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Silicon
Electrochemistry, Production, Purification and Applications
Eimutis Juzeliunas
̄
Silicon
Author All books published by WILEY-VCH are carefully
produced. Nevertheless, authors, editors, and
Prof. Eimutis Juzeli¯unas publisher do not warrant the information
Center for Physical Sciences and contained in these books, including this book,
Technology to be free of errors. Readers are advised to keep
Department of Electrochemical in mind that statements, data, illustrations,
Materials procedural details or other items may
Sauletekio Str 3 inadvertently be inaccurate.
10257 Vilnius
Lithuania Library of Congress Card No.: applied for
Cover Image: © Georgy British Library Cataloguing-in-Publication Data

Shafeev/Shutterstock A catalogue record for this book is available
from the British Library.
Bibliographic information published by

the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists
this publication in the Deutsche
Nationalbibliografie; detailed bibliographic
data are available on the Internet at
<http://dnb.d-nb.de>.
© 2023 WILEY-VCH GmbH, Boschstraße 12,

69469 Weinheim, Germany
All rights reserved (including those of

translation into other languages). No part of
this book may be reproduced in any form – by
photoprinting, microfilm, or any other
means – nor transmitted or translated into a
machine language without written permission
from the publishers. Registered names,
trademarks, etc. used in this book, even when
not specifically marked as such, are not to be
considered unprotected by law.
Print ISBN: 978-3-527-34897-8

ePDF ISBN: 978-3-527-83190-6
ePub ISBN: 978-3-527-83192-0
oBook ISBN: 978-3-527-83191-3
Typesetting Straive, Chennai, India

To my beloved family – wife Katerina and sons Laimis and Povilas,
To the memory of my parents – mother Zofija and father Enrikas
who inspired and supported.

and
vii
Contents
Preface xiii
List of Abbreviations xv
About the Author xix
1 Introduction 1
References 3
2 Silicon Electrochemistry – Toward Low-Carbon Economy 5

2.1 Silicon for Energy Storage – Electrochemical Batteries 6
2.2 Silicon for Energy Conversion – Photovoltaic Devices 9
2.2.1 Solar to Electricity 9
2.2.2 Solar-to-Chemical Conversion 15
References 17
3 Brief Historical Overview of Silicon Production.

Metallurgical-Grade Silicon 21
References 26
4 Physical and Chemical Properties of Silicon 27

References 30
5 Silicon Refining: From Metallurgical-Grade to

Electronic-Grade 33
5.1 Purification Based on Direct Si Chlorination 34
5.2 The Siemens Process 35
5.3 The Union Carbide Process 37
5.4 The Ethyl Process 38
5.5 Electrorefining in Molten Salts 40
5.6 Zone Refining, Acid Leaching 43
References 45
viii Contents
6 Silicon Electrowinning and Electrodeposition of

Thin Layers 49
6.1 Electrodeposition in Molten Fluoride, Chloride, and Oxide
Electrolytes 49
6.2 Substrate Materials for Silicon Electrodeposition 55
6.3 Electrodeposition of Photoactive Silicon and p–n Junction 56
6.4 Electrodeposition of Silicon from Ionic Liquids and Organic Solvents 60
6.5 Purity Concerns and Solutions 66
References 69
7 Photoelectrochemistry and Nanogravimetry of Si and Si-Oxide

Electrodes 77
7.1 Topicality of Si Photoelectrochemical Research 77
7.2 Basic Parameters: Photopotential, Photocurrent, and
Photocapacitance 80
7.3 Photoelectrochemical Features of the Si-Oxide Electrodes 85
7.3.1 Si–SiO2 Electrode 86
7.3.2 Si–HfO2 Electrode 93
7.3.3 Si–Al2 O3 Electrode 105
7.4 Quartz Crystal Nanogravimetry 106
References 112
8 Electro-Deoxidation of Solid Compounds in Molten Salts 121

References 127
9 Voltammetry and Basic Reactions of Silicon Electrode in

Molten CaCl2 129
References 140
10 Si–SiO2 Electrode in Molten CaCl2 145

References 147
11 Formation of Silicon Oxide Layer 149

References 155
12 In Situ Studies of SiO2 → Si Conversion – Synchrotron X-ray

Diffraction 159
References 162
13 Molten Oxide Electrochemistry at Ultra-High

Temperatures 165
References 172
14 Silicon Surface Structuring 175

14.1 Electrochemical Structuring, Porous Silicon 175
14.2 Chemical–Physical Structuring 178
Contents ix
14.2.1 Chemical Etching 178

14.2.2 Laser Engineering 180
14.2.3 Reactive Ion Etching 181
14.2.4 Plasma Immersion Ion Implantation Etching 182
14.2.5 Stain Etching 182
14.2.6 Metal-Assisted Chemical Etching 182
14.2.7 Vapor–Liquid–Solid Method 186
14.2.8 Nanostructuring Based on Porous Alumina Template 186
14.3 Black Silicon 190
References 195
15 Electrochemical Si Surface Structuring and Formation of Black

Silicon in High-Temperature Molten Salts 203
15.1 Anodic and Cathodic Processing in Molten CaCl2 203
15.2 Microcolumnar and Amorphous Structures 205
15.3 Electrodeoxidation of Thin SiO2 Layers 207
15.4 Globular Structures 208
15.5 Black Silicon from Molten Salts 212
15.6 Electrochemical Synthesis of Nanowires: Implications for Li-Ion
Batteries 216
References 221
16 Silicon Compositions – Perspectives for Semiconductor

Production 225
16.1 Silicon Carbide 225
16.2 Silicides 231
References 233
17 Silicon Photo-Electrodes for Water Splitting and Their

Protection 237
17.1 Relevance, Basic Principles, and Semiconductor Materials for
Photo-Electrodes 237
17.2 Protection of Silicon Photoelectrodes in Solar-Fuel Generators 243
17.2.1 Protection of Si Photoanodes 246
17.2.2 Protection of Si Photoanodes for Halide Reduction 247
17.2.3 Protection of Si Photocathodes 249
References 251
18 Conclusions, Outlook, and Challenges 257
Index 263
xi
Theodor von Grotthuss medal. Author: Petras Repšys. Produced by Lietuvos monetu˛
Theodor von Grotthuss (1785–1822)

“Though light illuminates darkness, nothing is darker than the light.”
kalykla (Lithuanian Mint)
xiii
Preface
Silicon lies at the heart of modern technology. Silicon can be used in various fields,
such as optoelectronics, sensors, batteries, optical fibers, photoelectrochemical
water splitting, terahertz emitters, and numerous other applications. As an abun-
dant, non-toxic, efficient, and robust material, silicon will dominate the solar energy
market at least for the next few decades.
Electrochemistry deals with the chemical transformations, which are induced by
an electric current, or vice versa – with the transformations, which generate an elec-
tric current. These processes provide an opportunity to store or produce electricity
with a minimum carbon footprint. Electrochemistry can, therefore, significantly
contribute to low-carbon economy; it offers an advancement in sustainable energy
solutions and environment-friendly technologies.
In the early 2000s, V. Lehman (2002) and X. G. Zhang (2004) published several
books on silicon electrochemistry. Since then, various breakthrough directions in
silicon electrochemistry have emerged. For instance, luminescent porous silicon
nanoparticles were electrochemically produced and applied as the carriers of
the drug payload in vivo. Electrochemical silicon surface modifications increased
the efficiency of photovoltaic devices used for solar energy harvest or for the
production of solar fuel. Silicon photoelectrodes have been successfully developed
for hydrogen and oxygen production by water splitting as well as CO2 reduction.
Electrochemically produced Si surface nano-architectures showed an intrinsic
quantum confinement effect. Environment-friendly and secure solutions offered
silicon electrochemistry in high-temperature molten salts. Electrochemical silicon
reduction from silica in high-temperature molten salts has been discovered. Elec-
trochemical deposition of doped silicon as well as formation of p-–n junction have
also been demonstrated.
This book aims to summarize the experimental and technological work done
in recent decades on silicon electrochemistry, production, and purification, high-
lighting subjects of technological significance and future perspectives. The book
aims to be highly beneficial to the communities of chemists and material scientists
working in academia and industrial sectors, especially in the field of sustainable
energy development: photovoltaics, light harvesting efficiency, solar-to-chemical
conversion, production of solar-grade silicon as well as production of batteries,
photoelectrodes, or silicon-based semiconductors. The secondary market of this
xiv Preface
book includes the education and socio-economic sectors with focal points on such
topicalities as the reduction in global climate change, replacement of fossil fuels by
renewable energy, and strategies of low-carbon economy.
Vilnius, Lithuania Eimutis Juzeliūnas

June, 2022
References
Lehman, V. (2002). Electrochemistry of Silicon. Instrumentation, Science, Materials and

Applications. Wiley-VCH.
Zhang, X.G. (2004). Electrochemistry of Silicon and Its Oxide. Kluwer Academic
Publishers.
xv
List of Abbreviations
3PI three-phase interface (interlines)

AFM atomic force microscopy
AL acetonitrile
Al-BSF aluminum backside field technology
ALD atomic layer deposition
BCE before the common (or current) era
BMIm 1-butyl-3-methylimidazolium
BMPy 1-butyl-3-methylpyridinium
BMPyrr N-butyl-N-methylpyrrolidinium
b-Si black silicon
CE contacting electrode
CNT carbon nanotubes
COP 21 Paris Climate Conference
CV cyclic voltammetry
CVD chemical vapor deposition
CZ Czochralski process
DMAE 2-dimethylaminoethanethiol
DMS dimethyl sulfide
DRC Democratic Republic of the Congo
DRE damage removal etching
EC The European Commission
EDX (EDS) energy-dispersive X-ray spectroscopy
EIS electrochemical impedance spectroscopy
EMIm 1-ethyl-3-methylimidazolium
EMPyrr N-ethyl-N-methylpyrrolidinium
EQCM electrochemical quartz crystal microbalance
EU the European Union
FAP tris(pentafluoroethyl)-trifluorophosphate
FBR fluidized bed reactor
fs femtosecond
FTIR Fourier transform infrared spectroscopy
FTO fluorine-doped tin oxide
GDMS glow discharge mass spectrometry
xvi List of Abbreviations
GDP Gross domestic product

GI-XRD grazing incidence X-ray diffractometry
ICE initial Coulombic efficiency
ICP inductive coupled plasma
IL ionic liquid
IPA isopropyl alcohol
IRENA International Renewable Energy Agency
ISFET ion-sensitive field effect transistor
ITO indium tin oxide
LCD liquid-crystal display
LIB lithium-ion battery
M, Me metal, metallic
MACE metal-assisted chemical etching
MG-Si metallurgical-grade silicon
MOE molten oxide electrolysis
MS magnetron sputtering
MT metric ton
MWT metal wrap through
NHE normal hydrogen electrode
NMR nuclear magnetic resonance
NPs nanoparticles
ns nanosecond
NTD neutron transmutation doping
NWs nanowires
P-Si porous silicon
PEC photoelectrochemical cells, photoelectrochemistry
PEDOT:PSS poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)
PERC passivated emitter and rear contact
PIII plasma immersion and ion implantation
PV photovoltaic(s)
PVD physical vapor deposition
QCN quartz crystal nanobalance
R&D research and development
RE reference electrode
RFMS radio frequency magnetron sputtering
RIE reactive ion etching
Si-H hydrogen-terminated silicon surface
Si-F fluoride-terminated silicon surface
Si-OH hydroxide terminated silicon surface
SCR space-charge region
SEM scanning electron microscopy
SERS surface-enhanced Raman spectroscopy
SoG-Si solar-grade silicon
SP solubility product
STC silicon tetrachloride
List of Abbreviations xvii
SWIR short-wavelength infrared

TBAB tetrabutylammonium bromide
TBAC tetrabutylammonium chloride
TBMA tributyl(methyl)ammonium
TCS trichlorsilane
TEAC tetraethylammonium chloride
TEOS tetraethylorthosilicate
TFO trifluoromethylsulfonate
TFSA bis(trifluoromethylsulfonyl)amide
TFSI bis(trifluoromethylsulfonyl)imide
TG-DTA thermogravimetry and differential thermal analysis
THF tetrahydrofuran
TMAH tetramethylammonium hydroxide
TMHA N-trimethyl-N-hexylammonium
TPAC tetrapropylammonium chloride
TRL technology readiness level
UPD underpotential deposition
UTE ultra-high temperature electrochemistry
VLS vapor–liquid–solid deposition
XRD X-ray diffraction
XPS X-ray photoelectron spectroscopy
xix
About the Author
Professor Dr. Eimutis Juzeliūnas is a principal research

associate and a head of the Department of Electrochemical
Materials Science at the Centre for Physical Sciences and
Technology in Vilnius, Lithuania. He worked previously
as a rector of Klaipėda university (2014–2018) and a direc-
tor of the Institute of Chemistry in Vilnius (2001–2009).
He was a Marie Curie International Fellow of the Euro-
pean Commission at the University of Cambridge, UK
(2009–2011, 2013–2014) where he carried out research on
silicon electrochemistry in high-temperature molten salts.
Eimutis Juzeliūnas, He also was a Fulbright fellow at the Vanderbilt University
photo by J. Stacevičius/ (USA), a fellow of the American Chemical Society at the
Lithuanian National Pennsylvania State University (USA), and an Alexander
Radio and
Television, LRT.
von Humboldt fellow at the company DECHEMA e.V.
(Germany). His main research area is electrochemical
materials science; current research interests are silicon electrochemistry for energy
applications, environmental and microbiological degradation of metals (corrosion),
physical vapor deposition of resistant alloys, and nanogravimetry of electrochemical
processes.
1
Introduction
World production of silicon (Si) reached (2010–2020) about eight millions of metric
tonnes in the last decade. This quantity was produced mainly by the carbothermic
silica (SiO2 ) reduction. The process requires a large supply of energy and emits
carbon oxides (COx ). A fundamental challenge is the electrochemical silicon extrac-
tion from silica or other solids using electricity instead of harmful chemistries.
Zero carbon footprint could be attained when using electrons as absolutely clean
reduction agents generated by renewable sources. Electrochemical methods can be
used on a wide scale of applications: extraction, purification, surface engineering,
or thin-film technologies. Thus, silicon electrochemistry has the potential to
significantly contribute to low-carbon economy; this field offers an advancement
in environmentally friendly and secure technologies of energy generation and
storage.
Breakthrough research topics have emerged in silicon electrochemistry in recent
decades. The electrochemical formation of porous silicon (P-Si) was discovered
in 1956 (Uhlir 1956). Canham reported in 1990 that a visible room-temperature
photoluminescence from P-Si layer formed electrochemically on Si wafer (Canham
1990). The discovery inspired wide studies of P-Si for applications in optoelectron-
ics, lasers, and sensors. Luminescent porous silicon nanoparticles were applied as
the carriers of the drug payload, whose infrared luminescence enabled monitoring
of the particles in vivo (Park et al. 2009). Electrochemical nano-micro-structuring
of silicon has been widely investigated. The surface modifications increased the
efficiency of photovoltaic (PV) devices used for solar energy harvest or for produc-
tion of solar fuel. Silicon photoelectrodes have been successfully used for hydrogen
and oxygen production by water splitting as well as CO2 reduction (Sun et al.
2014). Electrochemically produced Si surface nano-architectures showed intrinsic
quantum confinement effect. Electrochemical reduction of silicon dioxide to silicon
in a molten salt electrolyte has been reported, which formed the basis for new
processes in silicon semiconductor technology and high-purity silicon production
(Nohira et al. 2003). Environmentally friendly and secure solutions offered silicon
electrochemistry in high temperature molten salts (Juzeliūnas and Fray 2020).
Electrochemical deposition of doped silicon as well as formation of p–n junction
has been demonstrated (Zou et al. 2017, 2019; Peng et al. 2018). The approach has
Silicon: Electrochemistry, Production, Purification and Applications, First Edition. Eimutis Juzelīunas.
© 2023 WILEY-VCH GmbH. Published 2023 by WILEY-VCH GmbH.
2 1 Introduction
the potential of reducing capital cost and energy consumption for fabrication of
solar cells when compared with the conventional manufacturing process.
This book features recent achievements in silicon electrochemistry, particularly,
in electrochemical silicon extraction, purification, and processing in high-
temperature molten salts. The introductory part of the book (Chapters 2–4) is
devoted to general aspects of silicon application. A historical overview of silicon
production is provided, and its importance in a low-carbon economy is considered.
Chapter 4 addresses the physical and chemical properties of silicon, which are most
relevant for electrochemical materials science. The subsequent material is more
specific. Chapter 5 describes the major technologies used for silicon purification
such as Siemens, Union Carbide, or Ethyl Corporation processes. This chapter
also provides the principles of electrorefining in high-temperature molten salts,
highlighting the advantages and disadvantages when compared with conventional
industrial processes.
Chapter 6 addresses electrodeposition of thin layers and discusses the possibility
of replacing multiple processes of Si wafer fabrication with one-step electrochemi-
cal deposition. Traditional manufacturing entails an energy-intensive and environ-
mentally unfriendly production of metallurgical grade silicon (MG-Si), as well as
its upgrade to solar grade silicon (SoG-Si), ingot casting, and slicing. Electrodeposi-
tion from molten fluoride, chloride, and oxide electrolytes on various substrates is
discussed. A recently proposed strategy for electrodeposition of photoactive silicon
and p–n junction is highlighted in detail. Silicon deposition from ionic liquids – the
room-temperature molten salts – is also discussed in this chapter. Significant atten-
tion is given to the purity level of silicon electrodeposits, which are essential for
photo-electrochemical applications.
Chapter 7 discloses photoelectrochemical (PEC) properties of silicon-oxide
electrodes coated with ultrathin films of silica (SiO2 ), hafnia (HfO2 ), and alumina
(Al2 O3 ). The pivotal concept of PEC methodology is to obtain information, which
correlates with that of the solid-state cells so that there is no prior need to design a
solar cell that characterizes Si surface photo-responsiveness. Significant attention
is given to studies of Si-oxide interfacial stability by the quartz crystal nanobalance
(QCN) – a sensitive mass detector, which provides information about the electrode
mass change with nanogram resolution in situ and in real time.
Deoxidation of metal oxides in a molten salt electrolyte was discovered in the
year 2000 (Chen et al. 2000). The process was named the FFC Cambridge process.
Simplicity and rapidity of the process have attracted global interest. Over 30
metals or semimetals were extracted from solid compounds by this energy-efficient
and environment-friendly route. Chapter 8 addresses the FFC principle and its
application in silicon reduction from silica. The electrochemical extraction provides
a green alternative to conventional carbo-thermic silicon production. Chapters 9–12
provide further details on Si–SiO2 conversion in molten salts. Voltammetry, basic
reactions, and in situ studies by synchrotron X-ray diffraction are discussed, and
experimental conditions used by many authors are summarized.
Technological opportunities carry out the operation at ultra-high temperatures
and at liquid state of silica feedstock. Such processes are referred to as molten oxide
References 3
electrolysis (MOE). Chapter 13 discusses the MOE principles of silicon extraction in

