Page 40
2.4.3 Doped VO2

Although many sophisticated methods such as GW, local density approximation with

dynamical mean field theory (LDA + DMFT) and particular hybrid functionals are

known to yield better results for pure VO2, these methods are too computationally

consuming to deal with the large supercells, especially for metal doped VO2.

The phase transition temperature is 68 °C for pure VO2 and doping is one of the

effective ways to lower this temperature. A number of elements have been investigated

for the phase transition temperature lowering effect. However, the experimental method

cannot describe the electronic structure change after doping and DFT simulation may be

an appropriate tool to investigate the effect of doping from an atomic scale.

Different element doped VO2 has been simulated by DFT approach and interesting

results have been reported. Among them, W and Mo seem to have the most significant

effect to decrease the transition temperature.89,98,129 It is well known that doping with

high-valent cations will decrease the temperature while the low-valent doping will

increase the temperature. More detailed research has been carried out later to investigate

the W doping effect to the transition temperature and optical properties in the solar

region.130 It is found that W doping significantly lowers the transition temperature

between the R and M1 by reducing the energy difference between these two phases. The

calculations show that the doped W lowers the infrared light transmittance of the

monoclinic VO2 as well, which is consistent with the experimental results.

Page 41
Fig. 2-21 The calculated DOS of W-doped VO2(R) and VO2(M1) at the levels of GGA + U (a

& b) and HSE06 (c & d).130

Except for W doping, Pan et al. investigated the doping effect of Cr by DFT simulation

based on pseudo-potential and local spin density approximation (LSDA).101 A 2 * 2 * 2

supercell was built and one of the V atom was substituted by Cr atom. They reported

that the chromium substitution shortened some V-V distance to enhance the interaction

between V atoms. Therefore, they believed that the V-V bonding is an important driving

force to remain semiconductor phase and chromium substitution makes the VO2 system

more likely to stay in semiconductor phase rather than metallic phase. However, the

authors just modelled the Cr-doped VO2(R) without consideration of the doping effects

in monoclinic phase, which was not evident enough to investigate the doping effect.

Usually, high-valent metal doping can decrease the phase transition temperature even to

room temperature. Instead, low-valent metal doping increase the temperature. However,

Mg doping cannot only boost the luminous transmittance, but also lower the

Page 42
temperature.54 The effect of Mg doping has been researched by DFT simulation. The

Perdew-Burke- Ernzerhof (PBE) version of the generalized gradient approximation

functional and the Heyd-Scuseria-Ernzerhof (HSE) hybrid functional was used to

investigate the Mg doping effect.131 Different doping concentrations have been

simulated and they found that Mg doping can widen the band gap widening and lower

the luminous absorptance at the same time.

In order to investigate the interstitial doping effect for the phase transition temperature,

Be-doped VO2 has been investigated by DFT simulation with GGA + U method.132

Different to other DFT simulation for VO2 doping effect, they think that the Be atoms

do not substitute the V atoms, while they exist in the interstitial sites such as the

tetrahedral, octahedral and side cantered sites. Enthalpy associated with the phase

transition has been connected with the phase transition temperature by equation. After

applying such equation, they report an unprecedented reduction of 58 K per 1% Be for

the doping at the tetrahedral or side centred sites in the VO2. While the reduction of 52

K per 1% Be is observed for the doping at the octahedral site. After Be doping,

additional electrons can be injected into the VO2 systems, which will induce the internal

stress and affect the VO2 (R) significantly, leading to the reduction of the transition

temperature. Although DFT simulation has been carried out for the Be-doped VO2

structure, no experimental results have been reported to confirm this finding and it may

be difficult to doping Be interstitially by experimenting because of the high possibility

of new compound formation.

Despite the effect of lowering phase transition temperature, doping can also change

other properties of VO2. For instance, F doping may enhance the visible transmittance

Page 43
of the VO2 films while maintaining the thermochromic properties.96 Meanwhile, the F

doping can also effectively decrease the transition temperature as reported by Dai et

al..104 They prepared F-doped VO2 nanopatricles by hydrothermal method with

homogeneous size distribution. After casting these nanoparticles into VO2 smart glass

foils, the films exhibit good thermochromic property in the near-infrared region and an

appropriate visible transmittance (48.7%) has also been achieved. In order to investigate

the tuning mechanism for the optical properties (especially for the modified colours) by

F-doping, DFT simulation with GGA + U functional has been carried out. After F

doping, the band gap of VO2 has been reduced from 0.69 eV to 0.50 eV, which is

mainly due to the shift of the O2p states. However, only the F-doped VO2 monoclinic

phase has been calculated, therefore the doping effect of F to the phase transition

temperature is still not clear.

Fig. 2-22 The calculated VO2 and F-doped VO2 structures and electronic properties. The unit

cell (a) with 4 V atoms and 8 O atoms and 2 *2 * 2 supercell (c). V atoms are shown in gray, F

atom in blue and the O atoms in brown and red. Band structure, total density of states and

partial density of states for V and O calculated for pure VO2 (b) and F-doped VO2 with the F/(F

+ O) atom ratio 0.0156 (d).104

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2.5 Applications

VO2 has a metal-semiconductor transition at a critical temperature of 68 °C, which has

been a benchmark problem in solid state chemistry. Most of the applications regarding

the VO2 take the advantage of the transition between the VO2(R) and VO2(M1). At

temperature below 68 °C, VO2 is in a monoclinic phase, having an energy gap of about

0.6 eV.107,119 However, above the critical temperature, VO2 is in a metal state and the

overlap between the Fermi level and the V 3d band eliminates the band gap mentioned

above,120 making the material to be highly reflective or opaque in the near IR region.133

The critical temperature can be decreased to room temperature by doping68,119 or scaling

the materials to nano size122. Associated with the structure transition, the dramatic

changes in optical properties show promising application as smart windows. Different

to VO2(R) and VO2(M1), VO2(B) with metastable monoclinic structure has been widely

studied as candidate anode material.134-135 Because of its proper electrode potential and

tunnel structure, through which lithium ions can make intercalation and deintercalation

in reversible lithium ion battery, VO2(B) has attracted more and more interest as a new

battery materia.33,37,134,136 Apart from the applications for smart windows and lithium

ion battery, VO2 has also been considered for applications in field-effect transistors7,137 ,

swithches71,138 and sensors11,139.

2.5.1 Smart Window Coatings

When electromagnetic radiation falls on a material one fraction can be transmitted, a

second fraction is reflected, and a third fraction is absorbed. Energy conservation yields,

at each wavelength, that

T(λ) + R (λ) + A(λ) = 1,

Page 45
where T, R, and A denote transmittance, reflectance, and absorptance, respectively.

Another fundamental relationship, also ensuing from energy conservation and referred

to as Kirchhoff‟s Law, is

A(λ) = E(λ),

where E is the emittance, i.e., the fraction of the black body radiation that is given off at

a particular wavelength. The second equation is of practical relevance mainly for

wavelength λ > 3000 nm.

As described previously, the vanadium oxide has a phase transition at 68 °C, changing

from monoclinic to tetragonal rutile. Accompanied with this phase transition, the optical

properties change drastically. Below the temperature, the VO2(M1) is transparent to

both the visible and the infrared regions of the electromagnetic spectrum, which will

heat the building. While above 68 °C, the material becomes metallic in nature and

remains transparent in the visible region but becomes reflective in the infrared region,

which could prevent heat passing through the windows. Because the phase transition

temperature is relatively close to the room temperature, the vanadium dioxide has been

considered as the “smart windows” for a long history. Babulanam et al. first found that

the thermochromism may be utilized for regulating the energy throughput of windows.85

He also suggested that SiO2 can be coated on the films to increase the visible

transmittance. Now more than half of the research with regard to vanadium dioxide is

focused on this application. However, there are still some problems to overcome before

the vanadium oxide films can be prepared in large scale.

The most obvious problem is the low visible transmittance, which originates from the

strong innerband and interband absorptions in the short-wavelength range for both the

Page 46
metallic and semiconductive states.107 Though doping of F or depositing an

antireflection coating can increase the visible transmittance99, the result is not

satisfactory. Fluorine-doped films are not suited for window coating because of their

poor switching behaviour at room temperature due to the strong distortion of the VO2

host lattice.98 The AR coating seems a better choice compared with fluorine doping,

while this procedure inevitably increases the economical consumption. Zhang et al. has

reported the relatively high visible transmittance of 75.7% without doping or depositing

an antireflection coating. Although this is much better than the other references, further

research is still needed to improve the integral value of the films.

Secondly, the phase transition occurred at relatively high temperature (68 °C). Although

it can be reduced to room temperature by doping, especially by doping high-valence

atoms74, 67,140 such as W, Mo, or by scaling the materials to nano size122, the integrating

properties of the prepared thin film is not substantial enough for real applications. For

instance, tungsten doping alone does not provide an acceptable colour of the VO2

films97 and decreases the near-infrared switching efficiencies to around 20%.89

Therefore, a new method needs to be developed to decrease the transition temperature

while optimising the other properties of VO2 films at the same time.

Thirdly, for application as smart windows, the contrast transmittance in near-infrared is

crucial to the effect and this value is affected by several factors, for example film

thickness, doping, microstructure, and stoichiometry.72 Among these factors, the film

thickness determines the switching efficiency significantly. Increasing the film

thickness will cause great loss in the visible transmittance, which is quite important for

smart window application. Besides these three main problems, there are several other

Page 47
problems which need to be solved, such as the brown colour of vanadium oxide and the

broad hysteresis loop.

Fig. 2-23 (a) Digital photograph of the film; (b) temperature-dependent transmittance spectra; (c)

a hysteresis loop of a large-area (30*40 cm2) W-doped VO2 film; and (d) an image of model

house (1, temperature monitor; 2, VO2 glass; 3, temperature probe; 4, infrared lamp; and 5,blank

float glass).1

2.5.2 Lithium-ion Battery

Among all kinds of batteries, the high energy density of rechargeable lithium-ion

batteries has already made their wide application in the portable electronic market. The

VO2(B) has attracted more attention because it shows high capacity as the cathode for

the lithium-ion battery.37,134,141-144 The VO2(B) structure can be considered as formed by

Page 48
two identical layers of atoms along b axis. Therefore, hierarchical VO2(B)

nanostructures may be the prospective candidate for electrode materials in aqueous

lithium ion batteries.

Zhang et al. have studied the electrochemical lithium intercalation in VO2(B) electrodes

in aqueous electrolytes by means of electrochemical methods.145 They suggested that

the optimum pH range for the lithium intercalation reaction is found to be between 8

and 10 and it is important to find ways to minimize hydrogen evolution or to ensure its

recombination in electrolytes of small volume. Recently, Mai et al. synthesized

ultralong hierarchical vanadium oxide nanowires with diameter of 100-200 nm and

length up to several millimetres by electrospinning, combined with annealing with the

low-cost starting materials.141 The nanowires show quite good electrochemical

properties. The initial and 50th discharge capacities of the ultralong hierarchical

vanadium oxide nanowire cathodes are up to 390 and 201 mAh/g when the lithium ion

battery cycled between 1.75 and 4.0 V. When the battery was cycled between 2.0 and

4.0 V, the initial and 50th discharge capacities of the nanowire cathodes are 275 and

187 mAh/g. In order to increase the stability, the carbon coated VO2(B) has also been

investigated as lithium ion battery materials.20 All the results demonstrate that the

VO2(B) nanostructure may be one of the most promising materials as cathodes for

lithium ion batteries.

Page 49
Fig. 2-24 (a, b) Charge/discharge curves of hierarchical vanadium oxide nanowires at voltages

of 2-4 and 1.75-4 V, respectively. (c, d) Capacity vs cycle number, and Coulombic efficiency vs

cycle number of the ultralong hierarchical vanadium oxide nanowires.141

2.5.3 Sensor

Because of the existence of the phase transition in vanadium oxides, it can be utilized as

the different kinds of sensors.11,139,146 For example, Strelcov et al. synthesized the

thermistor based on metal-insulator transition in VO2 nanowire.139 By varying the

temperature of the nanowire close to the transition edge, the conductance of the

nanowire becomes extremely responsive to the tiny changes in molecular composition,

pressure, and temperature of the ambient gas environment. Hu et al. fabricated a flexible

strain sensor with a free-standing VO2 nanobeam.11 By loading the external strain, the

M2 phase fraction can be tuned and the resistance of the nanobeam can be controlled.

The high gauge factor in low strain ranges with short response time shows potential

application of the VO2 nanobeam for quantifying small strain.11

Page 50
Fig. 2-25 (a) The design and principle of operation of VO2 NW MIT gas sensor. PG and PL

indicate heat fluxes dissipating into the gas environment and metal contacts correspondingly. (b)

Realization of the sensor using thin long nanowire with its ends immersed in the Ga-In-Sn

liquid microdroplets. The electrodes of the NIST μhp served as the base for the liquid contacts.

(c) Alternatively, wide microscopic VO2 ribbons were employed when the imaging of the metal

(M) and insulator (I) domains dynamics was required. (d, e) The appearance and evolution of

the M domains (dark) with increasing the Joule heat (optical images were taken with 1000×

magnification, scale bars correspond to 10 μm).139

Vanadium oxide has also been reported as gas sensing application. For instance, Liu et

al. reported that the V2O5 nanobelts exhibited good response toward ethanol with a

detection limit ~10 ppm at a working temperature of 200 °C.147 The nanobelts were

synthesized by a hydrothermal method, which is feasible for large-scale production.

Although the response toward ethanol is not quite high, the as-prepared sensor showed

quicker response/recovery time. In order to increase the response, metal oxides

nanoparticles had been coated on the V2O5 nanobelts148, such as SnO2, Fe2O3 and TiO2.

SnO2 and Fe2O3 coated V2O5 nanobelts showed the highest response of 3.7 and 2.9 at

Page 51
290 °C, respectively. The enhanced response had been explained by the particular

electrical transport mechanism due to the coated metal oxide nanoparticles. One issue is

that after coating with other metal oxides, the optimal temperature has been increased to

290 °C, compared to the pure V2O5 at 250 °C.

To further improve the response, Jin et al. demonstrated that V2O5 nanotubes coated

with Fe2O3 nanoparticles (~15 nm) exhibited a response (S) of 3.37 toward 1000 ppm of

ethanol at an optimized temperature of 330 °C.149 Moreover, Fu et al. synthesized

vanadium pentoxide micro-urchins composed of nanorods (200 nm×1000 nm), and

these urchin-like V2O5 microstructures showed an enhanced gas-sensing response

compared with individual V2O5 nanorods at 150 °C.150 However, the response of

vanadium pentoxide toward alcohol is still low, which limits its practical gas-sensing

application. In order to increase the response, other methods rather than the surface

modification need to be carried out.

2.5.4 Switch

The principle of applying VO2 as the switch application also originates from the Metal-

Semiconductor phase transition. Guzman et al. utilized the electrical change along with

the phase transition to make electrical switches, which performed rather successfully

even after 108 circles151. Soltani and his colleges successfully fabricated two types of 1

x 2 optical switch devices, (all-optical switch (VO2/quartz) and electro-optical switch

(VO2/TiO2/ITO/glass)) based on the semiconductor-to-metallic phase transition

characteristic of vanadium dioxide (VO2) smart coatings.152 Because the phase

transition is related with the temperature, a temperature-controlling optical switch has

been successfully made.138 In their work, a metamaterial of metal/semiconductor/metal

Page 52
sandwich nanostrips structure, comprising of a pair of gold strips and a vanadium

dioxide VO2 strip, was fabricated. They explored the physical mechanical with the finite

difference time-domain method and found that the spectrum of the M phase has a

transmission dip at 1200 nm while the transmission dip disappears in the R phase.

Fig. 2-26 Schematic diagram of the sandwiched nanostrips (a, b) and SEM image of a sample

(c).138

2.6 Summary

The synthesis of vanadium dioxide nanoparticle/thin film has been widely investigated

in the past decade. Many methods for preparing VO2 nanoparticles and thin films have

been explored and the phase transition mechanism and thermochromic properties are

well studied. DFT simulation has also been successfully applied to explain the

mechanism in an atomic scale. Moreover, different applications have been proposed

and some of them may be commercialized very soon.

Page 53
The challenge that researchers currently face is whether the synthesized methods for

VO2 are efficient and/or practical on a large scale. The problems of VO2 nanoparticles

are the instability from oxidation and a low yield rate in producing. The production of

VO2 thin films may significantly increase the cost of smart window or cause

environment hazard. Nevertheless, the broad scientific research in theory has given

some insights for possible commercial applications. This study is to develop new

synthesis strategies for improving the efficiency of VO2 in future commercialisation.

Page 54
Chapter 3. Hydrothermal Synthesis of VO2 Nanoparticles
for Gas Sensing Performance

3.1 Introduction

Vanadium dioxide, a V4+ vanadium oxide, is quite a unique and interesting material due

to the thermochromic and electrochemical properties.9,134,153 VO2 nanoparticles have

been widely researched for many different applications, including smart window,

lithium ion battery and different kinds of devices.

Of different phases of VO2, VO2(B) phase has attracted increasing attention in recent

years because it shows good properties in the lithium ion battery application. Traditional

methods to synthesize VO2 usually involve thermal decomposition of V precursor145,154-

155
and these methods need high temperature or expensive apparatus. Recent advances

have shown that hydrothermal method is advantageous for synthesizing shape-

controlled VO2(B) nanostructures. Such advantages include lower reaction temperature,

eco-friendly reaction conditions and controllable morphology and size

distribution.20,35,37 V2O5 is usually utilized as the vanadium source, therefore a reducing

agent is required to reduce the V5+ in the experiment.20,37,143,156 Because of the layered

structure, nanobelts and nanorods are the most common morphologies of VO2(B)

products. Instead, the chemical properties of metal oxide is strongly related with the

morphology.157 For example, 3D hollow VO2(B) micro-spheres have been prepared by

the hydrothermal method and this structure shows discharge capacity as high as ca. 450

mA·h·g-1 when recorded at the current density of 10 mA·g-1.37 It is thus of great

Page 55
significance to control the morphology of VO2 nanostructures for lithium ion battery

application.

Apart from the lithium ion battery application, VO2(B) and VO2(M1) have also been

investigated as a humidity sensor158. It is found that VO2(M1) type sensor is more

sensitive at high relative humidity and the VO2(B) type sensor shows a higher

sensitivity at low relative humidity. Similar to the humidity sensor, VO2 may also be

sensitive to other flammable gas. The gas-sensing properties of the VO2(B) will be

investigated towards a variety of flammable and toxic gases for the first time in this

work.

In this chapter, a facile hydrothermal method has been utilized to synthesize the VO2(B)

nanostructure. Moreover, different reducing agents and surfactants have been

investigated to control the morphology of VO2(B) and the mechanism on morphology

control of VO2(B) have been discussed as well. Finally, the gas sensing application of

VO2(B) has been studied towards flammable gases.

3.2 Synthesis of VO2(B) Nanoparticles

3.2.1 Experimental Section

3.2.1.1 Materials

Vanadyl acetylacetonate (VO(acac)2, 99.99%), and various surfactants such as

poly(vinylpyrrolidone) (PVP, MW = 55000), dioctyl sodium sulfosuccinate (AOT, 98%)

and cetyltrimethyl-ammonium bromide (CTAB, ≥ 98%), Vanadium pentoxide (V2O5, ≥

99.6%), Ethylene glycol (EG, ≥ 99%), Citric acid (99.5%), titanium (IV) butoxide (TBT,
Page 56
97%) and absolute ethanol (C2H5OH, 99.9%) were all purchased from Sigma-Aldrich

and used as received without any further treatment. All solutions were freshly made,

and ultrapure water was used in all synthesis processes.

3.2.1.2 Synthesis

Synthesis of VO2(B). VO2(B) was prepared by the hydrothermal method. In a typical

procedure, 0.7005 g citric acid was dissolved into 40 ml deionised water, then 0.9094 g

V2O5 was added into the solution. 10 ml EG and 33 ml Ethanol was added into different

amount of deionised water, keeping the total volume constant at 40 ml. For the

investigation of effects of different surfactants, 0.1326 g VO(acac)2 was dissolved in 40

ml deionised water, then different amount of CTAB, AOT and PVP was added into the

above solution under strong stirring at room temperature, keeping the molar ratio

between the VO(acac)2 to surfactant at 10:1,1:1 and 1:10, respectively. The solution was

transferred to the Teflon-lined stainless-steel autoclave and heated at 180 °C for 24 h.

