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Oxide-Based Materials and
Structures
Oxide-Based Materials and
Structures
Fundamentals and Applications
Edited by
Rada Savkina
Larysa Khomenkova
First edition published 2020
by CRC Press
6000 Broken Sound Parkway NW, Suite 300,
Boca Raton, FL 33487-2742
and by CRC Press
2 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN
© 2020 Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, LLC
International Standard Book Number-13: 978-0-367-25239-7 (Hardback)
International Standard Book Number-13: 978-0-429-28672-8 (eBook)
Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot
assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers
have attempted to trace the copyright holders of all material reproduced in this publication and apologize to
copyright holders if permission to publish in this form has not been obtained. If any copyright material has not
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Library of Congress Cataloging-in-Publication Data
Names: Khomenkova, Larysa, editor. | Savkina, Rada, editor.

Title: Oxide-based materials and structures : fundamentals and applications / edited by Larysa Khomenkova &
Rada Savkina.
Description: First edition. | Boca Raton : CRC Press, 2020. | Includes bibliographical references and index.
Identifiers: LCCN 2019059106 | ISBN 9780367252397 (hardback) | ISBN 9780429286728 (ebook)
Subjects: LCSH: Oxides. | Oxides–Surfaces. | Materials science.
Classification: LCC QD181.O1 O947 2020 | DDC 620.1/6–dc23
LC record available at https://lccn.loc.gov/2019059106
Visit the Taylor & Francis Web site at

www.taylorandfrancis.com
and the CRC Press Web site at
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Dedication
To our families for their endless love, guiding, and patience.

To our friends and colleagues for their kind support and friendly critics.
Contents
Preface ................................................................................................................................... ix
Acknowledgments.................................................................................................................. xi
Editors ................................................................................................................................. xiii
Contributors ..........................................................................................................................xv
Abbreviations ......................................................................................................................xvii
Chapter 1 Oxide-Based Materials and Structures: General Remarks....................................1

Rada Savkina and Larysa Khomenkova
Chapter 2 Optical Characterization of Oxide-Based Materials Using Ellipsometry..............5

Peter Petrik
Chapter 3 Electrical Characterization of Oxide-Based Materials Using Impedance

Spectroscopy ......................................................................................................31
Aleksej Smirnov
Chapter 4 Analytical Techniques for Characterization of Oxide-Based Materials ..............75

Iraida N. Demchenko
Chapter 5 Low-Dimensional Structures of In2O3, SnO2 and TiO2 with Applications

of Technological Interest ....................................................................................99
Javier Bartolomé, María Taeño, Antonio Vázquez-López, Félix del Prado,
Miguel García-Tecedor, G. Cristian Vásquez, Julio Ramírez-Castellanos,
Ana Cremades, and David Maestre
Chapter 6 Transition Metal Oxides for Magnetic and Energy Applications......................137

Rada Savkina and Aleksej Smirnov
Chapter 7 Phonon and Plasmon–Phonon Interactions in ZnO Single Crystals and

Thin Films........................................................................................................163
Oleksandr Melnichuk, Lyudmyla Melnichuk, and Evgen Venger
Chapter 8 Zinc Oxide Grown by Atomic Layer Deposition: A Versatile Material

for Microelectronics .........................................................................................201
Elżbieta Guziewicz
Chapter 9 Wide and Ultrawide Bandgap Oxides for Photovoltaics and Photonics ...........229
Larysa Khomenkova
Index....................................................................................................................................245
vii
Preface
Oxide materials are becoming of increasing interest due to their potential applications in
advanced nanodevices and nanosystems toward energy, environmental, and sensing sectors.
As we know, oxide materials can be conductive, semiconductive, or dielectric, as well as
they can exhibit magnetic or multiferroic properties. They are used in field effect devices,
capacitors for nonvolatile memories, transparent electronics, tunable devices for wireless
communications, photocatalysis and environment protection, and so on. This book provides
a review of the original works and the patents received over the last years.
This book covers a wide range of materials, techniques, and approaches that could be
interesting for both experienced researchers and young scientists.
This book consists of nine chapters. Each of them is written individually. Chapter 1 con-
cerns general considerations of the oxide-based materials and some important fields of their
application. Chapter 2 focuses on the optical modeling of oxides and oxide-based structures
using spectroscopic ellipsometry. The parameterization of the dielectric function is discussed
for single-phase and composite multilayer materials, as well as for the vertical, lateral, and
optical anisotropy. Modeling of low-dimensional oxide structures such as nanotubes and
nanodots embedded in oxides is also presented. Some applications of these materials in
optical sensing are also mentioned in this chapter. Chapter 3 addresses the impedance spec-
troscopy of oxides and oxide-based structures. Chapter 4 gives an overview of the basic
principles and applications of synchrotron experimental methods for analyzing the local
environment of atoms and/or ions along with their electronic structure reorganization:
X-ray spectroscopy (including XAS, XES, and RIXS) and X-ray photoelectron spectros-
copy (including RPES).
Chapter 5 aims to review and highlight the recent developments and applications of low-
dimensional structures based on SnO2, TiO2, and In2O3. These wide-bandgap oxides have
attained growing attention during the last decade as they have become key materials in sev-
eral applications of technological interest including microelectronic, energy harvesting and
storage, optoelectronic, catalysis or gas sensing. However, challenges still remain in the
understanding of their fundamental properties and their functionalization in order to face
the advent of modern devices. In Chapter 6, the latest advances in the field of magnetic
properties and applications of transition metal oxides are discussed. In particular, an inter-
esting class of materials, known as magnetoelectric multiferroics, is considered. Isostructural
and isovalent iron and chromium oxides are the subjects of active experimental and theoret-
ical investigations. Recent advances in the use of transition metal oxides for water splitting
are presented.
The development of different express methods for the investigation of materials and struc-
tures is very important. Infrared spectroscopy, being one of the nondestructive, fast, and sen-
sitive methods, allows the investigation of vibrational properties of different materials. In
Chapter 7, main attention is paid to theoretical consideration of elementary excitations such
as surface polaritons and surface plasmon–phonon polaritons in anisotropic materials, as well
as to the effects of magnetic field on these collective interactions. An application of this
approach for the determination of electrophysical parameters of anisotropic materials is dem-
onstrated. As an example, undoped and doped ZnO single crystals and thin films are
addressed. It is shown that developed theoretical models can be implemented for the deter-
mination of the optical and electrophysical parameters of different anisotropic materials and,
especially, for textured thin films grown on semiconductor and dielectric substrates.
Given the increasing importance of atomic layer deposition in present semiconductor
industry, the basic objective of Chapter 8 is to highlight the versatility of zinc oxide grown
ix
x Preface
by this method. Depending on growth conditions, atomic layer deposition is able to provide
epitaxial or polycrystalline ZnO films with various orientations and diverse surface
morphologies.
Among the different oxide materials, Al2O3, HfO2, and ZrO2 as well as their silicates are
considered mainly as alternatives to SiO2 gate oxide and they are now mostly used in micro-
electronic devices. However, all these materials have unique optical and chemical properties.
Being doped with different ions, they can offer novel applications in light-emitting structures
and photovoltaic cells. In Chapter 9, some recent applications Al2O3, HfO2, and ZrO2
along with their silicates doped with rare-earth elements are presented.
We hope to present to the reader a recent survey of the topic of oxide-based composite
materials and structures as well as to depict the potential and broadness of the application
of such materials.
We would like to express our gratitude to all the contributors for their willingness to
share their experiences and in-depth insights into this field with the readers and for taking
the time off their schedules to write excellent chapters. We would also like to thank all our
current and former colleagues who helped and advised us in conducting some research
described in this book. Also, we are thankful to the staff of Taylor & Francis/CRC Press
who invited us to write this book and helped immensely in its preparation for publication.
Last but not least, we are extremely grateful to our families for their support, patience, and
understanding over the many busy years of our scientific career.

Acknowledgments
This book is a collective contribution of the authors from different countries: Hungary, Poland,
Spain, and Ukraine. The authors would like to acknowledge all the organizations that sup-
ported their research in different years. Among them are the National Research, Development
and Innovation Office of Hungary, the Polish National Science Centre, the Polish Academy of
Sciences, the Department of Chemistry of the University of Warsaw (Poland), the National
Academy of Sciences of Ukraine (NASU), the Ministry of Education and Science of Ukraine,
the French National Research Agency, the National Research Centre of France, and the
European Union Seventh Framework Programmeas well as the Ministry of Economy
and Competitiveness (MINECO), Spain. Most of the results described by the authors in their
chapters have been obtained while carrying out national and international projects such as:
• The project OTKA K131515 titled “Low-dimensional nanomaterials for the optical
sensing of organic molecules on liquid and gas interfaces” financed by the National
Research, Development and Innovation Office of Hungary;
• The project DEC-2018/07/B/ST3/03576 titled “Electrical conductivity and defect
clusters in zinc oxide formed as a result of intentional and unitentional doping”
financed by the Polish National Science Centre;
• Ukrainian–Polish joint research project “Characterization of the hybrid system of
the nanometric layers based on transition metals oxides useful for spintronic” (Pro-
ject # 23, 2018–2020) under the agreement on scientific cooperation between the
Polish Academy of Sciences and the National Academy of Sciences of Ukraine.
• The project “Affine sensor system based on ‘smart’ hybrid nanocomplexes for
determination of specific nucleic acid sequences” in the framework of target pro-
gramme of the NASU, “‘Intelligent’ sensor devices of a new generation based on
modern materials and technologies” (2018–2022, Ukraine);
• The project “Effect of the doping on structural, optical and electron-phonon prop-
erties and stability of anisotropic crystals” (No.: 89452, 2018–2020, Ukraine);
• The project “Development of technology and equipment for the creation of infrared,
THz and sub-THz radiation based on low-dimensional structures” in the framework of
the programme “Search and creation of promising semiconductor materials and func-
tional structures for nano- and optoelectronics” (No.: III-41-17, 2017–2022,Ukraine);
• The project “Study and nanoanalysis of irradiation effects group” within the “Invest-
ments for the Future Programme” and the “GENESIS EQUIPEX Programme”
(PIA, ANR, (ANR-11-EQPX-0020) and Normandy Region) (2014–2018, France);
• The project “High-k oxides doped with Si or Ge nanoclusters for microelectronic
and photonic applications” in the framework of the Ukrainian–French bilateral
programme “Dnipro”, 2015–2016 edition (Nos. M/115-2015 and M/27-2016
(Ukraine), No. 34820QH (France));
• The project “High-k dielectric structures with modulated architecture for non-
volatile memory application” in the framework of the Programme Investissements
d’Avenir (ANR-11-IDEX-0002-02; ANR-10-LABX-0037-NEXT) (2015, France);
• The project 008-ABELCM-2013, project MAT2015-65274-R, Project MAT2016-
81720-REDC, Project PCIN-2017-106, and RTI2018 -097195-B-100 supported by
NILS program EEA Grants/MINECO/FEDER/M-ERA.NET COFUND. M. T.
The FPI grant holder, M.T., thanks the financial support from MINECO. The
Postdoctoral “Atracción del talento” Grant holder, J.B., Thanks the financial sup-
port from the Comunidad de Madrid.
xi
xii Acknowledgments
• The European Union Seventh Framework Programme under Grant Agreement

