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Nanomaterials
in Energy
and Environmental
Applications
 1BO
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Nanomaterials
in Energy
and Environmental
Applications

editors
Preben Maegaard
Anna Krenz edited by
Wolfgang Palz
Junhui He

The Rise of Modern Wind Energy

Wind Power
for the World

PAN STANFORD PUBLISHING

Published by
Pan Stanford Publishing Pte. Ltd.
Penthouse Level, Suntec Tower 3
8 Temasek Boulevard
Singapore 038988

Email: editorial@panstanford.com
Web: www.panstanford.com

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

Nanomaterials in Energy and Environmental Applications

Copyright © 2016 by Pan Stanford Publishing Pte. Ltd.
All rights reserved. This book, or parts thereof, may not be reproduced in any form
or by any means, electronic or mechanical, including photocopying, recording
or any information storage and retrieval system now known or to be invented,
without written permission from the publisher.

For photocopying of material in this volume, please pay a copying fee through
the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923,
USA. In this case permission to photocopy is not required from the publisher.

ISBN 978-981-4463-78-2 (Hardcover)

ISBN 978-981-4463-79-9 (eBook)

Printed in the USA

 Contents

Preface xv

1. Multifunctional Coatings for Solar Energy Applications 1

Lin Yao and Junhui He
1.1 Introduction 1
1.2 Theoretical Aspects of Antireflection and
Self-Cleaning 3
1.2.1 Principle of Antireflection 3
1.2.1.1 Basic concept of antireflection 3
1.2.1.2 Strategies to achieve
antireflection 5
1.2.2 Principle of Self-Cleaning 7
1.2.2.1 Special wettability induced
self-cleaning 7
1.2.2.2 Photocatalysis-induced
self-cleaning 10
1.3 Fabrication Strategies and Methods 13
1.3.1 Fabrication of Antireflective Surfaces 13
1.3.1.1 Materials perspective for
antireflectivity 13
1.3.1.2 Bottom-up approach 17
1.3.1.3 Top-down fabrication 24
1.3.2 Fabrication of Self-Cleaning Surfaces 28
1.3.2.1 Fabrication of
superhydrophilic surfaces 28
1.3.2.2 Fabrication of
superhydrophobic surfaces 32
1.3.3 Other Substrates for Antireflective
and Self-Cleaning Coatings 35
1.3.3.1 Polymer 35
1.3.3.2 Metal foil 38
1.4 Progress in Antireflective Self-Cleaning
Coatings and Other Multifunctional Coatings 40
1.4.1 Progress in Antireflective
Self-Cleaning Coatings 40
vi Contents

1.4.2 Mechanical Integrity (Durability and

Adhesion) of Coatings 46
1.4.3 Smart Coatings 49
1.4.3.1 Self-healing coatings 49
1.4.3.2 Antimicrobial coatings 53
1.4.3.3 Superamphiphobic coatings 54
1.5 Applications 58
1.6 Conclusion and Outlook 61

2. Functionalization of Polyelectrolyte Multilayers

via Counterions 89
Xin Zhang and Zhaohui Su
2.1 Introduction 89
2.2 Counterions in Polyelectrolyte Multilayers 92
2.3 Surface Wettability Modulation 98
2.3.1 Surfaces with Tunable Wettability 99
2.3.2 Superhydrophobic and
Superhydrophilic Surfaces 102
2.3.3 Dual Superoleophobic Surfaces 102
2.3.4 Rewritable Wettability Gradient 104
2.3.5 Sticky Superhydrophobic Surfaces 106
2.4 PEM Supported Metal Nanoparticles 107
2.4.1 Monometallic Nanoparticles 108
2.4.2 Core-Shell Nanoparticles 111
2.4.3 Hollow Nanoparticles 113
2.5 Concluding Remark 116

3. Glass-Based Proton Exchange Membranes for

Fuel Cell Applications 121
Haibin Li, Qiang Xie, and Xiaojing Chen
3.1 Introduction 121
3.2 Proton-Conducting Glasses Synthesized
via the Hydrothermally Assisted Sol-Gel
Approach 123
3.2.1 High Proton-Conducting Monolithic
Phosphosilicate Glass Membranes 123
3.2.1.1 Preparation of PSMs 123
3.2.1.2 Characterization, analysis,
and discussion of PSMs 123
 Contents vii

3.2.2 Fast Proton-Conducting Glass

Membrane Based on Porous
Phosphosilicate and
Perfluorosulfonic Acid Polymer 131
3.2.2.1 Preparation of membranes 131
3.2.2.2 Characterization, analysis,
and discussion of NPS
membranes 132
3.3 Flexible Proton-Conducting
Perfluorosulfonate Glass-Based
Composite Membranes 143
3.3.1 Preparation of NPS/SPEEK Membrane 144
3.3.2 Characterization, Analysis, and
Discussion 146
3.3.2.1 Appearance and chemical
structure of the NPS/SPEEK
composite membranes 146
3.3.2.2 Morphology and pore
structure of the NPS/SPEEK
composite membranes 148
3.3.2.3 Proton-conducting
properties, water uptake,
and swelling ratio 150
3.3.2.4 H2/O2 fuel cell testing 154
3.4 Flexible Proton-Conducting
Perfluorosulfonate-Free Glass-Based
Composite Membranes 155
3.4.1 Preparation of SiO2-P2O5/SPEEK
Composite Membranes 156
3.4.2 Characterization, Analysis, and
Discussion of the Composite
Membranes 157
3.4.2.1 Structure of the
SiO2-P2O5/SPEEK
composite membranes 157
3.4.2.2 Thermal and mechanical
properties of the
SiO2–P2O5/SPEEK
composite membranes 161
viii Contents