The resulting black products were centrifuged, washed with deionised water and ethanol

for several times, finally dried at 60 °C.

Synthesis of VO2@TiO2 core-shell nanoparticles. For the preparation of VO2@TiO2

core-shell nanostructures, 0.05 ml TBT was added to 10 mL EG. The mixture was

magnetically stirred for 12 h at room temperature as solution A. 3 mL suspension

including 0.002 molar VO2(B) nanoparticles was poured into 10 mL acetone under

stirring for 5 min as solution B. 0.5 mL solution A was then added into solution B,

leaving it for 1 h. The grey precipitates were collected by centrifugation and these

precipitates were then heated in 100 °C water for 2 h. To produce VO2@TiO2 core-shell

Page 57
particles, the colloids were centrifuged at 3000 rps for 10min and washed with alcohol,

and finally dried in vacuum at 80 °C for 24 h.

3.2.1.3 Characterization

X-ray powder diffraction was performed on Philips X‟Pert Pro Super Diffractometer

with Cu Kα radiation (λ= 1.5406 Å). The field emission scanning electron microscopy

(FESEM) images were taken on a JEOL Nano SEM 230. The transmission electron

microscopy (TEM) images were obtained on the JEOL 1400 with the acceleration

voltage of 100 kV. High-resolution transmission electron microscopy (HRTEM) was

acquired on Philips CM200, at the accelerating voltage of 200 kV. Gas-sensing

properties of the as-prepared flower-like structure were measured by a computer-

controlled WS-30A gas-sensing measurement system. Firstly, the samples were mixed

with poly (vinylidene fluoride) (PVDF) binder and 1-methyl-2-pyrrolidone to form

slurry. Secondly, the slurry was painted on to a ceramic tube (2 mm in diameter) to

form a thin film between two gold electrodes, deposited on the ceramic tube and

connected with four platinum wires. Next, the ceramic tube was annealed at 350 °C for

3 h to remove the PVDF and the sensor has been aged for 6 h before the gas sensing

measurement until the base line becomes stable in air. The annealing process is to fix

the powder on the surface of ceramic tube and remove polymers. Because the relatively

low temperature (350 °C), the final composition of the material used for sensing could

be maintained. Finally, a certain amount of the test gas was injected into the testing

chamber by a micro-syringe.

Page 58
3.2.2 Structure and Morphology

3.2.2.1 Effects of Reducing Agents

Fig. 3-1 XRD patterns VO2(B) nanostructures using different reducing agents: (a) citric acid, (b)

ethanol and (c) ethylene glycol.

The crystal structure and phase composition of the as-prepared product was

characterized with XRD. Fig. 3-1 displays the XRD patterns of the VO2(B) samples,

which can be readily indexed into the monoclinic VO2 phase with lattice paramaters a=

12.093 Å, b= 3.702 Å, c= 6.433 Å and β= 106.97 °( space group: C2/m, JCPDS No. 07-

0514). One interesting thing is that VO2(B) grows along a different plane when different

reducing agents were applied. When citric acid and ethanol were used as the reducing

agent, the relative intensities of the (110) peaks are stronger than those of the JCPDS

card, indicating crystalline orientation along the [110] direction. However, the pattern

Page 59
shows relatively strong intensities of the (00n) peaks when ethylene glycol was utilized

as the reducing agent. The preferred growth direction may be explained by the different

properties of the reducing agents and their effects on different surfaces.

Fig. 3-2 shows the SEM images of VO2(B) obtained from the reaction of V2O5 with

different reducing agents. Leaf-like nanorods with length of 300 nm to several

micrometers and width ranging from 100 to 250 nm were obtained when ethylene

glycol was used as the reducing agent. Small nanorods were produced when ethanol

was used. These nanorods present length from 250 to 650 nm and width around 100 nm.

Some of these small nanorods self-assemble into microspheres. Similar nanorods were

obtained when citric acid was used and these nanorods show length from 500 nm to 1

µm.

Fig. 3-2 SEM images of VO2(B) nanostructures using different reducing agents: (a) ethylene

glycol, (b) ethanol and (c) citric acid.

Page 60
 Fig. 3-3 XRD patterns of products obtained with different molar ratio between V2O5 and citric

acid: (a) 1:2, (b) 2:3, (c) 1:1, (d) 3:2 and (e) 2:1.

3.2.2.2 Effects of Molar Ratios

Fig. 3-3 shows the XRD patterns of products obtained by varying the molar ratio

between V2O5 and citric acid. Theoretically, 1 molar citric acid can reduce 1.5 molar

V2O5 to VO2. If the molar ratio between V2O5 and citric acid is 3:2, then all the V2O5

will be reduced to VO2. The XRD patterns were constant with the theoretical analysis.

When the amount of citric acid is not enough to reduce all the V2O5, H2V3O8 (Fig. 3-4 b)

nanobelts were obtained. H2V3O8 (or V3O7·H2O), with a higher average V valence

(4.67), can be used as the electrode material for LIB batteries.159 Oka et al. reported that

H2V3O8 nanobelts could be prepared from a VOSO4 solution through a hydrothermal

reaction, and identified an orthorhombic crystalline phase of H2V3O8 with a V5+/V4+

ratio of 2/1.160 The existence of V5+ ions indicates that only part of V2O5 has been

Page 61
reduced into V4+ ions. Decreasing the molar ratio to 3:2, relatively uniform VO2(B)

nanorods were obtained. Further lowering the molar ratio, VO2(B) still remains and no

V2O3 was observed. This may be due to the low reducing capability of citric acid, which

cannot reduce the V2O5 into V3+.

Fig. 3-4 SEM images of products obtained with different molar ratio between V2O5 and citric

acid: (a) 2:1, (b) 3:2, (c) 1:1, (d) 2:3 and (e) 1:2.

3.2.2.3 Effects of Surfactants

Different surfactants were also investigated to control the morphology. In order to avoid

the use of reducing agent and simplify the reaction process, VO(acac)2 is chosen as the

vanadium source. Different molar ratios between VO(acac)2 and surfactants were varied

in order to investigate the effects systematically.

The crystal structure and phase composition of the as-prepared product was

characterized with XRD. Fig. 3-5 displays the XRD pattern of the VO2(B) samples,

which can be readily indexed into the monoclinic VO2 phase with lattice paramaters a=

Page 62
12.093 Å, b= 3.702 Å, c= 6.433 Å and β = 106.97°( space group: C2/m, JCPDS No. 81-

2392). It is obvious that no peaks of any other phases or impurities were detected.

Fig. 3-5 XRD pattern of the synthesized VO2(B) products and the standard JCPDS card.

The morphology of the products was investigated by FESEM as shown in Fig. 3-6.

Three different kinds of surfactants were used to study the effect of morphology control

with the molar ratio varied from 1:10, 1:1 and 10:1. When CTAB is utilized as the

surfactant, changing molar ratio has a significant effect. With the molar ratio of

VO(acac)2:CTAB at 10:1, nanosheets about 40 nm thickness are obtained and they

connect to each other to form flower-like nanostructure. While with the other two molar

ratio, the morphology of the products is not so uniform. Compared with CTAB, the PVP

works quite differently. At the same molar ratio, nanorods displaying uniform

Page 63
dimensions are obtained, 80-100 nm wide, 30-50 nm thick and 350-450 nm long.

Increasing the molar ratio causes the nanorods to become smaller. At the molar ratio of

1:10, the cuboids are just 150-180 nm long, although the thickness and wideth does not

change much. The reason the nanorods become shorter with increasing molar ratio is

because more PVP is adsorbed on certain planes of VO2(B), thus inhibiting the growth

of the nanorods. AOT presents a similar effect as PVP and leaf-like nanorods are

obtained. At the molar ratio of 1:1, the as-prepared products seem to be more uniform

with length in the range of 500-900 nm.

Among these three surfactants, CTAB has a more prominent effect on the morphology

control because of the formation of flower-like structure. Surfactants are usually utilized

to control the shape for nanoparticles, especially for metal nanoparticles, such as Ag and

Au.161-162 The selective adsorption of surfactant may lead to different growth rates for

different planes and hence direct the growth of nanoparticles into various shapes.

Similar flower-like structures with CTAB as the surfactant have also been observed in

other metal oxides.163 As we known, CTAB is often used as “capping reagent” in

nanoparticles synthesis because it can bond to surface and selectively adsorb on some

specific plane of crystals to control crystal growth direction consequently.

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Fig. 3-6 SEM images of VO2 nanostructures obtained with different surfactants and molar ratio:

(a-c) VO(acac)2:CTAB =10:1, 1:1 and 1:10, respectively; (d-f) VO(acac)2:PVP=10:1, 1:1 and

1:10, respectively; (g-i) VO(acac)2:AOT=10:1, 1:1 and 1:10, respectively.

As shown in Fig. 3-7, the loose flower-like structure is assembled from nanosheets

connecting to each other. The representative HRTEM image of the nanosheets displays

clear lattice fringes with a spacing of 0.308 nm, which can be indexed to the (002)

planes of the monoclinic VO2(B).

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 Fig. 3-7 TEM (a) and HRTEM (b) image of VO2(B) obtained at 180 °C for 24 h

with CTAB.

The possible formation mechanism of the flower-like structure is proposed, as

illustrated in Fig. 3-8. First, the VO(acac)2 is hydrolysed into [VO(H2O)5]2+,164 which is

responsible for the formation of VO6 octahedra. By vertex and edge sharing, the VO6

octahedra forms the final crystal structure of monoclinic VO2(B). Because of the

electronic interactions between CTAB and VO2, different amount of CTAB is then

absorbed to different planes of VO2. Thus some planes are inhibited for growth and

morphology controlling of VO2 is achieved. Finally, driven by the Vander Waals and

interactions between polymer molecules, the flower-like structure is formed in order to

minimize the total energy in the system. This growth mechanism may be similar with

the mechanism proposed by Zhang et al..134 Actually, the formation mechanism is pretty

complicated and there are many factors affecting this process, such as crystal plane

attraction, hydrogen bond and electrostatic interactions. Molecular dynamic simulation

may be required to fully understand the interactions between the crystal plane and

surfactants.

Page 66
 CTAB
H2O+ VO(acac)2
180 °C,24h

Fig. 3-8 Schematic illustration of the formation process of the as-obtained flower-like VO2(B)

structures.

3.2.3 VO2-TiO2 nanocomposites

Fig. 3-9 SEM images of VO2 particles (a) and VO2 particles coated with 0.1 ml (b), 0.3

ml (c) and 0.5 ml (d) TBT added into VO2 solution.

The TiO2 coated VO2(B) core-shell nanostructures were prepared in order to increase

the stability of VO2 for lithium ion battery application. Fig. 3-9 shows the SEM images

Page 67
of VO2 nanorods before and after TiO2 coating. Without any coating, the surfaces of

VO2(B) nanorods are quite smooth. However, after TiO2 coating the size of nanorods

remained the same while the surfaces become rougher, which means the coating of TiO2

will not affect the shape of the products. In order to investigate whether the coating is

dot coating or layer coating, TEM images have been taken. As shown in Fig. 3-10, the

TiO2 layer was coated on the whole surface of VO2(B) nanorods, forming core-shell

structure. After boiling in water, the thickness decreases from 12 nm to 10 nm. From the

Energy-dispersive X-ray spectroscopy (EDS) images, it is found that TiO2 was evenly

coated on the VO2. Moreover, the ratio between Ti and V could also be controlled by

adding different amount of TiO2 precursor solution. When adding 0.3 ml TBT solution,

the ration between Ti and V was about 0.18 and this value rose into 0.32 after adding

0.5 ml TBT solution. This VO2@TiO2 core-shell nanostructure may be beneficial for

lithium ion battery application because the TiO2 coating can improve high volumetric

energy density, high surface stability, and long cycle life compared with the commonly

used carbon nanocoating in electrode materials. 165-166

Fig. 3-10 TEM images of TiO2 coated VO2 particles before and after boiling.

Page 68
 Fig. 3-11 Energy Dispersive Spectroscopy images of the VO2 coated with TiO2.

3.3 Gas Sensing Properties

Nanoflowers are the most interesting morphology among these products due to the large

surface area compared to the nanobelts and nanorods.167 Compared to other

morphologies, such as VO2 nanobelts and carambola-like VO2 structure, the unique

flowerlike structure plays basic roles in electrochemical intercalation and

deintercalation properties with Lithium ion.134 Therefore, the gas sensing experiments

of nanoflowers structure are carried out in order to explore the potential ability of this

material. The gas-sensing property of the flower-like VO2(B) was investigated toward a

variety of flammable and toxic gases such as ethanol, acetone, butanol and isopropanol.

Fig. 3-12 presents the real-time sensing response characteristics toward the four gases

Page 69
based on the flower-like VO2(B) structure. As shown in the figure, the resistance

decreases after the injection of gas and recovers to its initial value after release of the

gas, this is the typical behaviour of n-type sensors. The base line of the sensor was not

quite stable, which may be due to the reaction between the sensor and measured gases.

Overall, the sensor showed high sensitivity towards butanol compared with other three

gases.

Fig. 3-12 Real time sensing characteristics of VO2 nano-structure towards ethanol, acetone,

butanol and isopropanol.

Fig. 3-13 shows that the sensing performance of VO2(B) sensor towards these four

gases are similar. The as-prepared flower-like structure displays the highest response to

butanol compared with other gases. Theoretically, the resistance will decrease as the

increase of the gas concentration for ideal n-type sensors. This is consistent with the

Page 70
experimental results. For the humidity sensor, at high humidity the density of free

electrons on the VO2(B) surface is decreasing in the adsorption process, causing the

increasing of resistance with humidity.158 While in this work the resistance in gas

decreases compared to the resistance in air. It is known that the dominant charge carrier

for VO2(B) is electron. When gas was injected, the oxygen species absorbed on the

surface of VO2(B) will react with the gas. Therefore, the trapped electron will be

released and the resistance decreased. However, there is a drop for the resistance in air

after several gases sensing measurement for ethanol, butanol and acetone. This may be

due to the reactions between the reductive gases and VO2, which make it difficult to

recover to its initial state. The stability of the nanoflower structure VO2 sensor has also

been measured towards 100 ppm ethanol. It shows relatively high stability over a period

of 7 days.

Fig. 3-13 Sensing responses versus vapor concentration of isopropanol, acetone, butanol and

ethanol.

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3.4 Transformation to VO2(M1)

The irreversible transition between VO2(B) and VO2(R) has also been investigated. As

shown in Fig. 3-14, the transformation from VO2(B) to VO2(R) begins at 550 °C. After

annealing at 550 °C for 2h, the product consists of a mixture of VO2(M1) and VO2(B).

Increasing annealing time to 3 h, the intensity of peaks indexed to VO2(M1) has been

increased. After annealing at 700 °C for 2 h, VO2(B) nanorods transformed to VO2(R)

completely and the nanorods aggregate together to micro-size particles.

Fig. 3-14 XRD patterns of products obtained after annealing VO2(B) at different conditions: (a)

500 °C 2 h, (b) 550 °C 3 h, (c) 700 °C 2 h and (d) magnified XRD region between 25°and 30°

(2θ).

Fig. 3-15 SEM (a, b) and TEM (c, d) images of VO2(M) and VO2 (B), respectively.

Page 72
3.5 Conclusions

The growth conditions of VO2(B) nanostructures and the effects of various surfactants

on the morphology control of VO2(B) have been studied and analysed. The findings can

be summarized below:

1. The synthesis of VO2(B) could be achieved by using different reducing agents at

appropriate molar ratio. The adsorption of surfactants (PVP, AOT and CTAB)

on different crystal planes of VO2(B) could effectively affect and control the

morphology. Flower-like nanostructure has been obtained by using CTAB as

surfactant and a possible growth mechanism is proposed to explain the

formation of this structure.

2. VO2(B) nanoflower showed good sensing performance towards a variety of

flammable and toxic gases such as ethanol, acetone, butanol and isopropanol.

Among them, the sensor showed higher sensitivity towards butanol when

measured at 150 °C.

3. VO2(M1) could be obtained by annealing VO2(B) nanorods at 700 °C for 2 h in

N2, although aggregation after annealing has been observed. The transformation

occurred gradually and the mixture of VO2(B) and VO2(M1) could be observed

during the process.

Although the VO2(M1) could be obtained by annealing VO2(B) at high temperature, the

synthesized nanoparticles aggregated together and the nano-size effect of these particles

might be significantly restrained. Therefore, a new method needs to be developed to

obtain monodispersed VO2(M1) nanoparticles with smaller size in the future.

Page 73
Chapter 4. The Electrodeposition Method to Prepare

VO2 Thin Films for Smart Window Coatings

4.1 Introduction

For the first time, humans are altering their world and the life in it by altering climate

and the global warming‟s impacts will only worsen.168 The greater use of fossil fuels as

main source of energy increases the amount of atmospheric carbon dioxide, which leads

to global warming. A considerable portion of energy consumption goes to building and

maintaining or forwarding today‟s general standard of living, such as heating, cooling,

ventilation, and lighting. Take the USA as an example, the combined residential and

commercial building sectors consume close to 40% of the total primary US energy. 169

Given such enormous energy consumption by the building sector, one effective

approach is to construct the “smart windows” as windows are an essential part of the

building.

Smart windows, usually composed of special coatings on glass, have the ability to keep

rooms cool in hot climates, while warm in cold climates. In other words, the coatings

will adjust the amount of solar radiation passing through the windows to achieve the

most comfortable environment. Meanwhile, the coatings should prevent the heat from

escaping to keep warmth inside the room in winter. The former issue can be achieved by

using thermochromic films and the latter can be solved with low emissivity films.

Therefore, the combination of thermochromic and low emissivity films seems to be an

effective way to save energy.

Page 74
Thermochromic is characterized by its optical properties being strongly temperature

dependant.85 During many thermochromic metal oxides, vanadium dioxide is the most

promising material for smart windows application because of the relative lower phase

transition temperature (68 °C).170 Doping with metals can decrease the critical

temperature from 68 °C to room temperature or even lower.86,91 Tungsten has proven to

be the most effective dopant as only 2 atom% tungsten loading reduces the transition

temperature to around 25 °C in films.98,171 Since the first report of VO2 thin films as

smart window, many efforts have been devoted to fabricate VO2 thin films by a variety

of methods, such as sputtering deposition,54,56 pulsed laser deposition (PLD),172,173 ion

implantation,174,175 and chemical vapor deposition (CVD).66,67 The composition of film

can be accurately controlled by PVD or CVD methods, though expensive equipment is

required. The sol-gel method for the deposition of VO2 films usually requires specific

expensive/toxic materials or treatments.71-72,79 Therefore, a simple, effective and

environmentally-friendly method for the preparation of VO2 films is urgently required.

Electrodeposition method, being an atomic deposition process, is a green way to prepare

VO2 thin film.176 It has many advantages, such as low cost, industrial applicability and

higher deposition rates.177 To the best of the authors‟ knowledge, only few papers have

been published on the preparation of VO2 films by this method.82-84

Cezar et al. first reported the electrodepositions of VO2 thin film with 0.15 M

VOSO4•xH2O solution as the electrolyte. After deposition at −0.75 V for 30 mins and

vacuum annealing, VO2 thin films with a few nanometers thickness grown on Si

substrates have been obtained.82 In order to increase the thickness, Koza et al. reported

an electrodeposition method based on V5+ reduction with triethanolamine as the

Page 75
complexing agent. VO2 films of approximately 140 nm can be deposited on Pt-coated

glass at 80 °C.83 Recently, Minch et al. has reported the cathodic deposition of VO2

from VOSO4 with a mixture of ethanol with water (10 vol%) as the electrolyte.84 As the

VOSO4 is not soluble in ethanol, sufficient amount of water is required in this approach

for the base generation for the forming of VO(OH)2 from VO2+ at the interface.

Although electrodeposition method has been utilized to prepare VO2 thin films, no

paper has been reported on smart window application with this method. The main

disadvantage of this method is that conductive substrate is necessary. Transparent

conductive films with low emissivity, such as indium tin oxide (ITO) and fluorine

doped tin oxide (FTO), are the ideal substrates to prepare VO2 thin films for smart

windows by electrodeposition method. In this chapter, double-layered

VO2/FTO/substrate films have been successfully prepared for smart window application.