312483 – ESTEEM2 (Integrated Infrastructure Initiative–I3) (2015, France)
• For the support via as well as for partial support of the scientific research. We also
acknowledge the support from Elettra Sincrotrone (Italy, project number 20150152)
and Helmholtz-Zentrum Dresden-Rossendorf (Germany) as well as Dr. Renata
Ratajczak of National Centre for Nuclear Research (Poland) and Dr. Yevgen Meli-
khov of Cardiff University (UK) for their invaluable help and insightful discussions
during RBS/XPS experiments and/or data interpretation.
Editors
Dr. Rada Savkina is senior staff researcher of V. Lashkaryov Institute of Semiconductor
Physics at National Academy of Sciences of Ukraine (Kyiv, Ukraine) as well as Associate
Professor of the Faculty of Natural Sciences at National University of “Kyiv-Mohyla Acad-
emy.” She obtained M.Sc. degree in Solid State Physics in 1993 from T. Shevchenko Kyiv
University; Ph.D. degree in Solid State Physics in 2002 and academic status of Senior
Researcher in Solid State Physics in 2013, both from V. Lashkaryov Institute of Semicon-
ductor Physics. She has gained valuable experience in developing new ideas from fundamen-
tal understanding to the manufacturing of multifunctional composite materials and devices
on their basis. She is an expert in the fabrication of materials by physical methods (laser
deposition, ion beam processing, and ultrasonic approach) as well as their characterization
with optical and electrical methods. She has elaborated infrared and terahertz detectors and
vision systems, which is covered by 5 patents. She has more than 70 papers in refereed jour-
nals and 2 book chapters in her name. She is a member of the editorial board of the inter-
national research journal “Recent Advances in Electrical & Electronic Engineering.” Her
novel field of activity concerns the elaboration of the concept of a new biocompatible
photovoltaic cell by sonochemical method. She is the editor of two books.
Dr. Larysa Khomenkova is senior staff researcher of V. Lashkaryov Institute of Semiconductor

Physics at National Academy of Sciences of Ukraine (Kyiv, Ukraine) as well as Associate
Professor of the Faculty of Natural Sciences at National University of “Kyiv-Mohyla Acad-
emy.” She obtained M.Sc. degree in Technology and Materials of Microelectronics in 1992
from T. Shevchenko Kyiv University; Ph.D. degree in Solid State Physics in 1999 and academic
status of Senior Researcher in Solid State Physics in 2003, both from V. Lashkaryov Institute of
Semiconductor Physics at National Academy of Sciences of Ukraine (Kyiv, Ukraine). Her
work is centered around the multifunctional composite materials, in particular their fabrication
with physical methods (solid state reaction, physical vapor deposition, and magnetron sputter-
ing) and materials’ characterization with optical, luminescent, and electrical methods. Her
interest is also focused on the elaboration of novel technological approaches for creation of
semiconductor and dielectric structures aiming at their photonic and microelectronic applica-
tions as well as on the instability and degradation phenomena in the devices. In addition, she
focuses on the materials for alternative energy sources as solid oxide fuel cells and hydrogen
storage. Novel field of her activity concerns the elaboration of the materials by atomic layer
deposition for photovoltaic and photonic applications. She is the author of more than 150
research papers and 4 book chapters, and also the editor of 4 books.
xiii
Contributors
Peter Petrik Miguel García-Tecedor
Institute of Technical Physics and Materials Departamento de Física de Materiales
Science Facultad de Ciencias Físicas
Centre for Energy Research Universidad Complutense de Madrid, Spain
Budapest, Hungary
Institute of Advanced Materials (INAM)
Ana Cremades Universitat Jaume I, Castelló
Departamento de Física de Materiales Madrid, Spain
Facultad de Ciencias Físicas
Universidad Complutense de Madrid G. Cristian Vásquez
Madrid, Spain Departamento de Física de Materiales
David Maestre Universidad Complutense de Madrid
Departamento de Física de Materiales Madrid, Spain
Universidad Complutense de Madrid Department of Physics
Madrid, Spain Centre for Materials Science and
Nanotechnology
Javier Bartolomé University of Oslo
Departamento de Física de Materiales Oslo, Norway
Universidad Complutense de Madrid Julio Ramírez-Castellanos
Madrid, Spain Departamento de Química Inorgánica
Facultad de Ciencias Químicas
María Taeño Universidad Complutense de Madrid
Departamento de Física de Materiales
Facultad de Ciencias Físicas Iraida N. Demchenko
Universidad Complutense de Madrid Laboratory of Electrochemistry
Madrid, Spain Division of Physical Chemistry
Faculty of Chemistry
Antonio Vázquez-López University of Warsaw
Departamento de Física de Materiales Warsaw, Poland
Universidad Complutense de Madrid Elżbieta Guziewicz
Madrid, Spain Division of Physics and Technology of Wide
Band Gap Semiconductor
Félix del Prado Nanostructures
Departamento de Física de Materiales Institute of Physics, Polish Academy of
Facultad de Ciencias Físicas Science
Universidad Complutense de Madrid Warsaw, Poland
Madrid, Spain
Aleksej Smirnov
Department of Neuroscience and Department of Physics and Technology of
Biomedical Engineering Low-Dimensional Systems
Engineered Nanosystems V. Lashkaryov Institute of Semiconductor
Aalto University – Micronova Physics NASU
Espoo, Finland Kyiv, Ukraine
xv
xvi Contributors
Oleksandr Melnichuk Evgen Venger

Mykola Gogol Nizhyn State University Department of Semiconductor
Nizhyn, Ukraine Heterostructures
V. Lashkaryov Institute of Semiconductor
Lyudmyla Melnichuk Physics NASU
Mykola Gogol Nizhyn State University Kyiv, Ukraine
Nizhyn, Ukraine
Abbreviations
AC alternating current
AFM antiferromagnetic
ALD atomic layer deposition
ATR attenuated total reflection
BEOL back-end-of-the line
BST BaxSr1-xTiO3
CB (CBM) conduction band minimum
CL cathodoluminescence
CMSA chromatography-mass spectrometric analysis
CPE constant phase element
CSE combinatorial substrate epitaxy
CVD chemical vapor deposition
DC direct current
DEZn Zn(C2H5)2
DFT density functional theory
DOS density of states
DSSC dye sensitized solar cell
EIS electrochemical impedance spectroscopy
EL electroluminescence
EMA effective medium approximation
ENZ epsilon-near-zero
EPR electron paramagnetic resonance
EXAFS extended X-ray absorption fine structure
FE ferroelectricity
FET field-effect transistor
FM ferromagnetism
FMR ferromagnetic resonance
FP Fabry–Pérot
FTO fluorine tin oxide
FWHM full width at half maximum
GO graphene oxide
GS solution of graphene oxide
HEV (EV) hybrid electric vehicles
HRXRD high-resolution x-ray diffraction
IR infrared
IRR infrared reflection
IS impedance spectroscopy
ITO indium tin oxide
ITRS International Technology Roadmap for Semiconductors
IUPAC International Union of Pure and Applied Chemistry
LIB lithium-ion batteries
LMAS light modulated absorption spectroscopy
LSPR localized surface plasmon resonance
MBE molecular beam epitaxy
MDF model dielectric function
xvii
xviii Abbreviations
ME magneto-electrics
MIEC mixed conductivity oxides
MIR mid infrared
MOD metal organic deposition
MOCVD metal organic chemical vapor deposition
MOSFETs metal-oxide semiconductor field-effect transistor
NMC nickel manganese cobalt oxide
NXES nonresonant X-ray emission spectroscopy
NWs nanowires
ODC oxygen deficient centers
ODR open dielectric resonators
OER oxygen evolution reaction
PEC photoelectrochemical
PEFC polymer electrolyte fuel cell
PBS phosphate-buffered saline
PL photoluminescence
PLD pulsed laser deposition
PMAS potentially modulated absorption spectroscopy
PMMA polymethylmethacrylate
PMMA polymethylmethacrylate
QSS-PC quasi steady state photoconductance
RBS Rutherford backscattering spectrometry
RE rare earth
RIXES resonant inelastic X-ray emission spectroscopy
RIXS resonant inelastic X-ray scattering
RMS root mean square
RPES resonant photoelectron spectroscopy
RT room temperature
RTP rapid thermal processing
SIMS secondary ion mass spectroscopy
SoC state of charge
SOFC solid oxide fuel cells
SP surface plasmon
SPM scanning probe microscopy
SPP surface plasmon–polariton
SPPP surface plasmon–phonon polariton
SSRT solid-state redox transitions
SSSRT solid surface state redox transitions
TCO transparent conductive oxides
TEM transmission electron microscopy
TFT thin-film transistors
TIR total internal reflections
TL Tauc–Lorentz
TM transition metal
UV ultraviolet
VB (VBM) valence band maximum
VLS vapor–liquid–solid
VS vapor–solid
WGM whispering gallery modes
Abbreviations xix
XANES X-ray absorption near edge structure