3.4.2.3 Proton-conducting
properties, water uptake,
and swelling ratios of the
SiO2–P2O5/SPEEK
composite membranes 163
3.4.2.4 H2/O2 single fuel cell testing 165
3.5 Anhydrous Proton-Conducting Glass
Membranes Doped with Ionic Liquid for
Intermediate-Temperature Fuel Cells 167
3.5.1 Preparation of [Dema][TfO]/SiO2
Hybrid Glass Membranes 168
3.5.1.1 Preparation of [dema]
[TfO]ionic liquid 168
3.5.1.2 Preparation of [dema]
[TfO]/SiO2 glass membranes 169
3.5.2 Characterization, Analysis, and
Discussion 169
3.5.2.1 Characterization of
[dema][TfO]ionic liquid 169
3.5.2.2 Morphology and structure
of the [dema][TfO]/SiO2
glass membranes 170
3.5.2.3 FTIR analysis of the
[dema][TfO]/SiO2 glass
membranes 171
3.5.2.4 Ionic conductivity of the
[dema][TfO]/SiO2 glass
membranes 172
3.6 Performance of Fuel Cells (FCs) with Novel
Proton-Conducting Glass Membrane or
Composite Membrane 175
3.6.1 Improved Performance of Fuel
Cell with Proton-conducting Glass
Membrane 175
3.6.1.1 Preparation 176
3.6.1.2 Characterization, analysis,
and discussion 178
3.6.2 Performance of a Direct
Methanol Fuel Cell Using
Flexible Proton-Conducting
Glass-Based Composite
Membrane 183
 Contents ix

3.6.2.1 Preparation of the

NPS/SPEEK composite
membrane 184
3.6.2.2 Measurement of methanol
permeability 185
3.6.2.3 Preparation and
characterization of DMFC 185
3.6.2.4 Characterization, analysis,
and discussion 186
3.7 Conclusion and Outlook 192

4. Silicon Nanowire Arrays: Fabrication, Properties

and Energy Applications 197
Yang Cao and Junhui He
4.1 Introduction 197
4.2 Fabrication Process and Formation
Mechanism of SiNW Arrays 198
4.3 Properties of SiNW Arrays 200
4.3.1 Optical Properties: Improved
Anti-Reflection and Broadband
Absorption 200
4.3.2 Electrical Properties: Enhanced
Carrier Collection Efficiency 203
4.4 Energy Applications of SiNW Arrays 205
4.4.1 Solar Cells 205
4.4.1.1 Solar cells based on radial
p-n junction SiNW arrays 206
4.4.1.2 Solar cells based on
graphene film/SiNW array
Schottky junction 211
4.4.2 Photoelectrochemical Solar Cells 212
4.4.3 Photocatalytic Water Splitting 214
4.5 Conclusions and Outlook 221

5. Positron-Positronium Annihilation Studies of

Energy- and Environment-Related Nanomaterials 227
Kiminori Sato
5.1 Introduction 227
x Contents

5.2 Positron-Positronium Annihilation

Spectroscopy 229
5.2.1 Positron and Positronium in Materials 229
5.2.2 Positron-Positronium Lifetime
Spectroscopy 231
5.2.3 Coincident Doppler Broadening (CDB)
Spectroscopy 231
5.2.4 Positron-Age-Momentum Correlation
(AMOC) Spectroscopy 233
5.2.5 Positron Diffusion Experiment 237
5.3 Application of Positron-Positronium
Annihilation Spectroscopy to Energy-
and Environment-Related Nanomaterials 238
5.3.1 Mechanism of Bi Precipitation in
Environmentally Friendly Sn-Bi
Eutectic System 238
5.3.2 Densification Dynamics of
Gadolinium-Doped Ceria Upon
Sintering 245
5.3.3 Formation Mechanism of Biogenic
Silica Quartz in the Steady-State
Environment 252
5.3.4 Elemental Migration in Geological
Environment 261
5.4 Conclusion 267

6. Graphene: A New Star Nanomaterial in Energy

and Environment Applications 273
Jiayi Zhu and Junhui He
6.1 Introduction 273
6.2 Preparations of Graphene-Based Materials 275
6.2.1 Graphene 275
6.2.2 Graphene-Based Thin Films 278
6.2.3 Graphene-Based Composites 280
6.3 Applications of Graphene-Based Materials
in Energy and Environment-Related Systems 281
6.3.1 Solar Cells 281
6.3.1.1 Thin film solar cells 282
 Contents xi

6.3.1.2 Dye sensitized solar cells 286

6.3.1.3 Heterojunction solar cells 288
6.3.2 Supercapacitors 289
6.3.3 Photo-Catalysts for Reduction of
CO2 and Degradation of Organic
Pollutants 293
6.4 Conclusion and Outlook 294

7. Recent Advances in Synthesis and Applications

of Metal-Added Carbon Nanotubes and Graphenes 307
K. P. Annamalai and Yousheng Tao
7.1 Introduction 307
7.2 Synthesis of Metal-Added Carbon
Nanotubes and Graphenes 309
7.2.1 Metal-Added Carbon Nanotubes 309
7.2.2 Metal-Added Graphene 313
7.3 Applications of Metal-Added Carbon
Nanotubes and Graphenes 316
7.3.1 Hydrogen Adsorption 316
7.3.2 Electrochemical Energy Storage 319
7.3.2.1 Applications in Li-ion
battery 319
7.3.2.2 Applications in
Supercapacitors 322
7.3.3 Catalysis for Flue Gas 323
7.3.4 Other Applications 325
7.4 Conclusion and Outlook 325

8. Roles of Reduced Graphene Oxide in Improving

Photocatalytic Hydrogen Generation Performance
over Metal Sulphide Nanocomposites 331
Jian Ru Gong
8.1 Introduction 331
8.2 RGO/Metal Sulphides for Photocatalytic
Hydrogen Generation 334
8.2.1 RGO/CdS Nanocomposites 334
8.2.2 RGO-ZnxCd1-xS Nanocomposites 344
8.3 Perspectives and Challenges 358
xii Contents