The synthesized films have been characterized with various techniques and

thermochromic properties have also been measured. The results show that

electrodeposition method may have great potential for preparing VO2 thin films for

smart windows.

Many applications of VO2 are based on the semiconductor to metal transition, including

the smart window application.85 The investigation of electrical properties of single

VO2(M) nanoparticle may be beneficial to understand the semiconductor to metal

transition. Therefore, this study may also contribute to the understanding of

thermochromic properties. Therefore, it is important to investigate the mechanism for

the semiconductor to metal transition. VO2, a strongly electronic related material, has

been studied intensively using ultrafast techniques due to the rapid transition.9,178

Page 76
However, the nature of the transition is still not clear and potential applications in

electrical and optical switching or detection are not available. The properties for one

dimensional VO2 nanobeam and nanowire have been widely researched. For example,

Wei et al. studied semiconductor–metal transition in single domain vanadium dioxide

nanobeams and observed supercooling of the metallic phase by 50 °C. The activation

energy of the nanobeam in the insulating phase was calculated to be around 0.3 eV,

which is consistent with the optical gap. A connection between the phase transition and

the equilibrium carrier density in the insulating phase has also been reported.179 Despite

a number of papers published regarding the investigation of single nanobeam device,

the electrical properties of single VO2 nanoparticle as a function of temperature were

less reported.

4.2 VO2 Thin Films Prepared by the Electrodeposition Method

4.2.1 Experimental Section

4.2.1.1 Materials

Vanadium oxide (V2O5, 99.60%, Sigma-Aldrich), Sodium hydroxide (NaOH, 97%,

Sigma-Aldrich), Triethanolamine (TEA, ≥99%, BDH), Sulfuric acid (H2SO4, Sigma-

Aldrich), Tungsten foil (99.99%, Shanghai Leading Metal, China), H 2O2 aqueous

solution (analytical reagent, UNIVAR, Australia) and propan-2-ol (99.5% analytical

reagent, UNIVAR, Australia) were used as received without any further treatment. All

solutions were freshly made, and ultrapure water was used in all synthesis processes.

Commercial FTO glasses with sheet resistances of 14 Ω per square were purchased

from Nippon Sheet Glass, Japan. They were rinsed and sonicated in acetone, ethanol

and pure water, in succession.

Page 77
4.2.1.2 Synthesis

Fabrication of VO2 thin film. The electrolyte used in the experiment was prepared

following the literature.83 The final composition of the electrolyte is 0.2 M V2O5, 0.25

M TEA, 0.5 M NaOH. The pH of the electrolyte was adjusted to 6.5 in all

circumstances. All the electrochemical experiments were performed using EG&G PAR

2273 Research Work Station in a home-made electrochemical glass cell. FTO-coated

glass was used as cathodic substrate after cleaning with acetone, and de-ionized water,

and a Pt foil was used as the counter electrode. All potentials are referred with respect to

the saturated calomel electrode (SCE) reference electrode. All the films are deposited at

room temperature. The as-prepared films were then annealed in a quartz tube furnace in

N2 atmosphere. First, they were put in a quartz tube and flushed with N2 for 2 h. Then

the temperature was raised to 150 °C for 30 mins to dehydrate the samples. Finally, the

films were annealed at 500 °C for 3 h to improve the crystallinity.

Fig. 4-1 Schematic illustration of the electrodeposition method to prepare VO2 thin film.

Page 78
Fabrication of WO3 thin film. WO3 thin films were prepared according to the

reference.180 In a typical procedure, Tungsten foil was put in 30% (w/w) H2O2 aqueous

solution in a beaker under stirring to form peroxotungstic acid (PTA) with composition

H2[(O2)2W(O)OW(O)(O2)2]·nH2O, where (O2) denotes a peroxide ligand. After

complete dissolution, excess H2O2 was eliminated by immersing a Pt foil into the PTA

solution and heating to 60 °C to catalyse the decomposition of H2O2 until gas evolution

ceased. The resultant PTA solution was diluted by the addition of propan-2-ol to give

tungsten concentrations of 0.05 M, which was utilized as the electrolytes for WO3

deposition. The existence of propan-2-ol is known to increase the stability of PTA

solution by preventing the precipitation of an amorphous WO3-based hydrated phase.181

4.2.1.3 Characterization

X-ray powder diffraction was performed on The Xpert Materials Research

Diffractometer (MRD) with Cu Kα radiation (λ= 1.5406 Å). The field emission

scanning electron microscopy (FESEM) images were taken on a JEOL Nano SEM 230.

The Raman measurements were carried out Renishaw inVia Raman Microscope using a

514.5 nm laser with the output power about 2.5 mW. The reflectance of the films was

measured using the LAMBDA 950 UV/Vis/NIR Spectrophotometer in the wavelength

range of 400-2600 nm, with the universal reflectance accessory at five different angles,

between 8°and 68°. This instrument produces absolute reflectance measurements that

do not need to be corrected with a reference mirror, and the minimum and the maximum

values of the incidence angle were limited due to the angular range covered by the

accessory of the spectrophotometer. The optical transmittance characteristics were

monitored on a Hitachi U-4100 spectrophotometer equipped with a film heating unit in

the wavelength range of 260–2500 nm. XPS was used to analyse the compositional
Page 79
depth profile and oxidation state. The depth profile of XPS data was measured using

sputtering with a 3 kV Argon ion gun (etching rate ~0.42 nm/s). The film thickness was

determined by SEM using samples sectioned by focused ion beam milling using xT

Nova NanoLab 200 with Ga+ FIB.

4.2.2 Fabrication of Pure VO2 thin film

4.2.2.1 Electrochemical Characteristics

Fig. 4-2 Linear sweep voltammogram measured at a scan rate of 10 mV·s-1.

The electrochemistry property of the V5+-TEA was studied by linear sweep

voltammetry (LSV). Fig. 4-2 shows the LSV curve of the electrolyte. The deposition on

FTO substrate begins when the power was applied. All the reactions were listed as

following:

𝑉 5+ + 𝑒 − → 𝑉 4+ (1)

𝑉 4+ + 4𝑂𝐻 − → 𝑉𝑂2 ·𝑛𝐻2 𝑂 + 2 − 𝑛 𝐻2 𝑂 (2)

1
𝐻 + + 𝑒 − → 2 𝐻2 (3)

1
𝐻2 𝑂 + 𝑒 − → 𝐻2 ↑ +𝑂𝐻 − (4)
2

Page 80
The current peak around -0.4 V may be due to the reduction of V5+ (equation 1),

however, the deposition rates are very low and do not allow the deposition of thick films.

A sharp increase was observed in the cathodic current at potentials more negative than

−0.95 V, which was attributed to the reduction of hydrogen production (equation 3). It is

evident that as the potential becomes more negative, the deposition rate increases. The

pH of the electrolyte is weakly acidic (pH 6.5). The hydrogen evolution at the working

electrode causes a local interfacial pH increase, that for nonbuffered electrolytes can be

significant.83 The reactions 3 and 4 happened during the whole process of

electrodeposition in order to keep the local interfacial concentration of OH- of working

electrode higher, so that the reaction 2 shifts to the right. At potential more positive than

-1.2 V, no film can be deposited with full coverage on the FTO substrate and this may

be due to the low deposition rate. At potential more negative than -1.35 V, the deposited

film was not flat and it was cracked. Therefore, we fabricated VO2 films at different

applied potentials ranging from −1.22 V to −1.35 V vs. SCE. There is no very strong

bubbling observed at the WE electrode surface during the deposition process.

Fig. 4-3 Deposition current densities j as a function of time t and voltages of VO2 thin films

deposited for 10 mins.

Page 81
To study the effect of deposition voltage on the reduction of V5+ electrolyte, the

deposition current density was tested as a function of time curves as shown in Fig. 4-3.

Once the voltage was applied to the electrochemical cell, the current density drops

sharply due to deposition of a VO2·nH2O layer on FTO glass, which induces a voltage

drop and consequently a dramatic current density decrease. When some grains have

been deposited on FTO substrate, the V5+ ions concentration at the interface between

FTO and electrolyte decreases rapidly. Therefore, the current density is relatively low

after the sharp decrease. Gradually, the current density increases and finally approaches

a stable level. The nucleation on pre-existing grains and outward growth of the grains

with time increases the film thickness. Apparently, the final (constant) deposition

current density is related with by the deposition voltage, due to the fact that the higher

the voltage is, the higher deposition current density is achieved, although the current

density has also been influenced by the deposition of VO2·nH2O layer and the diffusion

of ions.

4.2.2.2 Composition and Morphology

Fig. 4-4 XRD patterns of VO2 thin film on FTO substrate annealed at 400 °C for 2 h, 500 °C for

2 h and 500 °C for 3 h.

Page 82
Fig. 4-4 displays the XRD patterns of VO2 thin films annealed at different conditions.

For the films annealed at 400 °C for 2 h, no peaks can be indexed into the VO2(M)

phase. This is different from Zhang‟s work, which reported that the VO2(M) crystallized

at 390 °C because FTO and VO2 possess a same crystalline structure and similar lattice

indexes.182 This may be due to the different method of preparing the films; here

electrodeposition method was utilized while they used spin-coating method to prepare

VO2 films. Increasing the annealing temperature to 500 °C, diffraction peaks

corresponding to the VO2(M) can be indexed. After annealing at 500 °C for 3 h, as well

as the peaks belonging to FTO, diffraction peaks corresponding to the M-phase VO2

could be clearly observed. These results demonstrate that the crystallinity of VO2 films

on FTO-coated glass increases with increase of temperature and annealing time. From

the XRD results, the optimized annealing condition for the VO2 thin films was

determined to be 500 °C for 3 h. All the VO2 films in the following section were

annealed under this condition.

Fig. 4-5 Raman shift (left) and real pictures (right) of VO2 thin films deposited at -1.3 V for 10

mins before (a) and after (b) annealing.

Page 83
The real pictures of the films before and after annealing are shown in Fig. 4-5. Before

annealing, the colour of the film was blue-grey. After annealing, it turns a yellow colour,

which is the typical colour of VO2 thin films.80 Room-temperature Raman spectra was

also taken to compare the composition of the films before and after annealing as shown

in Fig. 4-5. For the as-prepared films, the high-frequency Raman peak at 885 cm-1

corresponds to the stretching mode of V4+ = O bonds. The other peak around 1000 cm-1

could be assigned as the terminal oxygen (V = O) stretching mode.183 After annealing,

all the peaks correspond to the VO2(M) phase and no Raman modes corresponding to

other vanadium oxides (e.g., V6O13, V2O5, V2O3) were detected.184

Fig. 4-6 XPS spectra of V2p peak and its fitting curves for V4+ and V5+ ingredients.

To further identify the composition of films after annealing, XPS was used to elucidate

the oxidation states of the ions present. The Vanadium was presented as V4+ and V5+

with a V3p binding energy of 517.7 eV and 516.6 ev, respectively. The V2p region

Page 84
indicates that there were two different valance states of V: the core level at 517.7 eV

with dominant V signal, assigned to V5+185-186, while the core level at 516.6 eV with

weak V signal, corresponding to V4+187-188, consistent with the present colour of the

films and many reports. The surface XPS analysis shows that the amount of V5+ is more

than the V4+. XPS is a surface chemical analysis technique that can be used to analyse

the surface chemistry of a material within the top 1-12 nm of the sample surface. The

surface of the film may be oxidization into V2O5 due to the exposure to the air or the

reaction happened during the annealing process. It is therefore reasonable to detect the

larger amount of V5+ than V4+ on the surface.

Fig. 4-7 SEM images of FTO substrate (a), VO2 thin films deposited at -1.3 V for 10 mins (b),

the inset is the higher magnification of the VO2 film, the cross section images of FTO substrate

(c) and VO2/FTO double layers (d).

Page 85
Fig. 4-7 presents the SEM images of FTO substrates and annealed films. The surface of

FTO substrate is composed of grains with large size distribution, ranging from 10 nm to

300 nm. The synthesized VO2 thin film is relatively flat with grain size around 47 nm,

although there are some small gaps between grains in the film. The formation of the

pores in the film may be due to the evaporation of water during the annealing. The inset

high resolution SEM image shows that the surface of the film is not quite flat and this

may be caused by the roughness of the FTO substrate. Fig. 4-7 c shows the cross section

image of FTO substrate and the thickness is around 400 nm, which is consistent with

the information the manufacture has provided. The white layer on the FTO layer was

deposited Au layer for FIB sample preparation. After the deposition of VO2 film, there

is an extra layer on FTO and some pores can be observed in this layer, which is

consistent with previous SEM images. The thickness of the films deposited at different

voltages was all measured with this method in the following section.

4.2.2.3 Reflectance of Films

Fig. 4-8 Reflectance spectra for the VO2/FTO double-layered films deposited at different

voltages.

Page 86
The reflectance property of the VO2/FTO double layer film is shown in Fig. 4-8. One of

the advantages of electrodeposition method is that it is easier to control the thickness

simply by applying different voltages or varying the electrodeposition time. Fig. 4-8

presents the reflectance spectra of the annealed films deposited at different potentials

from -1.22 V to -1.35 V. When higher applied voltage was applied, the film becomes

thicker, leading to higher reflectance of the film in the NIR region. The results are

consistent with the VO2 film coating on FTO substrate by spin-coating method.182

4.2.2.4 Thermochromic Properties

Fig. 4-9 Transmittance spectra of films that were deposited at 600 °C for 10 min at -1.22 V

(black line), -1.25 V (red line), -1.3 V (green line) and -1.35 V (blue line). The solid and dashed

lines present films measured at 20 and 90 °C, respectively.

Page 87
The thermochromic property of the VO2/FTO double layer film is shown in Fig. 4-9 and

summarized in table 4-1. The relatively lower transmittance is due to the lower

transmittance of the FTO compared to the silica glass substrate. However, as the

reference reported, the lower emissivity of the FTO in the MIR region makes this kind

of smart window less energy consuming. When the voltage is -1.22 V, the prepared film

shows the best transmittance, more than 50%, which is quite high when taking into

consideration the effect of FTO substrates. The transmittance of the FTO substrate is

about 82.4% in comparison with larger than 92.8% for fused-silica substrates. The

thickness of the films has been measured with FIB method and the thickness increases

with the increase of the working potential. The film deposited at -1.22 V shows

thickness around 107 nm, and it rises to around 145 nm when the deposition voltage

was -1.35 V. The transmittance of films in the visible and NIR region decreases with the

increase of the voltage, which is consistent with the FIB results. Overall, the high

transmittance of the film with reasonable thermochromic properties makes it attractive

for the smart window application.

Table 4-1 Summary of optical properties of the VO2/FTO double-layered films deposited at

different potentials.

Voltage T vis (%) Transmittance (%) ∆T (%) Thickness

at 2000 nm (2000nm) (nm)

Low High Low High

-1.22V 53.9 51.3 22.1 13.9 8.2 107

-1.25V 54.7 54.2 23.0 12.4 10.6 115

-1.30V 39.0 38.0 18.9 8.5 10.4 133

-1.35V 31.1 32.0 17.0 6.8 10.2 145

Page 88
Fig. 4-10 Temperature dependence of the optical transmittance at a fixed wavelength (2000 nm)

for VO2 film.

The SMT temperature has been measured as well and it turns out to be around 73 °C,

which is higher than that of the pure VO2. It is known that the SMT temperature may be

affected by the substrate.49 Grown on the (001) TiO2 plane, the temperature was

lowered to 300 K from 341 K for a single crystal due to an in-plane tensile stress at the

interface. Table 4-2 shows the lattice parameters for the F-doped SnO2 and VO2,

together with the corresponding mismatch. Obviously the lattice parameters of VO2 are

larger than those of FTO. Therefore the c length should decrease for the VO2 thin film

grown the FTO substrate because of the existence of an in-plane tensile stress at the

interface. Fig. 4-11 shows the schematic illustration of VO2 growth on (010) and (100)

plane of FTO. It is clear that VO2 can be easily grown on the FTO substrate due to

similar atoms arrangement. However, the difference of the lattice parameters between

them causes the stress, leading to the increase of the SMT temperature.

Page 89
 Table 4-2 Lattice parameters of FTO and VO2(R) and the mismatch between them.

P42/mnm a, b c

F doped SnO2 4.738 3.187

VO2 (Rutile) 4.554 2.856

Lattice Mismatch 4.04% 11.59%

Fig. 4-11 Schematic illustration of VO2 films (top) grown on FTO (bottom)

(010) and (100) planes.

4.2.3 Tungsten (W) Doped VO2 Thin Film

4.2.3.1 WO3 Thin Film

The XRD pattern of FTO substrate and the prepared film after annealing in nitrogen is

shown in Fig. 4-12. The peaks for FTO substrate have been indexed. All other peaks

can be indexed to monoclinic crystalline WO3 (space group P21/c) with the lattice

parameters a= 0.5261 nm, b= 0.5218 nm, c= 0.7650 nm and β= 92.05 °(JCPDS No. 04-

Page 90
007-2427). The XRD pattern indicates that some preferred orientation occurs, where the

(1 1 0) plane is favoured. This may be due to the fact that a and b axis length of WO3 is

close to that of FTO compared to the c axis. The effect of TiO2 and ZnO buffer layer

has been studied for preparation of VO2 thin films.184,189 The oxidation process has

been significantly hindered for films prepared on a TiO2 buffer layer, especially at the

VO2/TiO2 interface. In this work, WO3 film has been selected as the buffer layer

because the W Doping may be achieved by using the WO3 coated FTO as the substrate

to prepare VO2 thin films. It is known that when soda lime glass was used as the

substrate, the diffusion of sodium oxide from the soda lime glass into the titanium

dioxide layer during the calcination step causes the lower photoefficiency in films on

glass was tested and proven.190 Similar to this effect, in this work, VO2 has be deposited

on H2[(O2)2W(O)OW(O)(O2)2]·nH2O layers and W may be doped into VO2 layer after

annealing due to the extraction of W ions into the VO2 layer.

Fig. 4-12 XRD patterns of WO3 thin film on FTO substrate annealed at 500 °C for 3 h.

Page 91
4.2.3.2 Annealing Temperature and Deposition Time

Fig. 4-13 Raman shift of VO2/WO3 thin film on FTO substrate annealed at

different temperature for 3 h.

The existence of the buffer layer can change the growth condition of VO2 thin films.189

Without the H2[(O2)2W(O)OW(O)(O2)2]·nH2O layer, VO2 thin film can be obtained by

annealing at 500 °C for 3h due to close lattice relationship between FTO substrate and

VO2 thin films. However, with the existence of buffer layers, VO2 peaks cannot be

observed from the XRD pattern after annealing at the same condition. The Raman shift

shows weak signals for films annealed at 500 °C. Increasing the temperature to 530 °C,

the Raman shift of the films becomes stronger. After annealing at 550 °C for 3 h, pure

VO2 thin film can be obtained with good crystallinity, as shown in Fig. 4-13. Therefore,

the following films were obtained by annealing at 550 °C for 3h in order to obtain high

quality VO2 thin films.

Page 92
Fig. 4-14 XRD pattern of VO2/WO3 films obtained by annealing at 550 °C for 3h in comparison

with VO2 films, WO3 films and FTO substrate.

Fig. 4-14 shows the XRD patterns of VO2/WO3 films obtained by annealing at 550 °C

for 3h. Only the main peaks of VO2 can be observed due to small thickness of the film.

Obviously, the peak of VO2/WO3 film has a left shift compared with pure VO2 films.

According to the Bragg‟s equation, it is reasonable to assume that part of W has been

doped into the VO2 during the annealing process. However, XRD data alone are

insufficient to verify the structure and composition of the interface layer.

Fig. 4-15 XPS spectra of V 2p core level of VO2/WO3 films (a) and compositional depth profile

of films measured by XPS (b).

Page 93
In order to investigate the effect of buffer layer, the V2p XPS spectra of VO2/WO3 thin

film were measured to investigate the vanadium oxidation states. In the XPS spectrum,

the V2p region indicates that there were three different valance states of V: the core

level at 517.7 eV with dominant V signal, assigned to V5+, while the core level at 516.4

eV corresponding to V4+. Another core level at 515.0 eV with weak V signal can be

assigned to V3+.186 Compared with the pure VO2 thin film, the V3+ state appears and this

may be due to the doping effect of W. Takami et al. suggest that doped W6+ will make

part of V4+ reduce to V3+. 191

In order to confirm the doping effect of VO2, we examined the XPS depth profile. As

shown in Fig. 4-15 b, W element was observed to exit in the whole film including the

VO2 layer, which means that W has been diffused into VO2 films.