XAS X-ray absorption spectroscopy
XES X-ray emission spectroscopy
XPS X-ray photoelectron spectroscopy
XRD X-ray diffraction
YSZ yttria-stabilized zirconia
1 Oxide-Based Materials and
Structures
General Remarks
Oxide-based materials are characterized by a wide range of properties that make them
appropriate for multiple applications in the field of novel electronic devices, such as for
sensing, environment and human health diagnostics, use in nonvolatile memories memory,
and so on (Lorenz et al., 2016). Among them are oxide-based electronic materials for resist-
ive switching and thin film transistors (TFT) applications; perovskite-type materials for
photocatalysis, environment protection and energy conversion; silicon photonics enhanced
with functional oxides; complex-oxide field-effect transistors; topological oxide electronics;
magnetoelectric multiferroic, superconductor and giant magnetoelectric materials and struc-
tures for magnetic and energy applications, and many others. As we see, all important fields
of electronics and photonics, magnetics, and energetics are being based on achievements of
oxides material science.
As we know, oxide materials can be conductive, semiconductive, and dielectric, as well as
they can exhibit magnetic or multiferroic properties. In recent references, it is pointed out
novel functionalities at oxide (multi)ferroic 2D states (Li et al., 2015), magnetoelectric coup-
ling in multiferroic epitaxial thin film composites (Vaz, Hoffman, Ahn, & Ramesh, 2010)
and self-assembled multiferroic nanocomposites (Kim, Ning, & Ross, 2019), and new oxide
microcavities applications (Kalusniak, Sadofev, & Hennberger, 2014; Tyborski et al., 2015).
The tremendous interest in interfaces between insulating oxides with different electrical
polarizations has resulted in the study of the detailed atomic structure of the ferroelectric
domain wall, electrostatic boundary conditions as well as the role of ionic point defects
(Stemmer & Allen, 2018). These studies are directed at increasing the current density at the
walls and manipulation of their position.
Many works have been conducted on the fundamental understanding, fabrication pro-
cesses, and applications of magnetoelectric composite material systems, which has brought
the technology closer to realization in practical devices (Srinivasan, Nan, Ramachandra
Rao, & Sun, 2019). Efforts are focused on various electrically and magnetically cross-
coupled devices, in particular, using exchange or strain-coupled heterostructures. Besides,
biotechnological aspects (Madhumitha, Elango, & Roopan, 2016) and solar cell applications
of ZnO-based structures (Boro, Gogoi, Rajbongshi, & Ramchiary, 2018) as well as a novel
approach of oxide films epitaxy and bipolar oxide devices are discussed. There is increasing
interest in microelectronics for oxides with a high dielectric constant (so-called high-k
dielectrics) for use in integrated capacitors and different type transistors, in non-volatile and
dynamic random access memories (DRAM). In this regard, different oxides such as Al2O3,
HfO2, ZrO2, La2O3, and other rare-earth oxides, as well as their ternary and quaternary
compositions have become to be very attractive for microelectronic application. At the same
time, all these oxides have also unique optical and chemical properties that offer their appli-
cation in photovoltaic and photonic devices. For instance, rare-earth-doped Al2O3 materials
1
2 Oxide-Based Materials and Structures
demonstrate intense light emission in specific spectral range and are attractive alternatives to
rare-earth-doped Si-based materials because their crystalline structure allows higher solubility
of rare-earth ions without their clustering at high content. Similar properties are demon-
strated by rare-earth-doped HfO2 and ZrO2 materials. The fabrication of different waveguides
for optical communication and frequency conversion layers (both down and up-conversion,
down shifting) for solar cells were already demonstrated.
These materials, in powder or ceramic forms, along with TiO2 are used for catalytic
applications and water splitting. The development of solid oxide fuel cells and materials for
hydrogen storage continues today, extending a hand for the elaboration of environmental
friendly energetic solution.
Continuous down-scaling of electronic devices forces the elaboration of different nano-
materials that demonstrate high quality with tunable microstructure and morphology by
means of cost-effective technology in comparison with traditional high-tech microelectronics
fabrication. Among different oxides, wide bandgap SnO2, TiO2, and In2O3 and their solid
solutions become key materials for photovoltaics, microelectronics, energy harvesting and
storage, optoelectronic, catalysis, or gas sensing (Kumar, Kumari, Karthik, Sathish, & Shan-
kar, 2017; Tran et al., 2017). In the particular case of In2O3, there is a substantial interest
in developing devices with a low content of In, considered as a critical element (Critical
Raw Materials, 2017), without losing its high performance characteristics, which also could
be achieved by using nanomaterials. The combination of low-dimensional In2O3, SnO2, or
TiO2 structures with organic materials such as graphene, carbon nanotubes, or conductive
polymers results in a new generation of hybrid materials that are of low cost, easily processed
and scalable, and show the ability to be used in flexible substrates.
Discovering new materials remains as the top priority in defining the future research direc-
tions. For example, room-temperature piezoforce microscopy and macroscopic polarization
measurements have revealed that ε-Fe2O3 films display a typical ferroelectric switching with
significant polarization (~1 μC/cm2) and low switching voltages (Gich et al., 2014). It means
that ε-Fe2O3 is a new and unique intrinsic room temperature multiferroic material that could
find novel applications. New possibilities are opened by application of the graphene oxide,
which is a unique material viewed as a single monomolecular layer of graphite with
various oxygen-containing functionalities such as epoxide, carbonyl, carboxyl, and
hydroxyl groups. It is worth pointing out also new non-van der Waals 2D transitional
metal-based oxides – hematene and chromene. The nature of their magnetic ordering
was investigated by Bandyopadhyay, Frey, Jariwala, and Shenoy (2019), who have shown
that tuning the magnetic ordering in these materials controls the transport properties by
modulating the band gap, which may be of use in spintronic or catalytic applications.
Integration of various oxide-based nanostructures, having specific electrical, optical,
chemical, and magnetic properties as well as showing their biocompatibility, with wide-
spread silicon-based CMOS technology allows production of novel multifunctional silicon-
based structures and devices, with unique properties offering their application for energy
storage, catalysis, microelectronic, photonic, and biomedical applications.
Discussing oxides, one cannot but say a few words about the methods of growth and
study of these materials. To fully exploit the richness of oxide-based materials, it is paramount
to control their synthesis with subnanometric scale precision. Well-known high-vacuum thin-
film deposition techniques such as molecular beam epitaxy, pulsed laser deposition, and sput-
tering have rich opportunities. However, the continuous need for device miniaturization has
led to a demand of even thinner films, uniform coatings, vertical processing, higher aspect
ratios, and complex 3D structures with strict requirements for quality and functionality.
Atomic layer deposition (ALD) is a low-temperature (<400°C) and low-vacuum (10−2 to
10 mbar) chemical gas-phase deposition technique that uniquely relies on the alternate pulsing
of precursors, separate in time, that react with the surface in a self-limiting manner. Review of
Oxide-Based Materials and Structures 3
the rapid progress of atomic layer–deposited multicomponent oxides from doped to complex
oxides focusing on single perovskite, spinel, delafossite, and scheelite structures and highlighting
their potential technological applications was presented by Coll and Napari (2019). They say
that the ALD method gives access to homogeneous ultrathin coatings not only on planar sub-
strates but especially on complex features including nanorods and nanowires, nanoparticles,
and mesoporous and nanoporous surfaces. ALD also enables the preparation of pinhole-free
thin layers with atomically sharp interfaces for a wide variety of heterostructures offering, for
example, unprecedented opportunities to study the novel physics arising at the oxide interface.
ALD-grown films of wide band-gap high-k oxides as well as new applications in organic photo-
voltaics, electronics, and optoelectronics are demonstrated by Godlewski et al. (2017). A review
of recent research and development advances in oxide TFTs fabricated by ALD processes is
presented by Sheng, Park, Shong, and Park (2017).
Reducing the thickness of the layer down to a few unit cells is also interesting since novel
properties can emerge at the interfaces between two oxides. The main approach to metastable
compositions design and to generation of the novel electronic properties of the oxide films is
to use strain engineering where little changes can drastically modify the electronic properties.
It is possible, for example, to tune phase formation and preferred epitaxial orientation by
film-substrate pairs tuning. Polycrystalline substrates are widely used for industrial coatings,
but rarely used in epitaxial stabilization studies. Yet, they provide a large spread of surface
orientations in a single experiment, and offer a high throughput method to study the role of
orientation on film growth. Havelia et al. (2013) call this high-throughput method combina-
torial substrate epitaxy, a combinatorial synthesis method in which a large number of tem-
plate combinations are used to stabilize a precise composition in a specific structure.
And, finally, a few words about the research experimental techniques. Raman and photo-
luminescence spectroscopy investigations, ellipsometry and, in particular, spectroscopic ellip-
sometry are very capable optical methods used for oxides’ characterization due to their
numerous advantages. The high sensitivity of these methods combined with the non-
destructive nature results in rapid and non-destructive qualification of the samples qualified
as well as mapping on large surfaces. X-ray diffraction technique should also be noted, the
in-situ application of which gives the possibility to follow the transformation of oxide
during growth or deposition process. Besides, a combination of optical and X-ray methods
with charge carriers transport and electron states density study techniques provides precise
characterization of oxide-based materials. Local nanoscale domain structure, polarization
switching, and piezoresponse in ferroelectric oxides can be studied by using AFM equipped
with the piezoresponse force microscopy contact mode set up.
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two-dimensional non-van der Waals transition-metal oxides. Nano Letters, 19(11), 7793–7800.
Boro, B., Gogoi, B., Rajbongshi, B. M., & Ramchiary, A. (2018). Nano-structured TiO2/ZnO nanocom-
posite for dye-sensitized solar cells application: A review. Renewable and Sustainable Energy
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Coll, M., & Napari, M. (2019). Atomic layer deposition of functional multicomponent oxides. APL
Materials, 7(11), 110901.
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Gajewski, Z. (2017). Oxide-based materials by atomic layer deposition. Proc SPIE 10105, Oxide-
Based Materials and Devices, VIII, 101050L.
Havelia, S., Wang, S., Balasubramaniam, K. R., Schultz, A. M., Rohrer, G. S., & Salvador, P. A. (2013).
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2 Optical Characterization of
Oxide-Based Materials Using
Ellipsometry
Peter Petrik
2.1 INTRODUCTION
Since ellipsometry measures surface and interface properties with sub-nanometer preci-
sion, an inherent requirement is that the surfaces and interfaces must be of optical quality,
i.e. flat on the scale of nanometers or at most tens of nanometers. This is a challenge in
many cases even today, but back to the beginnings of the method only very few surfaces
could be investigated – they were typically polished metal surfaces (Rothen, 1945). As the
technology for microelectronics and thin film preparation developed, the precision, speed,
and non-destructive nature of ellipsometry made sense, and it could be applied very effect-
ively for the testing and the development of materials and structures for microelectronics
(Irene, 1993). Since the energies of the electronic transition in silicon and other semicon-
ductors are in the photon energy range that could easily be covered by standard instru-
mentation, ellipsometry was proved to be a powerful tool for structural characterization
of semiconductors (Petrik et al., 2014) except the first applications being the measurement
of thickness of dielectric materials, such as the thickness of thermal oxide layers on silicon
wafers (Irene, 2006).
For ellipsometry, as for any measurement method, the development of evaluation and
instrumentation goes hand in hand. In case of optical modeling, the direction of develop-
ment in ellipsometry is from well-defined dielectric layers with simple dispersions toward
complex systems both in terms of dispersion models (semiconductors with multiple oscil-
lators; see for example Petrik et al. (2009)) and layer structures (inhomogeneous multi-layer
structures (Petrik et al., 2005)). Because of the versatile structures and properties of oxides,
the modeling of all major categories of the dielectric functions will be discussed from dielectric
to semiconducting features (Fried et al., 2011; Petrik et al., 2001).
In case of instrumentation, the main driving forces are the capabilities to measure in
a broader wavelength range (Petrik, et al., 2019), in different environments (vacuum chamber
(Collins, 1990) or flow cells (Kalas, et al., 2019)), to measure anisotropic materials or large
surfaces (Fried et al., 2011; Shan et al., 2014).
In this chapter, the aspects of modeling and instrumentation will be discussed for oxide-
based materials. Since the field is already huge and covers a broad range of characteristics
(dielectrics, semiconductors or even metallic properties – as for transparent conductive oxides
(TCOs)), this summary is far from being comprehensive, only discussing some important
issues, mainly demonstrated by our own results, for those who are interested in oxides but
who are no experts of ellipsometry.
5
2.2 OPTICAL CHARACTERIZATION BY ELLIPSOMETRY