9. Micro/Nanostructured Materials and Their Structurally

Enhanced Performances for Environment 369
Xianbiao Wang, Weiping Cai, and Guozhong Wang
9.1 Introduction 369
9.2 Mass Production of Novel
Micro/Nanostructured Materials 370
9.2.1 Solvothermal/Hydrothermal Method 371
9.2.1.1 Novel micro/
nanostructured ZnO 371
9.2.1.2 Micro/nanostructured
porous Fe3O4 nanofibers 376
9.2.1.3 Tremella-like micro/
nanostructured Fe3S4/C
composites 379
9.2.2 Template-Etching Strategy 382
9.2.2.1 Magnesium silicate hollow
microspheres 383
9.2.2.2 Copper silicate hollow
microspheres 386
9.2.2.3 Hierarchical SiO2@γ-AlOOH
microspheres 388
9.2.2.4 Nobel-metal/ZnO hollow
nanospheres 390
9.2.3 Electrospinning Method 392
9.3 Structurally Enhanced Photocatalystic
Properties 395
9.3.1 Honeycomb-Like Micro/
Nanostructured ZnO 395
9.3.2 Nobel Metal/ZnO Hollow Nanospheres 398
9.4 Structurally Enhanced and Selective
Adsorption Performances 399
9.4.1 Micro/Nanostructured Porous
ZnO Plates 399
9.4.2 Removal of Organic Cationic
Pollutants 402
9.4.3 Removal of Anionic Pollutants 405
9.4.4 Removal of Hydrophobic Organic
Pollutants 406
9.5 Conclusion and Outlook 407
 Contents xiii

10. Utilization of Biological Polysaccharides as

Eco-Friendly Structural Materials 413
Mineo Hashizume and Kazutoshi Iijima
10.1 Introduction 413
10.2 Classification of Polysaccharides 414
10.2.1 Structural Polysaccharides 414
10.2.2 Reserve Polysaccharides 414
10.2.3 Other Polysaccharides 415
10.3 Polysaccharides as Non-Structural Materials 416
10.3.1 Industrial Applications 416
10.3.2 Biomedical and Biochemical
Applications 416
10.4 Structural Materials Made of Structural
Polysaccharides 418
10.4.1 Cellulose and Its Derivatives 419
10.4.2 Chitin and Chitosan 420
10.5 Structural Materials Made of Non-Structural
Polysaccharides 421
10.5.1 Bulk Materials and Hydrogels 421
10.5.2 Films, Coatings, and Fibers 422
10.6 Conclusion 424

11. Catalysts for Indoor Formaldehyde Control 429

Hua Tian and Junhui He
11.1 Introduction 429
11.2 Photocatalysts 430
11.3 Transition Metal Oxide Catalysts 434
11.3.1 Ceria Oxide 435
11.3.2 Manganese Oxide 435
11.3.2.1 Brief introduction to
manganese oxide 435
11.3.2.2 Effects of nanostructure,
surface area, and morphology 437
11.3.2.3 Supported manganese oxide 442
11.4 Supported Noble Metal Catalysts 444
11.4.1 Noble Metal Catalysts 444
11.4.2 Effect of support nature 446
11.4.3 Effect of Operating Parameters of
Formaldehyde Oxidation 450
xiv Contents

11.4.4 Reaction Mechanism 453

11.5 Conclusion and Outlook 455

12. Nanostructured Copper Oxide for Sensing Hydrogen

Cyanide Gas 461
Mingqing Yang and Junhui He
12.1 Introduction 461
12.2 Nanostructures of CuO 464
12.3 Sensing Properties of CuO-Functionalized
QCM Sensors 468
12.4 Sensing Mechanism of CuO-Functionalized
QCM Sensors 472
12.5 Conclusion and Outlook 474

13. Nanomaterials and Health 481

Wenjun Ding and Jieting Wang
13.1 Introduction 481
13.2 Nanomaterials 482
13.2.1 Carbon-Based Nanomaterials 482
13.2.1.1 Fullerenes (C60) 482
13.2.1.2 Carbon nanotubes
(SWNTs and MWNTs) 486
13.2.2 Metal Oxide Nanoparticles 492
13.2.2.1 Zinc oxide nanoparticles
(ZnO NPs) 492
13.2.2.2 Titanium nanoparticles
(TiO2 NPs) 507
13.3 Conclusion and Outlook 511

Index 523
 Contents xv

Preface

Nanoscience and nanotechnology are interdisciplinary fields that

bring together physicists, chemists, materials scientists, biochemists,
and engineers to meet current and potential future challenges that
humankind faces, including searching for renewable energies for
sustainable development and new technologies for carbon capture
and environmental protection. Among the current subjects in
nanoscience and nanotechnology, nanomaterials are developing
fast and explosively and attract a huge amount of attention. They
have recently shown emerging applications and continue to show
promising potentials in technologies such as solar cells, fuel cells,
secondary batteries, supercapacitors, air and water purification, and
removal of both domestic and outdoor air pollutants. The application
of nanomaterials has also drawn attention to their effects on human
health. This book invited experts in the fields of nanomaterials,
energy, and environmental science and assembled 13 reviews that
discuss the design and fabrication of nanostructured materials and
their energy and environmental applications.
This is the first book that summarizes the very recent efforts
through nanoscience and technology towards meeting the pressing
energy and environmental challenges that human beings are facing.
It also points out future directions of nanomaterial development and
encourages future efforts, especially by the younger generation.
Finally, I would like to take this opportunity to acknowledge all the
authors who had spent their precious time in preparing their great
contributions to the book. I would also like to thank Dr. Mingqing
Yang, who contributed a lot to the communication with the authors
and preparation and publication of the book. I am very grateful to
Pan Stanford Publishing for providing me an opportunity to publish
this book. I hope that the readers will find the contents both useful
and enjoyable.
Junhui He
Beijing
June 2016
Chapter 1