Fig. 4-16 SEM images of films obtained by varying VO2 deposition time while fixing

deposition time 5 mins for WO3 films: (a) 0, (b) 10 mins, (c) V 15 mins, (d) 20 mins

and (e) 25 mins.

Page 94
The morphology of the prepared WO3/VO2 films in different condition was investigated

by SEM, as shown in Fig. 4-16. First, WO3 films were deposited on FTO for 5 mins,

then VO2 films was deposited at different time varying from 10 to 25 mins at -1.3 V.

The surface of pure WO3 film was rough and the grain is composed of small particles.

The relative rough surface may be due to the short deposition time, which the nucleation

on pre-existing grains and outward growth of the grains has not been finished. When

depositing VO2 on the exiting films, the existing grains provide the nucleation site for

the V4+ and the grain keeps growing. Some relatively large grains around 200 nm were

observed. Increasing the depositing time to 15 mins for VO2, the grains keep growing.

While when the deposition was 20 mins, the grain on the surface become small and

further increasing the deposition time to 25 mins, the grains on the surface were

relatively uniform, this may be due to some new nucleation site appearing on the

deposited VO2 films. The effect of WO3 precursor film has been weakened when

increasing the deposition time to 25 mins.

4.3 Metal-to-semiconductor Transition Property

4.3.1 Experimental Section

4.3.1.1 Materials

Poly(vinylpyrrolidone) (PVP, MW=55000, Sigma-Aldrich), Citric acid (99.5%, Sigma-

Aldrich), Vanadium pentoxide (V2O5, ≥ 99.6%, Sigma-Aldrich) and Hydrochloric acid

(HCl, 32 wt%, UNIVAR, Australia) were used as received without further treatment.

All solutions were freshly made, and ultrapure water was used in all synthesis process.

The quartz glass had been cleaned under ultrasonication by sequentially immersing in

Page 95
ethanol, acetone and distilled water, and then treated with the H2O/NH3·H2O/H2O2

(5:1:1, in volume) solution, H2O/HCl/H2O2 (5:1:1, in volume) and ultrapure water.

4.3.1.2 Precursor and Film Preparation

In a typical procedure: 0.9094 g V2O5 was added into 8.5 ml distilled water, then 1.5 ml

32 wt% HCl was added into the solution and stirred for 1 min. After that, 1.5761 g citric

acid was added into the above solution and keeps stirring for 30 mins at 60 °C. Different

amount of WCl6 was added into the solution to achieve W doping. PVP was added into

the solution in gravimetrically determined proportions (6 wt%). Films were prepared by

spin-coating at 600 rpm for 9 s and then 3000 rpm for 30 s on quartz glass. After drying

at 60 °C for 10 mins in order to drive off the excess solvent, a smooth thin film of VO2

precursor was obtained. After heat annealing at 600 °C for 0.5 h in a nitrogen

atmosphere, the obtained precursor gel films were transformed into VO2 films with

isolated VO2 particles on the quartz substrate.

4.3.1.3 Characterization

X-ray powder diffraction was performed on PANalytical Xpert Materials Research

Diffractomter with Cu kα radiation (λ= 1.5406 Å). The field emission scanning electron

microscopy (FESEM) images were taken on a JEOL Nano SEM 230. The resistance of

the single VO2 particle was measured using a scanning electron microscope (SEM,

JEOL JSM-7000F) accessorised with cryostat (Variable Temperature Insert Cryostat,

CRYO Industries of America Inc.).

Page 96
4.3.1.4 Semiconductor-metal Transition Measurement

The device for measuring the semiconductor-metal transition measurement is shown in

Fig. 3-16. To fabricate the device by dielectrophoresis, the VO2 nanoparticles were

scratched from the films, then the particles were dispersed into solvent (DI water).

Sonicator was used to disperse VO2 particles in DI water. Then PVP (with a

concentration of ~1x10-4M) was added in order to avoid aggregation. The VO2

naoparticles then have been located between two Pt electrodes which were patterned by

electron-beam lithography in connection with photo-lithography pre-patterned Ti/Au

electrodes on a silicon wafer. Finally, the device was loaded into a cryostat (Variable

Temperature Insert Cryostat, CRYO Industries of America Inc.) for temperature-

dependent electrical characterization. The measurement was performed using a scanning

electron microscope (SEM, JEOL JSM-7000F).

Fig. 4-17 Illustration and SEM image of the measurement device.

4.3.2 Results and Discussion

4.3.2.1 Structure and Morphology

Fig. 3-17 shows the XRD pattern and Raman shift of the VO2 film after annealing at

600 °C for 0.5 h. The temperature (600 °C) is high enough to decompose the PVP

according to Kang‟s results.192 The XRD pattern indicates that the prepared VO2 films
Page 97
were preferentially orientated along the (011) plane with just two reflections at 27.8 °

and 57.5 °corresponding to the (011) and (022) planes of monoclinic VO2. The high

oriented VO2 film has also been observed in the VO2 film prepared by the APCVD

method.63 Raman measurements identified monoclinic VO2 with bands at 139, 192, 223,

261, 308, 338, 391,440, 491, 613 and 825 cm-1 for VO2 films (Fig. 3-17 b). These bands

agree well with the reported data for M-phase VO2.79 Based on the XRD and Raman

results, it is found that pure VO2 films can be prepared by the spin-coating method after

annealing in N2.

Fig. 4-18 XRD pattern (a) and Raman shift (b) of VO2 films prepared by spin-coating.

4.3.2.2 Effect of Coating Time

In order to investigate the effect of coating times, VO2 films has been prepared by spin-

coating method by varying the spin-coating times from 1 to 20 times. The average grain

size of the films after 1 time coating was around 210 nm and this value decreased to 180

nm after 5 times coating. The coverage of the substrate also increased for these films.

However, further increasing the coating times, the particles on the substrate became less

and less uniform. The coverage was much worse as well. For the films prepared after 20

times coating, there were just few particles present on the substrate. This may be due to

the damages of the films after coating too many times.

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 Fig. 4-19 SEM images of films prepared by spin-coating for different times: (a) 1 time, (b) 5

times, (c) 10 times, (d) 15 times and (e) 20 times.

4.3.2.3 Effect of W Doping

Different concentrations of W doping have been investigated by adding WCl6 into

vanadium precursor solution. The SEM images of W doped VO2 films were shown in

Fig. 3-19. Without any doping, sphere-like nanoparticles were obtained on the quartz

substrate with large size distribution. After doping with 0.5% W, the particles on the

substrate became more uniform and better coverage has also been achieved. Further

increasing the concentration of W doping, the density of the particles increased. One

interesting finding is that W doping can change the morphology of the particles from

sphere to square shape. One possible explanation is that W doping may disrupt the long

order structure of the VO2, which may cause the anisotropic growth of VO2 particles.

Another reason may be that the W doping has created new nuclei site for particle

growth, which leads to anisotropic growth of VO2 particles.

Page 99
 Fig. 4-20 SEM images of VO2 films with different concentration of W doping: (a) 0 %, (b)

0.5%, (c) 1%, (d) 1.5% and (e) 2%.

Fig. 4-21 Raman shift of VO2 films with different concentration of W doping.

Raman shift has also been performed on pure and W-doped VO2 films, as shown in Fig.

3-20. All the peaks become weaker after W doping and the intensity decreased with

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increasing W doping concentration. For thin films with 2% W doping, the peaks became

broad and the characteristic of VO2(M) is not quite obvious, suggesting that the film

was at the phase-transition point because of the reduction effect of the tungsten doping

on the transition temperature.79 In order to further investigate the W doping effect on

single VO2 nanoparticle, the nanoparticles were scratched from the films and used for

device fabrication.

4.3.2.4 Activation Energy of Single Particle

Fig. 4-22 The original I–V characteristic of the particle (left) and simultaneous temperature-

dependent resistance measurements (right).

Fig. 3-21 shows the original I – V characteristic of the single VO2 nanoparticle at

different temperatures. The particle showed gradual changes in resistance over a large

range of temperature. At room temperature, the single particle showed a resistance of 3-

4 GΩ, which is larger than the VO2 nanobeam.193 This might be due to the morphology

Page 101
difference and the nanobeam showed similar characteristic to bulk materials compared

to single nanoparticle.

The activation energy has also been calculated according to the following equation:
Ea
R  exp( )
kBT
At low temperature, the nanobeam is entirely in the M1 phase and the resistivity shows

a thermally activated behaviour with activation energy of 0.24 eV (Fig. 3-22). This

value is lower than the reported value of 0.45 eV for the bulk samples133, but close to

the value (0.3 eV) of nanobeam179. The activation energy for 2 % W-doped VO2 has

been calculated as well and a lower activation energy (0.15 eV) has been calculated.

Therefore, the W doping can lower the activation energy of VO2(M1), leading to the

decrease of transition temperature.

Fig. 4-23 Ln(R) vs 1/T plot showing thermally activated behaviour of VO2.

Page 102
4.4 Conclusions

VO2 thin films have been prepared by an electrodeposition method. The deposition

procedure and annealing conditions were investigated. VO2 hydrated films can be

obtained with in short deposition time, such as 10 mins. The as-prepared films could

transfer to pure VO2 film after annealing at 500 °C for 3 h. Films with thickness from

107 to 145 nm were obtained by varying the voltages from -1.22 to -1.35 V. The

thermochromic properties of the films have been investigated and high transmittance of

the film with reasonable thermochromic properties has been achieved. With the

introduction of tungsten oxide buffer layer, the annealing temperature increased to

550 °C and the extraction effect was confirmed by various techniques, such as XRD,

Raman and XPS. Overall, the electrodeposition method may have great potential for

industrializing the VO2 films for smart window application due to its low toxicity and

room temperature preparation.

The electrical properties of single VO2(M) nanoparticle were investigated by varying

the temperature. VO2(M1) thin films with isolated particles on the surface have been

obtained by the spin-coating method. The activation energy for single VO2(M1)

naoparticle was 0.24 eV. With 2% W doping, it has been lowered to 0.15 eV. The W

doping could lower the activation energy of VO2(M1) and lead to the decrease of

transition temperature.

The electrodeposition method has been proven to be effective to prepared VO2 thin

films for smart window coating. However, a large scale coating has not been

investigated. Therefore, it is important to carry out research on preparation of VO2 thin

films in large scale in order to make smart window coating commercialized.

Page 103
Chapter 5. Density Functional Theory (DFT) Simulation

of Al, Cr and Ti Doped VO2

5.1 Introduction

VO2, a strong electronic related material, undergoes a semiconductor-metal transition

from a high-temperature, rutile metal to a monoclinic insulating state at 68 °C.

Accompanying this phase transition, a reversible change of the optical and electrical

properties make VO2 quite promising for smart window, sensor and switch application.

However, the phase transition temperature is too high for some applications, such as the

smart window coatings. Doping is the most effective way to lower this temperature.

Usually, high-valent atoms doping can effectively decrease from 68 °C to room

temperature or even lower, while doping with low-valent atoms increase the transition

temperature.70 However, some recent findings indicated that certain low-valent atoms

doping could lower the temperature as well. The Al3+ doped VO2 thin films were

deposited at optimized processing conditions of 1.4 mTorr O2 process gas at 600 °C

substrate temperatures by PLD and it was found that doping 10 % Al 3+ into VO2

decreased the temperature from 68 to 40 °C.172 Similar to Al3+ doping, VO2 thin films

doped with Mg2+ can not only decrease the temperature with a rate around 3 K/ at.%

Mg2+ , but also enhance the visible transmittance of the film.54 Specifically, the

transmittance of visible spectra was increased by ~ 10% when the Mg content was ~7

at. %.

Page 104
In fact, doping with atoms can effectively change the V4+-V4+ bond distance, which is

quite crucial for the phase transition. Goodenou obtained a semiempirical expression for

the room temperature critical separation Rc (0.294 nm) for localized vs itinerant 3d

electrons in VO2.119 With the existence of rutile structure, the vanadium atoms align in

the linear chains along the c-axis and the nearest V4+-V4+ distance is 0.288 nm, and the

left electron can be shared by all of the V atoms in the same chains. While the

monoclinic VO2(M1) has two different V–V distances of 0.266 and 0.313 nm, forming

zigzag-type chains. The left electron is localized in the zigzag-type direction, giving the

semiconductor behaviour of VO2(M1).39 For example, Tan et. al investigated the V-V

and W-V distances using the XAFS technique.103 After W doping, the change of V–V

distances indicated that the monoclinic VO2 host lattice is largely distorted in the x=

0.95% sample and completely transformed into tetragonal rutile structure when x

increases to 1.45%.

Density functional theory is by far the most widely used method for the electronic

structure calculations. It is also called first principle method or ab initio method as it

allows people to determine various properties of a condensed matter system just by

giving some basic structural information without any controllable parameters. Apart

from the traditional experimental method, it can provide an alternative way to

investigate condensed matter systems. Therefore, it is becoming a useful tool to both

experimentalists and theorists for understanding characteristic properties of materials,

making specific predictions of experimentally observable phenomena, and even

designing new materials. For example, the doping effects of a wide range of elements in

Page 105
TiO2 have been studied,194-199 which significantly contributes to the development of

TiO2 for photocatalyst application.

DFT simulation, which is quite successful in describing the geometry and electronic

structure for transitional metal oxide, has been rarely reported to investigate the VO2

system. This may be due to the fact that DFT calculations with exchange-correlation

functionals of LDA and GGA fail to deal with a strongly correlated material, such as

VO2.120 However, with the gradual development of the GGA + U method and hybrid

functional, metal doped VO2 has been investigated with DFT simulation. W and Be

doped VO2 has been calculated by Xie group.130,132 It was reported that W doping could

effectively lower the transition temperature by narrowing the energy gap between the

rutile and monoclinic phase. The interstitial Be doping can significantly decrease the

phase transition temperature by 58 K /at.% Be. Cr doped VO2 has also been investigated

with DFT simulation, however, the strong related effect between the V atoms has not

been considered.101 Metal doping is an effective method to improve the optical

properties of VO2.

As mentioned, low-valent metal doping can lead to some unique effects. Among them,

Ti doping can narrow the hysteresis loop effectively although increase the transition

temperature.80 Many papers have been published on Ti-doped VO2 for smart window

application,80,94 however, no DFT simulation has been performed to investigate the

structure and optical properties changes. The doping effect of Al is particularly

interesting. At low doping concentration, it increased the phase transition temperature,

while high concentration Al doping decreased the temperature. Therefore, it is

Page 106
important to investigate the geometry and electronic structure of low-valent metal doped

VO2 by DFT simulation. Many advanced methods have been explored to simulate the

VO2 in recent years, such as GW and LDA+DMFT and hybrid functions. However,

these methods are too computationally intensive to deal with the large multiformula-unit

supercells necessary to treat metal doped VO2. On the other hand, the GGA + U

approximation method, taking the Hubbard on-site repulsion U into account, has

reached a good balance between the computational intensity and simulation accuracy.

Furthermore, the GGA + U method has been successfully applied to simulate the H-

doped VO2. Therefore, the GGA + U method is utilized to simulate the low-valent metal

doped VO2 system in this work.

In this chapter, the electronic structure and optical properties of Al3+, Ti4+ and Cr4+

doped VO2 have been investigated by GGA + U method. The appropriate U and cut off

energy have been chosen after tests. The doping effects of different metals have been

summarised and the response of the light metal-doped VO2 to the infrared light is

systematically studied.

5.2 Computational Details

Density Functional Theory calculations were performed using ab initio plane-wave

pseudopotential DFT with the CASTEP module.200 The widely used GGA (generalized

gradient approximation) for the exchange-correlation using PBE (Perdew, Burke and

Emzerhof), which is known to yield more accurate structural results, such as bond

lengths, compared with the local density approximation (LDA).201-202 The self-

Page 107
consistent ground state cell optimization was performed by density mixing scheme

using an ultrasoft pseudopotentials (USP) plane-wave basis set. Both the positions of all

ions and the unit cell parameters were relaxed to minimize the atomic forces and the

total energy. The vanadium pseudopotential contained n = 1, 2 shell electrons in the

core, and treated (3s2p6d34s2) electrons explicitly as valent. The Monkhorst-Pack was

used to determine the k-points, which was fixed at 0.05 Å-1 for all calculations. For

supercells that contained a larger number of vanadium atoms, a corresponding number

of k-points were used to keep the k-mesh spacing constant between different structures.

The GGA +U method was used, in which the effective strength of the interaction Ueff =

U – J was chosen to be 3.4 eV after U parameter optimisation.

5.3 Electronic and Optical Properties of Pure VO2

The most symmetrical phase for VO2 is the rutile phase VO2(R), which has the same

crystal structure as the TiO2 Rutile: the tetragonal cell has parameters a= b= 4.55 Å, c=

2.88 Å, Z= 2; the space group is P42 /mmm (136). This group possess a very symmetric

structure; vanadium atoms are at the centre of regular oxygen octahedra with two V-O

bonds at 1.963 Å, the other four at 1.910 Å, with their fourfold axes aligned

alternatively along (110) and (1 1 0). The different octahedras share edges, building

chains along the c axis of the structure. V-V has a distance of 0.288 nm along this chain

and the extra electron has been shared. Therefore, the metallic properties have been

observed in VO2(R). The properties of TiO2 have been widely investigated by DFT

simulation, while the electronic structure of VO2(R) has been rarely reported.

Page 108
 Fig. 5-1 (a) Unit cell of VO2(R), (b) the projection of the rutile structure along [001], showing

two perpendicular orientations of the octahedral and (c) projection along [010], vanadium atoms

built chains parallel to the c axis of the structure. (V atoms, grey and O atoms, red).

The monoclinic VO2(M1) is related to the appearance of a pairing between two V4+

along cR . The induced distortion leads to a lowering of the symmetry. The cell

parameters of the room temperature phase VO2(M1) are a= 5.75 Å, b= 5.42 Å, c= 5.38

Å, β= 122.6 °, Z= 4, the space group is P21/c (12).

Fig. 5- 2 (a) Unti cell of VO2(M1), (b) the projection of the monoclinic structure, (c) projection

along [001], vanadium atoms forms zigzag chains. (V atoms, grey and O atoms, red).

Due to the strongly correlated effect of the VO2, the GGA + U method is adopted to

calculate the electronic structure. The U value is quite crucial to accurately describe the

electronic structure and was tested first. Other simulation parameters, such as cut off

Page 109
energy, have also been tested, especially for the VO2(M1) because the band gap for this

phase is difficult to simulate. These parameters have also been applied to the metal

doped VO2 in the following section.

5.3.1 U Parameter Test

The U parameter was varied from 3 to 4.2 (Table 5-1). The simulated lattice parameter

is 6.09, 4.50 and 5.44 Å for a, b and c, respectively. The simulated parameter value for

VO2(M1) is larger than the experimental value, which is due to the over estimation of

the lattice parameter of the GGA method compared with the LDA. In order to be

consistent with the reference130,132, U value is chosen to be 3.4. All the simulation

carried out below uses this value to present the strongly correlated effect in VO2.

Table 5-1 Effect of U parameter towards the lattice parameter.

U a (Å) b (Å) c (Å) β (Å) V (Å3)

3 6.091 4.497 5.435 124.08 123.31

3.4 6.092 4.498 5.434 124.08 123.323

3.8 6.091 4.498 5.435 124.08 123.31

4.2 6.091 4.497 5.435 124.08 123.31

Exp.203 5.75 4.54 5.38 122.6 118.32

5.3.2 Cut-off Energy Test

The cur-off energy has also been investigated in order to obtain the proper balance

between the computation used and the accuracy. The cut-off energy was varied from

300 eV to 420 eV, as listed in Table 5-2. Increasing the cut off energy, a axis length

Page 110
decreased in total, although c length fluctuated a little. The β angle fluctuated when the

cut off energy rose. The volume of the unit cell decreased with the increase of cut off

energy. Overall, compared with the experimental results, the simulated lattice

parameters are larger, which may be due to the larger expectation when using the GGA

functional. Taking into consideration the simulation efficiency, the cut off energy of

380 eV was chosen to achieve a balance between accuracy and computational cost.

