(Andre Pierre Legrand Christiane Senemaud) Nanost

Nanostructured Silicon-based
Powders and Composites
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“fm” — 2002/9/6 — page ii — #2
Nanostructured Silicon-based
Powders and Composites
Edited by
André P. Legrand
and Christiane Sénémaud
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First published 2003 by Taylor & Francis
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Simultaneously published in the USA and Canada
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Cover: A laser irradiation cell observed through a KCl window
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Christiane Sénémaud was a CNRS Directeur de Recherches until she passed away in 1998.
Her area of expertise was the determination of the electronic structure of complex materials
by X-ray photoelectrons and soft X-ray spectroscopies. She had published more than one
hundred papers and communications in international meetings, and owing to her open mind
and vast knowledge, she skilfully established fruitful cooperation between foreign and French
laboratories. Moreover, she directed the theses of many young students and contributed to
graduate education at the university, more precisely the ‘Complex Materials’ doctoral school.
Finally, she was the leader of the CNRS research group that was the origin of this book. Her
merit was recognised with the attribution of the Charles-Louis de Saulces de Freycinet Award
by the French Academy of Sciences.
Christiane Sénémaud was above all smart, discrete, fair, active, efficient and kind. For
these reasons, the authors would like to dedicate this book to her memory.
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“fm” — 2002/9/6 — page vi — #6
Contents
List of contributors xi
Foreword xiii
Preface xv
Acknowledgements xvi
1 Objectives and state-of-the-art of nanocomposites 1

M I C HE L C AUC HE T I E R AND ANDR É P IE R R E L E G R A N D
1.1 Introduction 1
1.2 Nanostructured ceramic elaboration 2
1.3 Nanostructured Si 3 N4 /SiC materials 3
1.4 Analytical methods 4
1.5 Conclusion 5
References 5
2 Laser synthesis of nanosized powders 6

M I C HE L C AUC HE T I E R , E M M ANUE L M U S S E T, M IC H E L L U C E , NAT H A L IE
HE R L I N, XAVI E R AR M AND AND M A RT IN E M AY N E
2.1 Generalities on the synthesis of nanosized powders by laser

pyrolysis 6
2.2 Synthesis of Si, SiC, Si 3 N4 and SiC Si 3 N4 mixtures with SiH 4
and SiH 3 CH 3 as silicon precursors 8
2.3 Synthesis of silicon carbonitride (Si/C/N) powders using
hexamethyldisilazane as Si precursor 15
2.4 Silicon carbonitride (Si/C/N) powders containing in situ the
elements of the sintering aids (Al, Y): pre-mixed powders 19
2.5 Conclusion 22
References 23
3 Thermal behaviour of as-formed silicon-based

nanopowders 25
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viii Contents
3.1 Thermal behaviour in a high-temperature graphite
furnace 26
E M M ANUE L M USSE T, M ART I NE M AY N E , M IC H E L C AU C H E T IE R , X AV IE R
AR M AND, M I C HE L L UC E AND NAT H A L IE H E R L IN -B O IM E
3.1.1 Introduction 26
3.1.2 Weight evolution of SiC, Si/C/N and Si/C/N/Al/Y/O
nanopowders 26
3.1.3 Chemical evolution during annealing in a nitrogen
atmosphere 29
3.1.4 Structural changes 33
3.1.5 Information about changes in the grain sizes 39
3.1.6 Conclusion 40
References 40
3.2 Thermal reactivity of silicon-based nanopowders 41

DJAM I L A BAHL OUL - HOUR L I E R , B E N O ÎT D O U C E Y, J E A N -L O U IS B E S S O N A N D
PAUL GOUR SAT
3.2.2 Results and discussions 42
3.2.3 Conclusion 53
References 53
4 Structure of some nanopowders and micro/nano composites by

transmission electron microscopy 54
M AR C M ONT HI OUX, C AT HE R I N E B É R AU D A N D NA H IDA E L H O R R
4.1 As-prepared and heat-treated nanopowders 54

4.2 As-prepared sintered composites 95
4.3 TEM sample preparation prior to investigations and operating
conditions 105
References 109
5 From short- to long-range order 110
5.1 Chemical order studied by solid-state nuclear magnetic

resonance 111
ANDR É PI E R R E L E GR AND, JE A N -BA P T IS T E D ’E S P IN O S E D E L A C A IL L E R IE
AND YOUSSE F E L KORTOB I
5.1.1 Nuclear magnetic methods 111