Although the method of ellipsometry has been known since the end of the 19th century
(Drude, 1889), the word “ellipsometer” has only been coined in the middle of the 20th cen-
tury (Rothen, 1945), and the first major applications of ellipsometry are connected to the
microelectronics technology (Irene, 1993) later on. The number of publications in ellipsometry
increased rapidly in the years from ≈1980 to ≈2000, reaching a kind of saturation by
the year of 2010, as shown, for example, in Figure 2.2 of Kalas et al. (2019). At the begin-
ning, most publications have dealt with the development of the method, which gradually
turned to a situation in which most of the publications are about the application of ellipso-
metry, rather than its development. Of course, it is not because the activities on development
decreased, but because the number of papers on the application increased rapidly.
Compared to the numerous spectroscopic measurement methods, ellipsometry has some
important features. (i) First of all, it doesn’t require references, because it compares the reflec-
tion of two different polarizations of the same beam. Therefore, it is also very robust in terms
of instrumentation, because it is not sensitive to intensity fluctuations from the lamp or vibra-
tions. (ii) In spite all of these factors, it features a sub-nanometer sensitivity that can even be
achieved using simple optical components like regular lamps and film polarizers. (iii) But
most importantly, ellipsometry provides many data (e.g. as a function of wavelength and/or
angles of incidence) which can be fitted by optical models. This fact ensures fully quantitative
analysis as soon as proper optical models exist for the measured system. Consequently,
although it is an indirect method, it is highly sensitive, quantitative, robust, fast, simple – in
terms of instrumentation – and non-destructive. The latter feature is very important, because
with proper hardware extensions, such as vacuum chambers (Fried et al., 2011), flow cells
(Kalas, et al., 2017) or environmental cells (Petrik et al., 2019), real-time measurements can
be performed with high sensitivity and good time resolution.
The literature on the theory and applications of ellipsometry is already huge, covering most
areas of the field from the mathematical basics (Azzam & Bashara, 1977) and applications
(Tompkins & Irene, 2005 or Fried, et al., (2001)) to a comprehensive practical guide with many
excellent graphs and visualizations (Fujiwara, 2007). Therefore, in this chapter only some
“oxides-related” aspects of hardware and evaluation will briefly be discussed, primarily based
on first-hand experiences.
2.2.1 HARDWARE
The general components and working principle of an ellipsometer is shown in the example
of a mapping ellipsometer in Figure 2.1 (Fried et al., 2011). The minimum requirement is
FIGURE 2.1 Beam path of a divergent light source mapping ellipsometer using components of a (1)
light source, (2) film polarizer, (3) spherical mirror, (4) convergent beam, (5) sample, (6) cylindrical mirror,
(7) corrected beam, (8) analyzer, (9) pinhole, (10) divergent beam, (11) spectrograph.
Characterization Using Ellipsometry 7
a light source, two polarizers, and a detector. The light source doesn’t have to be coherent.
One of the polarizers is in the beam path of the light source, serving as a polarization state
modulator, sometimes combined with an additional compensator that changes the phase
shift (Lee, Rovira, An, & Collins, 1998). The light reflected from the sample changes its
polarization state, which can be measured by having another polarizer (called as analyzer in
this case) in the detector path, sometimes also combined with a compensator to change the
phase shift, increase the sensitivity, and allow measuring all the Muller matrix parameters.
There are many configurations from null ellipsometry to rotating component ellipsometry
(Aspnes & Studna, 1975; Collins, 1990), the latter of which utilizes one or two rotating
polarizers or compensators. The most advanced Muller matrix ellipsometry uses simultan-
eously rotating compensators in both arms of the ellipsometer to allow full Muller matrix
determination (Hauge, 1978; Lee et al., 2001). This kind of modulation ellipsometry results
in a sinusoidal intensity signal in the detector. The analysis of this line shape provides the
measured ellipsometric angles or elements of the Muller matrix (Fujiwara, 2007).
Our recent development of high-speed mapping ellipsometry (Figure 2.1) is only one of
the many instrumental possibilities. There are also micro imaging ellipsometry (Wurstbauer
et al., 2010), versatile in situ configurations in vacuum chambers (Cobet et al., 2018; Lee
et al., 1998; Mikhaylova et al., 2007; Petrik et al., 2001), flow cells (Arwin, 2005; Kalas et al.,
2017; Kozma et al., 2011; Poksinski & Arwin, 2004), or environmental cells (Petrik et al.,
2019; Welch et al., 2017). The mapping or macro imaging configuration in Figure 2.1 also
has numerous versions with or without a mirror after the sample (see also Figure 2.2), a line-
scan spectroscopic version and many configurations to integrate in vacuum chambers or in
a roll-to-roll environment. The advantage is (as in multichannel ellipsometry – see Collins
et al. (1998)) that utilizing a detector matrix, both the spectral and lateral points can be
measured simultaneously, by analyzing the line shapes of the signal at each pixel of the
detector, replacing a one-by-one measurement with a simultaneous acquisition. In this way,
the measurement speed of a typical (30-points by 30-points) matrix can be reduced from min-
utes to seconds, revealing an orders of magnitude improvement in terms of speed – but still
maintaining a sensitivity of thickness in the range of nanometers.
One of the most important advantages of ellipsometry is its speed and non-destructive
character, which results in applications such as in situ ellipsometry (Collins et al., 2000;
Tompkins & Irene, 2005). First, the integration of ellipsometry in vacuum chambers was
a major in situ application, but later, bioellipsometry (Arwin, 2005; Kalas et al., 2019), elec-
trochemical in situ ellipsometry, and ellipsometry in environmental cells gained increasing
interest. The reason is that the sub-nanometer sensitivity is usually possible even at high
acquisition speeds (seconds or even better). Advanced configurations of environmental cells
(Figure 2.3) even allow multiple angles of incidence or mapping measurements on heated
samples and in controlled ambient conditions (both liquid and gas are possible).
Finally, besides sophisticated configurations, many developments of ellipsometry expand
the wavelength range from the shortest ones (synchrotron – BESSY) through vacuum UV,
near UV, and extending the visible range towards the near infrared, mid infrared and tera-
hertz regions. A crucial problem in these fields is the availability of reliable references for
the refractive indices. In case of the in situ ellipsometry during annealing, the problem is
even larger due to the need of high temperature references. There are databases provided by
hardware manufacturers; however, global databases are currently lacking.
2.2.2 EVALUATION
From the analysis of the sinusoidal function generated on the detector as a function of the
angle of rotating element(s) (polarizer, analyzer or compensator), the change of polarization
FIGURE 2.2 Prototype of a roll-to-roll compatible mapping ellipsometer using a configuration sche-
matically plotted in Figure 2.1. The optical components of the ellipsometer are located on the left-hand
side of the picture, except for the mirror on the right-hand side at the back, partly covered by an iron
block. The mirror serves for imaging the divergent source on the pinhole camera and spectrograph, both
located at the right-hand side. The apparatus only uses the central line of the image for mapping – the
other index on the CCD detector is used for spectral information. This means that spectroscopic map-
ping can be done by moving the sample (i.e. the line with spectroscopic information in each point). The
advantage of this arrangement is that it can easily be integrated in a vacuum chamber with only the
mirror located in the chamber – all optical components are outside.
as a result of the reflection from the sample surface is calculated, described by the complex
reflection coefficient
rp
ρ ¼ tan eiΔ ≡ ð1Þ
rs
where ψ and Δ are the ellipsometry angles related to the amplitude and the phase, respectively,
whereas rp and rs denote the reflection coefficients of light polarized parallel and perpendicular
to the plane of incidence. The evaluation is only possible if one has an idea about the structure
of the sample. It is required in order to construct an optical model that is good enough to
supply a set of initial parameters from which spectra of ψ and Δ can be calculated. They should
be close enough to the measured one, so that a proper parameter search or gradient fit algo-