Multifunctional Coatings for Solar

Energy Applications

Lin Yaoa,b and Junhui Hea

aFunctional Nanomaterials Laboratory and Key Laboratory of
Photochemical Conversion and Optoelectronic Materials,
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences,
Zhongguancundonglu 29, Haidianqu, Beijing 100190, China
bUniversity of Chinese Academy of Sciences, Beijing 100049, China

jhhe@mail.ipc.ac.cn

1.1 Introduction
Transparent surface coatings with suitable optical path differences
can suppress the reflection of substrates. Such coatings are usually
called “antireflective coatings (ARCs).” Many antireflective surfaces
exist in nature. Taking some diurnal butterflies as an example, they use
arrays of nonclose-packed nipples (about 300 nm) as antireflective
structure (ARS) to reduce reflection from their compound eyes [1,2].
The ARS on the cornea can increase light transmission and suppress
reflection losses at the interfaces. Besides these excellent optical
properties, the ARS arrays also exhibit self-cleaning capability
because of the high fraction of air trapped between arrays [3,4].

Nanomaterials in Energy and Environmental Applications

Edited by Junhui He
Copyright © 2016 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4463-78-2 (Hardcover), 978-981- 4463-79-9 (eBook)
www.panstanford.com
2 Multifunctional Coatings for Solar Energy Applications

The antireflection phenomenon provides enormous inspirations

for scientists to mimic for many important applications. Antireflection
technology has been widely used in some high-precision optical
components, solar cells, flat panel displays, and light-emitting di-
ode lighting to increase the transmittance of incident light [5–8].
For solar cells, due to reflection at the air–glass interface of the pack-
aging glass and scattering by accumulated dust on outdoor panels,
part of incident energy on solar modules is lost. On the one hand,
ARC on the glass can help alleviate reflection in systems; on the
other hand, the self-cleaning property can, to some extent, solve the
dust accumulation problem [5]. Tseng et al. systematically studied
the antireflection and light trapping effects. Their results showed a
76.9% enhancement of short-circuit current density compared with
that of bare silicon due to suppression of surface reflection [9].
It is common knowledge that smooth surfaces shine more
than rough ones. It contains the very basic idea of antireflection
that roughness is necessary to reduce reflection of surfaces. The
reflection or optical disturbance will be zero if the medium for light
propagation does not change or if the two media have the same
refractive index (RI) [10]. Therefore, many materials with micro/
nanostructure are perspective to fabricate ARC, including silicon,
silica, titania, zirconia, zinc oxide, cobalt oxide, tin oxide, carbon, and
poly(ethylene terephthalate) (PET), polystyrene (PS), gallium nitride
[11–17]. To date, two kinds of approach are available for fabricating
ARCs. One is coating porous or multilayered films on the surface of
devices, and the other is fabricating sub-wavelength ARS directly
on the substrate [18–21]. The corresponding fabrication routes can
be classified into bottom-up and top-down modes. The bottom-up
technique usually uses nanoparticles as building block to form ARCs.
The top-down approach relies on etching or lithography and so on
techniques performed with or without masks. Recently, the two-step
method with a combination of top-down and bottom-up approaches
also attracts much attention [11].
When contamination or fogging occurs on ARCs, however, their
optical properties would dramatically deteriorate. Contaminants
accumulate and water molecules condense on the surface, leading
to scattering and reflection of light. This problem may be solved by
creation of a surface that has special wettability (superhydrophilicity
or superhydrophobicity) and photocatalytic property. ARCs with
 Theoretical Aspects of Antireflection and Self-Cleaning 3

self-cleaning property have developed rapidly in recent years from

window glass to various devices [22].
In this review, we aim to provide recent developments in
antireflective and self-cleaning surfaces, with particular emphasis
on silicon and fused silica materials, as they are both commonly
used in many functional devices. The current review is composed
of four sections. In the first section, the basic concept and principle
of antireflection and self-cleaning are briefly described. In the
following section, the fabrication pathways and their mechanisms
are discussed. Then, we introduce the latest typical progress in self-
cleaning ARCs in recent 5 years. In the last section, some applications
of the self-cleaning ARCs surfaces are introduced. A large number
of research articles have reported the fabrication of ARCs or
superhydrophobic/superhydrophilic surfaces within the past few
years. This paper intends to give readers both an integrated tour
of antireflective and self-cleaning coatings fabrication technologies
and a basic realization of their great application prospects.

1.2 Theoretical Aspects of Antireflection and

Self-Cleaning

1.2.1 Principle of Antireflection

1.2.1.1 Basic concept of antireflection
ARCs can effectively enhance the transmission of light. The Fresnel
equation offers the basic mathematical model of the reflection
of coatings [23]. We learn that RI that quantifies the speed of
light in the current medium with respect to that in vacuum is the
major parameter for characterizing the transmission of light in the
medium.
For single-layer coatings, the Fresnel equation, which offers the
basic preliminary mathematical model of reflection and refraction,
has the following two assumptions:
(1) The reflected waves have the same intensity and one wave is
reflected per interface;
(2) Other optical interactions such as scattering, absorption, and
so on are negligible.
4 Multifunctional Coatings for Solar Energy Applications

As illustrated in Fig. 1.1a, there would be no reflection if there is

a destructive interference between light reflected from the coating-
substrate and the air-coating interfaces. Therefore, nc for an ideal
homogeneous ARC has to meet the following two conditions:
(1) nc = (nans)1/2, where na and ns are the refractive indices of the
air and the substrate, respectively.
(2) d = λ/4nc, d is the thickness of the coating, λ is the wavelength
of the incident light.
On the basis of the Fresnel’s theory, the antireflection property
is also dependent on the s and p-polarization of the light [23]. The
s-polarization and p-polarization have the electric field perpendicu-
lar and parallel to the incidence plane, respectively. Sunlight shows
appreciable degree of polarization when light reflects at shallow an-
gles due to the fact that light reflecting at shallow angles has the p-
polarized light reflecting to the maximum.