5.1.2 SiC powders analysis 115
5.1.3 Si/C/N powders analysis 119
5.1.4 Pre-alloyed Si/C/N/Al/Y nanopowders 129
5.1.5 Conclusion 137
References 138
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Contents ix
5.2 Paramagnetic defect states in silicon-based nanopowders 139
AB DE L HADI KASSI BA AND ST É P H A N E C H A R P E N T IE R

5.2.2 Theoretical background 140
5.2.3 Experimental details 141
5.2.4 Si/C powders 141
5.2.5 Assignment of the paramagnetic species in Si/C nanopowders 144
5.2.6 Silicon carbonitride (Si/C/N) powders 146
References 152
5.3 Electronic structure studied by X-ray photoemission (XPS) and soft-X-ray

(SXS) spectroscopies 153
ADR I ANA GHE OR GHI U DE L A RO C QU E , G E O R G E S D U F O U R , F R A N Ç O IS
T É NÉ GAL AND C HR I ST I ANE SÉ N É M AU D
5.3.1 Principles 153

5.3.2 Experiments 154
5.3.3 Study by XPS–SXS of Si, Si/C, Si/N and Si/C/N laser synthetised
nanopowders produced from gaseous precursors 155
5.3.4 Effect of heat treatment on the electronic structure of nanometric
Si/C/N ex-HMDS and pre-alloyed Si/C/N/Al/Y powders studied by
XPS spectroscopy 165
References 180
5.4 Local order in Si/C/N nanopowders studied by X-ray absorption

spectroscopy: study at the Si K edge 182
FR ANÇ OI S T É NÉ GAL , ANNE - M AR IE F L A N K , A D R IA NA G H E O R G H IU -D E L A
ROC QUE AND C HR I ST I ANE SÉ NÉM AU D
5.4.1 X-ray absorption principles and data analysis 182

5.4.2 Study by EXAFS at the Si K edge of Si, SiN, SiC and Si/C/N
laser-synthetised nanopowders produced from
gaseous precursors 187
5.4.3 Short-range order determination in amorphous SiCN-HMDS
nanopowders: evolution as a function of the C/N ratio and
annealing treatment 192
5.4.4 Local structure of pre-alloyed Si/C/N/Al/Y nanopowders studied by
XAS at the Al K edge using fluorescence yield detection 205
References 209
5.5 Neutron and X-ray diffraction applied to the study of the medium-range
order in SiCN nanopowders 211
FR ANÇ OI S T É NÉ GAL , B R I GI T T E B O U C H E T-FA B R E , J E A N D IX M IE R A N D
ROB E RT B E L L I SSE NT
5.5.1 Diffraction applied to the study of disordered compounds 211
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x Contents
5.5.2 Early stages of the crystallisation of Si/C/N-HMDS nanopowders
studied by X-ray and neutron diffraction: Nano-ordered Si/C/N
structures 211
References 225
6 Conductivity and dielectric properties of Si/C

nanopowders 227
AB DE L HADI KASSI BA
6.1 Introduction 227

6.2 Material specifications 228
6.3 Experimental results and interpretation 228
6.4 Conclusion 237
References 237
7 Processing and tailoring of Si/C/N-based nanocomposites 238

PAUL GOUR SAT, DJAM I L A BAH L O U L -H O U R L IE R , B E N O ÎT D O U C E Y A N D
M ART I NE M AYNE

7.2 Sintering of silicon nitride with additives 238
7.3 Sintering of silicon carbide 241
7.4 Si 3 N4 /SiC nanocomposites 241
7.5 Conclusion 262
References 263
8 Mechanical properties 264

JE AN- L OUI S B E SSON
8.1 Room temperature properties 264

8.2 High-temperature properties 268
8.3 Conclusion 280
References 280
9 Theoretical investigations of Si/C/N-based alloys 282

FAB I O FI NOC C HI

9.2 Simulations of Si/C and Si/N disordered alloys 284
9.3 Simulations of ternary Si/C/N systems 290
References 297
Index 299
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Contributors
Xavier Armand Commissariat à l’Energie Atomique, Service des photons, atomes et