a liquid state.
This study focused majorly on electrochemical surface engineering. Chapter
14 discusses the chemical–physical methods of silicon surface structuring, such
as laser engineering and various etchings: chemical, photoelectrochemical, reac-
tive ion, plasma immersion ion implantation, and metal-assisted chemical. The
vapor–liquid–solid method is also discussed.
Chapter 15 features a comprehensive material obtained on electrochemical
Si structuring at high-temperature molten salts including formation of black
silicon (B-Si). B-Si is a nano-micro-porous material, which effectively absorbs the
light on a wide range of wavelengths. Electrochemical Si structuring in molten
salts is attractive due to its environmental friendliness, technical simplicity, and
cost-effectiveness.
The book also outlines the perspectives of electrochemical synthesis of semicon-
ductors (Chapter 16), the basic principles and materials for photo-electrodes, and
the preservation of solar-fuel generators (Chapter 17).
In conclusion, while silicon electrochemistry offers a range of technological oppor-
tunities, most of the developments are still on the conceptual or bench-scale level.
As a result, viable technological developments are still pending.
References
Canham, L.T. (1990). Quantum wire array fabrication by electrochemical and chemical
dissolution. Appl. Phys. Lett. 57: 1046–1048. https://doi.org/10.1063/1.103561.
Chen, G.Z., Fray, D.J., and Farthing, T.W. (2000). Direct electrochemical reduction of
titanium dioxide to titanium in molten calcium chloride. Nature 407: 361–364.
https://doi.org/10.1038/35030069.
Juzeliūnas, E. and Fray, D. (2020). Silicon electrochemistry in molten salts. Chem. Rev.
120: 1690–1709. https://doi.org/10.1021/acs.chemrev.9b00428.
Nohira, T., Yasuda, K., and Ito, Y. (2003). Pinpoint and bulk electrochemical reduction
of insulating silicon dioxide to silicon. Nat. Mater. 2: 397–401. https://doi.org/10
.1038/nmat900.
Park, J.-H., Gu, L., Maltzahn, G. et al. (2009). Biodegradable luminescent porous silicon
nanoparticles for in vivo applications. Nat. Mater. 8: 331–336. https://doi.org/10.1038/
NMAT2398.
Peng, J.J., Yin, H.Y., Zhao, J. et al. (2018). Liquid-tin-assisted molten salt
electrodeposition of photoresponsive n-type silicon films. Adv. Funct. Mater. 28:
1703551. https://doi.org/10.1002/adfm.201870194.
Sun, K., Shen, S., Liang, Y. et al. (2014). Enabling silicon for solar-fuel production.
Chem. Rev. 114: 8662–8719. https://doi.org/10.1021/cr300459g.
Uhlir, A. (1956). Electrolytic shaping of germanium and silicon. Bell System Tech. J. 35:
333. https://doi.org/10.1002/j.1538-7305.1956.tb02385.x.
4 1 Introduction
Zou, X., Ji, L., Yang, X. et al. (2017). Electrochemical formation of a p–n junction of thin
film silicon deposited in molten salt. J. Am. Chem. Soc. 139: 16060–16063. https://doi
.org/10.1021/jacs.7b09090.
Zou, X., Ji, L., Ge, J. et al. (2019). Electrodeposition of crystalline silicon films from
silicon dioxide for low-cost photovoltaic applications. Nat. Commun. 10: 5772.
https://doi.org/10.1038/s41467-019-13065-w.
5
Silicon Electrochemistry – Toward Low-Carbon Economy
Climate change is one the greatest challenges the world faces today. The renewable
energy (solar, wind, water, biomass, geothermal) is considered as a climate change
imperative today. Excessive exploitation of fossil energy sources had a negative
impact on climate, economy, and everyday lives. The growing threat from climate
change is apparent, such as natural disasters, halved mass of inland glaciers, rise of
sea level, and extinction of numerous terrestrial species. Volatile oil, gas, and coal
prices in recent decades and concerns about their supply from politically unstable
countries are amongst the drivers of the need for alternatives, such as renewables.
The European Green Deal plan was unveiled in 2019 – a three-decade effort to
make the climate neutral by 2050 (https://ec.europa.eu/info/strategy/priorities-
2019-2024/european-green-deal; Tamma et al. 2019; Simon 2019). The Commis-
sion’s President Ursula von der Leyen characterized the initiative as “Europe’s
man on the moon moment” adding that “the growth model based on fossil fuels
and pollution is out of date and out of touch with our planet” (Simon 2019). The
overarching objective in the plan is “Climate neutral Europe,” which aims to reach
net-zero greenhouse gas emissions by 2050. The ambition for 2030 is cutting-off the
emission by 50–55%. The plan addresses major actions such as circular economy,
building renovation, pollution-free environment, strategy of ecosystems and bio-
diversity, green and healthier agriculture, electric vehicles, and sustainable fuels,
such as biofuels and hydrogen.
Another global initiative is the Paris Agreement – an international treaty on
mitigation of climate change (https://unfccc.int/process-and-meetings/the-paris-
agreement/the-paris-agreement). In 2015, 196 parties in the Paris climate confer-
ence (COP 21) adopted an agreement to limit global warming below 2 ∘ C compared
to pre-industrial levels.
Such highly ambitious plans led to fundamental changes in the way we generate
and use the energy. Electrochemical technologies have shown great potential
in advancing the economy’s transition toward climate neutrality. Electrochem-
istry provides sustainable solutions in such fields as green-energy storage and
solar-to-chemical or solar-to-electricity conversion.
Materials used in solar devices play a major role in the cost breakdown of the over-
all utilization process of solar energy. Creation and synthesis of new effective mate-
rials for solar-energy applications, therefore, is very high on the agenda of materials
6 2 Silicon Electrochemistry – Toward Low-Carbon Economy
scientists and engineers. Vast majority of the solar cells are produced from silicon
where the total wafer cost dominates in the overall cell cost balance. It is assumed
that silicon, being a nontoxic, efficient, and robust material, will play a key role in
the solar energy market for the next few decades (Schmalensee et al. 2015; Green
2016; Polman et al. 2016). Mitigation of climate change, as a global task, could be
achieved by using technologies based on the Earth-abundant materials. The abun-
dance of silicon in the Earth’s crust (27%) makes it possible to expand the application
of this material to the terawatt scale by 2050 (Schmalensee et al. 2015).
2.1 Silicon for Energy Storage – Electrochemical

Batteries
Electrochemistry deals with relationship between electricity and chemical change.
Typical example of an electrochemical device used in everyday life is a battery – the
device, which generates electricity by chemical reactions. Batteries are widely
used in portable electronics, medical devices, or e-mobility including electric cars.
A vice versa process is when electricity generates chemical reactions, for instance,
electroplating of metals. The process is widely applied for the production of coatings
in order to protect metals and alloys from corrosion or to improve their aesthetic
appearance, as well as to decorate them.
Batteries represent a key technology for low-carbon economy to reduce CO2
emissions from transport, power, and industrial sectors. Batteries are essential
devices used to store stationary energy from sustainable sources such as solar or
wind. To reach the sustainability targets, batteries must exhibit ultra-high energy
and power performance close to theoretical limits. Other requirements include
outstanding lifetime, reliability, safety, and recyclability. Important requirement is
also scalability to electricity grid level, as well as cost-effectiveness and sustainable
battery production. The cost target set by the European Commission (EC) for the
next-generation batteries of stationary energy storage is below 0.05 €/kWh/cycle by
2030. The growth in global battery demand is anticipated to multiplied by a factor
14× from 2018 to 2030. The greatest part of this demand goes to the electric mobility
sector (Edström et al. 2020).
Lithium-ion (Li-ion) based technology dominates the current battery market.
Lithium-ion batteries (LIBs) are state-of-the-art technology for portable electronics
and electric vehicles. The Nobel Prize in chemistry has been awarded to J. B.
Goodenough, M. S. Whittingham, and A. Yoshito in 2019 for the development of
LIBs. These batteries, however, have several shortcomings, especially for stationary
energy storage applications.
Apart from Li, cobalt (Co) is a key electrode material in Li-ion batteries. For cath-
ode production, various co-containing materials have recently been investigated:
LiCoO2 , LiNix Coy Al1−x−y O2 , LiNix Mny Co1−x−y O2 , etc. (Huang et al. 2021; Chu et al.
2020; Liu et al. 2019a,b). Presently, about 60% of mined cobalt is used to produce
the LIBs electrodes. Congo (The Democratic Republic of the Congo, the DRC)
along with Zambia, Madagascar, Zimbabwe and the Republic of South Africa are
2.1 Silicon for Energy Storage – Electrochemical Batteries 7
mining about 70% of world cobalt. The DRC is a main global producer, which mines
about 60% of the world’s cobalt feedstock. The Amnesty International organization
reported in 2016 on the violation of human rights in this country – child labor in
health-endangering mines (https://www.amnesty.org/en/documents/afr62/3183/
2016/en).
The EC issues periodically the communications with a list of critical raw
materials, which specifies the materials that are most important for the EC
economically, alongside having high supply risk. As of 2020, the list also includes
the materials, from which key components of LIBs are produced: lithium, cobalt,
and graphite (Communication 2020). The list indicates 100% reliance of the
European Union (EU) import on lithium, 86% on cobalt, and 98% on natural
graphite. The communication states that the EU demand for lithium for electric
vehicle batteries and energy storage will increase by 18 times in 2030 and almost
up to 60 times in 2050. The corresponding figures for cobalt are 5 and 15 times,
respectively. The limited availability of lithium makes it doubtful whether LIBs
manufacturing can scale up to significantly larger production volumes.
The World Bank projected that the scenario of global warming below 2∘ (COP 21)
will increase the demand in metals for battery applications at the level of 1000% by
2050 (World Bank 2017). The list of relevant materials for battery manufacturing
includes metals such as Al, Co, Fe, Pb, Li, Mn, and Ni.
An important constraint of the stationary energy storage using LIBs is the
continuous consumption of Li-ion electrolyte, which limits both cycle and calendar
life. Another restriction lies in the limitations of operating temperature window.
The operation requires complex thermal management, which is impractical for
stationary storage applications, particularly in “hot” countries. These batteries also
contain hardly recyclable materials, such as lithium. LIBs are still facing safety
issues. Also, LIBs are relatively expensive.
Thus, there is great demand and a great challenge to create effective post-Li
electrochemical energy storage systems. An alternative suggests sodium with an
electrochemical charge transfer reaction Na ↔ Na+ + e− , which could be performed
in a solid compound, for instance, in a chloride. Oceans provide unlimited sodium
source, which is for free.
Metal-air batteries explore air oxygen as a major reactant:
O2 + 2H2 O + 4e− ↔ 4OH− (2.1)
This approach enables battery weight reduction, at the same time, increasing
the capacity for energy storage. Air–metal technologies are attractive because they
are green, safe, and cost-efficient in terms of feedstock. The technologies propose
usage of an unlimited source of oxygen from the atmosphere, which is for free.
The metal–air batteries can utilize various metal electrodes, e.g. Li, Zn, Al, Fe,
Mg (Tong et al. 2021). Of these metals, Li-air battery has the highest theoretical
energy density and practical operation voltage (13 000 W h kg−1 and 2.4–2.7 V vs.
standard hydrogen electrode (SHE), respectively). Lithium is followed by aluminum
(8073 W h kg−1 and 1.2–1.6 V) and magnesium (6815 W h kg−1 and 1.2–1.4 V). Iron
has the least performance (764 W h kg−1 and 0.8 V), however, the cost of iron metal
anode is substantially less when compared to other metals. Tong et al. summarized
that the cost of iron is about 200 times less when compared with the cost of lithium
and about 15 times less when compared with magnesium or aluminum (Tong et al.
2021). The authors also estimated that Mg, Al, and Zn electrodes are nearly 10 times
cheaper than the Li metal electrodes. Li–air batteries are limited due to dendrite
formation, poor-cycling efficiency, and difficulties in finding a suitable highly stable
electrolyte. Fe–air battery is very attractive in terms of excellent resource-efficiency.
Note also that the electrodes can be prepared combining them in the form of alloys,
for instance, Mg–Al, Mg–Al–Zn, Mg–Li, Mg–Zn, etc.
Silicon is an attractive material for LIBs anode production. The Li–Si binary
system is characterized by exceptionally high Li insertion capacity. One Si atom can
accommodate 4.4 Li atoms forming the alloy Li22 Si5 with theoretical specific inser-
tion capacity of 4200 mA h g−1 . The analogous value for Li15 Si4 is 3576 mA h g−1
(Ashuri et al. 2016; Huang et al. 2021). Such capacity values are the highest among
all anode materials used in LIBs. Silicon outperforms in terms of capacity the con-
ventionally used graphite (372 mA h g−1 for LiC6 ) (Liang et al. 2014). It is assumed
conceptually that electrode capacity can be substantially increased when moving
from classical intercalation reaction to alloying reaction (Ma et al. 2014). Lithium
can react with Si-forming Li22 Si5 alloy, while graphite accommodates much less
lithium forming LiC6 . However, a challenge is disintegration of the electrode due to
nearby 300–400% volume change during the lithiation–delithiation process, that is,
the expansion–contraction cycles (Ashuri et al. 2016; Li et al. 2017; Zuo et al. 2017).
This detrimental process reduces the intrinsic electrical conductivity and causes
the interfacial instability, which leads to capacity fading.
The restoration of electric properties after the damage, so called self-healing, is of
paramount importance in energy-storage device. This was stated in the BATTERY
2030+ Roadmap of the EC: “Establishing a new research community that includes
a wide range of R&D disciplines to develop self-healing functionalities for batteries”
(Edström et al. 2020). Scientists are in search of effective means of surface engineer-
ing that buffers the volume changes, for instance, by graphene films, silicon-carbon
nanocomposites, Si nanowires, nanotubes, and other nanoparticles, solid core–shell
structures, porous Si designs, controllable pores, or patterned silicon films on
foreign metal substrates, etc. These efforts have been summarized in review articles
(Liang et al. 2014; Ma et al. 2014; Ashuri et al. 2016; Li et al. 2017; Zuo et al. 2017;
Huang et al. 2021).
Oxidized silicon (SiOx ) has also been proposed as an alternative to pure Si. Such
electrodes show a lower volume change when compared to pure silicon (Liu et al.
2019a). However, silicon monoxide possesses some problematic features, such as
low intrinsic electrical conductivity, non-negligible volume change, and low initial
Coulombic efficiency (ICE) (Liu et al. 2019a). Thus, there is need to overcome these
drawbacks in order to use the material for LIBs practically. The improvement of ICE
could be achieved by pre-litiation methods, for instance, using stabilized lithium
metal powder (Huang et al. 2021). Various strategies have been proposed to reduce
the SiO volume change: (i) SiO disproportionation into a fraction of Si nanocrystals
by high-energy milling (Hwa et al. 2013) or heating at 900 ∘ C (Huang et al. 2021);
(ii) synthesis of porous SiOx via chemical etching (Yu et al. 2014); (iii) composites of
disproportionated Si–SiOx with carbon (Si–SiOx –C) (Yamada et al. 2011; Choi et al.
2012; Kim et al. 2013); (iv) core–shell porous silicon with nitrogen-doped carbon
layer (p-Si/NC) (Xing et al. 2018); (v) silicon monoxide coated with N-doped carbon
(SiO-NC) produced using N-containing ionic liquid (Lee et al. 2013) and analogous
system using pitch and melanine as carbon and nitrogen sources (Huang et al. 2021).
The materials based on porous silica (SiO2 ) have also been studied as an alternative
to graphite anodes in LIBs. Porous silica has shown improved cycling stability; its
discharge potential was similar to that of pure Si. Low Coulombic efficiency of SiO2
was modified by preparing a carbon-coated C/SiO2 composition (Buga et al. 2021).
The thin carbon layer of the composition diminished interfacial impedance of silica,
whereby the capacity increases to 714 mA h g−1 .
Despite intensive research, most of the proposed methods of the volume change
buffering remain on a bench scale. Vital industrial applications are still pending.
2.2 Silicon for Energy Conversion – Photovoltaic