R
0 1 R 1 2
R
23
R
34
R 2

d
n
substrate
3

Figure 1.1 Propagation of light rays through (a) a single-layer coating and
(b) multi-layer coating on substrate (ns > nn, where ns and nn are
the refractive indices of substrate and coatings, respectively)
[4]. Copyright 2014 Elsevier.

For multi-layer coatings, the mathematical model has some

differences. As shown in Fig. 1.1b, the reflected light from the
interface ij between the adjacent layers i and j is [24]:
Rij = |Rmn| exp [−2(δi + δj)]
in which, |Rmn| = [(ni − nj)/(ni + nj)], δi = 2πnidicosθi/λ (θi is the angle
of refraction, di is the physical thickness of the layer)
For the entire coating:
Rsum = R01 + R12 + R23 +…+ Rns
 Theoretical Aspects of Antireflection and Self-Cleaning 5

By adjusting the reflective index and the thickness of each layer,

a minimum Rsum can be obtained, and an ARC can be achieved.
In recent years, gradient-RI ARCs have received great
attention. Different profiles for gradient-RI layers, including linear,
parabolic, cubic, Gaussian, quintic, exponential, exponential-
sine, and Klopfenstein, have been investigated for broadband
and omnidirectional ARCs [25–27]. Typical expressions for the
continuous gradient-RI with linear, cubic, and quintic profiles are
presented below [28]:
Linear index profile: n = no + (ns – no)t, 0 ≤ t ≤ 1
Cubic index profile: n = no + (ns – no)(3t2 –2t3)
Quintic index profile: n = no + (ns – no)t(10t3 – 15t4 + 6t5)
where no and ns are the RIs of the incident and substrate media,
respectively, and t is the thickness of graded interface region.
Assembling a multilayer heterostructure that has a suited gradient-
RI profile is beneficial to obtained AR properties within a wide range
of wavelength.

1.2.1.2 Strategies to achieve antireflection

From the above discussion, we know that the antireflection prop-
erty is obtained when n of a single-layer coating is (nairns)1/2. As
for a glass substrate (ns =1.5), n of ARCs materials should be 1.22.
Unfortunately, natural materials having such a low RI are rare and
expensive to obtain. Some insect compound eyes (such as moth
eyes, fly eyes) present excellent optical and other properties (high
sensitivity, antireflection, and anti-fogging) because of their unique
multi-scale structures (Fig. 1.2) [29–31], which inspired continuous
efforts of scientists to introduce nanopores into coatings. They imi-
tated compound eyes to fabricate a periodic array of silicon nanotips
with a sub-wavelength structure that can suppress the reflection
from the ultraviolet, through the visible part of the spectrum, to the
terahertz region [32].
Subsequently, the introduction of nanopores becomes an
effective method to obtain appropriate RI, and by controlling the
quantity and volume of introduced nanopores, the RI of coatings can
be well tailored. There are also three requirements, which have to
be considered for fabricating an ideal ARC. First, the antireflection
6 Multifunctional Coatings for Solar Energy Applications

property must be maintained over a broad spectrum of wavelength

of the incident light in the ultraviolet, visible, and infrared regions.
Second, as some coatings need to be oriented to the sun throughout
the day, omni-directional antireflection is highly desired. Third, for
practical applications, the coatings should be mechanically robust.

Figure 1.2 (a) A photograph of antireflective and antifogging mosquito

eyes. (b) A SEM image of a single mosquito eye. (c) Two
neighboring ommatidia. (d) Hexagonally nonclose-packed
nanonipples covering an ommatidial surface [31]. Copyright
2007 Wiley-VCH.

It is important to distinguish between ARC and antiglare coating

(AGC). Glare is a type of light distortion commonly encountered
in our daily life. Discomfort glare reduces the contrast of visibility
of the object, while intense glare can lead to temporary vision
impairment [33]. For instance, when mineral glass is used for glazing
of paintings, the optical appearance of the painting is disturbed by
unwanted reflections, which are enhanced by bright daylight or
artificial illumination [34]. Therefore, different from ARCs, AGCs are
applied to decrease the glare caused by reflecting light coherently
from external light source in the environments. Adjustable gloss, low
haze, and good clarity are considered as important criteria for AGCs
performance [35–37].
 Theoretical Aspects of Antireflection and Self-Cleaning 7

1.2.2 Principle of Self-Cleaning

1.2.2.1 Special wettability induced self-cleaning

Wettability is an important property of a solid surface, and contact
angle (θ) has been commonly used to characterize the surface
wettability.
For a perfectly smooth and chemically homogeneous solid
surface, the contact angle of liquid is given by Young’s equation
[38]:
cosθ = (γSV – γSL) / γLV
where γSV, γSL, and γLV are the interfacial tensions of the solid–vapor,
solid–liquid, and liquid–vapor interfaces, respectively (Fig. 1.3a).
For a realistic solid surface that is rough and chemically
heterogeneous, the early theoretical works about its contact angle
were done by Wenzel and Cassie-Baxter.
I. Wenzel’s equation [39]
In the model developed by Wenzel, liquid completely penetrates
into the roughness grooves (Fig. 1.3b). The Wenzel’s equation
is:
cosθw = rcosθ
where θw is the contact angle on a rough surface, θ is the
Young’s contact angle on a similar smooth surface, and r is
the surface roughness factor, defined as the ratio of the actual
surface area to the projected surface area (for a perfectly
smooth surface: r = 1, and for a rough surface: r > 1).
The above equation points out that when θ is less than 90°,
the wetting could be enhanced by r; when θ is more than 90°,
the wetting is lessened by r.
II. Cassie-Baxter equation [40]
The Cassie-Baxter state considers that under some roughness
conditions, air bubbles may be trapped when θ is greater than
90° (Fig. 1.3c). In this case, the liquid-surface interface actually
consists of two phases, that is, the liquid–solid interface
and the liquid–vapor interface, respectively. Therefore, the
apparent contact angle is the sum of all the contributions of
the different phases:
cosθc = f1 cosθ1 + f2 cosθ2
8 Multifunctional Coatings for Solar Energy Applications