molécules, Bat 522. 91191 Gif-sur-Yvette Cedex, France
Robert Bellissent Laboratoire Léon Brillouin, CEA-Saclay, batiment 563, 91191 Gif-sur-
Yvette Cedex, France
Catherine Béraud Laboratoire de Physique de la Matière Condensée, INA,135 avenur de
Raugueil, 31077 Toulouse Cedex, France
Jean-Louis Besson SPCTS, UMR CNRS 6638, ENSCI, 47-73, avenue Albert Thomas,
87065 Limoges Cedex, France
Brigitte Bouchet-Fabre Laboratoire d’Utilisation du Rayonnement Electromagnétique, Bat.
209, Centre Universitaire Paris-Sud, 91405 Orsay Cedex, France
Michel Cauchetier Commissariat à l’Energie Atomique Service des photons, atomes et
Stéphane Charpentier Laboratoire de Physique de l’Etat Condensé, Université du Maine,
Faculté des Sciences, Boulevard Olivier Messiaen, 72085 Le Mans Cedex, France
Jean Dixmier Laboratoire de Physique du Solide, 1 place Aristide Briand, 92195 Meudon
Cedex, France
Benoît Doucey SPCTS, UMR CNRS 6638, Faculté desSciences, 123, avenue Albert Thomas,
Georges Dufour UMR CNRS 7614, Laboratoire de Chimie-Physique, Université Pierre et
Marie Curie, 11 rue P.M. Curie, 75231 Paris Cedex 05, France
Nahida El Horr CEMES, BP 4347, 29 rue Jeanne Marvig, 31055 Toulouse Cedex 4, France
Youssef El Kortobi FRE CNRS 2312, Laboratoire de Physique Quantique, Ecole Supérieure
de Physique et de Chimie Industrielles de la Ville de Paris, 10, rue Vauquelin, 75231 Paris
Cedex 05, France
Fabio Finocchi UMR CNRS 7588, Groupe de Physique des Solides, UPMC, 2, place Jussieu,
75251 Paris Cedex 05, France
Anne-Marie Flank Laboratoire d’Utilisation du Rayonnement Electromagnétique, Bat. 209,
Centre Universitaire Paris-Sud, 91405 Orsay Cedex, France
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xii Contributors
Adriana Gheorghiu-de La Rocque UMR CNRS 7614, Laboratoire de Chimie-Physique,
Université Pierre et Marie Curie, 11, rue P.M. Curie, 75231 Paris Cedex 05, France
Paul Goursat SPCTS, UMR CNRS 6638, Faculté des Sciences, 123, avenue Albert Thomas,
Nathalie Herlin-Boime Commissariat à l’Energie Atomique, DSM/DRECAM/SPAM-
Laboratoire Francis Perrin URA CNRS 2453, Bat 522. 91191 Gif-sur-Yvette Cedex,
France
Djamila Bahloul-Hourlier SPCTS, UMR CNRS 6638, Faculté des Sciences, 123, avenue
Albert Thomas, 87060 Limoges Cedex, France
Abdelhadi Kassiba Laboratoire de Physique de l’Etat Condensé, Université du Maine,
Faculté des Sciences, Boulevard Olivier Messiaen, 72085 Le Mans Cedex, France
Jean-Baptiste d’Espinose de la Caillerie FRE CNRS 2312, Laboratoire de Physique Quan-
tique, Ecole Supérieure de Physique et de Chimie Industrielles de la Ville de Paris, 10,
rue Vauquelin, 75231 Paris Cedex 05, France
André Pierre Legrand FRE CNRS 2312, Laboratoire de Physique Quantique, Ecole
Supérieure de Physique et de Chimie Industrielles de la Ville de Paris, 10, rue Vauquelin,
75231 Paris Cedex 05, France
Michel Luce Commissariat à l’Energie Atomique Service des photons, atomes et molécules,
Bat 522. 91191 Gif-sur-Yvette Cedex, France
Martine Mayne Commissariat à l’Energie Atomique, DSM/DRECAM/SPAM-Laboratoire
Francis Perrin URA CNRS 2453, Bat 522. 91191 Gif-sur-Yvette Cedex, France
Marc Monthioux CEMES, BP 4347, 29 rue Jeanne Marvig, 31055 Toulouse Cedex 4, France
Emmanuel Musset Commissariat à l’Energie Atomique, Service des photons, atomes et
Christiane Sénémaud UMR CNRS 7614, Laboratoire de Chimie-Physique, Université
Pierre et Marie Curie, 11, rue P.M. Curie, 75231 Paris Cedex 05, France
François Ténégal Laboratoire d’Utilisation du Rayonnement Electromagnétique, Bat. 209,
Centre Universitaire Paris-Sud, 91405 Orsay Cedex, France
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Foreword
The preparation of inorganic materials by thermolysis of preceramic compounds has become