Devices
2.2.1 Solar to Electricity
Solar energy could effectively act as a substitute to fossil fuels. The solar constant,
which measures the quantity of solar energy to a square meter of the Earth
surface, is estimated to be as high as 1367 W m−2 , according to the World Energy
Council. The constant translates into total amount of 3 400 000 EJ in a year
(EJ – Exajoule, 1 EJ = 1018 J) (Breeze 2019). The solar radiation, which reaches the
earth, covers more than 7000 times the world’s energy needs, that is, the annual
global primary energy consumption. Breeze estimates that if 0.1% of the solar
energy was converted into electricity with 10% efficiency, it would provide around
10 000 GW energy, which exceeds the world energy needs (Breeze 2019). Solar
energy provides the opportunity for decentralized supply of energy actually at
any place around the globe. It can be accumulated (as a heat) and/or converted
to electricity with no polluting emissions to the environment. Other advantages
include no-noise operation and unproblematic decommissioning.
Photovoltaic (PV) electricity generation is a rapidly expanding industry, which
aims to accelerate the development of clean, sustainable, and efficient energy
technologies with the scenarios to reach solar energy domination in the electricity
market. In fact, creation of efficient and low-cost devices of solar energy harvesting
plays a determining role in political-social landscape of twenty-first century. There
is a public awareness in the PV technology as a provider of clean, sustainable, and
secure energy from the most abundant source, which is for free. It is not surprising,
therefore, that world PV production has recently experienced close to exponential
growth.
It is now close to 70 years since the invention of the first reasonably efficient
silicon cells in 1954 (Green 2005). The first silicon-based module for outdoor appli-
cations was produced at Bell Laboratories in 1955. The module was an assembly
of 48 sub-modules and attained 2% efficiency. The reader interested in historical

development of silicon-based PV devices is referred to M. Green’s paper, which
reviews improvement in energy conversion as well as prices of commercial modules
over a 50-year period (Green 2005).
The International Renewable Energy Agency (IRENA) comprising of about
170 member countries declares its mission “supporting countries in their transition
to a sustainable energy future” (www.irena.org). IRENA is an intergovernmental
organization – a driver of actions, which advance the transformation of the global
energy system in the pursuit of low-carbon economy. This organization promotes
adoption of all forms of renewable energy. IRENA issued a global energy trans-
formation paper, which aims to highlight the future of solar PV, including the key
aspects, such as the deployment, investment, technology, grid integration, and
socio-economic aspects (IRENA 2019). IRENA’s analysts foresee that solar PV by
2050 would represent the second-largest power source behind wind power covering
a quarter of the total electricity needs. The total growth of solar PV capacity is
expected to rise from 480 GW produced in 2018 to 8519 GW projected by 2050. Asia
(mostly China) has a dominating position in terms of installed capacity and will
continue to dominate in the PV market reaching over 50% share in the world’s
production by 2050. The paper shows evolution of PV industry starting from mass
production of solar cells in 1963 to 480 GW global capacity by the end of 2018.
Important milestones in the provided timeline of PV development include the
beginning of mass production of solar cells (1963), the first solar building (1973),
the first solar plane flight around the world (2016), and the attaining of the global
installed solar capacity of 480 GW (2018). Efforts have been made to beat the cost
of photo-electricity down, below that of the power generated from fossil or nuclear
fuels. Cost reduction of photo-electricity is permanently high on agenda of PV
engineers and materials scientists. The IRENA’s paper shows a three-times reduc-
tion in the auction price during an eight-year period, that is, from 241 USD/MWh
in 2010 to 85 USD/MWh in 2018 (IRENA 2019).
Analysts estimated the PV capacity growth until 2050 (Figure 2.1) It is expected
that installations will reach 2840 GW globally by 2030. The figure will rise up to
8519 GW by 2050 assuming utility-scale (60–80%) and distributed rooftop (40–20%).
This means 18 times higher production in 2050 when compared to the amount pro-
duced in 2018.
Vast majority of the solar cells are produced from silicon. Various structural
forms of silicon are used in solar cell production: mono-Si, poly-Si, and amorphous.
Crystalline silicon has about 95% share of the PV solar production (IRENA 2019;
Fraunhofer 2019). Thanks to technological maturity and a fall in the price of raw
material, silicon will keep its dominating position in the PV market. Increased
outputs of the Si-based panels also strengthen positions of silicon over other
material. For instance, an average efficiency of multi-crystalline panels increased
from ∼13% in 2006 to ∼17% recently, and this positive tendency is expected to
continue (IRENA 2019; Fraunhofer 2019). A study of the Massachusetts Institute
of Technology (MIT) Energy Initiative has shown that silicon, as an abundant,
non-toxic, efficient and robust material, will maintain top position in the solar
9 000
Historical projections 8519 (2050)
43% 8.9%
CAGR 2000–18 CAGR 2019–50
8 000
7 000
Cumulative installed capacity (GW)
6 000
5 000
4 000
2840 (2030)
3 000
2 000
480 (2018)
1 000
1 (2000)
0
2000 2005 2010 2015 2020 2025 2030 2035 2040 2045 2050
Figure 2.1 PV capacity growth expected by 2050, as reported by IRENA analysts.

Source: IRENA 2019/IRENA/Public domain.
energy market at least for the next few decades (Schmalensee et al. 2015). Lowering
of the cost of Si-based PV devices remains very crucial.
Production of PV module is a multistep process comprising such procedures
as production of metallurgical-grade silicon (MG-Si), upgrading to solar-grade
silicon (SoG-Si), ingot casting, and slicing. Traditional manufacturing includes
high energy-intensive production and purification of silicon, such as carbothermic
silicon reduction from silica and purification to solar grade by the Siemens process.
The cost also increases due to significant material loss when sawing the silicon
ingot into wafers. Subsequent production of the PV cell from Si wafer also includes
numerous steps.
First-generation technologies (conventional solar cell architecture) explore crys-
talline silicon PV panels, whose evolution has covered a whole scope of technical
maturity (Technology Readiness Levels, TRLs): basic research and technology devel-
opment (R&D), demonstration, pilot lines, system launch and operations, enter into
market and penetration, and market maturity. There are many other kinds of solar
panel technologies. One modification becoming more common is the passivated
emitter and rear contact (PERC) cells. Efficiency of the PERC cells is 6–12% higher
when compared with conventional cells. The modification has an extra layer within
the backside, which allows the reflection of some rays back into the cell. The advan-
tages of the PERC cell includes the reduction in recombination, enhancement of
light absorption, and higher internal reflectivity. From an economical point of view,
it is important that the PERC cells, being a modification of the conventional cells,
Saw damage
Formation of Chemical edge Coating of Metallization
removal and Removal
p–n junction isolation SiNx layer printing and
surface of
by and polishing on the front firing of
texturization phosphorous
phosphoros of the rear side by metallic
in acidic silicate layer
diffusion side PECVD contacts
solution
Figure 2.2 Major steps of solar cell production from silicon wafer according to Al back
surface field (Al-BSF) technology. Source: Adopted from the technology route scheme
applied in the “Soli Tek R&D” (Vilnius, Lithuania). Courtesy of Dr. J. Denafas.
do not require great investment in acquiring additional equipment. These cells have
recently become the new industry standard.
Figure 2.2 demonstrates the major stages of the aluminum backside field (Al-BSF)
technology. The process starts from thorough wafer quality check: inspection of
as-cut wafer material, geometry, surface defects, and micro-cracks. Bare silicon
reflects more than 30% of the incident light (Singh et al. 2010; Szlufcik et al. 2005),
thus, antireflection textures are formed in acidic (typically in hydrofluoric acid, HF)
solutions. Further steps include p–n junction formation (e.g. by phosphorous diffu-
sion), chemical edge isolation, removal of phosphorous silicate layer, passivation of
silicon (e.g. by SiNx layer), and preparation of metallic contacts. The BSF formation
provides a good contact between Si and Al with limited penetration of the AlSi
alloy that is formed during the firing process, and it enables a significant reduction
in the thickness of Al deposited in the rear contact. The technology of passivated
emitter and rear cell (PERC) includes some additional steps: (i) edge isolation and
polishing of the rear side, (ii) back side passivation by the AlOx layer, and (iii) its
selective removal (e.g. by laser contact opening).
An innovative approach is metal wrap through (MWT) back-contact solar cell
technology. In this technology, the positive and negative electrodes are arranged
on the rear side of the cell. The back contacts enable avoiding of application of
busbars on the front side. Due to this, the shaded area is reduced, and the con-
version efficiency can be increased by a few percent. The MWT processing is close
to conventional fabrication sequences; thus, it does not require substantial addi-
tional investment. Photograph in Figure 2.3 demonstrates the examples of the solar
cells produced in “Soli Tek R&D” (the limited liability company (LLC) in Vilnius,
Lithuania) using MWT and Al-BSF technologies.
It is obvious that each of the technological steps discussed above contributes to the
cell cost and, in turn, to the cost of photo-electricity. Thin-film technologies provide
Figure 2.3 Solar cells produced according to Al-BSF technology (MWT cell on the left side
and the other two are Al-BSF samples). The photograph also shows the production unit in
the “Soli Tek R&D” (Vilnius, Lithuania). Source: Courtesy of Dr. J. Denafas.
the potential for reduction of the photo-electricity production cost. Depositing thin
silicon layers instead of thick individual cells, which have to be constructed, framed,
and wired together, could reduce the consumption of material and energy.
Thin films provide opportunity to produce large complete modules with improved
appearance for many visual applications (e.g. architectural glass, liquid crystal dis-
plays [LCD]). Mercaldo et al. presented analysis of architectural issues of thin-film
PVs, in particular, those related to applications of transparent and conductive oxides
and films of silicon solar cells (Mercaldo et al. 2009). Modern architectural theories
look at buildings as living organisms that should be able – during their life – to
generate the energy needed to be in operation. Thin-film technology is suitable
to satisfy such advanced architectural theory. It is a challenging goal to form thin

silicon films with effective light absorbance on technically important metallic
substrates such as steel, aluminum alloys, and copper. This makes it possible to
combine structural materials with silicon for facing panels on buildings, which
could be used to harness solar energy. Putting the silicon on thin metallic foils elec-
trochemically would expand the application fields to a wide range of subjects with
flexible geometries as well as on the metal-coated glass. Electrodeposition of thin
Si layers, including the electrochemical formation of a p–n junction, which could
replace multiple processes of Si wafer treatment, will be discussed in Chapter 6.
The main disadvantage of silicon is its poor intrinsic ability to absorb the
light – more than 30% of incident light is reflected if silicon surface is not specifi-
cally textured or coated by antireflection coatings. Also, high-processing complexity
of silicon significantly contributes to the cost of PV devices. Light-harvesting effi-
ciency of the Si-based photoelectrochemical (PEC) cells can be achieved by creating
silicon nano-micro architectures, which enhance light absorbance. To this end,
various surface engineering techniques have been applied, such as femtosecond
laser engineering, annealing in vacuum, coating by atomic layer deposition (ALD)
as well as various etchings: chemical, reactive ion, inductively coupled plasma, and
cryogenic. These methods, however, are costly and technically sophisticated. As
a result, the cost-competitive solutions for industrial-scale solar energy applica-
tions are limited. Furthermore, etchings usually involve toxic chemicals, such as
hydrofluoric acid, and rather expensive catalysts, such as gold.
Electrochemical methods of silicon surface engineering are very attractive due
to environmental friendliness, technical simplicity, and cost-effectiveness. Various
methods of electrochemical Si surface texturing in aqueous and molten salt elec-
trolytes will be surveyed in Chapters 14 and 15.
Non–silicon based thin-film technologies have been intensively investigated as
alternatives to silicon PVs. Particularly, there have been great expectations from
perovskite-based cells. This type refers to a broad class of ABX3 structures, which
originate from the mineral calcium titanium oxide (CaTiO3 ). The component A
can be either organic ions, such as methylamonium (MA, CH3 NH3 + ) or formami-
dinium (FA, CH(NH2 )2 + ), or inorganic ions, such as cesium (Cs+ ) or rubidium
(Rb+ ). The component B refers to a smaller divalent cation, in most cases lead
(Pb2+ ) or sometimes tin (Sn2+ ). The component X refers to halogen anions, typically
iodide (I− ), bromide (Br− ), or chloride (Cl− ). Such ABX3 structures show a high
light absorption under visible light as well as an extremely long charge diffusion
length. These features presuppose the high PV performance of the perovskite-based
cells. More than a dozen of firms from the USA, South Korea, China, UK, Poland,
Japan Switzerland, and Netherlands strived to commercialize the perovskite solar
cells (Extance 2019). The challenge to overcome, perovskite-cells have limited
lifetime due to sensitivity to air and moisture. Another issue lies in the structural
transformations and performance fading when the crystals warm up and cools
down. To be competitive, the operational durability of perovskite cell should be
comparable with the durability of the silicon-based cells with a 25-year warranty.
This is “now looking increasingly unlikely” according to Martyn Green from the
University of New South Wales in Sydney, Australia (Extance 2019). Another

limitation lies in scaling up matters: efficiency of the cells does not replicate when
their size increased. Increased efficiency up to theoretical limit of 45% can be
achieved in tandem cells, that is, a system of perovskite and silicon layers. Such
strategy is under active investigation (Extance 2019).
The rapid expansion of PV resulted in an increasing amount of end-of-life solar
panels, which poses a hazard for future PV development. It is a challenging goal
to find solutions for PV modules recycling. An innovative opportunity has recently
proposed a group consisting of 25 researchers from research establishments in
Singapore, China, and Japan (Cao et al. 2022). Their idea lies in the conversion of
PV waste into feedstock for thermoelectrics (Figure 2.2). Such conversion is in line
with the principles of circular economy: elimination of waste and pollution as well
as circulation of products and materials.
Figure 2.4 outlines the major conversion steps of Si-based solar cells into Si suitable
for thermoelectric application. Polycrystalline Si solar cells were used as a feedstock.
Aluminum and silver were removed from the cell by leaching in HCl, HNO3 , and
H3 PO4 . The dried cells were pulverized into fine powder by a ball milling using
the balls made of tungsten carbide. This was done in an argon atmosphere to avoid
silicon oxidation by air. Furthermore, dopants (P and Ge) were added and the pow-
ders were homogenized by ball milling. Finally, the powders were consolidated by
spark plasma sintering at 1150 ∘ C, and the specimens were cut into desired shapes.
The strategy provided low-cost and environmentally friendly recycling of silicon for
circular economy applications. The economic issues of the proposed process relate
to minimizing the cost associated with the application of Ge and P dopants as well
as the ball milling and spark plasma sintering. Cost minimization is expected when
the technology is used on a large-scale application (economy of scale).
2.2.2 Solar-to-Chemical Conversion