where θc is the apparent contact angle, f1 and f2 are the surface

fractions of phase 1 and phase 2, respectively; θ1 and θ2 are
the contact angles on phase 1 and phase 2, respectively.
If one of the surfaces is the air-liquid interface and f is defined
as the fraction of the solid surface that is wetted by the liquid,
the air fraction can be expressed as (1−f). With θ = 180° for air,
the resulting apparent contact angle can be calculated by the
following equation:
cosθc = f cosθ + (1−f ) cos180° = f cosθ + f − 1

a b c
7i.v

e
7sv

Figure 1.3 (a) A liquid droplet on a smooth surface. (b) A liquid droplet
in the Wenzel state. (c) A liquid droplet in the Cassie state [4].
Copyright 2014 Elsevier.

In the above equations, the contact angles are all static. However,
owing to chemical heterogeneity, surface roughness, and surface
reorganization, different contact angles can coexist along the contact
line upon contact with probe liquid [41]. As shown in Fig. 1.4a, the
contact angle of the droplet at the front is greater than that at the
back, and they correspond to the advancing and receding contact
angle, respectively. The difference between the advancing and
receding contact angles is defined as the contact angle hysteresis,
which is a measurement of how well a drop of liquid sticks to the
solid surface (Fig. 1.4b).

a b

ÔRec
•§Adv

Figure 1.4 (a) Schematic illustration of contact angle hysteresis on a tilted

surface, (b) advancing and receding contact angles on a flat
surface via increasing and decreasing the volume of droplet,
respectively [4]. Copyright 2014 Elsevier.
 Theoretical Aspects of Antireflection and Self-Cleaning 9

There are two kinds of surface with special wettability: super-

hydrophobic surface (water contact angle WCA > 150° and low con-
tact angle hysteresis) and superhydrophilic surface (water contact
angle <5° within 0.5 s or less). A self-cleaning superhydrophobic
surface should always have a low contact angle hysteresis. The leaf
of the lotus plant is a representative model for superhydrophobic
and self-cleaning surface. Due to the papillose epidermal cells cov-
ered with wax crystals (Fig. 1.5a), the leaf surface is very rough and
water-repelling. Therefore, water droplets on the surface are in the
Cassie-Baxter state, making them highly spherical and be able to roll
off easily. Usually, contaminants are larger than the cellular structure
of the leaves, leaving the particles resting on the tips of the surface
structure. When a water droplet rolls over the contaminants, dirt
particles are adsorbed to the water droplet and moved away from
the surface (Fig. 1.5b). On such intrinsic hierarchically structured
surfaces, both the contact area and adhesion to the surface are dra-
matically reduced.

R b

Figure 1.5 (a) SEM image of lotus leaf showing epidermal cells, and (b)
diagram showing the self-cleaning process on a rough surface
[42]. Copyright 2005 American Chemical Society.

Moreover, special wettability also endows the surfaces with

antifogging function. Fogging occurs when water vapor condenses on
the surface owing to temporary changes in humidity, temperature, or
convection [43]. If the surface has a rather low contact angle, it could
form a continuous or near-continuous film, scattering is suppressed,
10 Multifunctional Coatings for Solar Energy Applications

and optical transmission is enhanced. On the contrary, if the surface

has a quite high contact angle and low contact angle hysteresis,
the droplets may slide from the surface rapidly. Fog may thus be
difficult to cover the surface. Superhydrophobic or superhydrophilic
coatings are in line with the above requirements and have shown
good prospects for practical applications [22].

1.2.2.2 Photocatalysis-induced self-cleaning

Since Frank and Bard first discovered that TiO2 can decompose
cyanide in water in 1977 [44], TiO2 has been an ideal photocatalyst in
decomposing organic contamination for environmental applications.
TiO2 has a strong oxidation power under UV illumination, and various
organics accumulating on TiO2 thin films could be oxidized into CO2,
H2O, NO3-, or other simple basic products [45–47]. Moreover, under
UV illumination, the surface of TiO2 becomes superhydrophilic with a
water contact angle close to 0°, making the surface easily cleaned by
water. Due to these two characteristics, TiO2-coated substrates can
achieve outstanding self-cleaning property when they are exposed
outdoor, as shown in Fig. 1.6.

light light
a b

co 2

Figure 1.6 Schematic diagram of the decontamination process occurring

on TiO2-coated substrates. (a) Photocatalyic degradation of
organics. (b) Removal of contaminants by water sheet due to
the superhydrophilicity of TiO2 surface [4]. copyright 2014
Elsevier.
 Theoretical Aspects of Antireflection and Self-Cleaning 11

Mechanism of photocatalysis
The redox potential for TiO2 photo-generated holes is +2.53 V,
which can produce hydroxyl radicals (·OH). The redox potential
for conduction band electrons is –0.52 V, which is enough to
reduce dioxygen to superoxide, or to hydrogen peroxide [48]. The
basic processes for an electron-hole pair reducing or oxidizing an
adsorbate and forming a singly oxidized electron donor and singly
reduced electron acceptor can be summarized as Fig. 1.7 [49].
lu­

+0

(al ,0
lui
* +
o
D+

(h)
If) + RH-> R*+ H=
hu++
0 hu++
+ fU) > 'OH + H*
A id)
eu+ 0 ,-> O2 hu++O2 -> 'o.
+0
eu H2O2-> -••OH.
eu + R +H* -> RH
#
+ 0H
E
A

Figure 1.7 The processes occurring on bare TiO2 particle after UV

excitation [49]. Copyright 2008 Elsevier B.V.