of substantial interest for the production of innovative materials in recent years. The general
idea of this type of process route is that element-organic precursor molecules are constituted
of structural units of the inorganic material aimed for by this process, thus providing novel
paths of controlling the atomic array, composition and microstructure of materials. Of special
interest is the manufacture of amorphous or nano-crystalline covalently bounded inorganics
on the basis of silicon, boron, carbon and nitrogen, revealing a unique potential of properties
not known from conventionally prepared materials.
It is the intention of this book to provide a comprehensive survey on the French contribu-
tions to the synthesis of nano-sized powders and the production of nano-structured silicon-
based composites by liquid-phase sintering using nano-sized powders where interfaces play
a decisive role for the evolution of properties.
The infrared laser thermolysis of gaseous or liquid precursors is a highly versatile method
well-fitted for the production of silicon-based amorphous or crystalline nanopowders. Due to
the purity level and degree of dispersion, such powders are good candidates for the application
in ceramics. Apart from ‘pure’ powders consisting of silicon, carbon and/or nitrogen, such
ones containing homogeneously distributed alumina and yttria are typically used as sintering
aids for silicon carbide and silicon nitride based materials. It has been proven that there is a
strong influence of the carrier gases used for the synthesis laser process on residual hydrogen
bonded to silicon, carbon and/or nitrogen providing some functionality during further thermal
treatments.
For the analysis of the amorphous and nano-crystalline structure of the as-thermolysed
and heat treated powders, morphological and analytical transmission electron microscopy
studies are decisive. Chemical ordering of the material such as powders in particular is
analysed by nuclear magnetic resonance studies. Further analytical investigations are electron
paramagnetic resonance, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy,
X-ray and neutron diffraction. Furthermore, numerical simulations are used for the study of
the chemical disorder and to propose structural models for the structure of the amorphous
state of the materials.
The content of the book is – even though very comprehensive – very detailed and strongly
interdisciplinary. Therefore, the book is valuable for a broad readership in research and
education.
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xiv Foreword
The editors are well-known experts in the field of research covered by the book. They can
be congratulated for a proper selection of authors and for providing an excellent piece of
work.
Fritz Aldinger
Max-Planck-Institut für Metallforschung, Stuttgart, Germany
June 2001
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Preface
Physical properties of solids are greatly influenced by the arrangements of atoms present
in the network. Nanostructured systems can offer improved and new properties compared
to those of bulk materials. Consequently, in such materials, the influence of interfaces and
interphases are of noticeable importance. Such interactions between the grains can lead to
new physical and chemical properties.
In recent years, an increasing interest has been devoted to nanostructured composites. This
attention is largely due to exciting possible applications ranging from new catalysts to the
preparation of nanocomposite ceramics, with significant improvements in their properties.
Ceramic composites, obtained by dispersing nanoscale particles of one constituent into
larger particles of a second constituent, have shown such improvements in mechanical prop-
erties (micro/nano composites). In particular, superplasticity has been obtained by mixing
two equally fine constituents (nano/nano composites).
Different modes of preparation have been used to make nanosized particles in large
enough quantities. Among them, laser ablation of solid targets, plasma- or laser-induced
reactions of gaseous mixtures have been developed. Other methods are related to evaporation–
condensation, ball milling, self-propagating high temperature synthesis, sol–gel, spray drying
of solutions, aerosol pyrolysis and chemical vapour decomposition at low pressure.
Due to the large variety of such materials, comparative analysis is questionable. The
originality of the book consists principally of focusing on a series of identical materials
including preparation conditions, physical and chemical analysis, preparation and mechanical
property determination of silicon-based nanocomposites.
André P. Legrand
(andre-pierre.legrand@espci.fr)
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Acknowledgements
We thank the Chemistry Department of the Centre National de la Recherche Scientifique

(CNRS), which endorsed this work through a Groupe de Recherche (CNRS GdR 1168), for
its interest and partial support, and more particularly its Director Jean-Claude Bernier and
Associate Director Pierre Henri Dixneuf.
The Délégation Générale pour l’Armement contributed to the development of this research
through its financial support. We express here our sincere thanks.
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1 Objectives and state-of-the-art of
nanocomposites
Michel Cauchetier and André Pierre Legrand
1.1 Introduction
Processes to make new ceramic materials are many and depend on the final desirable structure
and macroscopic shape to be obtained. So silicon carbide can be used as an abrasive, refrac-
tory, structural material or semiconductor with a negative temperature coefficient. Processes
developed to produce such materials are extremely diversified. A process is selected based
on the required properties and structural shape of the parts to be obtained. As an example, the
preparation of carbon fibres, which needs specific polymer precursors for spinning followed
by heat and oxidation treatments, had been adapted to the preparation of silicon carbide
fibres. Other processes of transformation, descended from physics or chemistry domains
are chemical vapour deposition, chemical liquid deposition, etc. (Figure 1.1). They are able
to present improved mechanical, thermal or electrical properties, not solely depending on
a peculiar chemical composition but on the arrangement of the crystalline phases or the size
of the grains. Nanocomposites constitute a new class of extremely diversified materials which
have appeared in the last decade.
Monomer unit Liquid or gaseous