Collection of the solar energy in chemical form helps to conserve energy and makes
it sustainable. Electrochemical solar energy capturing in chemical bonds (e.g.
hydrogen production from water) mimics the process of photosynthesis in plants.
Production of hydrogen in combination with solar energy occurs with near-zero
greenhouse gas emissions. When captured in chemical form, the energy can be
converted to power in fuel cells with specifically high efficiency (up to 85%) or
in combustion engines. It is also possible to combine hydrogen generation with
a fuel cell to generate electricity and replace the water that has been consumed.
Electrochemical hydrogen generation means the usage of electrons as absolutely
clean agents, albeit at slightly lower efficiency but without pollutant emissions. The
electrochemical process offers such advantages as high purity, flexibility, supply
on-site and on-demand as well as fast start-up and shutdown opportunities. Of
particular interest is solar-to-fuel process, which occurs directly (wireless) on the
photo-electrodes.
Solar-to-chemical conversion offers important opportunity for solar energy accu-
mulation and transmission. In this respect, the most attractive process is hydrogen
Electricity Figure 2.4 The process of

conversion of the waste of solar
cells into thermoelectrics:
(a) – solar cells;
(e)
(a) (b) – recovering of Al and Ag;
(c) – pulverizing of Si in a ball
milling machine in Ar
atmosphere; (d) – doping of Si
powder with phosphorous and
germanium; (e) – final pellets
for thermoelectrics. Source:
Reproduced from (Cao et al.
2022) with permission from the
publisher, ©Wiley, 2021.
(b)
Precious metals recovery
Spark plasma sintering
(d)
(c)
Pulverization
Doping
Silicon waste
generation by PEC splitting of water. This process has recently attracted the attention
of researchers due to hydrogen production with a very low carbon footprint. Almost
zero greenhouse emission is achieved when hydrogen is generated by splitting water
using renewable energy sources such as solar, wind, hydro, or ocean. However,
renewable energy is irregular and sporadic in nature; thus, hydrogen generation
is applicable for energy storage and load management. Technologies demonstrate
the connection of the electrolyzers to electricity and gas grids (Bertucioli et al.
2014). With the power-to-gas approach, excess electricity generated from renewable
energy is converted into hydrogen, stored, and when needed, it is reconverted into
electricity. Certainly, the produced hydrogen can also be used as a feedstock in
chemical industry applications. The hydrogen can also be converted to hydrocarbon
fuels, for instance, methane. An international review was published about the
References 17
power-to-gas pilot plants for stationary applications (Gahleitner 2012). The review
evaluated 41 already realized and 7 planned power-to-gas large-scale systems.
Silicon, as a photosensitive, chemically inert, low-cost, and robust material, is
attractive in PEC applications. Effectiveness of solar energy conversion to chemical
bonds depends largely on the ability of a PEC device to absorb the light. Numerous
efforts have been undertaken to increase silicon absorbance by increasing its actual
surface area – the roughness at micro and nano scale. These techniques include
femtosecond laser engineering with subsequent sample etching, deposition of
transparent conducting oxides using ALD, reactive ion etching, chemical etching
using procures metal catalysts, inductively coupled plasma and cryogenic etching,
vapor–liquid–solid reactions, etc. These techniques are surveyed in detail in
Section 14.2. Electrochemical methods of silicon surface engineering in aqueous
and molten salt electrolytes are discussed in Chapters 14 and 15.
Of great interest is nanoporous silicon, known as black silicon, which effectively
absorbs light in a wide range of wavelengths due to internal trapping by porous
structures. Black silicon photocathode for hydrogen production has been reported
(Oh et al. 2011) and patented (Oh and Branz 2014). The authors showed that
nanostructured black silicon significantly accelerates hydrogen production with
reduced need for surfactants. Techniques to fabricate black silicon, such as laser
texturization, plasma treatment, metal-assisted etching, or cryogenic deep reactive
ion etching are discussed in Section 14.3. These techniques, however, are costly.
There is great demand for cost-effective and green technologies of black silicon
mass production. More cost-effective methods based on electrochemical Si surface
texturing in aqueous and molten salt electrolytes are surveyed in Chapters 14 and 15.
Black silicon is also a promising material for solar thermo-generating applica-
tions. Flexible black silicon on insulator has been formed, which is a potential
candidate for use as an absorber for the solar-thermo generators such as concen-
trating solar power parabolic trough (Mei et al. 2011). This is an alternative to
increasing the absorption efficiency of sunlight using antireflection coating and the
surface anodized metal on the heat transfer fluid container. Black silicon can absorb
sunlight from the ultraviolet (UV) and near-infrared (IR) regions non-sensitively to
the angles of incoming light.
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21
Brief Historical Overview of Silicon Production.

Metallurgical-Grade Silicon
Silicon is the second most abundant element after oxygen in the Earth’s crust. This
element very rarely occurs in its pure form. Consequently, it has been used since
the existence of mankind in the form of naturally occurring compounds. Flint or
quartz, for instance, has been used to prepare tools and weapons. The use of natural
glass, especially of volcanic origin, dates back to thousands of years over the Stone
Age. The earliest archeological discovery of glassware dates back to the middle of
the 3rd-millennium BCE.
There are uncertainties as to where and when the man-made glass precisely
originates. It is believed that the first man-made glass was produced as a by-product
of metalworking or faience making. The term faience basically refers to a tin-glazed
pottery. Egyptian faience originates from the Ancient Egypt; the material is pro-
duced from quartz by its vitrification at high temperatures. The first man-made
glass may have appeared in the Middle East regions, e.g. Egypt and Mesopotamia
3000–2000 BCE (Macfarlane and Martin 2004). Glass is thought to have been invented
by accident. Phoenician traders used the nitrate blocks for cooking, and during the
process, they noticed the formation of a clear liquid when the blocks melted and
mixed with the sand of the beach. A method for producing glass vessels invented
by Egyptian craftsmen dates back to about 1500 BCE (Macfarlane and Martin 2004).
The first manual of glassmaking has been “published” on Assyrian stone tablets
at about 650 BCE. Invention of glassblowing is credited to Syrian craftsmen, who
launched this technology about 2000 years ago. Furthermore, the Romans adopted
this “know-how” and transferred their skills and technology to Western Europe.
Venice in Italy became a glassmaking center in the thirteenth century where the
guild of crystal workers was established in 1284.
It is difficult to overestimate the significance of the glass to the development
of mankind. The importance of this material to everyday life and technological
progress is enormous. The first uses of glass do not appear very important: glass
was used in the manufacture of toys, vessels and vases, or in jewelry as a substitute
for precious stones. The importance of glass in everyday life has essentially been
on the increase when it was applied in the making of windows. Another key
22 3 Brief Historical Overview of Silicon Production. Metallurgical-Grade Silicon
area of application was making mirrors by coating glass with silver. Justus von
Liebig1 discovered the chemical process of glass silvering in 1835. Production of
lenses marks another key milestone in glass application – people were given the
opportunity to improve eyesight. The mass production of eyeglasses had begun in
Venice by the end of the fourteenth century. The products were exported to all over
Europe; the demand increased, and the possession of eyeglasses became a sign of
intelligence, prestige, and status.
Glass has contributed immensely to the acquisition of scientific knowledge. This
material led to the development of new scientific instruments, such as thermome-
ters, microscopes, or telescopes. Glass was a key material in the development of
powerful and precise laboratory instruments. Glass instrumentation revolutionized
studies of living things. Important glass-based instruments have been developed
for life sciences, such as micro- or molecular biology, cell biology, histology, and
bacteriology. With regards to glass, advanced methods of diagnosis and medical
treatment have been developed. Astronomers are grateful to glass discoverers and
manufacturers for developing the sky observation techniques; chemists – for the
rich laboratory glassware, electrochemists – for selective glass electrodes enabling
measurement of fundamental solution characteristics, such as pH or metal ion
concentration. Macfarlane and Martin say: “glass literally opened people’s eyes and
minds to new possibilities and turned western civilization from an aural to a visual
mode of interpreting experience”; glass is “a molten liquid that has shaped our
world” (Macfarlane and Martin 2004).
Start of the age of glass science is associated with the names of Otto Schott
(1851–1935) and Ernst Abbe (1840–1905). These glass technologists and scientists
created in Jena (Germany) numerous glass compositions that possessed novel
optical properties. Both scientists started collaboration in 1879. They studied
systematically the optical performance of glasses depending on their chemical
composition. Working together with Calr Zeiss (1816–1888), they developed the
glasses for optical instruments, such as microscopes and telescopes. Calr Zeiss was a
German instrument-maker and businessman who established, in 1846, a workshop
in Jena known as Carl Zeiss AG. Now, the company branded as ZEISS is active in
business worldwide. A catalog appeared in 1886, which referred to 44 optical glass
compositions. The work was named (in German) as “Glastechnisches Laborato-
rium, Schott und Genossen, Jena” (see the photo in (Kurkjian and Prindle 1998)).
In the twentieth century, studies were conducted to understand glass as a material
and to predict its properties. To this end, numerous advanced methods have been
used: X-ray techniques, optical spectroscopy, or physical investigations. Kurkjian
1 Justus Freiherr von Liebig (May 12, 1803–April 20, 1873) was a German chemist who
contributed significantly to organic chemistry, particularly, to agricultural and bioorganic
chemistry. He studied pharmacy at Bonn and Erlangen Universities and worked at the Sorbonne
with L. J. Gay-Lussac. Liebig was a professor at the Universities of Giessen, Heidelberg, and
Munich. He demonstrated the existence of free radicals, clarified basics of acids, and analyzed
body fluids. He also proved that plants use carbon dioxide, water, and ammonia. Liebig discovered
glass silvering for making mirrors. The mineral liebigite Ca2 (UO2 )(CO3 )3 11H2 O was named after
him. (Retrieved from Visuotinė Lietuviu˛ Enciklopedija, and the Encyclopedia Britannica Online,
March 2022).
3 Brief Historical Overview of Silicon Production. Metallurgical-Grade Silicon 23
and Prindle surveyed the development of glass compositions; they provided a brief
review of the early history of glass, the start of glass science, and the development of
more recent glass compositions, such as special glasses and optical fibers (Kurkjian
and Prindle 1998).
While natural silicon materials have been used for thousands of years, application
of silicon in its pure form began much latter. Silicon isolation for chemists was not a
trivial task because of high affinity of this element to oxygen. Jöns Jakob Berzelius2
(1779–1848) reduced potassium fluorosilicate (K2 SiF6 ) in 1823 with molten potas-
sium metal and obtained amorphous silicon. Berzelius is usually given credit for
silicon discovery. Other scientists are also thought to have significantly contributed
to silicon discovery. In 1811, Joseph Louis Gay-Lussac3 (1778–1850) and Louis
Jacques Thénard4 (1777–1857) heated potassium metal with silicon tetrafluoride
(SiF4 ) and obtained amorphous silicon. However, the authors did not identify
the product as a new element. Berzelius also was the first who prepared silicon
tetrachloride (SiCl4 ). Silicon was produced when passing silicon tetrachloride over
heated potassium. Silicon tetrachloride (or tetrachlorsilane) can be obtained by
silica chlorinating. Silicon tetrachloride is a very important compound used in
silicon purification technologies. Due to low boiling point of SiCl4 (57.6 ∘ C), silicon
purification can be achieved by SiCl4 rectification and its thermal decomposition.
Silicon purification principles will be discussed in Chapter 5.
At present, silicon is mainly produced by deoxidation of silica (SiO2 ). Deoxida-
tion is a process in which metal is converted from an oxide (Mex Oy ) to a metallic
form (Me)
Mex Oy + 2ye− ↔ xMe + yO2− (3.1)
Basically, this reaction means electron (e− ) transfer from a reducing agent to a
metal. This rather simple by-form reaction was and remains of paramount impor-
tance. Historically, advancement in utilization of this reaction marks the periods of
development of mankind known as Bronze and Iron ages. The Bronze Age relates
to the advancement in smelting of copper-tin bronze, which replaced stone in
2 Jöns Jakob Berzelius (August 20, 1779–August 7, 1848) was a Swedish chemist, one of the
founders of modern chemistry. Berzelius studied medicine at Uppsala University and was a
professor of medicine and pharmacy at the Karolinska Institute (1807–1832). His important
contributions to chemistry include determination of atomic weights, chemical symbols,
electrochemical theory, and discovery of several elements including the silicon. He also studied
isomerism and catalysis and developed analytical techniques. (Retrieved from the Encyclopedia
Britannica Online, March 2022).
3 Joseph-Louis Gay-Lussac (December 6, 1778–May 9, 1850) was a French chemist and physicist
who made important advances in behavior of gases and created new analytical techniques. He is
best known for the law of the combining volumes of gases (1808). He also determined with
Alexander von Humboldt the hydrogen/oxygen ratio in water (Retrieved from the Encyclopedia
Britannica Online, March 2022).
4 Louis Jacques Thénard (May 4, 1777–June 21, 1857) was a French chemist. He taught at the
École Polytechnique, the Sorbonne and was a chancellor at the University of Paris. He isolated
potassium and sodium metals, studied esters and organophosphorous compounds, discovered
hydrogen peroxide. A lot of his research was done together with Gay-Lussac. The mineral
thenardite is named after L. J. Thénard. Thenardite is non-marine evaporate – an anhydrous
sodium sulfate mineral, Na2 SO4 . (Retrieved from Visuotinė Lietuviu˛ Enciklopedija, March 2022).
production of tools and weapons (3000–1000 BCE). In the Iron Age, the technology
succeeded to extract iron, which became much more used as the bronze. The
transition from Bronze to Iron Age took hundreds of years (1000–500 BCE). Reversal
of the reaction (3.1) means the release of electrons by a metal. Such process is of
vital societal importance as well, however, usually with a negative sign. The process
is known as corrosion. According to the World Corrosion Organization, direct cor-
rosion damage to the society is estimated to be 3–4% of the gross domestic product
(GDP) of industrialized countries. This percentage translates into trillions of $US
(Schmitt et al. 2009). Thus, from the society’s point of view, the reaction (3.1) could
be either globally beneficial or detrimental depending on the reaction direction.
Many industrial processes of chemical deoxidation of metal ores are performed by
the reaction of carbothermic reduction. The most common example is the process
of industrial production of iron, in which iron ore is reduced with coke in a blast
furnace. Another example is the Kroll processes for extraction of titanium from rutile
(TiO2 ). Titanium forms alloys with other metals (Al, V, Mo), which due to lightness,
toughness, and high corrosion resistance are widely used in automotive, aerospace,
military, and in-vivo applications. In the Kroll process, rutile is reduced with coke
at 1000 ∘ C and converted by chlorine gas to volatile titanium tetrachloride (TiCl4 ).
The latter is separated by fractional distillation and titanium is reduced by liquid
magnesium:
( )
TiO2 + C + 2Cl2 → TiCl4 + CO2 1000∘ C (3.2)
( )
2Mg + TiCl4 → MgCl2 + Ti 800 − 850∘ C (3.3)
Silicon is produced industrially by carbothermic reduction as well. Quartzite or
sand is used as a feedstock and various types of coals (charcoal, coal, coke) are used
as a redactor. The reduction process is performed in electric arc furnace at c. 1800 ∘ C
(Zulehner et al. 1995):
SiO2 + C → Si + CO2 (3.4)
Silicon carbide may form as a byproduct at such temperatures (Greenwood and
Earnshaw 1997)
SiO2 + C → Si + 2CO; Si + C → SiC (3.5)
The reduction is performed with excess of silica, which prevents the carbide
production
2SiC + SiO2 → 3Si + 2CO (3.6)
Apart from carbon, other redactors can also be applied. For instance, silicon is
reduced by aluminum in an aluminothermal process (Zulehner et al. 2000)
3SiO2 + 4Al → 3Si + 2Al2 O3 (3.7)
World production of silicon over two decades (2001–2020) is presented in
Figure 3.1. The amount of produced silicon over the first decade increased more
than two times (2001–2011) and thereafter reached some saturation at approxi-
mately 7–8 millions of metric tons (MT). According to (3.4), such amount of Si
3 Brief Historical Overview of Silicon Production. Metallurgical-Grade Silicon 25
6
Si world production (MT)
0
01 002 003 004 005 006 007 008 009 010 011 012 013 014 015 016 017 018 019 020
20 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
Figure 3.1 Silicon world production over two recent decades (2001–2020) in millions of
metric tons (MT). The data of the Mineral Commodity Summaries 2022 – Silicon. US
Department of the Interior, US Geological Survey.
production means direct emission up to 11.8 MT of CO2 per year. Certainly, there
are non-direct emissions as well, for instance, those related to heat generation. The
carbothermic reduction is a very endothermic process with energy consumption of
about 10.5 MWh per one ton of produced silicon.
The carbothermic reduction gives the metal-grade silicon (MG-Si), which con-
tains a rather high content of impurities (Si – 96–99%, the rest – Fe, Al, B, P, Ca,
Mg, Mn, Ti, C, etc.). To obtain pure silicon (e.g. solar grade silicon, SoG-Si), MG-Si
is converted using hydrochloric acid to volatile trichlorsilane (SiHCl3 , the boiling
point − 31.8 ∘ C), which makes it possible to separate silicon from impurities by
distillation in fractionating columns. To decompose the silane, it is passed through
pure silicon bars heated to 1100 ∘ C. The decomposition reactions will be discussed
in Chapter 5.
The carbothermic deoxidation and purification requires large amount of energy
and emits greenhouse gases. A fundamental challenge is to extract metals using
electrons as absolutely clean reducing agents generated by sustainable renewable
sources, in particular, by solar energy. Such task orientates electrochemical research
toward new technologies of metals reduction in electrolytes as well as efficient
and cost-competitive energy conversion and storage, e.g. solar cells, batteries,
supercapacitors, and hydrogen production from water. Opportunity for electro-
chemical silicon reduction from oxide in high temperature molten salt is discussed
in Chapter 8.
References
Greenwood, N.N. and Earnshaw, A. (1997). Chemistry of the Elements, 2e, 330. Elsevier
Butterworth-Heinemann. ISBN: 0 7506 3365 4.
Kurkjian, C.R. and Prindle, W.R. (1998). Perspectives on the history of glass
composition. J. Am. Ceram. Soc. 81: 795–813. https://doi.org/10.1111/j.1151-2916
.1998.tb02415.x.
Macfarlane, A. and Martin, G. (2004). A world of glass. Science 305: 1407–1408.
https://doi.org/10.1126/science.1093597.
Schmitt, G., Schütze, M., Hays, G. F., et al. (2009). Global needs for knowledge
dissemination, research, and development in materials deterioration and corrosion
control. The World Corrosion Organization.
Zulehner, W., Elvers, B., Hawkin, S. et al. (1995). Ullmann’s Encyclopedia of Industrial
Chemistry, 5e, vol. A23, 721–748. Weinheim: VCH.
Zulehner, W., Neuer, B., and Rau, G. (2000). Silicon. In: Ullmann’s Encyclopedia of
Industrial Chemistry. Weinheim: Wiley-VCH https://doi.org/10.1002/14356007.a23_
721.
27
Physical and Chemical Properties of Silicon
We will briefly cover the physical and chemical properties of silicon, which are most
relevant for electrochemical material science. We look at silicon as an electrode
material to be applied in the studies of electrochemical processes.
Silicon (Si, atomic number 14) at room temperature is a crystalline brittle solid
semiconductor with a blue–gray luster. Its melting point is 1414 ∘ C (1687 K, 2577 ∘ F)
and the boiling point is 3265 ∘ C (3538 K, 5909 ∘ F). Density of solid silicon at room
temperature is 2.329 g cm−3 ; in a liquid state (at melting point), its density is
2.57 g cm−3 . Silicon band gap is 1.12 eV at 300 K, and the atomic radius is 1.18 Å.
Silicon has a face-centered diamond-cubic crystal structure with the√lattice constant
a = 5.43 Å. The distance between the nearest two atom neighbors is 3a∕4 = 2.35 Å
(Zhang 2004, p. 45). The list of other physical constants includes: the number of
the atoms per unit cell – 8; the dielectric constant – 11.9; the diffusion constant
for electrons – 34.6 cm2 s−1 , and that for hole – 12.3 cm2 s−1 ; the intrinsic carrier
density – 1.45 × 1010 .
Electric conductivity of silicon depends on temperature and impurities. Typically,
an intrinsic conductivity of 4.3 × 10−6 Ω−1 cm−1 and resistivity of 2.3 × 10−5 Ω cm at
300 K are quoted (Zhang 2004, p. 45). Conductivity of silicon increases with temper-
ature, and this property is at the heart of silicon electrochemistry in molten salts.
While pure silicon is not active at room temperature, it transforms into active elec-
trode at higher temperatures, such as those in high-temperature molten salts.
To increase conductivity, silicon materials are doped. Typically, phosphorous (P),
antimony (Sb), or arsenic (As) is used as the donors of n-type conductivity. Boron
(B), aluminum (Al), and gallium (Ga) are used as the acceptors of p-conductivity. For
instance, resistivity of n-Si doped with phosphorous reduces from 3.8 × 103 Ω cm at
the doping level 1012 cm−3 to 1.2 × 10−4 Ω cm at the doping level 1021 cm−3 and tem-
perature 23 ∘ C. Analogous values for p-Si with the boron dopant are 1.3 × 104 Ω cm
and 1.3 × 104 Ω cm, respectively (Zhang 2004, p. 45).
Silicon is a tetravalent metalloid, which is a type of chemical element with the
properties between metals and nonmetals. For instance, metalloids are brittle and
less electrically conductive when compared with metals.
Silicon is the second most abundant element in the Earth’s crust and eighth in the
universe by mass. This element is mostly available as silica (SiO2 ) or silicates – the
28 4 Physical and Chemical Properties of Silicon
[ ]
anions composed of silicon and oxygen with the general formula SiO(4−2x)− 4−x
with
x being 0, 1, or 2. It very rarely occurs in its pure form. The most common natural
forms of silicon minerals are silica sand, clays, and stone.
The standard electrode potential for the Si/SiO2 electrode is defined by the reaction
Si + 2H2 O → SiO2 + 4H+ + 4e− (4.1)
The potential is E∘ = −0.91 V at temperature 25 ∘ C and effective proton concen-