rithm can find suitable model parameters by minimizing the difference between the measured
and the fitted spectra.
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You walk up and through the cosy apartments, push back a folding
glass door, and step out upon a balcony of marble.
How still it all is! Only the plash of the water about the bows of the
gondolas, and the little waves snapping at the water-steps. Even the
groups of people around the small iron tables below, partly hidden by
the bloom of oleanders, talk in half-heard whispers.
You look about you,—the stillness filling your soul, the soft air
embracing you,—out over the blossoms of the oleanders, across the
shimmering water, beyond the beautiful dome of the Salute, glowing
like a huge pearl in the clear evening light. No, it is not the Venice of
your childhood; not the dream of your youth. It is softer, more
mellow, more restful, more exquisite in its harmonies.
Suddenly a strain of music breaks upon your ear—a soft, low strain.
Nearer it comes, nearer. You lean forward over the marble rail to
catch its meaning. Far away across the surface of the beautiful sea
floats a tiny boat. Every swing of the oar leaves in its wake a
quivering thread of gold. Now it rounds the great red buoy, and is lost
behind the sails of a lazy lugger drifting with the tide. Then the whole
broad water rings with the melody. In another instant it is beneath
you—the singer standing, holding his hat for your pennies; the
chorus seated, with upturned, expectant faces.
Into the empty hat you pour all your store of small coins, your eyes
full of tears.
GONDOLA DAYS
HAT first morning in Venice! It is the summer, of course—
never the winter. This beautiful bride of the sea is loveliest
when bright skies bend tenderly over her, when white mists
fall softly around her, and the lagoons about her feet are
sheets of burnished silver: when the red oleanders thrust their
blossoms exultingly above the low, crumbling walls: when the black
hoods of winter felsi are laid by at the traghetti, and gondolas flaunt
their white awnings: when the melon-boats, with lifeless sails, drift
lazily by, and the shrill cry of the fruit vender floats over the water:
when the air is steeped, permeated, soaked through and through
with floods of sunlight—quivering, brilliant, radiant; sunlight that
blazes from out a sky of pearl and opal and sapphire; sunlight that
drenches every old palace with liquid amber, kissing every moulding
awake, and soothing every shadow to sleep; sunlight that caresses
and does not scorch, that dazzles and does not blind, that illumines,
irradiates, makes glorious, every sail and tower and dome, from the
instant the great god of the east shakes the dripping waters of the
Adriatic from his face until he sinks behind the purple hills of Padua.
These mornings, then! How your heart warms and your blood tingles
when you remember that first one in Venice—your first day in a
gondola!
You recall that you were leaning upon your balcony overlooking the
garden when you caught sight of your gondolier; the gondolier whom
Joseph, prince among porters, had engaged for you the night of your
arrival.
On that first morning you were just out of your bed. In fact, you had
hardly been in it all night. You had fallen asleep in a whirl of
contending emotions. Half a dozen times you had been up and out
on this balcony, suddenly aroused by the passing of some music-
boat filling the night with a melody that seemed a thousand fold more
enchanting because of your sudden awakening,—the radiant moon,
and the glistening water beneath. I say you were out again upon this
same balcony overlooking the oleanders, the magnolias, and the
palms. You heard the tinkling of spoons in the cups below, and knew
that some earlier riser was taking his coffee in the dense shrubbery;
but it made no impression upon you. Your eye was fixed on the
beautiful dome of the Salute opposite; on the bronze goddess of the
Dogana waving her veil in the soft air; on the group of lighters
moored to the quay, their red and yellow sails aglow; on the noble
tower of San Giorgio, sharp-cut against the glory of the east.
Now you catch a waving hand and the lifting of a cap on the gravel
walk below. “At what hour will the Signore want the gondola?”
You remember the face, brown and sunny, the eyes laughing, the
curve of the black mustache, and how the wavy short hair curled
about his neck and struggled out from under his cap. He has on
another suit, newly starched and snow-white; a loose shirt, a wide
collar trimmed with blue, and duck trousers. Around his waist is a
wide blue sash, the ends hanging to his knees. About his throat is a
loose silk scarf—so loose that you note the broad, manly chest, the
muscles of the neck half concealed by the cross-barred boating-shirt
covering the brown skin.
There is a cheeriness, a breeziness, a spring about this young fellow
that inspires you. As you look down into his face you feel that he is
part of the air, of the sunshine, of the perfume of the oleanders. He
belongs to everything about him, and everything belongs to him. His
costume, his manner, the very way he holds his hat, show you at a
glance that while for the time being he is your servant, he is, in many
things deeply coveted by you, greatly your master. If you had his
chest and his forearm, his sunny temper, his perfect digestion and
contentment, you could easily spare one half of your world’s
belongings in payment. When you have lived a month with him and
have caught the spirit of the man, you will forget all about these
several relations of servant and master. The six francs a day that you
pay him will seem only your own contribution to the support of the
gondola; his share being his services. When you have spent half the
night at the Lido, he swimming at your side, or have rowed all the
way to Torcello, or have heard early mass at San Rosario, away up
the Giudecca, he kneeling before you, his hat on the cool pavement
next your own, you will begin to lose sight even of the francs, and
want to own gondola and all yourself, that you may make him guest
and thus discharge somewhat the ever-increasing obligation of
hospitality under which he places you. Soon you will begin to realize
that despite your belongings—wealth to this gondolier beyond his
wildest dreams—he in reality is the richer of the two. He has
inherited all this glory of palace, sea, and sky, from the day of his
birth, and can live in it every hour in the year, with no fast-ebbing
letter-of-credit nor near-approaching sailing day to sadden his soul or
poison the cup of his pleasure. When your fatal day comes and your
trunk is packed, he will stand at the water-stairs of the station, hat in
hand, the tears in his eyes, and when one of the demons of the
master-spirit of the age—Hurry—has tightened its grip upon you and
you are whirled out and across the great iron bridge, and you begin
once more the life that now you loathe, even before you have
reached Mestre—if your gondolier is like my own gondolier, Espero
—my Espero Gorgoni, whom I love—you would find him on his
knees in the church next the station, whispering a prayer for your
safe journey across the sea, and spending one of your miserable
francs for some blessed candles to burn until you reached home.
But you have not answered your gondolier, who stands with
upturned eyes on the graveled walk below.
“At what hour will the Signore want the gondola?”
You awake from your reverie. Now! as soon as you swallow your
coffee. Ten minutes later you bear your weight on Giorgio’s bent
elbow and step into his boat.
It is like nothing else of its kind your feet have ever touched—so
yielding and yet so firm; so shallow and yet so stanch; so light, so
buoyant, and so welcoming to peace and rest and comfort.
How daintily it sits the water! How like a knowing swan it bends its
head, the iron blade of the bow, and glides out upon the bosom of
the Grand Canal! You stop for a moment, noting the long, narrow
body, blue-black and silver in the morning light, as graceful in its
curves as a bird; the white awning amidships draped at sides and
back, the softly-yielding, morocco-covered seat, all cushions and silk
fringes, and the silken cords curbing quaint lions of polished brass.
Beyond and aft stands your gondolier, with easy, graceful swing
bending to his oar. You stoop down, part the curtains, and sink into
the cushions. Suddenly an air of dignified importance steals over
you. Never in your whole life have you been so magnificently carried
about. Four-in-hands, commodores’ gigs, landaus in triumphant
processions with white horses and plumes, seem tame and
commonplace. Here is a whole barge, galleon, Bucentaur, all to
yourself; noiseless, alert, subservient to your airiest whim, obedient
to the lightest touch. You float between earth and sky. You feel like a
potentate out for an airing, housed like a Rajah, served like
Cleopatra, and rowed like a Doge. You command space and
dominate the elements.
THE GATELESS POSTS OF THE PIAZZETTA