polymer precursor Chemical vapour precursor molecules
or liquid deposition
Solid state thermolysis Laser pyrolysis
Synthesis
Analys
ing
ter
is
Sin
Characterisation by
Mechanical, electrical XPS
and thermal properties X-ray and neutron diffraction
TEM, SEM, optic
solid state NMR
Figure 1.1 Schematic representation of ceramic preparation showing the feedback process lead-
ing to a new ceramic material involving three main steps: synthesis of a precursor;
analytical methods; and sintering and validation of the physical and chemical
properties.
2 Michel Cauchetier and André Pierre Legrand
Vitreous grain
boundary Si3N4
(SiAION-) SiC
(YSiAION)
80 nm
1 µm
Micro–nano composite Nano–nano composite
Figure 1.2 Ceramic/ceramic micro–nano and nano–nano composites’ aspects (from Figures 7.8
and 7.20(b)).
Sajgalik et al. (1996) proposed a classification into two main systems:
• micro–nano composites in which the matrix is constituted by micrometric crystals

embedded into a nanometric phase. Moreover, Niihara (1991) distinguishes three
different configurations: intragranular, intergranular, intra/intergranular (Figure 1.2);
• nano–nano composites in which the nanometric grains of the matrix and the second
phase are spread uniformly (Figure 1.2).
What makes a nanocomposite especially interesting is that at least one of its phases has
dimensions in the nanometer range (10–100 nm). In this range, chemical and physical inter-
actions have critical length scales and, if the nanoscale building block is made smaller than
this one, the corresponding fundamental properties can be to changed. An example of this is
light scattering, where by controlling the size of pores and nanocrystals in the range of 8 nm,
Nanophase Technologies Corporation was able to produce transparent ceramics in the visible
domain. Other enhanced properties have been developed (superplasticity, magnetoresistance,
low temperature densification, enhanced and finer homogeneity, etc.).
1.2 Nanostructured ceramic elaboration

Two main routes are generally used, depending on the densification rate and the properties
to be obtained.
1.2.1 Amorphous ceramics obtained by solid state thermolysis of

polymer precursors
Pyrolysis, under a controlled atmosphere, of polymers, such as polysilazane, polycarbosilane,
etc. is an efficient process for preparation of ceramics. According to Bill et al. (1999) ‘The
in-situ crystallisation of these materials permits the preparation of nanocrystalline materials
by a completely powder-free process. The structure and composition of the grain boundaries
that originate from these crystallisation processes strongly depend on the molecular structure
Objectives and state-of-the-art of nanocomposites 3
of the initially used precursors.’ Such processes are particularly interesting in the preparation
of fibres.
1.2.2 The powder-making processes

To obtain nanocomposites it is necessary to prepare nanopowders so as to increase the
reactivity of the different phases during the sintering process. This is due to a high sur-
face/volume ratio (generally diameter < 100 nm). To obtain such powders, which have
to present ideal characteristics (nanometric in size, spherical in shape, monodisperse, low
agglomerated, high or controlled purity), it is necessary to develop new processes. These
new methods must be innovative and need to be adapted to industrial production.
Such recently developed processes deal with reactions such as
• Solid phase: Evaporation–condensation, laser ablation, ball milling (or mechanical

alloying), self-propagating high-temperature synthesis (SHS);
• Liquid phase: Sol–gel, spray-drying of solutions, aerosol pyrolysis;
• Gaseous phase: Chemical vapour condensation at low pressure, plasma and laser
synthesis.
Some nanosized powders are now commercially available in the USA and in Japan:
• Nanophase Technologies Corp. has developed a gas condensation process to produce

different oxide powders (aluminium, titanium, zirconium oxides).
• Nanodyne is focused on the production of cobalt–tungsten carbide, a ceramic–metal
nanocomposite used to make tools for cutting and wear-resistant devices.
• Ultram International produces ceramic and composite powders by a super-high-
frequency plasma chemical process.
• MarkeTech International proposes nanosized silicon carbide, silicon nitride, silicon
carbonitride, boron carbide and silica powders obtained by a CO2 -laser pyrolysis process.
• Mitsubishi Mining & Cement Co. Ltd has prepared silicon/carbon/nitrogen nanocom-
posite powders from pyrolysis in a furnace of an organosilicon compound.
A second problem which needs to be solved concerns the sintering for the preparation of
complex shaped components so as to keep the initial size of the crystals.
Similarly, the identification of the most efficient methods of characterisation, all along the
different steps of preparation, is of significant importance.
1.3 Nanostructured Si3 N4 /SiC materials