trations of 1 mol l−1 . This rather negative value implies that pure silicon is a rather
active element with respect to oxidation. Thus, silicon readily oxidizes in water
or humid atmosphere. However, the oxidation leads to the formation of a thin
oxide film, which prevents oxidation and makes the material inert. This is true in
acidic and neutral aqueous solutions. In alkaline solutions, the oxidation reaction
is expressed as
Si + 6OH− → SiO2−
3 + 3H2 O + 4e
−
(4.2)
The standard potential of this reaction is as high as E∘ = −1.697 V. The

electronegativity and the silicide formation indicate that silicon actively dissolves
in alkaline medium.
Reaction (4.2) provides the basis for technologically important field – chemical
silicon texturing. Chemical etching in alkaline solutions is a state-of-the-art process
applied industrially. Micro-pyramid textures are produced by Si etching in KOH
solution with addition of isopropyl alcohol and potassium silicate (K2 SiO3 ) as
well as solution of tetramethylammonium hydroxide (TMAH) (Basu et al. 2013;
Khandelwal et al. 2013; Otto et al. 2015). Such etching yields the pyramidal textures,
which show around 90% of light absorbance in visual and near IR spectral ranges
due to light-trapping effect.
Silicon, when being in a passive state in acid solutions, dissolves in the presence
of fluoride ions:
Si + 6F− → SiF2−
6 + 4e
−
(4.3)
Protective silica layer on silicon substrate is not stable in the presence of fluoride
ions. Stability and protective ability of SiO2 layer are determined by the following
reactions:
SiO2 + 6HF −−−−→ SiF2− +

6 + 2H + 2H2 O (4.4)
SiO2 + 6F− + 4H+ −−−−→ SiF2−

6 + 2H2 O (4.5)
According to Pourbaix diagram, formation of the soluble hexafluoride SiF2− 6

is restricted by two pH boundaries at the SiO2 ∕SiF2− 6 interface. For instance, the
hexafluoride solubility region is restricted by the region approximately pH 2 to 3.8
at the electrode potential E > −1 V vs. saturated hydrogen electrode and fluoride
concentration 10−2 M (Osseo-Asare et al. 1996; Zhang 2004). The reaction (4.4)
determines SiO2 stability boundary at the low pH end, and the reaction (4.5)
determines the stability at the high pH end. The stability boundaries also depend
4 Physical and Chemical Properties of Silicon 29
on silica crystallinity and crystallographic structure. Apart from SiF2−6 , the presence
of other silicon fluoride species, such as SiF and SiF2−
5 , can also be considered.
Silica instability in fluoride-containing solutions (4.4) and (4.5) forms the basis
for silicon etchings technologies. For instance, a stain etching method is known,
which is based on the action of hydrofluoric and nitric acid mixture (HF-HNO3 ).
The hydrofluoric acid removes from the surface silicon oxide and prevents its further
formation, while the nitric acid oxidizes the Si and forms surface texture. Polished,
textured, or porous surface structures can be obtained by this method. The light
absorbance over 90% as well as luminescent nanostructures were achieved by the
stain etching procedures (Cullis et al. 1997; Liu et al. 2014). Another example is
the metal-assisted chemical etching (MACE). Such etching process is based on Si
interaction with hydrofluoric acid in the presence of a strong oxidizer (e.g. hydrogen
peroxide, H2 O2 ) and a noble metal catalyst (e.g. Au, Ag) catalyst:
Si + H2 O2 + 6HF → 2H2 O + H2 SiF6 + H2 (4.6)
The reaction yields the Si nanostructures of high-aspect ratio. The MACE process
is discussed in Chapter 14.
Pure silicon surface contains unsaturated bonds, so-called dangling bonds, or
surface states. The term surface states relates to the energy levels arising from the
orbitals in Si surface plane where atoms cannot be surrounded by the tetrahedral
symmetry, as that observed in the silicon bulk structure (Bard and Faulkner 2001,
p. 751). The surface states are characterized by specific energies (e.g. in the band
gap); they substantially influence the electronic properties of the surface junction.
These surface atoms actively react with the chemical species, for instance, with
environmental oxygen. Thus, silicon surface is newer and ideally pure; some
layer of foreign species is an inevitable component under ambient conditions. In
aqueous solutions, silicon atoms can react with hydrogen, hydroxyl, and oxygen.
Typically, in water, silicon surface is covered by thin oxide film. Thickness of this
film is up to several nanometers, depending on conditions. The chemical surface
passivation when Si atoms are bonded to other atoms is referred to as termination.
In HF solutions, hydrogen-terminated surface (Si–H) is formed. Some oxygen-
and fluorine-terminated site could be present as well. One to three hydrogen
atoms (mono-, di-, and tri-hydride) can terminate each Si atom depending on
its position in the lattice. As assumed in classical electrochemistry, the idealized
solid surface of an electrode is composed of various crystallographic singularities,
such as adsorbed atoms (adatoms), kink-sites (semi-crystal positions), crystal
steps, planes, and vacancies. (Vetter 1967). These positions have different activities
(surface energy) and can accommodate different number of passivation species. The
hydrogen-terminated surfaces are hydrophobic and luminescent. These surfaces are
also amenable to further chemical modifications by various functional groups, e.g.
addition of alkenes. Hydrogen termination occurs over whole pH range, including
alkaline solutions under high etching rates. It is assumed that dipping in HF
solution leads to termination by mono-, di-, and tri-hydride, whereas, in basic
fluoride (pH 9–10), the surface is terminated by mono-hydride (Zhang 2004, p. 57).
It is important to note that surface termination is modified by water rinsing after HF
30 4 Physical and Chemical Properties of Silicon
treatment. Water removes di- and tri-hydrides leaving mono-hydride termination

behind. This effect is referred to as an atomic scale surface flattening. Fluorine
termination in HF solution is typically very low when compared with hydrogen
termination. However, content of the attached fluoride increased with fluoride
concentration: over half surface was fluorine terminated when HF concentration in
the electrolyte was increased by 50% or more (Takahagi et al. 1988).
Apart from hydrogen- or oxygen-termination, silicon surface can also adsorb elec-
trolyte impurities. Metal cations can be reduced on Si surface, as its electrochemical
potential is rather negative, that is, E∘ = −0.91 V (Eq. (4.1)). Si surfaces with chemi-
cal oxides were immersed into dilute nitric acid solutions of ten metals: Al, Ba, Ca,
Cr, Cu, Fe, K, Ni, Sr, and Zn (Loewenstein and Mertens 1998). These metals were
deposited on Si surface, and its content increased when pH was increased from 3 to
5.6. Some of them can occur due to physical or chemical adsorption.
Silicon surface can be hydrophobic or hydrophilic. Hydrophilicity arises from
Si–OH termination, whereas hydrophobicity is caused by Si–H, Si–CHx , or Si–F
termination. Silicon dipped into HF solution becomes hydrophobic due to Si–H
termination. Silicon electrode in a passive state (Si–SiO2 ) is hydrophilic; however,
it becomes hydrophobic when polarized negatively below the breakdown potential
of passivity zone. Hydrophilic and hydrophobic properties can change due to
aging: hydrophilic Si–OH surface changes to a hydrophobic one when it losses the
hydroxyl groups. On the contrary, appearance of hydroxide groups on an aging
hydrophobic surface leads to surface hydrophilicity.
Comprehensive materials on silicon surface chemistry, silicon-electrolyte
interface, and interdisciplinary aspects are available in literature (Lehman 2002;
Zhang 2004).
References
Bard, A.J. and Faulkner, L.R. (2001). Electrochemical Methods: Fundamentals and
Applications, 2e. Wiley.
Basu, P.K., Sarangi, D., Shetty, K.D., and Boreland, M.B. (2013). Liquid silicate additive
for alkaline texturing of mono-Si wafers to improve process bath lifetime and reduce
IPA consumption. Sol. Energy Mater. Sol. Cells 113: 37–43. https://doi.org/10.1016/j
.solmat.2013.01.037.
Cullis, A.G., Canham, L.T., and Calcott, P.D.J. (1997). The structural and luminescence
properties of porous silicon. J. Appl. Phys. 82 (3): 909–965. https://doi.org/10.1063/1
.366536.
Khandelwal, R., Plachetka, U., Min, B. et al. (2013). A comparative study based on
optical and electrical performance of micro- and nano-textured surfaces for silicon
solar cells. Microelectron. Eng. 111: 220–223. https://doi.org/10.1016/j.mee.2013.03
.162.
Lehman, V. (2002). Electrochemistry of Silicon. Instrumentation, Science, Materials and
Applications. Wiley-VCH Verlag GmbH & Co https://doi.org/10.1002/3527600272.
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Le 9 janvier [1840]. — La fin de mon dernier cahier a coupé net