Table 5-2 Effect of cut-off energy towards the lattice parameter.

Cut off energy

a (Å) b (Å) c (Å) β (Å) V (Å3)
(eV)

300 6.103 4.595 5.444 124.05 126.49

340 6.097 4.557 5.417 124.20 124.508

380 6.091 4.498 5.434 124.08 123.323

420 6.088 4.494 5.428 124.11 122.946

Exp.203 5.75 4.54 5.38 122.6 118.32

5.3.3 Electronic and Optical Properties Investigation

The electronic and optical properties of the VO2(M1) and VO2(R) phase have been

calculated with GGA + U method. The simulated band structure shows that the R phase

presents a metallic property and the M phase shows a semi-conductor property with two

band gaps Eg1 and Eg2 at 1.81 and 0.59 eV, respectively, which are in line with well-

established data.51,60,131 It is important to note that the majority of the valence bands are

dominated by the O 2p orbitals, although the V 3d orbitals contribute to the top of the

balance bands as well. On the other hand, the conduction bands obtain significant

Page 111
contribution from the V 3d orbitals. The bands are split into two parts, which may be

due to crystal field splitting effects. There is also some contribution from the O 2p states

to the conduction bands. The optical properties of VO2(M1) and VO2(R) in the near

infrared range has been shown in Fig. 5-4. Due to the optically anisotropic, the

components of the dielectric function, corresponding to the electric field parallel to

(notated as P) and vertical to (notated as V) the V–V chains, have been considered in

our calculations. Overall, the VO2(R) displays a higher reflectivity in the near infrared

range than the VO2(M1) , which is consistent with the experimental results.

Fig. 5-3 (a) Band structure of VO2(M1), (b) Total DOS plots of VO2(M1), (c) PDOS plot of O

2p orbitals and (d) PDOS plots of V 3d orbitals.

Page 112
 Fig. 5-4 Reflectivity spectra of pure VO2 in the infrared spectral range. Subscripts P and V

represent E // chain and E ⊥ chain, respectively.

5.4 Effect of Al Doping

In the monoclinic VO2(M1) structure, one of V atoms was substituted by Al. The

structures after optimisation have been shown in Fig.5-5. It is shown that the structure

of Al-doped VO2(R) has been significantly changed due to the doping effect. After Al

doping, the V–Al and Al-V distances are 0.296 and 0.308 nm, respectively. Compared

to pure VO2(M1) with two different V-V distances of 0.291 and 0.321 nm , the doped

Al3+ may lead to the shift of nearest V atom. This can be understood by the charge

compensation effect. This effect can be clearly observed from the structure change of

the Al doped VO2(R) as well. After doping, the four nearest O atoms don‟t shrink

inward after Al substitution; while the two next–nearest O atoms move toward Al

having d(Al-O) = 1.95 Å instead of the original d(V-O) = 1.97 Å. It is also evident that

the two near V atoms move toward the centre in order to balance the charge introduced

by the Al3+.

Page 113
Fig. 5-5 Crystal structure of (a) pure VO2(M1), (b) Al doped VO2(M1), (c) Pure VO2(R) and (d)

Al doped VO2(R). Vanadium atoms are grey and oxygen atoms are red.

Fig. 5-6 shows the DOS plots of Al-doped VO2. The Eg1, Eg2 band gap of Al-doped

VO2(M1) is 1.53 and 0.36 eV, respectively. In comparison with the pure VO2(M1) , the

band gap becomes smaller, leading to increased luminous absorptance in thin films. Fig.

5-6 b shows the DOS plot of doped Al atom, the 2p orbitals are mainly located in the

valance band, which may hybridize with the O 2p orbitals. In comparison with the DOS

plot of pure VO2(M1) , there is one peak exiting just above the Fermi level, which may

be caused by the hybridization of Al 2p orbitals with O 2p orbitals. The conduction

bands of VO2(M1) have not been influenced by Al doping significantly. The VO2(R)

still shows the metallic property after Al doping although significant structure change

has been observed.

Page 114
Fig. 5-6 DOS plots of (a) Al-doped VO2(M1), (b) doped Al in VO2(M1), (c) Al-doped VO2(R)

and (d) doped Al in VO2(R).

Fig. 5-7 Reflectivity spectra of Al-doped VO2 in the near infrared spectral region.

Page 115
The optical properties of Al doped VO2 have also been calculated and shown in Fig. 5-7.

After doping, the reflectivity of VO2(M1) decreases while the reflectivity of VO2(R)

increases. This implies that Al doping increases the switch efficiency for the reflectance

of VO2.

5.5 Effect of Ti Doping

The structure of Ti doping after optimisation has been shown in Fig. 5-8. Monoclinic

VO2 (M1) has two different V–V distances of 0.266 and 0.313 nm, forming zigzag-type

chains. The extra electron is localized in the zigzag-type direction, giving the

semiconductor behaviour of M1. The Ti-doped VO2 M has V–Ti and Ti-V distances of

0.295 and 0.318 nm. Compared to the pure VO2(M1) with V–V distances of 0.291 and

0.321 nm, the substitution of V by Ti does not significantly change the structure.

However, the doped Ti may increase the nucleation sites for VO2 when it grows. This

may lead to smaller grain size compared with pure VO2.

Fig. 5-8 Crystal structure of (a) pure VO2(M1) and (b) Ti-doped VO2(M1).

Page 116
The DOS of Ti-doped VO2 has been shown in Fig. 5-9. Doping Ti can widen the Eg1,

Eg2 band gap from 1.81 and 0.59 eV to 1.94 and 0.64 eV, respectively. The strong

displacement of Eg1 leads to significantly decreased luminous absorptance in thin

films.131 Fig. 5-9 b displays the DOS plot of doped Ti in VO2(M1) . The Ti 3d orbitals

are mainly located in the conduction bands, ranging from 1.8 to 3.2 eV. This is the main

reason for the widening of the band gap after Ti doping. The VO2(R) remains the

metallic property and the 3d orbitals of Ti located close to the Fermi level compared to

the VO2(M1) . With the change of electronic structure, the reflectivity property of the

Ti-doped VO2 has been changed. Fig. 5-10 shows the reflectivity properties of VO2

after Ti doping. After Ti doping, the reflectivity of VO2(M1) decreases while the

reflectivity of VO2(R) increases. This implies that the reflectance switching ability of

VO2 has been enhanced by Ti doping, which may lead to the improvement of

thermochromic properties.

Fig. 5-9 DOS plots of (a) Ti-doped VO2(M1), (b) doped Ti in VO2(M1), (c) Ti-doped VO2(R)

and (d) doped Ti in VO2(R).

Page 117
 Fig. 5-10 Reflectivity spectra of Ti-doped VO2 in the near infrared spectral region.

5.6 Effect of Cr Doping

Cr doping has been studied by researchers widely and DFT simulation has been

performed as well.101 However, Pan et al. just built the model of Cr-doped VO2(R)

supercell. In order to study the effects of Cr doping, it is necessary to carry out the

simulation of Cr doping effect on both VO2(M1) and VO2(R) structure. After

optimization of the Cr-doped VO2(R) structure, it is found that Cr doping does not

significantly affect the crystal structure. The four nearest O atoms extend having d(Cr-O)

= 1.96 Å from the original d(V-O) = 1.92 Å before substitution, the two next–nearest O

atoms also extend having d(Cr-O) = 1.99 Å instead of the original d(V-O) = 1.97 Å. For

the monoclinic VO2(M1) , the Cr-doped VO2(M1) has V–Cr and Cr-V distances of

0.281 and 0.314 nm, respectively.

Page 118
The DOS plot of Cr-doped VO2 has been shown in Fig. 5-11. Doping Cr can reduce the

Eg1, Eg2 band gap from 1.81 and 0.59 eV to 1.44 and 0.52 eV, respectively. The

decrease of the band gap is mainly due to the shift of the conduction band, compared to

the pure VO2(M1). It is noticed that the conduction band splits into several parts more

clearly, which indicates that Cr doping helps to sharpen the crystal field splitting effects.

This effect may be due to more extra electrons of Cr compared to V. Specifically, the

bottom of the conduction splits into three parts, similarly to the t2g state. The top of the

conduction bands also splits into several parts, which is different to the eg state. Fig. 5-

10 b shows the DOS of doped Cr and it mainly contributes to the top of the balance

bands near the Fermi level. The Cr doped VO2(R) still shows metallic property and

doped Cr contributes to the band from -2 to 2 eV. In comparison with the doping effect

in VO2(M1), the DOS of doped Cr in VO2(R) located far from the Fermi level, which

indicates that there is less effect on the band gap.

Fig. 5-11 DOS plots of (a) Cr-doped VO2(M1), (b) doped Cr in VO2(M1), (c) Cr-doped VO2(R)

and (d) doped Cr in VO2(R).

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The optical properties of Cr-doped VO2 have also been calculated as shown in Fig. 5-12.

The reflectivity of Cr-doped VO2(R) is higher than that of VO2(M1), which is consistent

with the experimental results. Compared to the pure VO2(M1), the reflectance of Cr-

doped VO2(R) becomes higher and the Cr-doped VO2(M1) doesn‟t change much. This

leads to the improvement of the reflectance switching efficiency in the NIR region after

Cr doping.

Fig. 5-12 Reflectivity spectra of Cr-doped VO2 in the near infrared spectral region.

5.7 Summarisation

Fig. 5-13 Crystal structure of (a) Al-doped, (b) Ti-doped and (c) Cr-doped VO2(R).

Page 120
 Table 5-3 Optimized structural parameters (in nm) of pure and metal-doped VO2(R).

Exp. 204 Pure Al Ti Cr

2 M/V-O 1.96 1.97 1.95 1.99 1.99

4 M/V-O 1.91 1.92 1.92 1.96 1.96

V-V/M 2.88 2.85 3.06 2.94 2.93

V/M-V 2.88 2.85 2.79 2.93 2.92

Fig. 5-13 shows the structure of metal doped VO2(R) after optimisation. It is shown that

the structure has been significantly changed after Al doping, while Ti and Cr doping

seems to not significantly influence the structure. The d(Al-O) is smaller than d(V-O),

while both Ti and Cr doping increase the distance of d(M-O). The V-V distance of

VO2(R) has also been changed after doping. After doping, the V-V distance has been

changed into two different lengths. The distance of V-V is 2.79 and 3.06 nm after Al

doping, while it increased to ~2.93 nm after Ti and Cr doping. Different V-V bond

distances may lead to different effect on the phase transition temperature. It is important

that after the Al substitution of the original V atom, among the six O atoms around the

Al atom, two of them with the longer distance shrink inwards, making the slightly

distorted octahedron more distorted. In contrast, the Ti and Cr substation causes the six

O atoms to expand outward. The structure change can be easily understood by the

charge compensation theory. Substituting V by Al will cause the charge to be

imbalanced. Therefore, the electron will be transferred from the neatest V ions, leading

to significant change of the structure. In contrast, Ti and Cr substitution is already

balanced and no electron transfer is required.

Page 121
 Table 5-4 The optimized structural parameters of pure and metal-doped VO2(M1).

Al Ti Cr
Exp. Pure
doping doping doping

V-V/M
3.13205 3.21 3.08 3.11 3.14
(nm)

V/M-V
2.66205 2.91 2.96 2.97 2.81
(nm)

2.06,1.77 2.18,1.80 1.96,1.91 1.98,1.95 2.15,1.97

V/M-O
2.04,2.01 2.10, 2.05 1.85,1.89 2.01,2.04 2.00,2.00
(nm)
1.86,1.88 1.90,1.93 1.81,1.91 1.97,1.93 2.02,2.00

Eg1 (eV) 1.7851 1.81 1.53 1.94 1.44

Eg2 (eV) 0.70206 0.59 0.36 0.64 0.52

Table 5-4 lists the band gap and structural parameters of experimental results, pure

VO2(M1) and VO2(M1) after doping. The simulated V-V bond distance for pure VO2 is

larger than the experimental results and this may be due to the overestimation of the

GGA functional. The band gap, however, is quite close to the experimental results,

especially the Eg1 result. It is important to note that after the Al substitution, most of the

six O atoms around the Cr atom shrink inwards. One interesting finding is that with the

increase of the doped metal‟s valance, the octahedron composed of M-O becomes more

regular, which is particularly true when looking at the case of Cr doping. It is reported

that certain metals doping, such as Al and Cr, can promote the formation of VO2(M2).10

The band gap also varies by different metal doping; it increased with Ti doping and

decreased with Al and Cr doping. Al doping causes the upward shift of the valance band

Page 122
and Cr doping leads to the downward shift of the conduction band. While Ti doping

does not impact the band gap greatly due to the same valance state.

5.8 Doping Effect on Phase Transition Temperature

Doping of VO2 with low-valent cations, such as Al3+ and Fe3+, was reported to raise the

semiconductor–metal phase transition temperature in most previous papers. The raise of

the temperature was due to extra energy need to overcome generated during the doping

procedure. Specifically, the substitution of V4+ by low-valent cations would cause

nearest V4+ to V5+ in order to balance the charge. The radius of V5+ ions (=0.4 Å) is

smaller than that of the paired V4+ ions which are between 0.4 and 0.61 Å. Therefore,

the monoclinic lattice may be distorted toward triclinic lattice and the distortion energy

will increase the transition temperature.207 However, from our calculations there is not

so much lattice distortion which occurred for Al doping, especially for the monoclinic

phase. However, substituting the V4+ ions with Al3+ ions in Rutile phase causes some

V4+ to move towards centre. The moving of V4+ ions leads to the change of V–V

distances from 0.285 nm to 0.279 and 0.306 nm along c axis. The change of V–V

distances may simplify the transition from Monoclinic to Rutile, which means that the

energy needed for the phase transition is lower. Therefore, the transition temperature

decreases with the low-valent cations doping. Some recent experimental results confirm

that doping the low-valent cations can also lower the phase transition temperature. Chen

et al. reported that 10% Al3+ doping can decrease the temperature to 40 °C. They do not

find any noticeable lattice distortion for the VO2(M1) as the XRD peak‟s position does

not shift with Al3+ doping, and does not change with doping level. Similar to the Al3+

doping, the metal-insulator transition temperature decrease of ~ 3 K/ at. % Mg was

Page 123
reported on Mg2+ doped VO2 thin films prepared by reactive dc magnetron sputtering.

The Mg2+ doped VO2 has been calculated, too. However, there is strong lattice

distortion due to the low valent of Mg2+. Instead, Ti4+ doping does not affect the lattice

of VO2(M1) or VO2(R) greatly and the transition temperature is almost the same as the

pure VO2.80

Another mechanism for explaining the decrease of the transition temperature is that it is

essentially attributed to the injected carriers by the dopant in the compound.132 If the

doped atoms can provide more extra electrons in a system, the transition temperature
132
between VO2(R) and VO2(M1) decreases much more. Therefore, W and Mo doping

can effectively decrease the transition temperature. However, doping with low-valent

cations leads to the increase of transition temperature. This is not consistent with the

experimental results reported on Al3+ doping and Mg2+ doping.

To conclude, low-valent cations doping decreases the phase transition temperature of

VO2 mainly due to the lattice distortion of VO2(R) based on DFT simulation. Doping

with Al3+ leads to the change of V–V distances and this change lowers the energy

required for transferring VO2 from monoclinic to rutile.

5.9 Conclusions

The doping effects of Al, Ti and Cr on VO2 were investigated using DFT simulations.

The structure, band gap and optical properties have been changed after substitution

doping. The findings can be summarized below:

Page 124
 1) The Al doping causes a more significant distortion of VO2(R) than the Ti and Cr

doping. In addition, the doped metals make the slightly distorted octahedron to

be more regular in VO2(M1).

2) The Al doping decreases the band gap of VO2(M1) due to the upward shift of

the valence band, while Cr doping decreases the band gap because of the

downward shift of the conduction band. Ti doping leads to the increase of the

band gap of VO2(M1).

3) The reflectivity of VO2(M1) decreases while the reflectivity of VO2(R)

increases after doping. This implies that low-valent metals doping increases the

switching efficiency for the reflectance of VO2.

The simulated results could provide useful information of metal-doped VO2 systems for

understanding the doping effects towards the crystal structure and electronic structure of

VO2 with promising application in energy and environment.

Page 125
Chapter 6. Hydrothermal Synthesis of Sodium Vanadium

Oxide Nanoparticles for Gas Sensing Application

6.1 Introduction

The design and construction of gas-sensing devices with high sensitivity and selectivity

are important due to the increasing concerns about environmental pollution and

industrial safety issues. Various materials have been used for the gas sensing materials.

Amongst them, semiconductor metal oxides have been extensively studied as gas-

sensing materials due to the low cost and high compatibility with microelectronic

processing. However, some challenges still exit in this area, such as the low selectivity

and the long-term stability. To improve the gas-sensing performance, various

approaches have been investigated including increasing the surface area, metal doping

and surface modifications with noble metal particles.

Vanadium oxide nanostructures have been investigated as gas-sensing materials because

of the unique layered structure and electronic properties, including V2O5 nanofibres 208,
147 209
V2O5 nanobelts , and VO2 nanowires . For example, Liu et al. reported that the

V2O5 nanobelts exhibited good sensitivity toward ethanol with a detection limit ~10

ppm at a working temperature of 200 °C.147 To further improve the sensitivity, Wei et al.

demonstrated that V2O5 nanotubes coated with Fe2O3 nanoparticles (~15 nm) exhibited

a sensitivity (S) of 3.37 towards 1000 ppm of ethanol at an optimized temperature of

330 °C.149 Recently, our group synthesized vanadium pentoxide micro-urchins

composed of nanorods (200 nm×1000 nm), and these urchin-like V2O5 microstructures

showed an enhanced gas-sensing sensitivity compared with individual V2O5 nanorods at

Page 126
150 °C.150 However, the sensitivity of vanadium oxides towards alcohol is still low,

which limits its practical gas-sensing applications.

Intercalation of metal atoms (e.g., sodium) into the layered structure of V2O5 may be an

effective way to enhance the sensitivity of V2O5-based sensors. Sodium vanadium

oxides have been studied because of their layered structure and novel applications in
210-211 212
lithium ion battery , field emission application and room-temperature

ferromagnetic semiconductor 188. Among the various forms of sodium vanadium oxides,
213
Na1.08V3O8 has attracted more attention , which consists of V3O8 layers and

interstitial Na+ ions. However, very few reports exist on the gas-sensing properties of

sodium vanadium oxides.

Fig. 6-1 Supercell structure of V2O5 (a) and Na1.08V3O8 (b).

Page 127
 214
In this chapter, inspired by the existence of Barnesite , which is formed in slightly

acidic environment in nature, we demonstrate a simple but efficient hydrothermal

method to intercalate the sodium atoms into the layer(s) of vanadium oxides for

reducing the resistance and increasing the gas-sensing sensitivity. The as-prepared one-

dimensional nanostructures will be characterized by various advanced techniques

including field emission scanning electron microscopy (FESEM), transmission electron

microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray

diffraction (XRD), Fourier transform infrared (FT-IR) spectra and X-ray photoelectron

spectroscopy (XPS). The gas sensing properties of the Na1.08V3O8 nanorods will be

investigated, for the first time, toward a variety of alcohols such as methanol, ethanol

and 1-butanol. Finally, the possible gas-sensing mechanism will be discussed.

6.2 Experimental Section

6.2.1 Chemicals

The chemicals used in this study are NaVO3 (99.9% trace metals basis, Sigma-Aldrich),

sodium hydroxide (NaOH, 99%), acetone (99.9%, Sigma-Aldrich), methanol (CH3OH,

99.9%, Sigma-Aldrich), absolute ethanol (C2H5OH, 99.9%, Sigma-Aldrich) and

hydrochloric acid (HCl, analytical reagent, UNIVAR). All chemicals were purchased

and used as received without further purification. Distilled water was used in all the

synthesis processes.