But Giorgio is leaning on his oar, millions of diamonds dripping from
its blade.
“Where now, Signore?”
Anywhere, so he keeps in the sunlight. To the Piazza, perhaps, and
then around San Giorgio with its red tower and noble façade, and
later, when the shadows lengthen, away down to the Public Garden,
and home again in the twilight by way of the Giudecca.
This gondola-landing of the Piazza, the most important of the cab-
stands in Venice, is the stepping-stone—a wet and ooze-covered
stone—to the heart of the city. Really the heart, for the very life of
every canal, campo, and street, courses through it in unending flow
all the livelong day and night, from the earliest blush of dawn to the
earliest blush of dawn again; no one ever seems to go to bed in
Venice. Along and near the edge of this landing stand the richest
examples of Venetian architecture. First, the Royal Gardens of the
king’s palace, with its balustrade of marble and broad flight of water-
steps; then the Library, with its cresting of statues, white against the
sky; then the two noble columns, the gateless posts of the Piazzetta,
bearing Saint Theodore and the Lion of Venice; and beyond, past the
edge of San Marco, the clock tower and the three great flag-staffs;
then the Palace of the Doges, that masterwork of the fifteenth
century; then the Prison, with a glimpse of the Bridge of Sighs,
caught in mid-air; then the great cimeter-sweep of the Riva, its point
lost in the fringe of trees shading the Public Garden; and then, over
all, as you look up, the noble Campanile, the wonderful bell-tower of
San Marco, unadorned, simple, majestic—up, up, into the still air, its
gilded angel, life-size, with outstretched wings flashing in the
morning sun, a mere dot of gold against the blue.
Before you touch the lower steps of the water-stairs, your eye falls
upon an old man with bared head. He holds a long staff studded with
bad coins, having a hook at one end. With this in one hand he
steadies your gondola, with the other he holds out his hat. He is an
aged gondolier, too old now to row. He knows you, the poor fellow,
and he knows your kind. How many such enthusiasts has he helped
to alight! And he knows Giorgio too, and remembers when, like him,
he bent his oar with the best. You drop a penny into his wrinkled
hand, catch his grateful thanks, and join the throng. The arcades
under the Library are full of people smoking and sipping coffee. How
delicious the aroma and the pungent smell of tobacco! In the shadow
of the Doges’ Palace groups idle and talk—a little denser in spots
where some artist has his easel up, or some pretty, dainty child is
feeding the pigeons.
A moment more and you are in the Piazza of San Marco; the grand
piazza of the doges, with its thousands of square feet of white
pavement blazing in the sun, framed on three sides by marble
palaces, dominated by the noblest campanile on the globe, and
enriched, glorified, made inexpressibly precious and unique by that
jewel in marble, in porphyry, in verd antique and bronze, that despair
of architects of to-day, that delight of the artists of all time—the most
sacred, the Church of San Marco.
In and out this great quadrangle whirl the pigeons, the pigeons of
Dandolo, up into the soft clouds, the light flashing from their throats;
sifting down in showers on gilded cross and rounded dome; clinging
to intricate carvings, over and under the gold-crowned heads of
saints in stone and bronze; across the baking plaza in flurries of gray
and black; resting like a swarm of flies, only to startle, mass, and
swirl again. Pets of the state, these birds, since the siege of Candia,
when the great Admiral Dandolo’s chief bearer of dispatches, the
ancestor of one of these same white-throated doves, brought the
good news to Venice the day the admiral’s victorious banner was
thrown to the breeze, and the Grand Council, sitting in state, first
learned the tidings from the soft plumage of its wings.
At one end, fronting the church, stand the three great flag-poles, the
same you saw at the landing, socketed in bronze, exquisitely
modeled and chased, bearing the banners of Candia, Cyprus, and
the Morea—kingdoms conquered by the state—all three in a row,
presenting arms to the power that overthrew them, and forever
dipping their colors to the glory of its past.
Here, too, in this noble square, under your very feet, what
solemnities, what historic fêtes, what conspiracies! Here for
centuries has been held the priestly pageant of Corpus Christi,
aflame with lanterns and flambeaux. Here eleven centuries ago blind
old Dandolo received the Crusader chiefs of France. Here the
splendid nuptials of Francesco Foscari were celebrated by a
tournament, witnessed by thirty thousand people, and lasting ten
days. Here the conspiracies of Tiepolo and Faliero were crushed—
Venetian against Venetian the only time in a thousand years. And
here Italy suffered her crowning indignity, the occupation by the
French under the newly-fledged warrior who unlimbered his cannon
at the door of the holy church, pushed the four bronze horses from
their pedestals over the sacred entrance—the horses of Constantine,
wrought by Lysippus the Greek,—despoiled the noble church of its
silver lamps, robbed the ancient column of its winged lion, and then,
after a campaign unprecedented in its brilliancy, unexampled in the
humiliation and degradation it entailed upon a people who for ten
centuries had known no power outside of Venice, planted in the
centre of this same noble square, with an irony as bitter as it was
cruel, the “Tree of Liberty,” at which was burned, on the 4th of June,
1797, the insignia of the ancient republic.
And yet, notwithstanding all her vicissitudes, the Venice of to-day is
still the Venice of her glorious past, the Venice of Dandolo, Foscari,
and Faliero. The actors are long since dead, but the stage-setting is
the same; the same sun, the same air, the same sky over all. The
beautiful dome of the Salute still dominates the Grand Canal. The
great plaza is still perfect in all its proportions and in all that made up
its beauty and splendor. The Campanile still raises its head,
glistening in the morning light. High over all still flash and swoop the
pigeons of Venice—the pigeons of Dandolo—now black as cinders,
now flakes of gold in the yellow light. The doors of the sacred church
are still open; the people pass in and out. Under the marble arcades,
where the soldiers of the army of France stacked their arms, to-day
sit hundreds of free Venetians, with their wives and sweethearts,
sipping their ices and coffee; the great orchestra, the king’s band,
filling the air with its music.
When you ask what magician has wrought this change, let the old
guide answer as once he answered me when, crossing the Piazza
and uncovering his head, he pointed to a stone and said, in his soft
Italian:—
“Here, Signore,—just here, where the great Napoleon burnt our flag,
—the noble republic of our fathers, under our good King and his
royal spouse, was born anew.”
But you cannot stay. You will return and study the Piazza to-morrow;
not now. The air intoxicates you. The sunlight is in your blood; your
cheeks burn; you look out and over the Grand Canal—molten silver
in the shimmer of the morning. Below, near the Public Garden,
beyond San Giorgio, like a cluster of butterflies, hovers a fleet of
Chioggia fishing-boats, becalmed in the channel. Off the Riva, near
Danieli’s, lies the Trieste steamer, just arrived, a swarm of gondolas
and barcos about her landing-ladders; the yellow smoke of her
funnel drifting lazily. Farther away, on the golden ball of the Dogana,
the bronze Goddess of the Wind poises light as air, her face aflame,
her whirling sail bent with the passing breeze.
You resolve to stop no more; only to float, loll on your cushions,
watch the gulls circle, and the slow sweep of the oars of the luggers.
You would throw open—wide open—the great swinging gates of
your soul. You not only would enjoy, you would absorb, drink in, fill
yourself to the brim.
For hours you drift about. There is plenty of time to-morrow for the
churches and palaces and caffès. To-day you want only the salt air in
your face, the splash and gurgle of the water at the bow, and the low
song that Giorgio sings to himself as he bends to his blade.
Soon you dart into a cool canal, skirt along an old wall, water stained
and worn, and rest at a low step. Giorgio springs out, twists a cord
around an iron ring, and disappears through an archway framing a
garden abloom with flowering vines.
It is high noon. Now for your midday luncheon!
You have had all sorts of breakfasts offered you in your wanderings:
On white-winged yachts, with the decks scoured clean, the brass
glistening, the awning overhead. In the wilderness, lying on balsam
boughs, the smell of the bacon and crisping trout filling the bark
slant, the blue smoke wreathing the tall pines. In the gardens of
Sunny Spain—one you remember at Granada, hugging the great
wall of the Alhambra—you see the table now with its heap of fruit
and flowers, and can hear the guitar of the gypsy behind the
pomegranate. Along the shore of the beautiful bay of Matanzas,
where the hidalgo who had watched you paint swept down in his
volante and carried you off to his oranges and omelette. At St.
Cloud, along the Seine, with the noiseless waiter in the seedy dress
suit and necktie of the night before. But the filet and melon! Yes, you
would go again. I say you have had all sorts of breakfasts out of
doors in your time, but never yet in a gondola.
A few minutes later Giorgio pushes aside the vines. He carries a
basket covered with a white cloth. This he lays at your feet on the
floor of the boat. You catch sight of the top of a siphon and a flagon
of wine: do not hurry, wait till he serves it. But not here, where
anybody might come; farther down, where the oleanders hang over
the wall, their blossoms in the water, and where the air blows cool
between the overhanging palaces.
Later Giorgio draws all the curtains except the side next the
oleanders, steps aft and fetches a board, which he rests on the little
side seats in front of your lounging-cushions. On this board he
spreads the cloth, and then the seltzer and Chianti, the big glass of
powdered ice and the little hard Venetian rolls. (By the bye, do you
know that there is only one form of primitive roll, the world over?)
Then come the cheese, the Gorgonzola—active, alert Gorgonzola,
all green spots—wrapped in a leaf; a rough-jacketed melon, with
some figs and peaches. Last of all, away down in the bottom of the
basket, there is a dish of macaroni garnished with peppers. You do
not want any meat. If you did you would not get it. Some time when
you are out on the canal, or up the Giudecca, you might get a fish
freshly broiled from a passing cook-boat serving the watermen—a
sort of floating kitchen for those who are too poor for a fire of their
own—but never meat.
Giorgio serves you as daintily as would a woman; unfolding the
cheese, splitting the rolls, parting the melon into crescents, flecking
off each seed with his knife: and last, the coffee from the little copper
coffee-pot, and the thin cakes of sugar, in the thick, unbreakable,
dumpy little cups.
There are no courses in this repast. You light a cigarette with your
first mouthful and smoke straight through: it is that kind of a
breakfast.
Then you spread yourself over space, flat on your back, the smoke
curling out through the half-drawn curtains. Soon your gondolier
gathers up the fragments, half a melon and the rest,—there is
always enough for two,—moves aft, and you hear the clink of the
glass and the swish of the siphon. Later you note the closely-eaten
crescents floating by, and the empty leaf. Giorgio was hungry too.
But the garden!—there is time for that. You soon discover that it is
unlike any other you know. There are no flower-beds and gravel
walks, and no brick fountains with the scantily dressed cast-iron boy
struggling with the green-painted dolphin, the water spurting from its
open mouth. There is water, of course, but it is down a deep well
with a great coping of marble, encircled by exquisite carvings and
mellow with mould; and there are low trellises of grapes, and a
tangle of climbing roses half concealing a weather-stained Cupid
with a broken arm. And there is an old-fashioned sun-dial, and sweet
smelling box cut into fantastic shapes, and a nest of an arbor so
thickly matted with leaves and interlaced branches that you think of
your Dulcinea at once. And there are marble benches and stone
steps, and at the farther end an old rusty gate through which Giorgio
brought the luncheon.
It is all so new to you, and so cool and restful! For the first time you
begin to realize that you are breathing the air of a City of Silence. No
hum of busy loom, no tramp of horse or rumble of wheel, no jar or
shock; only the voices that come over the water, and the plash of the
ripples as you pass. But the day is waning; into the sunlight once
more.
Giorgio is fast asleep; his arm across his face, his great broad chest
bared to the sky.
“Si, Signore!”
He is up in an instant, rubbing the sleep from his eyes, catching his
oar as he springs.
You glide in and out again, under marble bridges thronged with
people; along quays lined with boats; by caffè, church, and palace,
and so on to the broad water of the Public Garden.
But you do not land; some other day for that. You want the row back
up the canal, with the glory of the setting sun in your face. Suddenly,
as you turn, the sun is shut out: it is the great warship Stromboli,
lying at anchor off the garden wall; huge, solid as a fort, fine-lined as
a yacht, with exquisite detail of rail, mast, yard-arms, and gun
mountings, the light flashing from her polished brasses.
In a moment you are under her stern, and beyond, skirting the old
shipyard with the curious arch,—the one Whistler etched,—sheering
to avoid the little steamers puffing with modern pride, their noses
high in air at the gondolas; past the long quay of the Riva, where the
torpedo-boats lie tethered in a row, like swift horses eager for a
dash; past the fruit-boats dropping their sails for a short cut to the
market next the Rialto; past the long, low, ugly bath-house anchored
off the Dogana; past the wonderful, the matchless, the never-to-be-
unloved or forgotten, the most blessed, the Santa Maria della Salute.
THE ONE WHISTLER ETCHED