M. Sainte-Beuve ; je reprends par vous et pour vous causerie et
écriture, ce journal de sœur qui se continue au continuateur de
Maurice, avec mes croyances, mes convictions, mes réflexions, qui
en sont la conséquence, ma manière d’être et de sentir, ce de moi à
vous et que vous ne voudriez pas autre, comme vous venez de me
le dire, et comme je viens de le lire au soleil dans le bois de Sept-
Fonts, à la place où j’allais m’asseoir avec Maurice. C’est là aussi
que j’ai lu souvent de ses lettres, comme je viens de lire la vôtre,
seule devant Dieu. Suivant la lecture et l’état de ces pauvres frères,
je le prie ou bénis, et m’en retourne, repliant dans ma poche et en
mon cœur cette bien-aimée écriture. La vôtre aujourd’hui ne m’a pas
fait trop de mal ; vous paraissez moins abattu que de coutume, et ce
mot : Je suis quelquefois religieux par raison, m’a fait plaisir.
Espérons ! la foi au cœur peut venir, la croyance par sentiment, vous
l’aurez peut-être. C’est un effet de la grâce, et on la demande pour
vous ; à deux cents lieues de Paris, dans un désert, il est une âme
qui demande à Dieu le salut d’une âme. Les affections qui nous
tombent du ciel et y remontent sont bien fortes. C’est la charité qui
soulèverait le monde pour un élu. Vous me comprendrez. Maurice
m’occupait une grande partie du cœur ; lui ôté, Dieu s’avance dans
cette place restée vide, et bientôt tout sera envahi, et tout en moi
porté là-dessus, comme l’arche sur les eaux, tout ce qui s’est sauvé
du déluge.
Le 10. — Presque résolue de ne pas écrire, jour de privations ;
mais la vue de ce papier blanc me tente la main qui se laisse aller
doucement là-dessus, et y marque une pose rare dans le calme. Lu
la vie de saint Paul ermite, qui, après cent ans de solitude,
demandait ce qui se passait dans le monde. Quelque jour, mais pas
si tard apparemment, je pourrai faire la même question ; car je ne
pense plus sortir d’ici, du fond de ce Cayla où Dieu m’a mise, où je
me trouve bien, où je ne désire rien, où tout ce qu’il me faut m’arrive
comme à Paul par le corbeau merveilleux, par quelque moyen
inattendu et de providence. N’est-ce pas vrai tant pour la vie du
cœur que pour l’autre ? J’ai toujours eu besoin d’amitié, et il m’en est
venu comme du ciel de rares, d’introuvables, qu’on ne peut ni faire ni
imaginer, et tout d’abord dans mon frère, ce cher Maurice que j’ai
perdu. Louise datait d’avant. Celle-ci est pour moi d’un différent
goût : fruit d’une autre saison. Je l’ai rencontrée à dix-sept ans. Son
charme est à part, comme l’âge où nous nous sommes liées ; quoi
qu’il soit survenu de triste, nous nous voyons à travers des fleurs.
Rayssac, charmant paysage où je vois en bas la jeunesse ; à cela,
Paris, les Coques contrastent en noir, et dans l’éloignement, sous la
même vue, le Cayla avec une tombe. Tout pour moi maintenant finit
là et s’y rattache. Voilà pourquoi je ne voudrais plus m’éloigner d’ici,
pour toujours garder et regarder cette chère tombe. Mon regard
cependant ne demeure pas tout là ; il monte au ciel, où est le
meilleur de ce que je pleure, au ciel qu’on voit de partout, où de
partout je pourrai voir où est Maurice. Ainsi, si Dieu m’appelait
ailleurs, j’irais ; cette raison de cimetière ne m’empêcherait pas d’un
devoir de charité, ou d’amitié, ou de vocation, où qu’il fût. Le chrétien
est-il d’aucun lieu ?
Le 11. — O Marie, Marie ! quelle femme avec sa tendresse, sa

vive et si délicate et si entendue façon d’amitié ! Je la retrouve avec
ses charmes dans la boîte tant attendue, toute pleine d’objets
choisis par elle pour moi. Que j’aime surtout la statuette de la Vierge,
cette céleste envoyée m’apportant tant de pensées du ciel !
Le 19. — Hier, je vous ai écrit une longue et bien franche lettre,
véritablement comme à lui-même, en parler de ma façon, comme il
vient. Je ne saurais pas me changer, il y paraîtrait, n’ayant jamais
dissimulé nulle chose. Et pourquoi, quand on n’a risque ni de
déplaire, ni de se compromettre ? Je vous envoie mes pensées, ma
vie en sûreté : confiance la plus grande qu’une femme puisse
donner, qui met bien haut dans son estime celui en qui elle croit.
Six mois, six mois aujourd’hui de cette mort, de cette séparation !
Mon Dieu, que le temps est rapide ! il me semble que c’est d’hier.
D’où vient cela, que tant d’événements, d’autres choses, soit
douloureuses ou non, qui touchent à ce cher ami, me semblent dans
un lointain infini : tels son dernier départ d’ici, mon arrivée à Paris,
son mariage, et que sa mort soit toujours là récente, présente ? Je le
vois : il y a six mois, et c’est comme s’il n’y avait rien du tout, tant on
y touche par l’âme ! il n’y a ni temps ni espace pour l’âme, cela fait
bien voir que nous sommes esprits. Oh ! tant mieux, tant mieux de
n’être pas bornés par ce temps si court et si triste ! de n’être pas tout
en ce corps de si peu de chose ! Convenons-en, la foi nous ouvre de
belles perspectives. Mais quelle douleur de penser qu’il y en a qui ne
feront que les apercevoir, sans y atteindre par la possession, par la
jouissance en l’autre vie, hélas ! comme il adviendra à ces pauvres
chrétiens de nom, hommes sans œuvres, sans pratique de foi ! C’est
martyre d’avoir des amis de la sorte.
Le 21 janvier. — Pauvre Louis XVI ! J’étais enfant que je vénérais

ce martyr, j’aimais cette victime dont j’entendais tant parler dans ma
famille aux approches du 21 janvier. On nous menait au service
funèbre à l’église, et je regardais fort le haut catafalque, trône
lugubre du bon roi. Mon étonnement m’impressionnait de douleur et
d’indignation ; je sortais pleurant cette mort et haïssant les méchants
qui l’avaient faite. Que d’heures j’ai passées cherchant par quels
moyens j’aurais pu sauver Louis XVI et la reine, et toute la
malheureuse famille, si j’avais vécu de leur temps ! Tout calculé,
cherché, combiné, rien de bon ne se présentait guère, et je laissais
ces prisonniers fort à regret. Le beau petit dauphin surtout me faisait
compassion, le pauvre enfant, entre des murs, ne pouvant plus jouer
en liberté. Celui-là, je l’emportais, je le cachais ici au Cayla, et Dieu
sait le bonheur de courir avec un prince dans nos champs ! Que de
rêves au sujet de la triste famille !
Il y a deux sortes d’hommes qui m’inspirent répulsion : les
régicides et les impies. Pour si débordé que soit un jeune homme, je
l’estime toujours quelque peu, s’il est réservé sur la religion. J’ai vu
avec une profonde satisfaction que, dans la correspondance de
Malise Allen avec Georges, il ne se trouvait pas une plaisanterie
incrédule. Oh ! que cela m’a consolée ! que d’espoir j’ai mis en ce
bon côté restant ! Je ne me suis pas trompée du moins pour
Georges ; quant à Malise, je ne sais, l’avenir nous l’apprendra. C’est
encore un fameux pécheur, une sorte d’Augustin, que Dieu a à
conquérir sur le monde.
Le 22. — Il y a des jours où l’âme se retourne plus que de

coutume vers le passé, où elle revoit à tout moment ce qu’elle a
perdu. Ces visions lui plaisent ; quoique tristes, on les conserve, on y
demeure, on vit dans l’ombre de ce qu’on a aimé. Tout aujourd’hui je
vois passer et repasser cette chère figure pâle ; cette belle tête pose
en moi dans toutes ses poses, souriante, éloquente, souffrante,
mourante ; surtout je me suis arrêtée, je ne sais pourquoi, à le voir
chez l’abbé Legrand, vicaire de la paroisse, quand nous allâmes lui
parler pour les arrangements du mariage. Je me trouve dans ce
salonnet, décoré de croix, de saintes gravures, de beaux meubles et
de beaux livres d’un goût pieusement exquis ; là, tout éclatante de
paroles et d’air affairé ; Maurice dans le plein calme du visage et de
la voix, sur un fauteuil, laissant tomber parfois quelques mots ; l’abbé
causant avec distinction, tout surpris de plaisir quand, par hasard, je
lui nomme l’abbé de Rivières, un de nos voisins, qu’il a connu à
Saint-Sulpice. Je revois cela, et quand, abordant la question
religieuse sur ce qui nous amenait, l’abbé toucha avec un tact parfait
les préparations chrétiennes, Maurice répondit en homme qui
comprend et qui croit. J’en fus touchée, l’abbé de même, peut-être
avec surprise. Je remarquai tout, tout m’est resté. Je ferais tableau
du jeune prêtre et du fiancé chrétien en ce moment. Maurice était
parfait. Frère bien-aimé !
Le 23. — Pourquoi des larmes montent-elles ce matin ? pourquoi

ce retombement dans la douleur et l’angoisse ? Demandez au
malade pourquoi son mal lui revient ! il n’y a que suspension aux
souffrances ; si j’étais près d’une église, je m’en irais les y apaiser,
me perdre, m’absorber dans la communion. Dans cet acte de foi et
d’amour est tout mon soutien, toute ma vie, même celle du corps
peut-être. Dieu me prend en lui ; et que ne peut l’amour tout-puissant
sur une âme qu’il possède ! La consoler d’abord, de ce qu’elle
souffre en aimant.
Le 24. — Ces paroles sont bien mystiques, incompréhensibles

peut-être à qui n’a pas le sens pieux d’un sacrement ineffable, d’un
mystère d’amour divin, la plus étonnante chose de Dieu pour les
hommes. Galimatias spirituel pour le monde, tout ce qu’on en
pourrait dire ; mais ceci n’est pas pour le monde, et les solitaires
peuvent mettre sur leur papier ce qu’ils veulent. C’est l’imprimerie
cachée de mon âme qui se fait sur ce cahier, j’y trace tous ses
caractères. Quelquefois je dis : « A quoi sert ? A qui serviront ces
pages ? Ce n’était de prix que pour lui, Maurice, qui retrouvait là sa
sœur. Que me fait de me retrouver ? » Mais si j’y trouve une
distraction innocente, si je m’y fais une pause dans les fatigues du
jour, si j’y mets pour les y mettre les bouquets de mon désert, ce que
je cueille en solitude, mes rencontres et mes pensées, ce que Dieu
me donne pour m’instruire ou pour m’affermir : oh ! il n’y a pas de
mal sans doute. Et si quelque héritier de ma cellule trouve cela et
trouve une bonne pensée, et qu’il la goûte et devienne meilleur,
quand ce ne serait qu’un instant, j’aurai fait du bien. Je veux le faire.
Sans doute, je crains de perdre le temps, ce prix de l’éternité ; mais
est-ce le perdre de l’employer pour son âme et pour une autre ?
Qu’ai-je à faire d’ailleurs qu’à coudre ou à filer ? Si mes doigts
étaient utiles au ménage, je ne les mettrais pas ici, je n’ai jamais
donné le devoir au plaisir. Mais puisque ma bonne sœur veut bien
prendre sur elle ces soins matériels, qu’elle m’en décharge avec
autant d’amitié que d’intelligence, puisqu’elle est Marthe, je puis bien
être Marie. Oh ! le doux rôle de mon goût ! Quand quelquefois tout
s’agite et bruit en la maison, et que j’entends cela du calme de ma
chambrette, le contraste me fait délices ; dans mon haut reclusoir, je
sens quelque chose des stylites sur leur colonne. Mais, discoureuse
que je suis ! me voilà bien loin de mon premier mot, de mon idée
sainte. Oh ! les courants de l’âme, qui les suivra ? On les remonte.
Je retrouverai celui-ci quelque autre fois.
[Le 25.] — C’est bien fait pour l’écrire ! une lettre de ma chère
Marie, sur mon chevet, à mon réveil ce matin. Aurore d’un beau jour,
tant en moi qu’au dehors : soleil au ciel et dans mon âme : Dieu soit
béni de ces douces lueurs qui ravivent parmi les angoisses ! Je sais
bien que c’est à recommencer, mais on s’est reposé un moment et
on marche avec plus de force ensuite. La vie est longue, il faut de
temps en temps quelques cordiaux pour la course : il m’en vient du
ciel, il m’en vient de la terre, je les prends tous, tous me sont bons,
c’est Dieu qui les donne, qui donne la vie et la rosée ! Les lectures
pieuses, la prière, la méditation fortifient ; les paroles d’amitié aussi
soutiennent. J’en ai besoin : nous avons un côté du cœur qui
s’appuie sur ce qu’on aime ; l’amitié, c’est quelque chose qui se tient
bras à bras. Comme Marie me donne le sien tendrement, et que je
me trouve bien là ! Ainsi nous irons jusqu’à la mort : Dieu nous a
unies.
Le 26. — Il y a deux ans, ici, à la même place, dans la même

chambre d’où il venait de sortir, je pleurais. Jamais sien départ ne
m’avait tant brisé l’âme, c’était comme un pressentiment que ce
serait le dernier. Lui aussi s’en fut plus affligé, plus retenu que de
coutume. Ces six mois avec nous, étant malade et tant aimé,
l’avaient fort rattaché ici. Cinq ans sans nous voir lui avaient fait
perdre peut-être un peu de vue notre tendresse ; l’ayant retrouvée, il
y avait remis toute la sienne ; il avait si bien renoué tous les liens de
famille, en nous quittant, que la mort seule aurait pu les rompre. Il
m’en avait donné l’assurance. Ses erreurs étaient passées, ses
illusions de cœur évanouies ; par besoin, par goût primitif, il se ralliait
à des sentiments de bon ordre. Je savais tout, je suivais ses pas ; du
cercle de feu des passions (bien court pour lui), je l’ai vu passer
dans celui de la vie chrétienne. Belle âme, âme de Maurice ! Dieu
l’avait retirée du monde pour la retirer au ciel. Hélas ! que tout cela
me revient, que j’en suis suivie, entourée, aujourd’hui, triste
anniversaire de notre séparation ! De ce jour nos rapports intimes
ont été brisés ou dehors : il s’en allait…
S’il fût resté ici, si ce fatal hiver se fût passé au Cayla, le pauvre
jeune homme ne serait pas mort. L’air de Paris lui était mauvais
évidemment, il retombait malade en arrivant ; puis tant de choses qui
ont tourné à malheur ! Il s’est fait un enchaînement de circonstances,
d’événements, qui l’ont conduit au cimetière, et cela sans qu’on ait
su comment l’éviter. O fatalité ! si je croyais à la fatalité. Mais non,
c’est Dieu qui nous mène, Dieu tout bon, quoique la nature gémisse,
quoiqu’on soit tous malheureux, sans qu’on sache pourquoi.
Comprenons-nous le mystère de rien ? Celui des souffrances me fait
croire à quelque chose à expier et à quelque chose à gagner. Je le
vois dans Jésus-Christ, l’homme de douleurs. Il fallait que le Fils de
l’homme souffrît. Nous ne savons que cela dans les peines et
calamités de la vie. La raison des choses est en Dieu. C’est le secret
du gouvernement que le souverain se réserve. Se soumettre à ce
qui advient, c’est unir notre volonté à la sienne, c’est la diviniser,
c’est la porter aussi haut que l’homme puisse atteindre. Aussi je
trouve dans l’acte de résignation chrétienne, qui peut sembler une
acceptation passive, une sorte d’affaissement sous la nécessité ; j’y
trouve, dis-je, le mouvement le plus sublime de l’âme. Il est tout de
foi, il porte tout à coup de la terre au ciel. Si tous les affligés
croyaient en Dieu, non d’une croyance du monde, mais d’une
croyance de catéchisme, on ne verrait pas tant de suicides. Oh ! le
suicide, qu’il me fait frémir !
Le 27. — Trois douces heures à écrire à Marie. Note du cœur. Je

marque toutes ses lettres et les miennes pour retrouver les jours où
nous avons causé, qui font époque. Je n’en ai pas de plus chères
que ces épanchements d’amitié. Tout, hormis ce qui me touche à
l’intime, passe en ma vie sans sensations. Tout m’est indifférent de
ce qui est affaires, cours du monde, nouvelles ; quoi qu’il se passe
sur la terre, je n’en suis plus. Ici ma présence, mon âme au ciel. Ce
petit cahier est la seule chose pour laquelle je me détourne un peu
de mes pensées d’habitude. Et encore est-ce pour les y reposer.
Aujourd’hui il se marie à Gaillac une de nos cousines qui nous

voulait à sa noce ; mais c’est fait de noces ! Je ne saurais même dire
combien cette invitation, cette vue de fêtes m’a attristée.
Le 28. — Saint François de Sales, celui que Rousseau appelait

le plus aimable des saints, m’a fort occupée aujourd’hui. C’est sa
fête que j’aime particulièrement, que je fais en mon cœur en lisant
cette belle vie, en pensant aux choses qu’elle a faites, conversions,
écrits, lutte de vingt ans contre la colère, douceur divine dans cette
fougue, au point d’être comparé au Sauveur du monde, ineffables
traits de charité, dires charmants tels que ce mot : « Il vaut mieux
taire une vérité que de la dire de mauvaise grâce », tendresse de
cœur débordante, compassion maternelle pour les pécheurs, enfin,
mille choses célestes, mille perles qui couronnent le front de ce
bienheureux, m’y attirent l’âme, me le font aimer, vénérer, invoquer
d’une façon particulière. Le cœur au ciel a ses élus aussi, et ceux-là
du moins ne font pas souffrir pour leur bonheur ! Il faut tout dire : à
mes prédilections spirituelles pour ce saint il s’en joint une un peu
humaine, les de M… sont alliés aux de Sales, Marie est parente de
saint François, de sorte que l’amitié et la sainteté me font relique et
s’enchâssent ineffablement au cœur l’une dans l’autre.
Le 1er février. — Du monde pendant deux jours ; cela passé, je