Page 128
6.2.2 Synthesis Procedures

In a typical procedure, 0.3658 g NaVO3 was dissolved in 15 ml of deionized water and

stirred for a few minutes to obtain homogeneous solution. Secondly, 15 ml of 0.1 M

HCl solution was added into the above solution while stirring. The colour of the

solution changed rapidly from yellow to brown. Thirdly, the above brown-colour

solution was transferred to the Teflon-lined stainless-steel autoclave and heated at

180 °C for 6 h. The resulting product was washed with deionized water for several

times, and dried overnight at 60 °C. Finally, the dried samples were annealed at 350,

400 and 500 °C for 3 h in air, respectively, for gas sensing measurement.

6.2.3 Characterizations

X-ray powder diffraction of the samples was performed on Philips X‟Pert Pro Super

diffractometer with Cu Kα1 radiation (λ= 1.5406 Å). FESEM images were taken on a

JEOL Nano SEM230. TEM images were obtained on the JEOL1400 with an

acceleration voltage of 100 kV. High-resolution transmission electron microscopy

(HRTEM) was acquired on Philips CM200, at an accelerating voltage of 200 kV. The

surface area and pore size distribution of the as-synthesized nanostructures were

measured with Brunauer-Emmett-Teller (BET) equipment (TriStar 3000) via nitrogen

gas adsorption and desorption isotherms. FT-IR spectrum was recorded using

PerkinElmer Spotlight 400 FT-IR Microscope. The chemical states and compositions of

the as-prepared products were investigated by X-ray photoelectron spectroscopy (XPS),

using a Thermo Scientific spectrometer equipped with an Al-Kα source (λ= 1486.68 eV).

Page 129
6.2.4 Gas Sensing Measurements

The gas-sensing performance was measured with the WS-30A gas-sensing

measurement system (Zhengzhou Weisheng Lty‟s Co., China). Firstly, the samples

were mixed with poly (vinylidene fluoride) (PVDF) binder and 1-methyl-2-pyrrolidone

to form slurry. Secondly, the slurry was painted on to a ceramic tube (2 mm in diameter)

to form a thin film between two gold electrodes, deposited on the ceramic tube and

connected with four platinum wires. Next, the ceramic tube was annealed at 350 °C for

3 h to remove the PVDF and the sensor has been aged for 6 h before the gas sensing

measurement until the base line becomes stable in air. Finally, a certain amount of the

test gas was injected into the testing chamber by a micro-syringe. The gas sensitivity (S)

is defined as the ratio of the stationary electrical resistance of the sensor in air (Ra) to its

resistance in the tested gas (Rg)149, that is, S= Ra/Rg. The output voltage was set at 2 V

and the gas sensing measurements were carried out at a relative humidity of 40-60%.

Fig.6-2 Schematic illustration of the gas sensor device and the gas

sensing measurement equipment.

Page 130
6.2.5 Computational Details

Density Functional Theory calculations were performed using the commercial software:

Materials Studio (Version 4.3, Accelrys Inc, 2007) with the DMol3 module.215 The

widely used generalized gradient approximation (GGA) with the exchange-correlation

functional parametrized by Perdew and Wang (PW91) was adopted.216-217 All-electron

calculations and a double numerical basis set with polarization functions (DNP) were

employed with global orbital cut off of 3.7 Å. The total energy convergence was set to

be 1×10−6 Hartree.

6.3 Structure and Morphology

The as-prepared product is reddish-brown in colour, which could be attributed to

vanadium oxides with V5+ ions. Fig. 6-4 displays the XRD patterns of the as-prepared

product before and after annealing at 350 °C. The diffraction peaks of the product

obtained after the hydrothermal treatment can be readily indexed to monoclinic

crystalline Na2V6O16·3H2O (space group P21/m) with the lattice parameters a = 1.2170

nm, b = 0.3602 nm, c = 0.7780 nm and β = 95.03 °(JCPDS No. 16-0601). No peaks can

be indexed to other phases, indicating the high purity of the sample. The product

obtained with annealing at 350 °C for 3 h can be indexed to Na1.1V3O7.9 (JCPDS No.

045-0498). Due to the sufficient amount of oxygen in the air during the calcination

process, Na1.1V3O7.9 should not be present. Wang et al. investigated the actual formula

of this product which could be written as Na1.08V3O8 based on their atomic absorption

spectrophotometer measurements.213 In comparison, the XRD patterns for

Na2V6O16·3H2O and Na1.08V3O8 are analogical, but the intense diffraction peak is (001)

located at around 2 = 11 °for the former but rather (002) at 2 = 12.5 °for the latter.

Page 131
 Fig. 6-3 Photograph of the as-prepared product in deionized water.

Fig. 6-4 XRD patterns of the as-prepared Na2V6O16·3H2O products: (a) without thermal

treatment, (b) with thermal treatment at 350 °C for 3 h, (c) with thermal treatment at 400 °C for

2 h, and (d) with thermal treatment at 500 °C for 2 h.

The morphology of the product was characterized by SEM and TEM techniques. Fig. 6-

5 shows the SEM images of the Na2V6O16·3H2O nanostructures. The dominant

Page 132
component of the product was nanobelts with lengths of several hundreds of nanometers

to a few micrometers and with widths of 80-250 nm. Furthermore, a number of

nanorings with diameter of 3-12 µm were also observed in the product. The possible

formation mechanism of such nanorings could be attributed to the typical layered

structure of vanadium oxide. This may be similar to previous studies by Xue et al. 188,

where the polarization-induced self-coiling of nanobelts was proposed to be responsible

for the formation of the nanorings. Fig. 6-5 d shows the HRTEM image of an individual

nanobelt with lattice spacing of ~0.23 nm, which can be indexed to the (303) plane of

Na2V6O16·3H2O.

Fig. 6-5 SEM and TEM images of as-prepared Na2V6O16·3H2O product: (a) SEM image, (b)

High magnification SEM image of the nanorings, (c) TEM and (d) HRTEM image.

Page 133
Fig. 6-6 presents the TEM images of the products when NaVO3 concentration was

controlled to be 0.02 M with the molar ratio of NaVO3 to HCl from 2:1 to 2:3. The

products obtained at different molar ratios showed a little difference in terms of

morphology. The width of nanobelts ranged from 40 to 100 nm when the molar ratio

was set at 2:1. Some nanobelts aggregated together at the molar ratio of NaVO3 to HCl

1:1 to urchin-like structure. No nanoring has been observed at this low concentration of

NaVO3, which may be due to the reduced chance of bending of the nanobelts.

Fig. 6-6 TEM images of samples obtained from 0.02 M NaVO3 solution with different molar

ratio of NaVO3 to HCl: (a) 2:1, (b) 3:2, (c) 1:1 and (d) 2:3.

Fig. 6-7 shows TEM images of the samples obtained when the vanadium concentration

was fixed at 0.1 M and the molar ratio of NaVO3 to HCl was varied from 2:1 to 2:3. The

morphology and size was varied correspondingly. When the molar ratio was fixed at 2:1,

uniform nanobelts were obtained as the only products. When the molar ratio was fixed

at 3:2, the nanobelts with a few micrometers in length and 100-200 nm in width and

Page 134
several nanorings (diameter of 3-12 µm) co-existed in the product. With the increase of

the molar ratio of HCl to NaVO3, a mixture of nanorods and nanobelts were formed

with width varying from 40 to 120 nm. The formation of such nanorods may be caused

by collapse of the nanobelts at a high acidity (e.g., pH<1). Therefore, the nanoring can

only be synthesised at appropriate condition, while the nanobelts can be synthesised at

more tolerant condition.

Fig. 6-7 TEM images of samples obtained from 0.1 M NaVO3 solution with different molar

ratio of NaVO3 to HCl: (a) 2:1, (b) 3:2, (c) 1:1 and (d) 2:3.

Table 6-1 Nanostructures obtained by controlling the synthesis conditions.

Molar ratio
2:1 3:2 1:1 2:3
CNaVO3 (M)

urchin-like
0.02 nanobelts nanobelts nanobelts
structure

nanorings &
0.1 nanobelts nanorods nanorods
nanobelts

Page 135
All the synthesis conditions have been listed in Table 6-1. It is clear that the nanorings

can be obtained only when the molar ration between NaVO3 to HCl is 3:2, and the

concentration of NaVO3 is 0.1M.

Fig. 6-8 shows the SEM and TEM images of the product generated after thermal

treatment at 350 °C for 3 h. Short or broken rod-like structures were observed, which

were probably caused by the loss of crystalline water of Na2V6O16·3H2O and/or the

phase change during the thermal treatment.210 As the gas-sensing performance is highly

related to the surface area, BET technique was used to measure the surface area of the

as-prepared sodium vanadium oxide nanostructures. The specific BET surface areas

were estimated at 18.7 and 20.2 m2g−1 for Na2V6O16·3H2O and Na1.08V3O8 nanorods,

respectively. A slight increase in the surface area after annealing could be caused by the

shortened or breakage of the belt-like structures into smaller rod-like structures. This

high BET surface area may be beneficial for the gas sensing application due to the

increased adsorption area.

Fig. 6-8 SEM (left) and TEM (right) images of Na2V6O16·3H2O with thermal treatment at

350 °C for 3 h.

Page 136
 Fig. 6-9 Nitrogen adsorption–desorption isotherm of as-prepared Na2V6O16·3H2O product.

6.4 Gas Sensing Performance

The gas-sensing performance of the as-prepared Na1.08V3O8 nanorods was investigated

toward VOCs, such as methanol, ethanol, 1-butanol and acetone. Temperature is one of

the key factors affecting gas sensing performance. Therefore, to optimize the operating

temperature, the gas sensitivity (S) toward 100 ppm of ethanol was examined as a

function of operating temperature. As shown in Fig. 6-10 a, the sensitivity of the

Na1.08V3O8 and V2O5 sensor exhibits similar behaviour to a function of temperature and

both achieved the highest sensitivity at 260 °C. However, the sensor fabricated from

Na1.08V3O8 nanorods showed a relatively higher sensitivity of 3.45 toward 100 ppm of

ethanol, compared to the V2O5 gas sensor (S = 1.89). Moreover, the sensitivity of the

Na1.08V3O8 sensor toward 100 ppm of ethanol (S = 3.45) was much higher than that of
149
Fe2O3-V2O5 nanotubes (S ≈ 2.0) at 330 °C and other metal oxides coated V2O5
Page 137
nanobelts148, as listed in Table 6-2. Currently, the sensitivity of the sodium vanadium

oxide sensor toward ethanol is not as high as some other metal oxides (Table 6-1), such

as ZnO and SnO2. However, in this work we have demonstrated that the intercalation of

Na+ into metal oxide structure can increase the sensing sensitivity. Further surface

modification with noble metals or formation of nanocomposites with other sensing

materials may be needed to further increase the sensing sensitivity.

Fig. 6-10 The sensitivity comparison between V2O5 and Na1.08V3O8 gas sensor towards 100ppm

ethanol as a function of temperature (a), the gas sensitivity of sodium vanadium oxide based

sensors with increasing gas concentrations of ethanol (b), stability measurement of the sodium

vanadium oxide sensor (c) and the sensitivity toward four gases as a function of operating

temperature (d).

Page 138
Fig. 6-10 b shows the gas sensitivity of Na1.08V3O8 sensor as a function of ethanol

concentration. The voltage increased with the increase of ethanol concentration in the

concentration range of 10-500 ppm. The stability measurements of the Na1.08V3O8

sensor given in Fig. 6-10 c clearly reveal the high sensing stability of these nanorods as

the voltage values vary only slightly over a period of 6 days. Fig. 6-10 d shows the

sensitivity of sodium vanadium oxide sensing material toward four kinds of gases as a

Table 6-2 Comparison of the ethanol sensing performance of the Na1.08V3O8 nanorods

with other sensing materials.

Concentration Operating Sensitivity

Materials References
(ppm) T (°C)

Current
Na1.08V3O8 nanorods 100 260 3.5
work
218
ZnO nanoflakes 100 330 15.5
219
SnO2 nanorods 100 300 13.9
220
Co3O4 spinel oxide 100 300 ~3.5

V2O5 nanobelts 100 250 1.7

V2O5 nanobelts/Fe2O3 100 290 2.3

V2O5 nanobelts/SnO2 100 290 3.1

148

V2O5 nanobelts/TiO2 100 250 2.0

221
FeVO4 nanorods 100 270 3.7
222
In2O3 nanowires 100 370 ~2

TiO2 hierarchical
223
100 350 6.4
nanostructures

Page 139
function of temperature. One interesting thing is that the sensor exhibited higher

sensitivity to alcohol with longer carbon chains. Similar result has also been reported

with SnO2 nanoparticles for gas sensing application toward alcohols.224 This

phenomenon has been investigated by DFT simulation in the following mechanism

section.

6.5 Gas Sensing Mechanism

During the sensing process, there are several oxygen species on the surface of the

Na1.08V3O8 sensor at a high temperature, such as O2−, O− and O2−. The adsorption of

these oxygen species would lead to a band bending and a space-charge layer. The depth

of this space-charge layer was a function of the concentration of oxygen adsorbates and

intrinsic electrons in the semiconducting oxides.225 When the injected gas reached the

surface of sensing material, the gas molecules reacted with the oxygen species and

released some trapped electrons. With the decrease in the number of electrons, the

space-charge layer became thinner, leading to an increase in conductance. When

exposed to air , the oxygen species would adsorb on the surface again, which therefore

increases the resistance of the sensor, as described below.226

O2 (gas) → O2(ads) (1)

O2(ads) + e−→ O2−(ads) (2)

O2−(ads) + e−→ 2O−(ads) (3)

O− (ads) + e−→ O2−(ads) (4)

C2H5OH(ads) + 6O−(ads)→ 2CO2(gas) + 3H2O(gas) + 6e− (5)

C2H5OH(ads) + 6O2−(ads)→ 2CO2(gas) + 3H2O(gas) + 12e− (6)

Page 140
The higher sensing sensitivity of Na1.08V3O8 nanorods towards ethanol compared to

V2O5 nanobelts and Fe2O3-V2O5 nanotubes could be attributed to two main factors:

Firstly, existence of extra Na+ ions (Fig. 6-11), which may result in the V atoms in a

lower valence state (V4+) compared to V2O5 (V5+). As a further confirmation, the XPS

spectra (Fig. 6) revealed that the nanorods consist of Na (1071.0 eV, Na1s), O (530.5

eV, O1s) and V (517.7 and 516.4 eV) (Fig. 6-11 a). In the XPS spectrum, the V2p

region indicates that there were two different valance states of V: the core level at 517.7

eV with dominant V signal, assigned to V5+ 186

, while the core level at 516.4 eV with

weak V signal, corresponding to V4+ 187, consistent with the presence of sodium-rich

Na1.08V3O8. The existence of Na+ may improve the gas sensitivity due to the increased

possibility of adsorbing more oxygen ions (O2− and O−) at a high temperature, leading

to the increase of the depth of the space-charge layer. Moreover, the interstitial Na+ may

increase the mobility of main carriers, which may enhance the change of electrical

conductivity.

Page 141
Fig. 6-11 XPS spectra of the as-prepared Na1.08V3O8 nanorods (a) and XPS spectra of V2p peak

and its fitting curves for V4+ and V5+ ingredients (b).

Second, the lengthened V ̶ O bond of Na 1.08V3O8 compared to V2O5. The introduction of

Na ions into the layers of vanadium oxide may lead to the change of the V ̶ O

bond.213,227 The FT-IR spectrum of the Na1.08V3O8 nanorods shown in Fig. 6-12 is quite

different to that of V2O5. The three main peaks of V2O5 located at ~617, ~827 and

~1022 cm−1 are different from those of the Na1.08V3O8 nanorods. For Na1.08V3O8

nanorods, the absorption bands around 1000 cm−1 could be assigned to V=O bond

stretching in distorted octahedral and square pyramids, while those at 737.7 and 550.4

cm−1 could be assigned to the asymmetric and symmetric stretching vibrations of V–O–

Page 142
V bond, respectively210. With the changes in the structure arrangement, the surface of

the Na1.08V3O8 nanorods is quite different to that of the V2O5 nanoparticles, and hence

different gas sensing capabilities are expected.

Table 6-3 Comparison of V-O bonds between V2O5 and Na1.08V3O8.

Materials V-O bond length (Å) Average (Å)

V2O5 1.748 2.033 1.840 1.767 1.568 1.791

Na1.08V3O8 1.599 2.007 1.875 1.875 1.927 1.857

1.889 2.144 1.618 1.732 1.889 1.854

Table 6-3 shows the V-O bond length for both V2O5 and Na1.08V3O8. The average V-O

bond length for V2O5 is 1.791 Å. There are two different types of V-O bond existing in

Na1.08V3O8 structure and the average bond length is 1.857 and 1.854 Å. Clearly, the V-O

bond length in Na1.08V3O8 is longer than V2O5. The exposed V ions on the surface

determine the ability of absorbing oxygen species. The longer the V-O bond is, the

more positive the V ions are. More oxygen species may be absorbed on the surface.

Therefore, a deeper space-charge layer has been created. When the gas molecule reacted

with the oxygen species, more electrons are released and higher conductivity change has

been achieved. As a result, the Na1.08V3O8 sensor shows higher sensitivity than V2O5

sensor.

Page 143
 Fig. 6-12 FT-IR curves of as-prepared Na1.08V3O8 nanorods and commercial V2O5 powder.

In the gas sensing test, it was found that the Na1.08V3O8 exhibited a high sensitivity

towards 1-butanol than methanol, ethanol and acetone. DFT simulation was performed

in order to investigate the higher sensitivity towards longer carbon chains, which has

also been reported when using the SnO2 nanoparticles as the gas sensor.224 In general,

the diffusion rate of the molecule decreases with increase of the molecular weight. In

other words, the heavier the molecule is, the less active the molecule should be. DFT

simulation has been utilized to understand the phenomena. The calculated C-C and C-O

bond lengths in ethanol are 1.520 and 1.433 Å, respectively, which are in good

agreement with experimental values (1.51 and 1.43 Å).228 The nearest distance from C

to O for methanol, ethanol and 1-butanol are 1.427, 1.432 and 1.434 Å, respectively,

which means the C-O bond in methanol is more difficult to break down. In addition, as

we know, the electrostatic interaction between the oxygen species and the gas molecule

is one of the important factors to influence the gas sensing performance. The calculated

Mulliken atomic charges of O is -0.502, -0.496, -0.493 e for methanol, ethanol and 1-
Page 144
butanol, respectively. The repulsion interaction between the molecule and the oxygen

species becomes weaker with the increase of carbon chains. More 1-butanol molecules

are adsorbed on the surface and the C-O bond is relatively easier to break due to the

longer bond length. Therefore, the highest sensitivity has been achieved for the 1-

butanol molecule among the four tested samples. In addition, the Density of State (DOS)

of the three molecules in Fig. 6-13 also shows that the 1-butanol molecule is more

localized at the bottom of the conduction band, which will make it easier to hybridize

with the metal oxide d orbital. Further effects of viscosity, interaction between V3O8

and gas molecule, and the diffusion rate of various gas species on the surface/interface

of the prepared nanostructures will be investigated in the near future.

Fig. 6-13 Total DOS plots of methanol, ethanol and 1-butanol molecules.

6.6 Conclusions

We have demonstrated a simple but effective synthesis strategy to prepare Na1.08V3O8

nanorods. The potential of Na1.08V3O8 nanorods as a gas sensing material was tested and

Page 145
explored for the first time. The gas sensing measurement shows that the Na1.08V3O8

nanorods have a good sensitivity with S= 3.45 towards 100 ppm ethanol at the

optimized working temperature of 260 °C. The existence of extra Na+ ions and the

lengthened V-O bond(s) of the Na1.08V3O8 nanorods may contribute to the enhanced gas

sensing performance, compared to V2O5 nanobelts or metal oxide coated V2O5

nanobelts. The higher sensitivity towards longer carbon chains has been experimentally

confirmed.

The DFT simulation has been utilized to understand the sensing mechanisms. The

calculated Mulliken atomic charge of O is -0.502, -0.496, -0.493 e for methanol, ethanol

and 1-butanol, respectively, suggests that the repulsion interaction between the

molecule and the oxygen species becomes weaker with the increase of carbon chains.

More 1-butanol molecules are adsorbed on the surface and the C-O bond is relatively

easier to break due to the longer bond length. Beside the impact of diffusion rate of the

gas molecules, the interaction between the oxygen species and gas molecules may also

play an important role at 260 °C. This study may open a new venue to fabricate layered

NaxVyOz nanostructures for potential applications in environmental monitoring and

detection.