Previous results have shown that many liquid and solid organic
compounds can be photocatalytically decomposed into nontoxic gas-
phase products. The decomposition of organic compounds (alkanes,
alcohols, ketones, carboxylic acids, and so on) can be summarized
as Scheme 1.1 with alcohols as an example [50,51]. As reported by
Schwitzgebel et al. [52], long-chain organic compounds (e.g., C16
and C17 acids) and even polymers can also be decomposed by chains
breaking.

RCH2COOH + h+ (·OH) Æ RCH2· + CO2 + H+ (H2O)

RCH2· + O2 Æ RCH2OO·
RCH2OO· + ·OOH Æ RCH2OOOOH
RCH2OOOOH Æ RCHO + O2 + H2O
Scheme 1.1 Processes proposed for decomposition of organic compounds,
for example, alcohols, on the surface of TiO2 [50].
12 Multifunctional Coatings for Solar Energy Applications

Mechanism of photo-induced superhydrophilicity

TiO2 surface becomes superhydrophilic via UV light irradiation;
however, the reduced WCA gradually revert to origin WCA in the
dark. Fujishima’s group [48,49,53,54] proposed a mechanism for
photoinduced wettability conversion of TiO2 surface, which has been
widely accepted by scientists. The mechanism was proposed on the
basis of the reconstruction of surface hydroxyl groups under UV
irradiation in air. The density of surface hydroxyl groups is strongly
correlated with the reciprocal of WCA. As illustrated in Figs. 1.7 and
1.8, molecular oxygen captures the photoexcited electrons, while
the holes diffuse to the TiO2 surface, being trapped at lattice oxygen
atoms. Afterward, the hole weakens the binding energy between the
Ti atom and the lattice oxygen, and the bond is interrupted by one
adsorbed water molecule, forming new hydroxyl groups. In the dark
circumstance, the hydroxyl groups gradually desorb from the surface
in the form of H2O2 or H2O + O2. Compared with the OH groups bound
to oxygen vacancies, the OH groups produced by UV irradiation are
thermodynamically less stable because of the different desorption
temperature [53]. As a result, the reconstruction between the stable
OH groups and the thermodynamically metastable OH groups
changes the surface energy of the TiO2 and switches the surface
between superhydrophilicity and hydrophobicity.

-o
Ti Ti:
c H H
O O

hv(h )
+
_1/2H2O2
or
ÎTl' Ti;
H
- ( Í H 0 + Í0 )
2 2
o
b
•O
Ti (h, )+
Ti
O

Figure 1.8 Surface structural models for the TiO2 surface. (a) (Before UV
irradiation) the OH group is bound to oxygen vacancy, (b) (at
the transition state) the photogenerated hole is trapped at the
lattice oxygen, and (c) (after UV irradiation) new OH groups
are formed [53]. Copyright 2003 American Chemical Society.
 Fabrication Strategies and Methods 13

1.3 Fabrication Strategies and Methods

For nearly two centuries, researchers have been seeking novel
methods to increase light transmission in optical systems as well
as to eliminate unwanted reflection. Meanwhile, self-cleaning
surfaces in nature have also attracted more and more attention
of scientists due to their unique properties. The technology of
fabricating antireflective surfaces with highly efficient and durable
self-cleaning properties has an extensive range of applications from
glasses, displays, and solar panels to window optical lenses. Different
chemical and physical methods for fabricating ARCs and how to
form rough surfaces with special surface energy are discussed in the
following section.

1.3.1 Fabrication of Antireflective Surfaces

ARCs are a basic way to increase light transmission. Varied methods
have been used to generate ARCs, which can be classified into both
bottom-up and top-down approaches. Accurate control over the
morphology of ARCs is crucial in order to achieve ideal antireflective
surfaces. The techniques combining both bottom-up and top-down
approaches may pave an effective way toward making the dream of
application in industry come true.

1.3.1.1 Materials perspective for antireflectivity

(1) Silicon based
Fabrication of antireflective layers on silicon surfaces has at-
tracted much attention since the 1980s to effectively improve
the efficiency of silicon solar cells, both in first-generation
photovoltaic cells based on bulk materials and second-gener-
ation structures based on thin films [55–60]. Silicon has been
explored in almost all types of ARCs, starting from porous
silicon on solar cells to Moth’s eye inspired biomimetic struc-
tures and silicon nanotips [23]. For instance, Hong’s group
[61] developed a self-masking reactive ion etching process for
fabricating the large-area (15 × 15 cm2) antireflective silicon
surface by creating a high density of nano-pyramids on the
surface. Large-area poly-crystalline silicon surfaces with low
reflectance (<2%) and high uniformity could be reproducibly
Another random document with
no related content on Scribd:
 A brightly lighted window was open, around which
grew a honeysuckle. Up the vine ran Teenie Weenie,
closely followed by Nibbles, and, sitting on the
windowsill, they looked into a beautiful room.

On a long table there were numbers of lighted

candles in high silver candle-sticks, and never had
Nibbles seen such wonderful things to eat,—nuts and
raisins, figs and dates, oranges and grapes, cakes
and candy.

In a moment, Teenie Weenie and Nibbles had run

across the room and jumped up on the table. Nibbles
tried first one thing and then another, each tasting
better than the last.