remonte à ma solitude avec trois lettres d’amies et un regret de
départ. Parmi ces visites se trouvait le confesseur de Maurice, ce
bon M. Fieuzet, qui vient de temps en temps prier sur cette tombe et
voir où nous en sommes en tristesse. C’est l’âme de prêtre la plus
saintement tendre, qui porte sur le fond le plus doux l’austérité de
son ministère, Évangile imprimé sur velours. Je fus bien consolée de
le voir au lit de mort de Maurice. De quoi vais-je me souvenir ? Oh !
qu’un tel prêtre, qu’un saint prêtre m’assiste aussi dans mon agonie !
Ainsi mes cahiers s’emplissent de tristesse, de choses lugubres, de
vues de mort : ma vie s’en va toute maintenant sur ce fond noir avec
un peu de sérénité de ciel par-dessus.
Le 3. — On me presse d’aller à Gaillac. Non, je ne puis m’ôter

d’ici ; ma vie se plaît toute petite au plus petit endroit possible, là où
j’ai mes chers vivants et mes morts.
Le 4. — J’aurais bien une lettre à écrire, mais j’aime mieux

tourner ma plume ici ; ici par goût, ailleurs par convenance, et la
convenance est bien froide. Le cœur ne s’y plaît pas, il s’en
détourne, s’en retire tant qu’il peut. Hormis les devoirs, je le laisse.
La lettre, je la ferai ; c’est peu de chose d’ailleurs, et ce n’est pas
grand effort de surmonter un court ennui. Il en est de si longs qu’il
faut tenir jusqu’au bout. Les uns accoutument aux autres. Les petits
combats mènent aux grands et y forment. Ces contre-goûts sont
bons comme une amertume, ils font agir la volonté pour les prendre
et fortifient ensuite. Si tout nous venait en douceur et plaisance, que
serait-ce de nous à la fin, au choc terrible de la mort ? Il est bon de
prévoir cela. De là vient que les solitaires, tous les saints, ces
hommes qui entendent si bien l’âme, se vouent au sacrifice, se
privent volontairement, se font mourir tous les jours rien qu’en cette
vue qu’il faut mourir. Ils sortent aussi bien doucement de ce monde.
On m’a parlé d’une jeune fille, religieuse à Alby, qui s’est mise à
pleurer de joie quand elle a entendu les médecins dire entre eux qu’il
n’y avait plus d’espérance.
Je ne sais pourquoi, du temps du choléra, je me faisais aussi
comme un bonheur de mourir, j’enviais toutes les agonies. Cela
m’impressionnait au point d’en parler à mon confesseur. Était-ce
langueur de jeunesse, était-ce désir du ciel ? Je ne sais. Ce qui est
sûr, c’est que c’est passé ou à peu près. Je me trouve vis-à-vis de la
mort dans des sentiments de soumission, quelquefois de crainte,
rarement de désir. Le temps nous change. Ce n’est pas en cela seul
que je m’aperçois de l’âge. Quand j’aurai des cheveux blancs, je
serai tout autre encore. O métamorphoses humaines, s’enlaidir,
vieillir ! Pour se consoler de cela, on a besoin de croire à la
résurrection ! Comme la foi sert à tout ! Oui, cette pensée de la
résurrection pour tant de femmes qui se font un amour de leur corps,
un bonheur de leur beauté, leur serait bonne à la fin de leurs
charmes, et il peut se faire que plus d’une belle chrétienne s’en
serve, de celles à qui vient grand chagrin du visage. Celle-là, par
exemple, qui disait : « Ce n’est rien de mourir, mais de mourir
défigurée ! » C’était l’insupportable pour elle. Pauvre femme ! J’en ris
beaucoup alors ; à présent j’en ai compassion, je souffre de voir
qu’on ne porte pas son âme plus haut que son corps. Qui sait ? Si
j’étais jolie, peut-être ferais-je de même.
Le 5. — Quelle lecture, quelle amitié, quelle mort, quel

rapprochement ! quelle impression j’en ai dans l’âme ! Je veux parler
des derniers moments d’Étienne de La Boëtie que j’ai rencontrés au
fond d’un livre de Montaigne. Sachant que ces deux hommes
s’aimaient beaucoup, j’ai été touchée de savoir comment s’était faite
leur séparation, et j’en ai le cœur dans les larmes. C’est si
douloureux de voir mourir, surtout quand cette mort vous en rappelle
une autre ! Que de traits saillants m’ont frappée dans cette vie sitôt
faite, dans cette âme s’en allant jeune de ce monde, et si belle, si
élevée, si chrétienne, si exquise de douceur et d’amitié ! Oh !
vraiment, j’ai trouvé Maurice aux beaux endroits, et vous et lui dans
l’étroite union et si profonde de ces deux amis. Mais vous manquiez
aux derniers moments du vôtre. Que j’ai eu regret à cela, et que la
distance vous eût séparés à ces derniers jours ! Je veux vous dire
comme ils se sont passés, car cela manque aux détails que je vous
ai donnés de sa mort, tout comme à l’intérêt que vous portez à cette
fin de vie.
Mais d’abord je veux laisser ici mémoire de ce qui se fait
aujourd’hui sur cette tombe. Elle était nue encore, simplement
gazonnée ; et, pour la couvrir comme il lui convient et nous la
conserver à jamais, on y place une blanche pierre de marbre en
obélisque surmonté d’une croix. La pauvre veuve a fait cet envoi, ce
triste et dernier don d’amour, et mis elle-même l’inscription. Je n’ai
rien vu encore. Oh ! j’y serai assez à temps ! Tous les dimanches
n’irons-nous pas prier là tous, autour de notre pauvre Maurice ? Et
vous, son frère aussi, ne viendrez-vous jamais vous y mettre à
genoux ? Que je voudrais vous voir prier pour lui ! « Ce sont les
meilleurs offices que les chrétiens puissent faire les uns pour les
autres », disait cet Étienne de La Boëtie mourant à son ami
Montaigne. Je ne doute pas que si Maurice pouvait se faire
entendre, il ne vous dît de même. C’était, lui aussi, une âme
croyante de son fond, une âme des anciens temps, sur laquelle le
temps qui court avait pu passer par malheur, mais rien que passer.
Vous le verrez par la suite.
Le 11. — Demeuré plusieurs jours sans écrire. Il m’en coûte de

commencer ce douloureux récit, de parler de cette mort, quoique j’y
pense sans cesse. Il est des souvenirs qui déchirent l’âme en sortant
plus qu’en demeurant, ce me semble. Même la douleur se fait
quelque chose de doux et dépose avec le temps au fond du cœur
comme un limon sur lequel elle s’endort. Peu après cette mort, j’en
parlais sans trop de peine ; à présent, quand on revient sur ce sujet,
que nous y tombons par entretien en famille, une souffrance me
prend l’âme.
Cette nuit, il a fallu faire garder ce mausolée, à cause de
quelques paysans d’Andillac qui ne voulaient pas le laisser mettre.
Ils trouvent que cela choque l’égalité de la mort et ont fait opposition
violente, ayant l’autorité. Pauvre peuple souverain ! c’est ce qu’il faut
en souffrir, c’est ce qu’il sait faire. Au temps passé, tous se seraient
signés devant cette croix qu’ils parlent d’abattre aujourd’hui, au
temps lumineux où nous sommes. Malheureux temps, où se perd le
respect des choses saintes, où les plus petits s’enorgueillissent
jusqu’à se révolter contre la triste élévation d’une tombe ! Le paysan
dont l’esprit en est là ne vaut plus rien : fruit des lectures, en partie.
Aussi, qu’il vaut bien mieux un chapelet qu’un livre dans la poche
d’un laboureur !
Ce fut le 8 juillet, vingt jours après le départ de Paris, vers six