Page 146
Chapter 7. Summary and Future Work

7.1 Summary

Vanadium oxide nanoparticles and thin films have been extensively investigated in this

thesis, focusing on the synthesis, characterization and functional properties, through

comprehensive experimental and theoretical studies. The main results from each chapter

are summarized below:

1) Different morphologies of VO2 nanostructures were prepared under the reported

conditions by hydrothermal method (Chapter 3). The adsorption of surfactants

(such as, PVP, AOT and CTAB) on different crystal planes of VO2(B) could

effectively affect the growth of the nanostructures, which promotes a uniform

morphology. A possible growth mechanism was proposed to explain the formation

of flower-like structure. The fabricated VO2(B) sensor showed a higher sensitivity

towards butanol in comparison with ethanol, acetone, and isopropanol when

measured at 150 °C. Furthermore, VO2(B) nanorods transformed to VO2(M1) by

annealing in N2 with aggregation being observed after annealing.

2) Electrodeposition method for the preparation of VO2 thin films for smart window

coatings has been studied in Chapter 4. The as-prepared films could transfer to pure

VO2 film after annealing. Films with thickness of 107 to 145 nm could be obtained

by varying the voltages from -1.22 to -1.35 V. The thermochromic properties of the

films have been investigated and the high transmittance with reasonable

thermochromic properties of the film has been achieved. W doping was achieved

by depositing another W precursor buffer layer.

Page 147
3) VO2(M1) thin film with isolated particles on the surface could be prepared by spin-

coating method (Chapter 4). By measuring the electronic properties of these

particles, the activation energy has been calculated and 2% W doping could lower

the activation energy of VO2(M1) from 0.24 to 0.15 eV, leading to the decrease of

transition temperature.

4) DFT simulation was used to investigate the effects of Al, Cr and Ti doping on VO2,

as described in Chapter 5. The results show that substitution doping could change

the lattice parameter, band gap and optical properties. Specifically, Al and Cr

doping decreased the band gap while Ti doping lead to the increase of the band gap

of VO2(M1). The Al doping lead to a more significant distortion of VO2(R) than the

Ti and Cr doping and the doped metal caused the slightly distorted octahedron to

become more regular in VO2(M1). The reflectivity of VO2(M1) decreased after

doping while the reflectivity increased for Al, Ti and Cr doped VO2(R).

5) A simple but effective synthesis strategy has been utilized to prepare Na1.08V3O8

nanorods by hydrothermal method and gas sensing performance was tested and

explored for the first time, as demonstrated in Chapter 6. The gas sensing

measurement shows that the Na1.08V3O8 sensor has a good sensitivity with S= 3.45

towards 100 ppm ethanol at the optimized working temperature of 260 °C, higher

than that of V2O5 and metal oxides coated V2O5 sensors. The gas sensing

mechanism has been discussed and simulation has been carried out to investigate the

mechanism. It is found that along with the impact of diffusion rate of the gas

Page 148
 molecules, the interaction between the oxygen species and gas molecules may also

play an important role at 260 °C.

These studies have provided new insights for the synthesis of VO2 nanoparticles and

thin films for smart window applications. By using DFT simulation, it is possible to

investigate the doping effect of metal into VO2 at atomic scale. Moreover, the

investigation of sodium vanadates as gas sensing materials may create a new venue for

the fabrication of layered NaxVyOz nanostructures for potential applications in

environmental monitoring and detection.

7.2 Future Work

Despite many efforts made in this thesis, more work needs to be conducted,

experimentally and theoretically in the future, for example,

1) The thermochromic properties of VO2 are strongly dependent on the nanoparticle

size. Unique and interesting properties may present when the nanoparticle size is

small enough. Although VO2(M) has been successfully synthesized by

hydrothermal method directly, small size VO2(M) particles (<10 nm) have been

rarely reported. Further research focusing on the effects of different surfactants on

the morphology and size control needs to be carried out.

2) Thin films composed of VO2 nanocomposite show better optical and

thermochromic properties than that of pure VO2 thin film, such as high visible

transmittance and preferable colour. It is worthwhile to utilize electrodeposition

method to prepare nanocomposite, such as VO2/ZnO, VO2/CrO2.

Page 149
3) The DFT simulation is a useful technique to study the doping effect in VO2.

Although metal substitution doping effect has been investigated, the interstitial

doping effects of certain small ions, such as Li and H, due to their significant

impacts on the phase transition temperature of VO2, need to be investigated by DFT

method. H doped VO2 nanoparticles have been reported to lower the phase

transition to room temperature, while thin films with H doping have not been

researched, and a combination of DFT simulation and experiments may provide a

clear investigation toward H doped VO2.

4) Sodium vanadate nanostructure have been investigated as gas sensing materials and

presents better gas sensing performance than pure or metal oxide coated V2O5.

Although different characterization methods have been used to explain the reason,

the detailed adsorption process investigation by DFT or MD may be beneficial to

understand the mechanism more deeply. Meanwhile, other metal vanadates, such as

zinc vanadate, may show better performances and need to be further explored.

Page 150
Chapter 8. References

(1) Gao, Y.; Luo, H.; Zhang, Z.; Kang, L.; Chen, Z.; Du, J.; Kanehira, M.; Cao, C.

Nano Energy 2012, 1, 221.

(2) Kanu, S. S.; Binions, R. Proceedings of the Royal Society a-Mathematical

Physical and Engineering Sciences 2010, 466, 19.

(3) Parkin, I. P.; Manning, T. D. Journal of Chemical Education 2006, 83, 393.

(4) Leroux, C.; Nihoul, G.; Van Tendeloo, G. Phys. Rev. B 1998, 57, 5111.

(5) Galy, J.; Miehe, G. Solid State Sci. 1999, 1, 433.

(6) Wentzcovitch, R. M.; Schulz, W. W.; Allen, P. B. Phys. Rev. Lett. 1994, 72,

3389.

(7) Kim, H. T.; Chae, B. G.; Youn, D. H.; Maeng, S. L.; Kim, G.; Kang, K. Y.; Lim,

Y. S. New J. Phys. 2004, 6.

(8) Kim, H. T.; Chae, B. G.; Youn, D. H.; Kim, G.; Kang, K. Y.; Lee, S. J.; Kim, K.;

Lim, Y. S. Appl. Phys. Lett. 2005, 86.

(9) Qazilbash, M. M.; Brehm, M.; Chae, B. G.; Ho, P. C.; Andreev, G. O.; Kim, B.

J.; Yun, S. J.; Balatsky, A. V.; Maple, M. B.; Keilmann, F.; Kim, H. T.; Basov,

D. N. Science 2007, 318, 1750.

(10) Pouget, J. P.; Launois, H.; Rice, T. M.; Dernier, P.; Gossard, A.; Villeneuve, G.;

Hagenmuller, P. Phys. Rev. B 1974, 10, 1801.

(11) Hu, B.; Ding, Y.; Chen, W.; Kulkarni, D.; Shen, Y.; Tsukruk, V. V.; Wang, Z. L.

Adv. Mater. 2010, n/a.

(12) Guo, H.; Chen, K.; Oh, Y.; Wang, K.; Dejoie, C.; Syed Asif, S. A.; Warren, O.

L.; Shan, Z. W.; Wu, J.; Minor, A. M. Nano Lett. 2011, 11, 3207.

Page 151
(13) Park, J. H.; Coy, J. M.; Kasirga, T. S.; Huang, C.; Fei, Z.; Hunter, S.; Cobden, D.

H. Nature 2013, 500, 431.

(14) Oka, Y.; Yao, T.; Yamamoto, N. J. Mater. Chem. 1991, 1, 815.

(15) Tsang, C.; Manthiram, A. J. Electrochem. Soc. 1997, 144, 520.

(16) Zhang, K. F.; Liu, X.; Su, Z. X.; Li, H. L. Mater. Lett. 2007, 61, 2644.

(17) Byrappa, K.; Adschiri, T. Progress in Crystal Growth and Characterization of

Materials 2007, 53, 117.

(18) Liu, X. H.; Xie, G. Y.; Huang, C.; Qian, X.; Zhang, Y. F.; Luo, Y. B. Mater.

Lett. 2008, 62, 1878.

(19) Liu, J. F.; Li, Q. H.; Wang, T. H.; Yu, D. P.; Li, Y. D. Angew. Chem.-Int. Edit.

2004, 43, 5048.

(20) Rui, X.; Sim, D.; Xu, C.; Liu, W.; Tan, H.; Wong, K.; Hng, H. H.; Lim, T. M.;

Yan, Q. RSC Advances 2012, 2, 1174.

(21) Jiang, W. T.; Ni, J. A.; Yu, K.; Zhu, Z. Q. Appl. Surf. Sci. 2011, 257, 3253.

(22) Chen, W.; Peng, J. F.; Mai, L. Q.; Yu, H.; Qi, Y. Y. Solid State Commun. 2004,

132, 513.

(23) Li, X. L.; Chen, X. J.; Chen, X. Y.; Han, C. L.; Shi, C. W. J. Cryst. Growth 2007,

309, 43.

(24) Jiang, L. L.; Wei, M. D.; Ye, B. H.; Wei, K. M. J. Cryst. Growth 2008, 310,

4301.

(25) Chen, X. Y.; Wang, X.; Wang, Z. H.; Wan, J. X.; Liu, J. W.; Qian, Y. T.

Nanotechnology 2004, 15, 1685.

(26) Wu, X. C.; Tao, Y. R.; Lin, D.; Wang, Z. H.; Zheng, H. Mater. Res. Bull. 2005,

40, 315.

Page 152
(27) Armstrong, G.; Canales, J.; Armstrong, A. R.; Bruce, P. G. Journal of Power

Sources 2008, 178, 723.

(28) Cheng, Y.; Wong, T. L.; Ho, K. M.; Wang, N. J. Cryst. Growth 2009, 311, 1571.

(29) Li, M.; Kong, F. Y.; Zhang, Y. X.; Li, G. H. Crystengcomm 2011, 13, 2204.

(30) Li, G. C.; Chao, K.; Zhang, C. Q.; Zhang, Q. S.; Peng, H. R.; Chen, K. Z. Inorg.

Chem. 2009, 48, 1168.

(31) Mao, L. J.; Liu, C. Y. Solid State Commun. 2008, 146, 403.

(32) Zhang, K. F.; Bao, S. J.; Liu, X.; Shi, J.; Su, Z. X.; Li, H. L. Mater. Res. Bull.

2006, 41, 1985.

(33) Ni, J. A.; Jiang, W. T.; Yu, K.; Gao, Y. F.; Zhu, Z. Q. Electrochimica Acta 2011,

56, 2122.

(34) Cao, C. X.; Gao, Y. F.; Luo, H. J. J. Phys. Chem. C 2008, 112, 18810.

(35) Son, J. H.; Wei, J.; Cobden, D.; Cao, G. Z.; Xia, Y. N. Chem. Mat. 2010, 22,

3043.

(36) Li, J.; Su, Z. X.; Yang, B.; Cai, S. L.; Dong, Z. P.; Ma, J. T.; Li, R. J. Phys.

Chem. Solids 2010, 71, 407.

(37) Liu, H. M.; Wang, Y. G.; Wang, K. X.; Hosono, E.; Zhou, H. S. J. Mater. Chem.

2009, 19, 2835.

(38) Cao, C. X.; Gao, Y. F.; Kang, L. T.; Luo, H. J. Crystengcomm 2010, 12, 4048.

(39) Wu, C. Z.; Zhang, X. D.; Dai, J.; Yang, J. L.; Wu, Z. Y.; Wei, S. Q.; Xie, Y. J.

Mater. Chem. 2011, 21, 4509.

(40) Dai, L.; Cao, C. X.; Gao, Y. F.; Luo, H. J. Sol. Energy Mater. Sol. Cells 2011,

95, 712.

(41) Nguyen, T. D.; Do, T. O. Langmuir 2009, 25, 5322.

Page 153
(42) Gao, Y.; Wang, S.; Kang, L.; Chen, Z.; Du, J.; Liu, X.; Luo, H.; Kanehira, M.

Energy Environ. Sci. 2012, 5, 8234.

(43) Zheng, C. M.; Zhang, J. L.; Luo, G. B.; Ye, J. Q.; Wu, M. M. J. Mater. Sci. 2000,

35, 3425.

(44) Peng, Z.; Jiang, W.; Liu, H. The Journal of Physical Chemistry C 2006, 111,

1119.

(45) Li, Y.; Ji, S.; Gao, Y.; Luo, H.; Kanehira, M. Sci. Rep. 2013, 3.

(46) Li, Y.; Ji, S.; Gao, Y.; Luo, H.; Jin, P. ACS Appl. Mater. Interfaces 2013, 5,

6603.

(47) Gao, Y.; Wang, S.; Luo, H.; Dai, L.; Cao, C.; Liu, Y.; Chen, Z.; Kanehira, M.

Energy Environ. Sci. 2012, 5.

(48) Zhou, Y.; Huang, A.; Li, Y.; Ji, S.; Jin, P. Nanoscale 2013.

(49) Muraoka, Y.; Hiroi, Z. Appl. Phys. Lett. 2002, 80, 583.

(50) Greenberg, C. B. Thin Solid Films 1983, 110, 73.

(51) Luo, Z. F.; Wu, Z. M.; Xu, X. D.; Wang, T.; Jiang, Y. D. J. Vac. Sci. Technol. A

2010, 28, 595.

(52) Kim, J.; Ko, C.; Frenzel, A.; Ramanathan, S.; Hoffman, J. E. Appl. Phys. Lett.

2010, 96.

(53) Claassen, J. H.; Lu, J. W.; West, K. G.; Wolf, S. A. Appl. Phys. Lett. 2010, 96.

(54) Mlyuka, N. R.; Niklasson, G. A.; Granqvist, C. G. Appl. Phys. Lett. 2009, 95.

(55) Chen, S. H.; Ma, H.; Dai, J.; Yi, X. J. Appl. Phys. Lett. 2007, 90.

(56) Ruzmetov, D.; Zawilski, K. T.; Narayanamurti, V.; Ramanathana, S. J. Appl.

Phys. 2007, 102.

(57) Youn, D. H.; Lee, J. W.; Chae, B. G.; Kim, H. T.; Maeng, S. L.; Kang, K. Y. J.

Appl. Phys. 2004, 95, 1407.

Page 154
(58) Kim, B.-J.; Lee, Y. W.; Choi, S.; Lim, J.-W.; Yun, S. J.; Kim, H.-T.; Shin, T.-J.;

Yun, H.-S. Phys. Rev. B 2008, 77, 235401.

(59) Gupta, A.; Aggarwal, R.; Gupta, P.; Dutta, T.; Narayan, R. J.; Narayan, J. Appl.

Phys. Lett. 2009, 95.

(60) Choi, H. S.; Ahn, J. S.; Jung, J. H.; Noh, T. W.; Kim, D. H. Phys. Rev. B 1996,

54, 4621.

(61) Pauli, S. A.; Herger, R.; Willmott, P. R.; Donev, E. U.; Suh, J. Y.; Haglund, R. F.

J. Appl. Phys. 2007, 102.

(62) Suh, J. Y.; Lopez, R.; Feldman, L. C.; Haglund, R. F. J. Appl. Phys. 2004, 96,

1209.

(63) Manning, T. D.; Parkin, I. P. J. Mater. Chem. 2004, 14, 2554.

(64) Manning, T. D.; Parkin, I. P.; Clark, R. J. H.; Sheel, D.; Pemble, M. E.;

Vernadou, D. J. Mater. Chem. 2002, 12, 2936.

(65) Manning, T. D.; Parkin, I. P.; Pemble, M. E.; Sheel, D.; Vernardou, D. Chem.

Mat. 2004, 16, 744.

(66) Binions, R.; Hyett, G.; Piccirillo, C.; Parkin, I. P. J. Mater. Chem. 2007, 17,

4652.

(67) Blackman, C. S.; Piccirillo, C.; Binions, R.; Parkin, I. P. Thin Solid Films 2009,

517, 4565.

(68) Piccirillo, C.; Binions, R.; Parkin, I. P. Thin Solid Films 2008, 516, 1992.

(69) Piccirillo, C.; Binions, R.; Parkin, I. P. Chem. Vapor Depos. 2007, 13, 145.

(70) Nag, J.; Haglund, R. F. J. Phys.-Condes. Matter 2008, 20.

(71) Partlow, D. P.; Gurkovich, S. R.; Radford, K. C.; Denes, L. J. J. Appl. Phys.

1991, 70, 443.

Page 155
(72) Zhang, Z. T.; Gao, Y. F.; Chen, Z.; Du, J.; Cao, C. X.; Kang, L. T.; Luo, H. J.

Langmuir 2010, 26, 10738.

(73) Kang, L. T.; Gao, Y. F.; Zhang, Z. T.; Du, J.; Cao, C. X.; Chen, Z.; Luo, H. J. J.

Phys. Chem. C 2010, 114, 1901.

(74) Yan, J. Z.; Zhang, Y.; Huang, W. X.; Tu, M. J. Thin Solid Films 2008, 516, 8554.

(75) Chae, B. G.; Kim, H. T.; Yun, S. J. Electrochem. Solid State Lett. 2008, 11, D53.

(76) Ningyi, Y.; Jinhua, L.; Chan, H. L. W.; Chenglu, L. Appl. Phys. A-Mater. Sci.

Process. 2004, 78, 777.

(77) Yin, D. H.; Xu, N. K.; Zhang, J. Y.; Zheng, X. L. Mater. Res. Bull. 1996, 31,

335.

(78) Guzman, G.; Morineau, R.; Livage, J. Mater. Res. Bull. 1994, 29, 509.

(79) Kang, L.; Gao, Y.; Luo, H. ACS Appl. Mater. Interfaces 2009, 1, 2211.

(80) Du, J.; Gao, Y. F.; Luo, H. J.; Kang, L. T.; Zhang, Z. T.; Chen, Z.; Cao, C. X.

Sol. Energy Mater. Sol. Cells 2011, 95, 469.

(81) Du, J.; Gao, Y. F.; Luo, H. J.; Zhang, Z. T.; Kang, L. T.; Chen, Z. Sol. Energy

Mater. Sol. Cells 2011, 95, 1604.

(82) Cezar, A. B.; Graff, I. L.; Rikers, Y.; Schreiner, W. H.; Mattoso, N.

Electrochemical and Solid-State Letters 2011, 14, D23.

(83) Koza, J. A.; He, Z.; Miller, A. S.; Switzer, J. A. Chem. Mat. 2011, null.

(84) Minch, R.; Es-Souni, M. Crystengcomm 2013, 15, 6645.

(85) Babulanam, S. M.; Eriksson, T. S.; Niklasson, G. A.; Granqvist, C. G. Solar

Energy Materials 1987, 16, 347.

(86) Jin, P.; Nakao, S.; Tanemura, S. Thin Solid Films 1998, 324, 151.

(87) Batista, C.; Ribeiro, R.; Carneiro, J.; Teixeira, V. J. Nanosci. Nanotechnol. 2009,

9, 4220.

Page 156
(88) Batista, C.; Teixeira, V.; Ribeiro, R. M. J. Nanosci. Nanotechnol. 2010, 10,

1393.

(89) Manning, T. D.; Parkin, I. P.; Blackman, C.; Qureshi, U. J. Mater. Chem. 2005,

15, 4560.

(90) Xu, S. Q.; Ma, H. P.; Dai, S. X.; Jiang, Z. H. J. Mater. Sci. 2004, 39, 489.

(91) Hanlon, T. J.; Coath, J. A.; Richardson, M. A. Thin Solid Films 2003, 436, 269.

(92) Piccirillo, C.; Binions, R.; Parkin, I. P. Eur. J. Inorg. Chem. 2007, 4050.

(93) Phillips, T. E.; Murphy, R. A.; Poehler, T. O. Mater. Res. Bull. 1987, 22, 1113.

(94) Béteille, F.; Morineau, R.; Livage, J.; Nagano, M. Mater. Res. Bull. 1997, 32,

1109.

(95) Lee, M. H.; Kim, M. G.; Song, H. K. Thin Solid Films 1996, 291, 30.

(96) Kiri, P.; Warwick, M. E. A.; Ridley, I.; Binions, R. Thin Solid Films 2011, 520,

1363.