Different methods have been developed for the preparation of Si3 N4 /SiC nanocomposites by
hot pressing sintering using:
• Micrometric silicon nitride, previously recovered with carbon, so as to produce the

carboreduction of silicon oxide present at the surface of the initial material:
SiO2 + 3C → SiC + 2CO ↑

(Ishizaki and Yanai 1995; Watari 1989; Bahloul et al. 1993).
4 Michel Cauchetier and André Pierre Legrand
• Micrometric silicon nitride with nanometric Si/C/N or Si/C powders and sintering addi-
tives (Al2 O3 , Y2 O3 ) (Niihara 1990). Nevertheless, the mixture, in a liquid medium, of
such different sized powders containing so many different chemical groups on the sur-
face, is difficult to obtain. This produces agglomerates and a heterogeneous distribution
of the second phase in the matrix.
• Nanometric Si/C/N or Si/C powders with sintering additives (Al2 O3 , Y2 O3 ) (Sasaki
1993; Kaiser 1996; Kennedy 1996).
1.4 Analytical methods

Different methods can be used for the characterisation of initial to heat-treated and/or
pressurised precursors such as:
• Chemical analysis (CA)

• Electron paramagnetic resonance (EPR)
• Extended X-ray absorption fine structure (EXAFS)
• Infrared spectroscopy (IR)
• Soft X-ray spectroscopy (SXS)
• Solid state nuclear magnetic resonance (NMR)
• Specific surface area determination (SA)
• Transmission electron microscopy and electron diffraction (TEM)
• X-ray (XD) and neutron (ND) diffraction
• X-ray photoelectron spectroscopy (XPS).
Such methods are able to provide information of varied nature, depending on the origins
of the physical phenomena involved (Table 1.1).
Another important remark concerns the method of preparation of the sample. From the
as-formed, heat treated and sintered sample, it is necessary to arrive at a condition adapted
to the method of measurement. Crushing the material and filling, dispersing, spreading it
in/on the sample holder are able to influence the results. This is why cross measurements are
necessary.
Table 1.1 Available information depending on the method used

Method Surface Bulk Crystalline Amorphous Local or Average or Sample type
short order long order
CA × × Powder
EPR × × Powder
EXAFS × × × Powder
IR × × × Powder
ND × × × Powder
NMR × × × × × Powder
SXS × × Any
TEM × × × Nanopowder
XD × × × Powder
XPS × × × × Any
SA × × Any
Note
× Indicates the dominant domain of expertise of the method.
Objectives and state-of-the-art of nanocomposites 5
Some examples shown in this book demonstrate such phenomena:
• X-ray, TEM and NMR. Figure 2.3, section on Si/C-based powders in Chapter 4 and
Figure 5.1.6: α-β-SiC and amorphous detected in different proportions;
• NMR and TEM. Figures 4.65, 4.66 and 5.1.27: Si3 N4 detected in the bulk and not into
grains;
• XPS and NMR. Figures 5.3.10 and 5.1.10: SiO2 detected on the surface and not in the
bulk;
where the different phases are not evaluated with the same efficiency.
1.5 Conclusion
Although till now many studies on that subject have been published, results are contradictory
and fragmentary. No interdisciplinary studies, till now, have been done on the silicon nitride–
silicon carbide system. A better knowledge of the behaviour and potential of such materials
is needed.
Elaboration of high-temperature ductile nanocomposites is one of the objectives of this
work. Consequently, systematic studies and analyses of the preparation proceed from step
by step. Chemical bonding, nanostructure, microstructure and monolith material properties
are determined.
Such an approach allows us to obtain original results for each step of the preparation and to
establish relations between the synthesis of powders, their sintering aptitude, the development
of the microstructure and the properties obtained. The spiral in Figure 1.1 represents this
symbolically.
References
Bahloul, D., Pereira, M. and Goursat, P. (1993) J. Am. Ceram. Soc., 76(5), 1156–68.
Bill, J., Wakai, F. and Aldinger, F. (1999) Precursor-Derived Ceramics. Wiley-VCH.
Ishizaki, K. and Yanai, T. (1995) Silic. Indus., 7–8, 215.
Kaiser, A. (1996) Silic. Indus., 5–6, 215.
Kennedy, T. (1996) Silic. Indus., 9–10, 201.
Niihara, K. (1990) J. Mater. Sci. Lett., 10, 112.
Niihara, K. (1991) The Centennial Memorial Issue of the Ceramic Society of Japan, 99(10), 974.
Sajgalik, P., Dusza, J., Hofer, F., Warbichler, P., Reece, M., Boden, G. and Kozankova, J. (1996)
J. Mater. Sci. Lett., 15, 72.
Sasaki, G. (1993) Mater. Res. Soc. Symp., 287, 335.
Watari, K. (1989) Mater. Sci. Eng., A109, 89.
2 Laser synthesis of nanosized powders
Michel Cauchetier, Emmanuel Musset, Michel Luce,
Nathalie Herlin, Xavier Armand and Martine Mayne
2.1 Generalities on the synthesis of nanosized powders by