heures du soir, que nous fûmes en vue du Cayla, terre d’attente, lieu
de repos de notre pauvre malade. Sa pensée n’allait que là sur la
terre, depuis longtemps. Je ne lui ai jamais vu de plus ardent désir,
et toujours plus vif à mesure que nous approchions. On aurait dit
qu’il avait hâte d’arriver pour être à temps d’y mourir. Avait-il
pressenti sa fin ? Dans les premiers transports de sa joie, à la vue
du Cayla, il serra la main d’Érembert, qui se trouvait près de lui. Il
nous fit signe à tous comme d’une découverte, à moi qui n’eus
jamais moins d’émotion, de plaisir ! Je voyais tout tristement dans ce
triste retour, jusqu’à ma sœur, jusqu’à mon père, qui nous vinrent
joindre à quelque peu de distance. Affligeante rencontre ! Mon père
fut consterné ; Marie pleura en voyant Maurice. Il était si changé, si
défait, si pâle, si branlant sur ce cheval assis à l’anglaise, qu’il ne
semblait pas animé. C’était effrayant. Le voyage l’avait tué. Sans la
pensée d’arriver qui le soutenait, je doute qu’il l’eût achevé. Vous en
savez quelque chose, et ce qu’il a dû souffrir, pauvre cher martyr !
Mais je ne veux parler que d’ici. Lui embrassa son père et sa sœur
sans se montrer trop ému. Il semblait dans une sorte d’extase dès la
première vue du château ; l’ébranlement qu’il en eut fut unique, et
dut épuiser toute sa faculté de sensation ; je ne lui ai plus vu l’air
vivement touché de rien depuis cela. Cependant il salua
affectueusement les moissonneurs qui coupaient nos blés, tendit la
main à quelques-uns, et à tous les domestiques qui nous vinrent
entourer.
Arrivés au salon : « Ah ! dit-il, qu’on est bien ici ! » en s’asseyant
sur le canapé, et il se mit à embrasser mon père, qu’il n’avait pu
atteindre que du bout des lèvres à cheval. Nous étions tous à le
regarder content. C’était encore une joie de famille. Sa femme sortit
pour quelque déballement ; je pris sa place auprès de lui, et le
baisant au front, ce que je n’avais fait depuis longtemps : « Dis, mon
ami, comme je te trouve bien ! Ici tu vas guérir vite. — Je l’espère…
je suis chez moi. — Que ta femme aussi se regarde comme chez
elle ; fais-le-lui comprendre, qu’elle est de la famille, et d’agir comme
dans sa maison. — Sans doute, sans doute. » Je ne me souviens
plus des autres choses que nous dîmes dans ces moments de seul
à seul. Caroline descendit, on annonça le souper que Maurice trouva
exquis. Il mangea de tout avec appétit. « Ah ! dit-il à Marie, que ta
cuisine est bonne !… »
— Mon Dieu, que ce passé me tient au cœur ! Ma vie n’est que
là. Je n’ai d’avenir que par la foi, de liens que ceux qui se rattachent
à Maurice, et de lui au ciel.
La première de la famille j’ai vu le mausolée ce matin. Cela s’est
ainsi rencontré ; mais, lui et moi, ne nous sommes-nous pas toujours
rencontrés tout d’abord et mis à part ? Cela se continue, et le tête-à-
tête, hélas ! sur un cimetière ! J’étais seule à genoux sur cette
tombe, vis-à-vis de la blanche pierre où j’ai lu son nom et sa mort :
Maurice. 19 juillet.
Mais revenons à sa vie, à ce qu’il m’en est resté de derniers et
précieux souvenirs. Oh ! que n’ai-je écrit alors à mesure qu’il nous
parlait et s’en allait ! Que n’ai-je fait un journal d’agonie, inestimable
recueil dont celui-ci n’est que l’ombre ! Se rappeler n’est pas voir ;
les plus vivants détails sont morts, quoique le cœur les conserve.
Mais pensais-je à rien de lui qu’à lui ? Pensais-je même qu’il dût
finir ? Et je le craignais cependant. Je ne me comprends plus quand
je reviens à ces souvenirs.
Nous espérions beaucoup du climat, de l’air natal, de la chaude
température de notre Midi. Le second jour de notre arrivée, il fit
froid ; le malade s’en ressentit et eut des frissons. Ses bouts de
doigts, son nez glacés, me firent craindre ; je vis bien qu’il n’y avait
pas tout le mieux que nous espérions, qu’il ne guérirait pas si vite,
puisque les accès revenaient. Il n’y eut pas de chaleur ensuite, et le
médecin nous rassura. Ces médecins sont souvent trompés ou
trompeurs. Nous décidâmes le malade à ne pas sortir de sa
chambre le lendemain, attribuant le froid qu’il avait eu à quelque
fraîcheur du salon. Comme il se laissait toujours faire, il se résigna,
quoique contrarié, à ce qu’on voulut ; mais il s’ennuyait tant là-haut,
et il fit tant de chaleur bientôt, que je l’engageai moi-même à
redescendre. « Oh ! oui, me dit-il, ici je suis loin de partout. Il y a plus
de vie là-bas avec tous, et puis la terrasse, je pourrai m’y promener.
Descendons. » Cette terrasse surtout l’attirait pour y jouir du dehors,
de l’air, du soleil, de cette belle nature qu’il aimait tant. Je crois que
ce fut ce jour-là qu’il arracha des herbes autour du grenadier et
piocha quelques pieds de belles-de-nuit ; aidé de sa femme, il tendit
un fil de fer le long du mur sur un jasmin et des treilles. Cela parut
l’amuser. « Ainsi chaque jour j’essayerai un peu mes forces », fit-il en
rentrant. Il n’y revint plus. La faiblesse survint, les moindres
mouvements le fatiguaient. Il ne quittait son fauteuil que par
nécessité ou pour faire quelques pas à la prière de sa femme, qui
essayait de tout pour le tirer de son atonie. Elle chantait, faisait de la
musique, et le tout souvent sans effet. Du moins je ne me suis pas
aperçue qu’il en eût quelque impression. Il demeurait le même à
toutes choses, la tête penchée sur le côté du fauteuil, les yeux
fermés.
Cependant il avait des mieux passagers, des espèces de
soubresauts vers la vie. Ce fut dans un de ces moments qu’il se mit
lui-même au piano et joua un air, pauvre air que j’aurai toujours dans
le cœur ! Ce piano s’en est allé à Toulouse. Je l’ai vu partir avec le
regret qu’y avait gravé Maurice. J’aurais voulu y noter ces mots :
« Ici un jeune malade a chanté son dernier air. » Peut-être quelque
main en passant sur ce clavier se serait arrêtée pour la prière. Chère
âme de trépassé, je voudrais de partout lui tirer des secours ! Ce
sont les meilleurs offices que les chrétiens puissent se faire. Je
reviens à ce mot de foi de l’ami de Montaigne, qui revient si bien à
mon cœur.
Je veux vous dire aussi comme ce cher frère m’a laissé sujet de
consolation dans ses sentiments chrétiens. Ceci ne date pas de ses
derniers jours seulement ; il avait fait ses pâques à Paris. Au
commencement du Carême, il m’écrivait : « L’abbé Buquet est venu
me voir ; demain, il revient encore pour causer avec moi comme tu
l’entendais. » Cher ami ! oui, j’avais entendu cela pour son bonheur,
et lui l’avait fait pour le mien, non en cédant par complaisance, mais
en faisant par conviction : il était incapable du semblant d’un acte de
foi. Je l’ai vu seul à Tours, dans sa chambre, lisant les prières de la
messe un dimanche. Depuis quelque temps il se plaisait aux
lectures de piété, et je me suis applaudie de lui avoir laissé sainte
Thérèse et Fénelon, qui lui ont fait tant de bien. Dieu ne cessait de
m’inspirer pour lui. Ainsi j’eus la pensée d’emporter pour la route un
bon petit livre, pieux et charmant à lire, traduit de l’italien, le Père
Quadrupani, qui lui fit grand plaisir. De temps en temps il m’en
demandait quelque page : « Lis-moi un peu du Quadrupani. » Il
écoutait avec attention, puis faisait signe quand c’était assez, se
recueillait là-dessus, fermait les yeux et restait là à se pénétrer de
ces douces et confortantes paroles saintes. Ainsi, chaque jour, au
Cayla, nous lui avons lu quelques sermons de Bossuet et des
passages de l’Imitation. A cela il voulut joindre quelques lectures de
distraction, et nous commençâmes les Puritains de Scott, n’ayant
rien de nouveau dans notre bibliothèque. Il en parcourut un volume
avec quelque air d’intérêt, et puis laissa cela. Il était bientôt las de
tout, nous ne savions que trouver pour lui faire plaisir. Les visites lui
apportaient peu de distractions ; il ne causait qu’avec son médecin,
homme d’esprit, qui par cela plaisait au malade et soutenait son
attention. J’ai remarqué ces influences morales, et qu’au plus fort
abattement, cette nature intelligente se relevait à tout contact de
rapport. — Ainsi, la veille ou l’avant-veille de sa mort, n’en pouvant
plus, il se prit à rire vivement à votre feuilleton si plaisamment
spirituel : Il faut que jeunesse se passe, dont il fut charmé. Il en
voulut deux fois la lecture : « Écris cela à d’Aurevilly, me dit-il, et que
depuis longtemps je n’avais ri comme je viens de le faire. » Hélas ! et
il n’a plus ri ! Vous lui avez donné le dernier plaisir d’intelligence qu’il
ait eu. Tout lui était jouissance de ce qui lui venait de vous. L’amitié a
été le plus doux et le plus fort de ses sentiments, celui qu’il a senti le
plus à fond, dont il aimait le plus à parler, et qu’il a pris, je puis dire,
avec lui, dans la tombe. Oh ! oui, il vous a aimé jusqu’à la fin. Je ne
sais à quelle occasion, parlant de vous étant seuls, je lui dis : « Es-tu
content, mon ami, que j’écrive à ton ami ? — Si je suis content ! » me
fit-il avec le cœur dans la voix. Ce jour-là même, en le quittant, je
vous envoyai son bulletin de santé.
Nous le trouvions bien faible ; cependant j’espérais toujours.
J’avais écrit au prince de Hohenlohe. J’attendais un miracle. La toux
s’était apaisée, l’appétit se soutenait ; la veille fatale, il dîna encore
avec nous ; hélas ! dernier dîner de famille ! On servit des figues dont
il eut envie, et que sur sa consultation j’eus la cruauté de lui
interdire ; mais d’autres ayant approuvé, il en mangea une qui ne lui
fit ni bien ni mal, et je fus sauvée sans préjudice de l’amertume de
l’avoir privé de quelque chose. Je veux tout dire, tout conserver de
ses derniers moments, bien fâchée de ne pas me souvenir
davantage. Un mot qu’il dit à mon père m’est resté. Ce pauvre père
revenait de Gaillac avec l’ardente chaleur, lui rapportant des
remèdes. Dès que Maurice le vit : « Il faut convenir, dit-il en lui
tendant la main, que vous aimez bien vos enfants. » Oh ! en effet,
mon père l’aimait bien ! Peu après, le pauvre malade se levant avec
peine de son fauteuil pour passer dans la chambre à côté : « Je suis
bien bas », parlant comme à lui-même. Je l’entendis, cet arrêt de
mort, de sa bouche, sans lui rien répondre, sans trop y croire peut-
être ; mais j’en fus frappée. Le soir, on le porta avec son fauteuil
dans sa chambre. Du temps qu’il se mettait au lit, je disais avec
Érembert : « Il est bien faible, ce soir ; mais la poitrine est plus libre,
la toux disparaît. Si nous pouvons aller au mois d’octobre, il sera
sauvé. » C’était le 18 juillet, à dix heures du soir !
La nuit fut mauvaise. J’entendis sa femme lui parler, se lever
souvent. Tout s’entendait de ma chambre, j’écoutais tout. Dès qu’il
fut possible, j’entrai le matin pour le voir, et son regard me frappa.
C’était quelque chose de fixe : « Qu’est-ce que cela augure ? dis-je
au docteur qui vint bientôt. — C’est que Maurice est plus malade. —
Ah ! mon Dieu ! » Érembert alla avertir mon père, qui accourut.
Bientôt il sortit, et s’étant concerté avec le médecin, celui-ci annonça
qu’il fallait penser aux derniers sacrements. M. le curé fut mandé,
ainsi que ma sœur, qui se trouvait à l’église. Je ne sais si j’aurai tout
présent. Mon père pria M. Facieu, le médecin, de préparer Caroline
à la terrible nouvelle. Il la prit à part. J’allai la joindre bientôt et la
trouvai tout en larmes ; j’entendis : « Je le savais. » Elle savait qu’il
devait mourir ! « Depuis trois mois je me prépare au sacrifice. » Aussi
ce coup de mort ne l’effraya pas, mais je la vis désolée.
« Ma pauvre sœur, lui dis-je en lui passant les bras au cou, voici
le terrible moment ; mais ne pleurons pas, il faut l’annoncer au
malade, il faut le préparer aux sacrements. Vous sentez-vous la
force de remplir ce devoir, ou voulez-vous que je le fasse ? — Oui,
faites-le, Eugénie, faites ! » Elle étouffait de sanglots. Je passai de
suite au lit du malade, et, priant Dieu de me soutenir, je me penchai
sur lui et le baisai au front, qu’il avait tout mouillé : « Mon ami, lui dis-
je, je veux t’annoncer quelque chose. J’ai écrit pour toi au prince de
Hohenlohe. — Oh ! que tu as bien fait ! — Tu sais qu’il a fait des
miracles de guérison, notamment à Alby, dans une famille qui vient
de m’en faire part. Dieu opère par qui il veut et comme il veut. C’est
surtout le souverain médecin des malades. N’as-tu pas bien
confiance en lui ? — Confiance suprême (ou pleine, je ne me
souviens pas). — Eh bien, mon ami, demandons-lui en toute
confiance ses grâces, unissons-nous en prières, nous à l’Église, toi
dans ton cœur. On doit dire une messe où nous communierons : toi,
tu pourrais communier aussi. Jésus-Christ allait trouver les malades,
tu sais ? — Oh ! je veux bien ! oui, je veux m’unir à vos prières. —
C’est très-bien, mon ami. M. le curé devait venir, tu vas te confesser.
N’est-ce pas que tu n’as pas de peine à parler à M. le curé ? — Pas
du tout. — Tu vas donc te préparer à ta confession. » Il demanda un
livre d’examen, se fit faire toutes les prières qui précèdent la
confession par sa femme. Je sortis ; j’allai lui préparer de la fécule
au lait d’amande. Dans ce temps, M. le curé arriva. Le malade le pria
d’attendre encore un peu, ne se trouvant pas, dit-il, assez préparé.
On le voyait tout pénétré et recueilli. Hélas ! dernier recueillement de
son âme ! Au bout de dix minutes à peu près, il fit appeler le prêtre,
et demeura avec lui près d’une demi-heure, causant, nous fut-il dit,
avec toute la lucidité et facilité d’esprit qu’il aurait eue étant bien
portant. « Jamais je n’ai entendu confession mieux faite », nous dit
M. le curé. Ce qui m’assure bien de ses dispositions, c’est ce qu’il fit
comme M. le curé s’en allait. Il le rappela pour lui parler de M. de
Lamennais et faire une haute et dernière rétractation de ses
doctrines. Puis il ajouta : « M. le curé, je ne sais si je m’abuse, mais
me croyez-vous bien malade ? Alors je recevrai l’extrême-onction.
Pour communier, je voudrais le faire à jeun et attendre à demain. »
Sur la réponse que les malades étaient dispensés du jeûne, il fut
prêt à tout et se prépara aux derniers sacrements. Nous allions et
venions, ma sœur et moi, pour les arrangements convenables dans
cette chambre qui s’allait changer en église. Sa femme, avec la
tristesse et la piété d’un ange, lui récitait les prières de la
communion, qui sont si belles, et celles des mourants, si
touchantes ; lui-même demanda celles de l’extrême-onction, calme
et naturel comme pour une chose attendue.
Cependant il avait faim, il défaillait, et me demanda sa fécule,
que je lui portai. Comme il suait beaucoup, je lui dis : « Mon ami, ne
sors pas le bras, je te ferai manger comme un néné (enfant au
berceau). » Un sourire vint sur ses lèvres, où je posai la cuiller, où je
fis couler le dernier aliment qu’il ait pris. Ainsi j’ai pu le servir une fois
encore, lui donner mes soins comme autrefois. Il m’a été rendu
mourant. Je remarquai cela comme une faveur de Dieu accordée à
ma tendresse de sœur, que j’ai rendu à ce cher frère les derniers
services à l’âme et au corps, qu’il s’est rencontré que je l’ai disposé
aux derniers sacrements, et que je lui ai préparé sa dernière
nourriture : aliments des deux vies. Cela ne semble rien, n’est rien,
en effet, pour personne ; je suis seule à le remarquer et à bénir la
Providence de ces rapports repris avec mon cher Maurice avant de
nous quitter. Triste et indéfinissable compensation à tant de mois
d’amitié passive ! Avais-je tort de vouloir le servir ? Qui sait ?… Mais
je veux achever ce douloureux mortuaire ; laissons le cœur de côté,
qui n’en finirait pas de dire.
Quand le saint viatique arriva, le malade se trouvait mieux, ce me
semblait ; ses yeux, rouverts, n’avaient pas cette fixité effrayante du
matin, ni ses sens le même affaissement ; il parut moralement ravivé
et en pleine jouissance de ses facultés tout le temps des saintes
cérémonies. Il suivait tout de cœur, bien pieusement. Quand ce fut à
l’extrême-onction, comme il ne sortait qu’une main, le prêtre ayant
dit : « L’autre », il la présenta vivement. Il écouta de bien simples et
touchantes paroles, et reçut le saint viatique avec toute l’expression
de la foi. Il vivait encore, il nous entendait, il choisit entre de l’eau et
de la tisane qu’on lui offrait à boire, serra la main à M. le curé, qui
toujours lui parlait du ciel, colla ses lèvres à une croix que lui
présentait sa femme, puis il s’affaiblit ; nous nous mîmes tous à le
baiser, et lui à mourir. Vendredi matin, 19 juillet 1839, à onze heures
et demie. Onze jours après notre arrivée au Cayla. Huit mois après
son mariage.
La voilà cette fin de vie, si liée à la vôtre, telle que j’ai pu la
retrouver pour vous dans mes larmes. Que n’étiez-vous là ! Que
n’avez-vous assisté à la mort chrétienne de votre ami !
Le 27. — Enfin vous voilà ! comme disait Billy, le charmant enfant

indien, quand il me voyait revenir. Il paraissait tout réjoui, comme je
le suis de votre lettre, si tardive et si désirée. Ce n’était cependant
qu’un silence un peu long qui me donnait tant de craintes funèbres.
C’est que je crois si vite à la mort, à présent ! Me voilà donc bien
rassurée. Mais qu’est-ce que nos impressions ? Je n’éprouve pas en
certitude ce que j’ai senti dans le doute, un sentiment profond. Le
plaisir chez moi ne descend pas comme la peine.
Douce journée aujourd’hui : j’attends encore mon père, absent
depuis toute une semaine. Sa présence m’est nécessaire plus que
jamais depuis que je me trouve plus que jamais seule au Cayla. En
regardant du côté par où il doit venir, je pense à tant d’absents qui
ne reviendront pas. J’en ai bien vu s’en aller par ce chemin. Il y a au
bas de la colline une croix où, deux ans passés, nous nous sommes
quittés avec mon cher Maurice. Je l’accompagnai jusque-là. Il s’y est
longtemps conservé sur le terrain l’empreinte d’un pied de cheval, à
l’endroit où Maurice s’arrêta pour me tendre la main. Je ne passe
jamais par là que je ne regarde à cette marque effacée d’adieu près
d’une croix.
Comme toute ma vie va à ce frère, comme tout ce qui a rapport à
lui me pénètre ! Les sentiments uniques grandissent dans la solitude
jusqu’à l’immensité. Comme ce marronnier qui s’étend seul là-bas
dans la prairie, ils couvrent toute l’âme. Je ne sais si je ne ferais pas
bien de sortir d’ici pour quelques jours. Les idées fixes, oh ! les idées
fixes que tout nourrit et rappelle ! La vie est un devoir. Sous ce
rapport religieux on y tient, et on doit vouloir sa conservation. Le
dépérissement en serait un mal devant Dieu. Mais sans cela, sans le
ciel que je vois, je me laisserais tomber ; mais j’aurais tort, bien tort
comme chrétienne de m’abattre comme ceux qui vont sans soutien.
Dieu n’est-il pas là qui nous dit : Je suis près de ceux qui souffrent ?
Foi soutenante ! Oh ! que nous avons d’obligations à la foi ! Je la
considère comme le seul vrai soutien de l’homme. D’autres choses
en ont bien l’air ; mais ce sont appuis d’apparence, colonnes de
vapeur.
De Montels, vieux château dans les montagnes.
Le 14 mars. — Ce que j’aime me suit partout : ce cahier a pris

mon chemin, comme, hélas ! naguère un autre était venu ici au
même lieu, lorsque j’allais voir Louise, mon amie, quelque peu avant
mon départ pour Paris. Ainsi les pareilles choses reparaissent
quelquefois dans la vie, sans qu’on pense à les ramener. Bien sûr, je
ne comptais pas revenir ici. J’ai remarqué de ces consonnances du

Silicon Electrochemistry Production Purification and Applications Eimutis Juzeliunas Full Chapter PDF

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Silicon: Electrochemistry, Production,

Purification and Applications Eimutis

Silicon Containing Hybrid Copolymers: Synthesis,

Current Developments in Biotechnology and

Inorganic and composite fibers: production, properties,

Biomass-Derived Carbon Materials: Production and

Nanocarbon electrochemistry First Edition Foord

Silicon Carbide Biotechnology, Second Edition: A

Thermodynamics and Applications in Hydrocarbon Energy

Sustainable Water Purification M. R. Islam

Cover Image: © Georgy British Library Cataloguing-in-Publication Data

Bibliographic information published by

© 2023 WILEY-VCH GmbH, Boschstraße 12,

All rights reserved (including those of

Print ISBN: 978-3-527-34897-8

Typesetting Straive, Chennai, India

who inspired and supported.

2 Silicon Electrochemistry – Toward Low-Carbon Economy 5

3 Brief Historical Overview of Silicon Production.

4 Physical and Chemical Properties of Silicon 27

5 Silicon Reﬁning: From Metallurgical-Grade to

6 Silicon Electrowinning and Electrodeposition of

7 Photoelectrochemistry and Nanogravimetry of Si and Si-Oxide

8 Electro-Deoxidation of Solid Compounds in Molten Salts 121

9 Voltammetry and Basic Reactions of Silicon Electrode in

10 Si–SiO2 Electrode in Molten CaCl2 145

11 Formation of Silicon Oxide Layer 149

12 In Situ Studies of SiO2 → Si Conversion – Synchrotron X-ray

13 Molten Oxide Electrochemistry at Ultra-High

14 Silicon Surface Structuring 175

14.2.1 Chemical Etching 178

15 Electrochemical Si Surface Structuring and Formation of Black

16 Silicon Compositions – Perspectives for Semiconductor

17 Silicon Photo-Electrodes for Water Splitting and Their

18 Conclusions, Outlook, and Challenges 257

Theodor von Grotthuss (1785–1822)

Vilnius, Lithuania Eimutis Juzeliūnas

Lehman, V. (2002). Electrochemistry of Silicon. Instrumentation, Science, Materials and

3PI three-phase interface (interlines)

GDP Gross domestic product

SWIR short-wavelength infrared

About the Author

Professor Dr. Eimutis Juzeliūnas is a principal research

electrolysis (MOE). Chapter 13 discusses the MOE principles of silicon extraction in

Silicon Electrochemistry – Toward Low-Carbon Economy

2.1 Silicon for Energy Storage – Electrochemical

2.2 Silicon for Energy Conversion – Photovoltaic

of 48 sub-modules and attained 2% efficiency. The reader interested in historical

Figure 2.1 PV capacity growth expected by 2050, as reported by IRENA analysts.

to satisfy such advanced architectural theory. It is a challenging goal to form thin

University of New South Wales in Sydney, Australia (Extance 2019). Another

2.2.2 Solar-to-Chemical Conversion

Electricity Figure 2.4 The process of

Spark plasma sintering

Amnesty International report (2016): “This Is What We Die For”, https://www.google

Brief Historical Overview of Silicon Production.

Physical and Chemical Properties of Silicon

Si + 2H2 O → SiO2 + 4H+ + 4e− (4.1)

The potential is E∘ = −0.91 V at temperature 25 ∘ C and effective proton concen-