(97) Burkhardt, W.; Christmann, T.; Franke, S.; Kriegseis, W.; Meister, D.; Meyer, B.

K.; Niessner, W.; Schalch, D.; Scharmann, A. Thin Solid Films 2002, 402, 226.

(98) Burkhardt, W.; Christmann, T.; Meyer, B. K.; Niessner, W.; Schalch, D.;

Scharmann, A. Thin Solid Films 1999, 345, 229.

(99) Khan, K. A.; Granqvist, C. G. Appl. Phys. Lett. 1989, 55, 4.

(100) Marini, C.; Arcangeletti, E.; Di Castro, D.; Baldassare, L.; Perucchi, A.; Lupi, S.;

Malavasi, L.; Boeri, L.; Pomjakushina, E.; Conder, K.; Postorino, P. Phys. Rev.

B 2008, 77.

(101) Pan, M.; Zhong, H. M.; Wang, S. W.; Li, Z. F.; Chen, X. S.; Lu, W. Chem. Phys.

Lett. 2004, 398, 304.

(102) Sobhan, M. A.; Kivaisi, R. T.; Stjerna, B.; Granqvist, C. G. Sol. Energy Mater.

Sol. Cells 1996, 44, 451.

Page 157
(103) Tan, X.; Yao, T.; Long, R.; Sun, Z.; Feng, Y.; Cheng, H.; Yuan, X.; Zhang, W.;

Liu, Q.; Wu, C.; Xie, Y.; Wei, S. Sci. Rep. 2012, 2.

(104) Dai, L.; Chen, S.; Liu, J.; Gao, Y.; Zhou, J.; Chen, Z.; Cao, C.; Luo, H.;

Kanehira, M. Phys. Chem. Chem. Phys. 2013.

(105) Soltani, M.; Chaker, M.; Haddad, E.; Kruzelecky, R. V.; Margot, J. Appl. Phys.

Lett. 2004, 85, 1958.

(106) Takahashi, I.; Hibino, M.; Kudo, T. Japanese Journal of Applied Physics Part 1-

Regular Papers Short Notes & Review Papers 2001, 40, 1391.

(107) Qazilbash, M. M.; Schafgans, A. A.; Burch, K. S.; Yun, S. J.; Chae, B. G.; Kim,

B. J.; Kim, H. T.; Basov, D. N. Phys. Rev. B 2008, 77.

(108) Jin, P.; Xu, G.; Tazawa, M.; Yoshimura, K. Appl. Phys. A-Mater. Sci. Process.

2003, 77, 455.

(109) Xu, G.; Jin, P.; Tazawa, M.; Yoshimura, K. Sol. Energy Mater. Sol. Cells 2004,

83, 29.

(110) Yang, T. H.; Aggarwal, R.; Gupta, A.; Zhou, H. H.; Narayan, R. J.; Narayan, J. J.

Appl. Phys. 2010, 107.

(111) Shibuya, K.; Tsutsumi, J. y.; Hasegawa, T.; Sawa, A. Appl. Phys. Lett. 2013,

103, 021604.

(112) Hohenberg, P.; Kohn, W. Physical Review 1964, 136, B864.

(113) Born, M.; Oppenheimer, R. Ann. Phys.-Berlin 1927, 389, 457.

(114) Kohn, W.; Sham, L. J. Physical Review 1965, 140, A1133.

(115) Mattsson, A. E.; Schultz, P. A.; Desjarlais, M. P.; Mattsson, T. R.; Leung, K.

Modelling and Simulation in Materials Science and Engineering 2005, 13, R1.

(116) Wang, L.; Maxisch, T.; Ceder, G. Phys. Rev. B 2006, 73, 195107.

(117) Morgan, B. J.; Watson, G. W. Surface Science 2007, 601, 5034.

Page 158
(118) Laubach, S.; Schmidt, P. C.; Thi; Fernandez-Madrigal, F. J.; Wu, Q.-H.;

Jaegermann, W.; Klemm, M.; Horn, S. Phys. Chem. Chem. Phys. 2007, 9, 2564.

(119) Goodenou.Jb J. Solid State Chem. 1971, 3, 490.

(120) Eyert, V. Ann. Phys.-Berlin 2002, 11, 650.

(121) Zylbersztejn, A.; Mott, N. F. Phys. Rev. B 1975, 11, 4383.

(122) Whittaker, L.; Jaye, C.; Fu, Z. G.; Fischer, D. A.; Banerjee, S. J. Am. Chem. Soc.

2009, 131, 8884.

(123) Korotin, M. A.; Skorikov, N. A.; Anisimov, V. I. The Physics of Metals and

Metallography 2002, 94, 17.

(124) Biermann, S.; Poteryaev, A.; Lichtenstein, A. I.; Georges, A. Phys. Rev. Lett.

2005, 94.

(125) Liebsch, A.; Ishida, H.; Bihlmayer, G. Phys. Rev. B 2005, 71.

(126) Continenza, A.; Massidda, S.; Posternak, M. Phys. Rev. B 1999, 60, 15699.

(127) Eyert, V. Phys. Rev. Lett. 2011, 107, 016401.

(128) Grau-Crespo, R.; Wang, H.; Schwingenschlögl, U. Phys. Rev. B 2012, 86,

081101.

(129) Whittaker, L.; Wu, T.-L.; Stabile, A.; Sambandamurthy, G.; Banerjee, S. ACS

Nano 2011, 5, 8861.

(130) Zhang, J.; He, H.; Xie, Y.; Pan, B. The Journal of Chemical Physics 2013, 138,

114705.

(131) Hu, S.; Li, S.-Y.; Ahuja, R.; Granqvist, C. G.; Hermansson, K.; Niklasson, G. A.;

Scheicher, R. H. Appl. Phys. Lett. 2012, 101, 201902.

(132) Zhang, J.; He, H.; Xie, Y.; Pan, B. C. Phys. Chem. Chem. Phys. 2013.

(133) Verleur, H. W.; Barker, A. S.; Berglund, C. N. Physical Review 1968, 172, 788.

Page 159
(134) Zhang, S. D.; Li, Y. M.; Wu, C. Z.; Zheng, F.; Xie, Y. J. Phys. Chem. C 2009,

113, 15058.

(135) Yang, S.; Gong, Y.; Liu, Z.; Zhan, L.; Hashim, D. P.; Ma, L.; Vajtai, R.; Ajayan,

P. M. Nano Lett. 2013, 13, 1596.

(136) Mai, L. Q.; Xu, L.; Han, C. H.; Luo, Y. Z.; Zhao, S. Y.; Zhao, Y. L. Nano Lett.

2010, 10, 4750.

(137) Yin, H. H.; Luo, M.; Yu, K.; Gao, Y. F.; Huang, R.; Zhang, Z. L.; Zeng, M.;

Cao, C. X.; Zhu, Z. Q. ACS Appl. Mater. Interfaces 2011, 3, 2057.

(138) Huang, W. X.; Yin, X. G.; Huang, C. P.; Wang, Q. J.; Miao, T. F.; Zhu, Y. Y.

Appl. Phys. Lett. 2010, 96.

(139) Strelcov, E.; Lilach, Y.; Kolmakov, A. Nano Lett. 2009, 9, 2322.

(140) Kim, C.; Shin, J. S.; Ozaki, H. J. Phys.-Condes. Matter 2007, 19.

(141) Mai, L.; Xu, L.; Han, C.; Xu, X.; Luo, Y.; Zhao, S.; Zhao, Y. Nano Lett. 2010,

null.

(142) Luo, J. Y.; Cui, W. J.; He, P.; Xia, Y. Y. Nature Chemistry 2010, 2, 760.

(143) Li, R.; Liu, C. Y. Mater. Res. Bull. 2010, 45, 688.

(144) Wu, C. Z.; Hu, Z. P.; Wang, W.; Zhang, M. A.; Yang, J. L.; Xie, Y. Chem.

Commun. 2008, 3891.

(145) Zhang, M. J.; Dahn, J. R. J. Electrochem. Soc. 1996, 143, 2730.

(146) Kim, B. J.; Lee, Y. W.; Chae, B. G.; Yun, S. J.; Oh, S. Y.; Kim, H. T.; Lim, Y. S.

Appl. Phys. Lett. 2007, 90.

(147) Liu, J.; Wang, X.; Peng, Q.; Li, Y. Adv. Mater. 2005, 17, 764.

(148) Liu, J.; Wang, X.; Peng, Q.; Li, Y. Sensors and Actuators B: Chemical 2006,

115, 481.

Page 160
(149) Jin, W.; Dong, B. T.; Chen, W.; Zhao, C. X.; Mai, L. Q.; Dai, Y. Sensors and

Actuators B-Chemical 2010, 145, 211.

(150) Fu, H.; Jiang, X.; Yang, X.; Yu, A.; Su, D.; Wang, G. Journal of Nanoparticle

Research 2012, 14, 1.

(151) Guzman, G.; Beteille, F.; Morineau, R.; Livage, J. J. Mater. Chem. 1996, 6, 505.

(152) Soltani, M.; Chaker, M.; Haddad, E.; Kruzelesky, R. Meas. Sci. Technol. 2006,

17, 1052.

(153) Appavoo, K.; Lei, D. Y.; Sonnefraud, Y.; Wang, B.; Pantelides, S. T.; Maier, S.

A.; Haglund, R. F. Nano Lett. 2012, 12, 780.

(154) Guiton, B. S.; Gu, Q.; Prieto, A. L.; Gudiksen, M. S.; Park, H. J. Am. Chem. Soc.

2005, 127, 498.

(155) Lopez, R.; Haynes, T. E.; Boatner, L. A.; Feldman, L. C.; Haglund, R. F. Phys.

Rev. B 2002, 65.

(156) Li, G. C.; Chao, K.; Peng, H. R.; Chen, K. Z.; Zhang, Z. K. Inorg. Chem. 2007,

46, 5787.

(157) Gurlo, A. Nanoscale 2011, 3, 154.

(158) Yin , H.; Yu, K.; Zhang, Z.; Zeng, M.; Lou, L.; Zhu, Z. Electroanalysis 2011, 23,

1752.

(159) Toulemon, D.; Pichon, B. P.; Cattoen, X.; Man, M. W. C.; Begin-Colin, S.

Chemical Communications 2011, 47, 11954.

(160) Oka, Y.; Yao, T.; Yamamoto, N. J. Solid State Chem. 1990, 89, 372.

(161) Jiang, X.; Zeng, Q.; Yu, A. Nanotechnology 2006, 17, 4929.

(162) Smith, D. K.; Korgel, B. A. Langmuir 2008, 24, 644.

(163) Zhai, H.-J.; Wu, W.-H.; Lu, F.; Wang, H.-S.; Wang, C. Mater. Chem. Phys.

2008, 112, 1024.

Page 161
(164) Tapramaz, R.; Karabulut, B.; Köksal, F. J. Phys. Chem. Solids 2000, 61, 1367.

(165) Zhang, Z.; Gong, Z.; Yang, Y. The Journal of Physical Chemistry B 2004, 108,

17546.

(166) Wang, Y.-Q.; Gu, L.; Guo, Y.-G.; Li, H.; He, X.-Q.; Tsukimoto, S.; Ikuhara, Y.;

Wan, L.-J. J. Am. Chem. Soc. 2012, 134, 7874.

(167) Huang, J.; Wu, Y.; Gu, C.; Zhai, M.; Yu, K.; Yang, M.; Liu, J. Sensors and

Actuators B: Chemical 2010, 146, 206.

(168) Kerr, R. A. Science 2007, 316, 188.

(169) Glicksman, L. R. Physics Today 2008, 61, 35.

(170) Morin, F. J. Phys. Rev. Lett. 1959, 3, 34.

(171) Livage, J. Coordination Chemistry Reviews 1999, 190–192, 391.

(172) Chen, B.; Yang, D. F.; Charpentier, P. A.; Zeman, M. Sol. Energy Mater. Sol.

Cells 2009, 93, 1550.

(173) Zhou, H.; Chisholm, M. F.; Yang, T. H.; Pennycook, S. J.; Narayan, J. J. Appl.

Phys. 2011, 110.

(174) Heckman, E. M.; Gonzalez, L. P.; Guha, S.; Barnes, J. O.; Carpenter, A. Thin

Solid Films 2009, 518, 265.

(175) Yuan, N. Y.; Li, J. H.; Li, G.; Chen, X. S. Thin Solid Films 2006, 515, 1275.

(176) Switzer, J. A. Science 2012, 338, 1300.

(177) Gurrappa, I.; Binder, L. Science and Technology of Advanced Materials 2008, 9,

043001.

(178) Cavalleri, A.; Toth, C.; Siders, C. W.; Squier, J. A.; Raksi, F.; Forget, P.; Kieffer,

J. C. Phys. Rev. Lett. 2001, 87.

(179) Wei, J.; Wang, Z.; Chen, W.; Cobden, D. H. Nat Nano 2009, 4, 420.

(180) Kwong, W. L.; Savvides, N.; Sorrell, C. C. Electrochimica Acta 2012, 75, 371.

Page 162
(181) Shen, P. K.; Tseung, A. C. C. J. Mater. Chem. 1992, 2, 1141.

(182) Zhang, Z.; Gao, Y.; Luo, H.; Kang, L.; Chen, Z.; Du, J.; Kanehira, M.; Zhang,

Y.; Wang, Z. L. Energy Environ. Sci. 2011, 4, 4290.

(183) Lee, S.-H.; Cheong, H. M.; Seong, M. J.; Liu, P.; Tracy, C. E.; Mascarenhas, A.;

Pitts, J. R.; Deb, S. K. Solid State Ion. 2003, 165, 111.

(184) Zhang, Z. T.; Gao, Y. F.; Kang, L. T.; Du, J.; Luo, H. J. J. Phys. Chem. C 2010,

114, 22214.

(185) Mendialdua, J.; Casanova, R.; Barbaux, Y. J. Electron Spectrosc. Relat. Phenom.

1995, 71, 249.

(186) Silversmit, G.; Depla, D.; Poelman, H.; Marin, G. B.; De Gryse, R. J. Electron

Spectrosc. Relat. Phenom. 2004, 135, 167.

(187) Wu, C.; Zhu, H.; Dai, J.; Yan, W.; Yang, J.; Tian, Y.; Wei, S.; Xie, Y. Advanced

Functional Materials 2010, 20, 3666.

(188) Xue, Y.; Zhang, X.; Zhang, J.; Wu, J.; Sun, Y.; Tian, Y.; Xie, Y. J. Mater. Chem.

2012, 22, 2560.

(189) Chiu, T. W.; Hong, R. T.; Tonooka, K.; Kikuchi, N. Thin Solid Films 2013, 529,

119.

(190) Paz, Y.; Heller, A. J. Mater. Res. 1997, 12, 2759.

(191) Takami, H.; Kanki, T.; Ueda, S.; Kobayashi, K.; Tanaka, H. Applied Physics

Express, 3, 063201.

(192) Kang, L. T.; Gao, Y. F.; Luo, H. J. In Functional and Electronic Materials; Li,

C. M., Jiang, C. B., Zhong, Z. Y., Zhou, Y., Eds.; Trans Tech Publications Ltd:

Stafa-Zurich, 2011; Vol. 687.

(193) Wei, J.; Wang, Z. H.; Chen, W.; Cobden, D. H. Nat. Nanotechnol. 2009, 4, 420.

Page 163
(194) Di Valentin, C.; Pacchioni, G.; Selloni, A.; Livraghi, S.; Giamello, E. The

Journal of Physical Chemistry B 2005, 109, 11414.

(195) Tian; Liu The Journal of Physical Chemistry B 2006, 110, 17866.

(196) Finazzi, E.; Di Valentin, C.; Pacchioni, G. The Journal of Physical Chemistry C

2008, 113, 220.

(197) Wang, J.; Tafen, D. N.; Lewis, J. P.; Hong, Z.; Manivannan, A.; Zhi, M.; Li, M.;

Wu, N. J. Am. Chem. Soc. 2009, 131, 12290.

(198) Graciani, J.; Álvarez, L. J.; Rodriguez, J. A.; Sanz, J. F. The Journal of Physical

Chemistry C 2008, 112, 2624.

(199) Janisch, R.; Gopal, P.; Spaldin, N. A. Journal of Physics: Condensed Matter

2005, 17, R657.

(200) Clark, S. J., Segall, M.D., Pickard, C.J., Hasnip, P.J., Probert, M.I.J., Refson, K.,

Payne, M.C. Zeitschrift für Kristallographie 2005, 220, 567.

(201) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865.

(202) Becke, A. D. The Journal of Chemical Physics 1992, 96, 2155.

(203) Rogers, K. D. Powder Diffraction 1993, 8, 240.

(204) McWhan, D. B.; Marezio, M.; Remeika, J. P.; Dernier, P. D. Phys. Rev. B 1974,

10, 490.

(205) Rakotoniaina, J. C.; Mokrani-Tamellin, R.; Gavarri, J. R.; Vacquier, G.; Casalot,

A.; Calvarin, G. J. Solid State Chem. 1993, 103, 81.

(206) Shin, S.; Suga, S.; Taniguchi, M.; Fujisawa, M.; Kanzaki, H.; Fujimori, A.;

Daimon, H.; Ueda, Y.; Kosuge, K.; Kachi, S. Phys. Rev. B 1990, 41, 4993.

(207) Kitahiro, I.; Watanabe, A. Jpn. J. Appl. Phys. 1967, 6, 1023.

(208) Raible, I.; Burghard, M.; Schlecht, U.; Yasuda, A.; Vossmeyer, T. Sensors and

Actuators B: Chemical 2005, 106, 730.

Page 164
(209) Strelcov, E.; Lilach, Y.; Kolmakov, A. Nano Lett. 2009, 9, 2322.

(210) Wang, H.; Wang, W.; Ren, Y.; Huang, K.; Liu, S. Journal of Power Sources

2012, 199, 263.

(211) Liu, H.; Wang, Y.; Li, L.; Wang, K.; Hosono, E.; Zhou, H. J. Mater. Chem.

2009, 19, 7885.

(212) Lim, S. H.; Lin, J. Y.; Zhu, Y. W.; Sow, C. H.; Ji, W. J. Appl. Phys. 2006, 100,

016105.

(213) Wang, H.; Liu, S.; Ren, Y.; Wang, W.; Tang, A. Energy Environ. Sci. 2012, 5.

(214) Weeks, A. D.; Ross, D. R.; Marvin, R. F. American Mineralogist 1963, 48, 1187.

(215) Delley, B. The Journal of Chemical Physics 2000, 113, 7756.

(216) Baker, J.; Kessi, A.; Delley, B. J. Chem. Phys. 1996, 105, 192.

(217) Perdew, J. P. Physica B: Physics of Condensed Matter 1991, 172, 1.

(218) Kaneti, Y. V.; Yue, J.; Jiang, X.; Yu, A. The Journal of Physical Chemistry C

2013, 117, 13153.

(219) Chen, Y. J.; Xue, X. Y.; Wang, Y. G.; Wang, T. H. Appl. Phys. Lett. 2005, 87,

233503.

(220) Li, C. C.; Yin, X. M.; Wang, T. H.; Zeng, H. C. Chem. Mat. 2009, 21, 4984.

(221) Kaneti, Y.; Zhang, Z.; Yue, J.; Jiang, X.; Yu, A. Journal of Nanoparticle

Research 2013, 15, 1.

(222) Xiangfeng, C.; Caihong, W.; Dongli, J.; Chenmou, Z. Chem. Phys. Lett. 2004,

399, 461.

(223) Wang, C.; Yin, L.; Zhang, L.; Qi, Y.; Lun, N.; Liu, N. Langmuir 2010, 26,

12841.

(224) Chiu, H.-C.; Yeh, C.-S. The Journal of Physical Chemistry C 2007, 111, 7256.

(225) Shimizu, Y.; Egashira, M. MRS Bulletin 1999, 24, 18.

Page 165
(226) Yue, J.; Jiang, X.; Yu, A. The Journal of Physical Chemistry C 2013, 117, 9962.

(227) Liang, S.; Zhou, J.; Fang, G.; Liu, J.; Tang, Y.; Li, X.; Pan, A. ACS Appl. Mater.

Interfaces 2013, 5, 8704.

(228) Lide(Ed.), D. R. CRC Press, 2000, Boca Raton, FL.

Page 166