Oh! this drift back, square in the face of the royal sun, attended by all
the pomp and glory of a departing day! What shall be said of this
reveling, rioting, dominant god of the west, clothed in purple and fine
gold; strewing his path with rose-leaves thrown broadcast on azure
fields; rolling on beds of violet; saturated, steeped, drunken with
color; every steeple, tower, and dome ablaze; the whole world on tip-
toe, kissing its hands good-night!
Giorgio loves it, too. His cap is off, lying on the narrow deck; his
cravat loosened, his white shirt, as he turns up the Giudecca,
flashing like burning gold.
Somehow you cannot sit and take your ease in the fullness of all this
beauty and grandeur. You spring to your feet. You must see behind
and on both sides, your eye roving eagerly away out to the lagoon
beyond the great flour-mill and the gardens.
Suddenly a delicate violet light falls about you; the lines of palaces
grow purple; the water is dulled to a soft gray, broken by long,
undulating waves of blue; the hulls of the fishing-boats become inky
black, their listless sails deepening in the falling shadows. Only the
little cupola high up on the dome of the Redentore still burns pink
and gold. Then it fades and is gone. The day is done!
ALONG THE RIVA
HE afternoon hours are always the best. In the morning the
great sweep of dazzling pavement is a blaze of white light,
spotted with moving dots of color. These dots carry gay-
colored parasols and fans, or shield their eyes with aprons,
hugging, as they scurry along, the half-shadows of a bridge-rail or
caffè awning. Here and there, farther down along the Riva, are larger
dots—fruit-sellers crouching under huge umbrellas, or groups of
gondoliers under improvised awnings of sailcloth and boat oars.
Once in a while one of these water-cabmen darts out from his shelter
like an old spider, waylays a bright fly as she hurries past, and
carries her off bodily to his gondola. Should she escape he crawls
back again lazily and is merged once more in the larger dot. In the
noonday glare even these disappear; the fruit-sellers seeking some
shaded calle, the gondoliers the cool coverings of their boats.
Now that the Sun God has chosen to hide his face behind the trees
of the King’s Garden, this blaze of white is toned to a cool gray. Only
San Giorgio’s tower across the Grand Canal is aflame, and that but
half way down its bright red length. The people, too, who have been
all day behind closed blinds and doors, are astir. The awnings of the
caffès are thrown back and the windows of the balconies opened.
The waiters bring out little tables, arranging the chairs in rows like
those in a concert hall. The boatmen who have been asleep under
cool bridges, curled up on the decks of their boats, stretch
themselves awake, rubbing their eyes. The churches swing back
their huge doors—even the red curtains of the Chiesa della Pietà are
caught to one side, so that you can see the sickly yellow glow of the
candles far back on the altars and smell the incense as you pass.
Soon the current from away up near the Piazza begins to flow down
towards the Public Garden, which lies at the end of this Grand
Promenade of Venice. Priests come, and students; sailors on a half
day’s leave; stevedores from the salt warehouses; fishermen;
peddlers, with knick-knacks and sweetmeats; throngs from the
hotels; and slender, graceful Venetians, out for their afternoon stroll
in twos and threes, with high combs and gay shawls, worn as a
Spanish Donna would her mantilla—bewitching creatures in cool
muslin dresses and wide sashes of silk, with restless butterfly fans,
and restless, wicked eyes too, that flash and coax as they saunter
along.
Watch those officers wheel and turn. See how they laugh when they
meet. What confidences under mustachios and fans! Half an hour
from now you will find the four at Florian’s, as happy over a little
cherry juice and water as if it were the dryest of all the Extras. Later
on, away out beyond San Giorgio, four cigarettes could light for you
their happy faces, the low plash of their gondolier’s oar keeping time
to the soft notes of a guitar.
Yes, one must know the Riva in the afternoon. I know it every hour in
the day; though I love it most in the cool of its shadows. And I know
every caffè, church, and palace along its whole length, from the Molo
to the garden. And I know the bridges, too; best of all the one below
the Arsenal, the Veneta Marina, and the one you cross before
reaching the little church that stands aside as if to let you pass, and
the queer-shaped Piazzetta beyond, with the flag-pole and marble
balustrade. And I know that old wine-shop where the chairs and
tables are drawn close up to the very bridge itself, its awnings half
over the last step.
My own gondolier, Espero—bless his sunny face!—knows the owner
of this shop and has known her for years; a great, superb creature,
with eyes that flash and smoulder under heaps of tangled black hair.
He first presented me to this grand duchess of the Riva years ago,
when I wanted a dish of macaroni browned on a shallow plate.
Whenever I turn in now out of the heat for a glass of crushed ice and
orange juice, she mentions the fact and points with pride to the old
earthen platter. It is nearly burnt through with my many toastings.
But the bridge is my delight; the arch underneath is so cool, and I
have darted under it so often for luncheon and half an hour’s siesta.
On these occasions the old burnt-bottomed dish is brought to my
gondola sizzling hot, with coffee and rolls, and sometimes a bit of
broiled fish as an extra touch.
This bridge has always been the open-air club-room of the entire
neighborhood,—everybody who has any lounging to do is a life
member. All day long its habitués hang over it, gazing listlessly out
upon the lagoon; singly, in bunches, in swarms when the fish-boats
round in from Chioggia, or a new P. and O. steamer arrives. Its hand-
rail of marble is polished smooth by the arms and legs and blue
overalls of two centuries.
There is also a very dear friend of mine living near this bridge, whom
you might as well know before I take another step along the Riva. He
is attached to my suite. I have a large following quite of his kind,
scattered all over Venice. As I am on my way, in this chapter, to the
Public Garden, and can never get past this his favorite haunt without
his cheer and laugh to greet me; so I cannot, if I would, avoid
bringing him in now, knowing full well that he would bring himself in
and unannounced whenever it should please his Excellency so to
do. He is a happy-hearted, devil-may-care young fellow, who haunts
this particular vicinity, and who has his bed and board wherever, at
the moment, he may happen to be. The bed problem never troubles
him; a bit of sailcloth under the shadow of the hand-rail will do, or a
straw mat behind the angle of a wall, or even what shade I can spare
from my own white umbrella, with the hard marble flags for feathers.
The item of board is a trifle, yet only a trifle, more serious. It may be
a fragment of polenta, or a couple of figs, or only a drink from the
copper bucket of some passing girl. Quantity, quality, and time of
serving are immaterial to him. There will be something to eat before
night, and it always comes. One of the pleasures of the
neighborhood is to share with him a bite.
This beggar, tramp, lasagnone—ragged, barefooted, and
sunbrowned, would send a flutter through the hearts of a matinée full
of pretty girls, could he step to the footlights just as he is, and with
his superb baritone voice ring out one of his own native songs. Lying
as he does now under my umbrella, his broad chest burnt almost
black, the curls glistening about his forehead, his well-trimmed
mustache curving around a mouth half open, shading a row of teeth
white as milk, his Leporello hat thrown aside, a broad red sash
girding his waist, the fine muscles of his thighs filling his overalls,
these same pretty girls might perhaps only draw their skirts aside as
they passed: environment plays such curious tricks.
This friend of mine, this royal pauper, Luigi, never in the recollection
of any mortal man or woman was known to do a stroke of work. He
lives somewhere up a crooked canal, with an old mother who adores
him—as, in fact, does every other woman he knows, young or old—
and whose needle keeps together the rags that only accentuate
more clearly the superb lines of his figure. And yet one cannot call
him a burden on society. On the contrary, Luigi has especial duties
which he never neglects. Every morning at sunrise he is out on the
bridge watching the Chioggia boats as they beat up past the Garden
trying to make the red buoy in the channel behind San Giorgio, and
enlarging on their seagoing qualities to an admiring group of
bystanders. At noon he is plumped down in the midst of a bevy of
wives and girls, flat on the pavement, his back against a doorway in
some courtyard. The wives mend and patch, the girls string beads,
and the children play around on the marble flagging, Luigi
monopolizing all the talk and conducting all the gayety, the whole
coterie listening. He makes love, and chaffs, and sings, and weaves
romances, until the inquisitive sun peeps into the patio; then he is up
and out on the bridge again, and so down the Riva, with the grace of
an Apollo and the air of a thoroughbred.
When I think of all the sour tempers in the world, all the people with
weak backs and chests and limbs, all the dyspeptics, all the bad
livers and worse hearts, all the mean people and the sordid, all those
who pose as philanthropists, professing to ooze sunshine and
happiness from their very pores; all the down-trodden and the
economical ones; all those on half pay and no work, and those on
full pay and too little—and then look at this magnificent condensation
of bone, muscle, and sinew; this Greek god of a tramp, unselfish,
good-tempered, sunny-hearted, wanting nothing, having everything,
envying nobody, happy as a lark, one continuous song all the day
long; ready to catch a line, to mind a child, to carry a pail of water for
any old woman, from the fountain in the Campo near by to the top of
any house, no matter how high—when, I say, I think of this prince of
good fellows leading his Adam-before-the-fall sort of existence, I
seriously consider the advisability of my pensioning him for the
remainder of his life on one lira a day, a fabulous sum to him, merely
to be sure that nothing in the future will ever spoil his temper and so
rob me of the ecstasy of knowing and of being always able to find
one supremely happy human creature on this earth.
But, as I have said, I am on my way to the Public Garden. Everybody
else is going too. Step to the marble balustrade of this three-
cornered Piazzetta and see if the prows of the gondolas are not all
pointed that way. I am afoot, have left the Riva and am strolling down
the Via Garibaldi, the widest street in Venice. There are no palaces
here, only a double row of shops, their upper windows and balconies
festooned with drying clothes, their doors choked with piles of fruit
and merchandise. A little farther down is a marble bridge, and then
the arching trees of the biggest and breeziest sweep of green in all
Venice—the Giardini Pubblici—many acres in extent, bounded by a
great wall surmounted by a marble balustrade more than a mile in
length, and thickly planted with sycamores and flowering shrubs. Its
water front commands the best view of the glory of a Venetian
sunset.
This garden, for Venice, is really a very modern kind of public
garden, after all. It was built in the beginning of the present century,
about 1810, when the young Corsican directed one Giovanni Antonio
Selva to demolish a group of monasteries incumbering the ground
and from their débris to construct the foundations of this noble park,
with its sea-wall, landings, and triumphal gate.
Whenever I stretch myself out under the grateful shade of these
splendid trees, I always forgive the Corsican for robbing San Marco
of its bronze horses and for riding his own up the incline of the
Campanile, and even for leveling the monasteries.
And the Venetians of to-day are grateful too, however much their
ancestors may have reviled the conqueror for his vandalism. All over
its graveled walks you will find them lolling on the benches, grouped
about the pretty caffès, taking their coffee or eating ices; leaning by
the hour over the balustrade and watching the boats and little
steamers. The children romp and play, the candy man and the
sellers of sweet cakes ply their trade, and the vender with cool drinks
stands over his curious four-legged tray, studded with bits of brass
and old coins, and calls out his several mixtures. The officers are
here, too, twisting their mustachios and fingering their cigarettes; fine
ladies saunter along, preceded by their babies, half smothered in
lace and borne on pillows in the arms of Italian peasants with red
cap-ribbons touching the ground; and barefooted, frowzy-headed
girls from the rookeries behind the Arsenal idle about, four or five
abreast, their arms locked, mocking the sailors and filling the air with
laughter.
Then there are a menagerie, or rather some wire-fenced paddocks
filled with kangaroos and rabbits, and an aviary of birds, and a big
casino where the band plays, and where for half a lira, some ten
cents, you can see a variety performance without the variety, and
hear these light-hearted people laugh to their heart’s content.
And last of all, away down at one end, near the wall fronting the
church of San Giuseppe, there lives in miserable solitude the horse
—the only horse in Venice. He is not always the same horse. A few
years ago, when I first knew him, he was a forlorn, unkempt, lonely-
looking quadruped of a dark brown color, and with a threadbare tail.
When I saw him last, within the year, he was a hand higher, white,
and wore a caudal appendage with a pronounced bang. Still he is
the same horse—Venice never affords but one. When not at work
(he gathered leaves in the old days; now I am ashamed to say he
operates a lawn-mower as well), he leans his poor old tired head
listlessly over the rail, refusing the cakes the children offer him. At
these times he will ruminate by the hour over his unhappy lot. When
the winter comes, and there are no more leaves to rake, no gravel to
haul, nor grass to mow, they lead him down to the gate opening on
the little side canal and push him aboard a flat scow, and so on up
the Grand Canal and across the lagoon to Mestre. As he passes
along, looking helplessly from side to side, the gondoliers revile him
and the children jeer at him, and those on the little steamboats pelt
him with peach pits, cigar ends, and bits of broken coal. Poor old
Rosinante, there is no page in the history of Venice which your
ancestors helped glorify!
There are two landings along the front of the garden,—one below the
west corner, up a narrow canal, and the other midway of the long
sea-wall, where all the gondolas load and unload. You know this last
landing at once. Ziem has painted it over and over again for a score
of years or more, and this master of color is still at it. With him it is a
strip of brilliant red, a background of autumn foliage, and a creamy
flight of steps running down to a sea of deepest ultramarine. There is
generally a mass of fishing-boats, too, in brilliant colorings, moored
to the wall, and a black gondola for a centre dark.
When you row up to this landing to-day, you are surprised to find it
all sunshine and glitter. The trees are fresh and crisp, the marble is
dazzling white, and the water sparkling and limpid with gray-green
tints. But please do not criticise Ziem. You do not see it his way, but
that is not his fault. Venice is a hundred different Venices to as many
different painters. If it were not so, you would not be here to-day, nor
love it as you do. Besides, when you think it all over, you will admit
that Ziem, of all living painters, has best rendered its sensuous,
color-soaked side. And yet, when you land you wonder why the
colorist did not bring his easel closer and give you a nearer view of
this superb water-landing, with the crowds of gayly dressed people,
swarms of gondolas, officers, fine ladies, boatmen, and the hundred
other phases of Venetian life.
But I hear Espero’s voice out on the broad water. Now I catch the
sunlight on his white shirt and blue sash. He is standing erect, his
whole body swaying with that long, graceful, sweeping stroke which
is the envy of the young gondoliers and the despair of the old;
Espero, as you know, has been twice winner in the gondola races.
He sees my signal, runs his bow close in, and the next instant we
are swinging back up the Grand Canal, skirting the old boatyard and
the edge of the Piazzetta. A puff of smoke from the man-of-war
ahead, and the roll of the sunset gun booms over the water. Before
the echoes have fairly died away, a long sinuous snake of
employees—there are some seven thousand of them—crawls from
out the arsenal gates, curves over the arsenal bridge, and heads up