Suddenly Teenie Weenie gave a little gasp of

terror, which startled Nibbles so that he nearly fell
into a finger-bowl.
 “What is the matter, Teenie?” he asked, rather
crossly, for in his fright he had dropped a particularly
nice bit of cake on the floor.
“The Cat,” whispered Teenie Weenie, in a terrified
voice.

Nibbles looked around,

and suddenly he saw, in a
chair close by, a big gray and
white animal, which was
evidently just waking up, and
was stretching itself and
yawning. Such terrible teeth
and sharp claws as it had!

While Nibbles gazed at it, too frightened to move,

the Cat turned around, and its green eyes glared as it
saw the two trembling little mice.
 Before the sleepy Cat could jump on the table
however, Nibbles and Teenie Weenie were on the
floor, and an instant later they were fairly tumbling
out of the window into the garden. Down the village
street they ran, and never stopped until they were
safe in the open country once more.

“Well,” said Nibbles, “I have never seen a Cat

before, and I sincerely hope that I never may again.
You may live in a village if you like, Teenie Weenie,
but I prefer the quiet woods.”
 Chapter V

Down the River

They traveled on for several days, close to the river,

until Nibbles suggested that it would be more fun and
easier to sail than to walk.

They at once began to make a little raft with willow

twigs and bits of birch bark, and to prevent the water
coming through, they filled up the cracks with clay.
The big bandanna handkerchief they used as a sail,
and with his jack-knife Nibbles whittled out a nice
little rudder.

One warm, sunny day, they hoisted their sail and

were just starting off, when they heard some one
shouting. Looking around, they saw, on the bank
above them, a big gray Rat, waving his hat and
calling: “Wait a minute, and take me with you.”

“I am very sorry,” answered Nibbles, “but the raft is

small and there is not room enough.”

“But I will go,” shouted the Water Rat very rudely,

“and I am in a hurry too.”

Poor Teenie Weenie was frightened, for she knew

that Water Rats sometimes ate mice, especially if
they were cross or very hungry, so she begged
Nibbles not to go near the shore.

As they sailed away, the Water Rat, I regret to say,

danced with rage, making frightful faces at Nibbles
and Teenie Weenie, and saying things which were
not at all polite.
 Day after day they sailed down the winding river,
sometimes landing for dinner, and at night always
tying their raft to a tree or bush in some sheltered
cove, where they could find a comfortable nest to
sleep in.
 One afternoon they came to a pretty wood, where
they decided to spend the night. Near the bank was a
dark, gravelly point, which seemed an excellent place
to land. Nibbles got out, and was just beginning to
pull the raft up high and dry, when suddenly the
whole point began to move, and then something
struck poor Nibbles, and sent him whizzing far out
into the river.

Down down, down he sank, until he felt sure that

he was going through to China. His head was buried
in the soft sand at the bottom of the river, and he had
to struggle hard to free himself. Finally he came up to
the surface of the water, and was able to swim to the
raft, where little Teenie Weenie still sat, too terrified to
move.
 Chapter VI

Mr. Scratchetty-Claw

Floating on the water, so near the raft that he could

have touched it, Nibbles saw a huge animal covered
with brown scales. It had small black eyes, and a
long tail, while its head was mostly made up of a very
long nose, and a huge mouth full of sharp teeth.
“Hullo!” said the Animal, “I thought you were never
coming up. What kept you so long under the water?”

Poor Nibbles was dripping wet, covered with sand,

and still gasping for breath, but he tried to answer
politely:

“I could not come up any sooner, Sir, because my

head was stuck in the sand. Will you please tell me
what you are? I thought you were a landing place.”

“No, no,” replied the Animal, “my name is

Scratchetty-Claw, and I am an Alligator of a very fine
old family. I have lived in this river for a hundred
years, and I probably shall live a thousand. I am very
sorry that I upset you, but I thought a fly had lighted
on my back, so I swished my tail, and I am afraid that
you rolled off.”

“I certainly did,” said Nibbles sadly, as he tried to

wipe the sand out of his eyes and ears.
 Suddenly Mr. Scratchetty-Claw opened his eyes
very wide, and staring at Nibbles, he shouted:

“Why, what have you got around your neck?”

Nibbles put up his paw, and, sure enough, there

was something which felt like a ring. How it came
there he could not imagine, but he must have pushed
his head through it while he was floundering in the
sand at the bottom of the river.
 Teenie Weenie helped him pull it off, and when
they had brushed the sand away, they found that it
was a gold ring, beautifully carved, and set with
diamonds and rubies.

“That must surely be the Lucky Ring of the foreign

Prince, who owns all this part of the country,” said the
Alligator. “He lost it one day last summer, while out
sailing, and nobody was able to find it. The Prince
offered a big reward for its recovery, as he prized the
ring more than anything he owned.”

“Then we must take it to him as soon as we can,”

said Nibbles.
 Chapter VII

The Lucky Ring

The next morning Nibbles asked Mr. Scratchetty-

Claw where the Prince lived.
“Just fasten your raft to my tail,” said the Alligator,
“and I’ll take you there before you know that you’ve
started. Only wait until I get my shade hat, as I don’t
like the sun in my eyes.”

“Please don’t go too fast, Mr. Scratchetty-Claw,”

said little Teenie Weenie, timidly, “or we might be
upset again.”
 Scratchetty-Claw promised to be very careful, and
after he had tied on his shade hat, and Nibbles had
fastened the raft to his tail, away they went.
The Prince’s beautiful garden was close to the
river, so when Nibbles and Teenie Weenie landed,
they soon found their way to his palace.

Nibbles had put the ring around his neck again for
safe keeping, but when he showed it to a footman in
the palace hall, he took Nibbles and Teenie Weenie
at once to the Prince, who was sitting in a lovely rose
arbor in the garden.