laser pyrolysis
2.1.1 The laser pyrolysis process

Infrared laser pyrolysis (IRLP) is a highly versatile method for the production of a wide range
of nanopowders including SiC, SiCN, SiCO, BN and carbon (Haggerty and Cannon 1981;
Cauchetier et al. 1988, 1994; Herlin et al. 1996; Boulanger et al. 1995; Ehbrecht et al. 1993;
Voicu et al. 1996). A summary of the syntheses performed so far for materials applications
is given in Table 2.1 and completes the review appearing in Knudsen (1997).
In the IRLP process, the reactants are heated by IR laser radiation and decompose, causing
clusters to nucleate and grow rapidly. This process is inherently very clean because homo-
geneous nucleation occurs in a well-defined reaction zone without interaction with chamber
walls. The small reaction volume and the ability to maintain steep temperature gradients
(106 ◦ C/s) allow precise control of the nucleation rate, growth rate and residence times. The
physical and chemical properties of the particles can be controlled by changing the molecular
precursors and the synthesis parameters (laser power, pressure, etc.). The resulting powders
are very fine, spherical, extremely pure, more or less agglomerated and nearly monodispersed
in size. The mean particle size can be adjusted from 10 to 100 nm. All these character-
istics (i.e. nanometric size (<100 nm) spherical shape, narrow size distribution, limited
agglomeration and high purity) make laser powders good candidates for use in ceramics.
2.1.2 Developments and economic analysis

Since the synthesis of Si and Si3 N4 (Haggerty and Cannon 1981), the production of ultrafine
powders from gaseous reactants has become an innovative application of lasers in chem-
istry. Although the CO2 laser synthesis of powders for use in ceramics is a new process
compared with plasma or sol–gel processes, it offers considerable promise and it has been
developed in several countries: in Europa (France at the CEA, Italy at the ENEA and the
CISE, The Netherlands at the TU Delft, Germany in Jülich), in Japan and China.
The laser synthesis technique requires the presence of a species which absorbs laser radi-
ation such as SiH4 . This precursor has been widely used to obtain silicon-based ceramic
powders (see Table 2.1 and references therein). Production rates at laboratory scale have
reached 100 g/h or more for silicon carbide (Cauchetier et al. 1988) and the development of
the process for a pilot can be estimated to require a production rate of 1–10 kg/day (Garifo
1995). Recent economic considerations have shown that SiH4 which is only available as
Laser synthesis of nanosized powders 7
Table 2.1 CO2 laser synthesized nanometric powders
Powders Chemical systems References
Si SiH4 Haggerty and Cannon 1981; Cauchetier