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PDF Oxide Based Materials and Structures Fundamentals and Applications 1St Edition Rada Savkina Editor Ebook Full Chapter

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Oxide Based Materials and Structures

Fundamentals and Applications 1st

Graphene Oxide: Fundamentals and Applications Dimiev

Geotechnics Fundamentals and Applications in

Extending Structures Fundamentals and Applications 1st

Fundamentals and applications of magnetic materials 1st

Metal Oxide Powder Technologies: Fundamentals,

Nanoelectronic Materials Fundamentals and Applications

Engineering Design Applications II: Structures,

Fundamentals of Electroceramics Materials Devices and

Library of Congress Cataloging-in-Publication Data

Names: Khomenkova, Larysa, editor. | Savkina, Rada, editor.

Visit the Taylor & Francis Web site at

To our families for their endless love, guiding, and patience.

Chapter 1 Oxide-Based Materials and Structures: General Remarks....................................1

Chapter 2 Optical Characterization of Oxide-Based Materials Using Ellipsometry..............5

Chapter 3 Electrical Characterization of Oxide-Based Materials Using Impedance

Chapter 4 Analytical Techniques for Characterization of Oxide-Based Materials ..............75

Chapter 5 Low-Dimensional Structures of In2O3, SnO2 and TiO2 with Applications

Chapter 6 Transition Metal Oxides for Magnetic and Energy Applications......................137

Chapter 7 Phonon and Plasmon–Phonon Interactions in ZnO Single Crystals and

Chapter 8 Zinc Oxide Grown by Atomic Layer Deposition: A Versatile Material

Rada Savkina and Larysa Khomenkova

• The European Union Seventh Framework Programme under Grant Agreement

Dr. Larysa Khomenkova is senior staﬀ researcher of V. Lashkaryov Institute of Semiconductor

Oleksandr Melnichuk Evgen Venger

XANES X-ray absorption near edge structure

2.2 OPTICAL CHARACTERIZATION BY ELLIPSOMETRY

THE GATELESS POSTS OF THE PIAZZETTA

THE ONE WHISTLER ETCHED

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