et al. 1987
SiC SiH4 + C2 H4 Sumaya et al. 1985; Cauchetier et al.
1987; Förster et al. 1991
SiH4 + C2 H2 Cauchetier et al. 1987; Curcio et al.
1989; Fantoni et al. 1990; Tougne
et al. 1993
SiH4 + Cx Hy with x = 4 Cauchetier et al. 1988
SiH2 Cl2 + C2 H4 Suzuki et al. 1992
(CH3 )2 Si(C2 H5 O)2 vapour Li et al. 1994a
Si3 N4 SiH4 + NH3 Haggerty and Cannon 1981; Kizaki
et al. 1985; Symons and Danforth
1987; Buerki et al. 1990
SiH2 Cl2 + NH3 Bauer et al. 1989
SiC + Si3 N4 or [(CH3 )3 Si]2 NH vapour Rice 1986; Li et al. 1994b
Si/C/N SiH4 + CH3 NH2 + NH3 Cauchetier et al. 1989; Cauchetier et al.
1991
SiH4 + (CH3 )2 NH + NH3 Alexandrescu et al. 1991; Borsella et al.
1992
SiH4 + C2 H4 + NH3 Suzuki et al. 1993
(CH3 SiHNH)x with x = 3 or 4 Gonsalves et al. 1992
(aerosol)
[(CH3 )3 Si]2 NH (aerosol) Cauchetier et al. 1994; Herlin et al.
1994; Musset et al. 1997
SiO2 Si(C2 H5 O)4 (aerosol) Luce et al. 1994
SiO2 + SiC + C (RO)4−x Si(R )x with Armand et al. 1995; Martinengo et al.
or Si/C/O 0 = x = 3, R = C2 H5 O, R = CH3 1996; Herlin et al. 1996; Fusil et al.
and [(CH3 )3 Si]2 O (aerosol) 1997
BN BCl3 + NH3 Luce et al. 1993; Baraton et al. 1994;
Willaime et al. 1995
B4 C BCl3 + CH4 + H2 Knudsen 1987a
BCl3 + C2 H2 + H2 Luce et al. 1993
TiB2 TiCl4 + B2 H6 Casey and Haggerty 1987a
TiCl4 + BCl3 + H2 Knudsen 1987b
ZrB2 Zr(BH4 )4 Cauchetier et al. 1987; Rice and
Woodin 1988
TiO2 Ti[OCH(CH3 )2 ]4 Casey and Haggerty 1987b; Rice 1987;
Curcio et al. 1991
TiC TiCl4 + C2 H4 Alexandrescu et al. 1997
Al2 O3 Al(CH3 )3 + N2 O + C2 H4 Borsella et al. 1993
WC WF6 + C2 H2 + H2 + SF6 Bourgeois et al. 1995
electronic grade remains too expensive (Cauchetier et al. 1994) for use in large quantities
(>1 ton/year) even if energy and laser equipment costs are low compared to the raw material
costs. In the case of Si3 N4 laser synthesis, a study of the economics shows that a price for
SiH4 less than one-fourth of its current price is needed to compete with a classic method of
synthesis (Schoenung 1991). Alternative methods have been proposed with the substitution
8 Michel Cauchetier et al.
of chlorosilanes (Bauer et al. 1989; Suzuki et al. 1992) or organosilicon compounds (Rice
1986; Gonsalves et al. 1992; Cauchetier et al. 1994) for silane. Technical improvements
in two different fields have enhanced the versatility of the method. First, new introduction
systems for the silicon (Si) precursors have been tested. Liquid organosilicon compounds
are introduced into the laser beam in the aerosol form, fine liquid droplets being obtained
by ultrasonic nebulisation (Gonsalves et al. 1992; Cauchetier et al. 1994). Second, the use
of high-power tunable continuous wave (c.w.) CO2 lasers, now available, has increased the
area of applications of the process (Luce et al. 1994).
In this chapter, the synthesis of Si-based powders by two methods, using gaseous or liquid
precursors, will be presented:
• SiH4 as gaseous precursor for the synthesis of Si, SiC, Si3 N4 and SiC–Si3 N4 mixture
powders and also methylsilane, SiH3 CH3 , for the synthesis of SiC powder,
• hexamethyldisilazane [(CH3 )3 Si]2 NH or HMDS as liquid precursor for the synthesis
of Si/C/N (silicon carbonitride) powders; mixture of organosilicon precursors for the
synthesis of Si/C/N powders containing the elements of sintering additives.
2.2 Synthesis of Si, SiC, Si3 N4 and SiC Si3 N4 mixtures

with SiH4 and SiH3 CH3 as silicon precursors
2.2.1 Experimental setup

The experimental device is presented in Figure 2.1 (Cauchetier et al. 1991). The unfo-
cused Gaussian beam (diameter = 12 mm) of a high-power c.w. CO2 laser (CILAS CI1000,
Marcoussis, France) enters the reaction cell through a KCl window and crosses the path of
the gaseous flow of the reactants injected through an inlet capillary (inner diameter = 2 mm).
Pumping
IR spectrometer
powder collector
CO2 laser
beam
(600 W)
Ar
SiH4 + CH2NH2 (+C2H2 + NH3)
Figure 2.1 Schematic laser irradiation cell for gaseous precursors. (Reprinted from Cauchetier,
M., Croix, O., Luce, M., Baraton, M. I., Merle, T. and Quintard, P., (1991) Jour-
nal of the European Ceramic Society, Nanometric Si/C/N Composite Powder: Laser
Synthesis and IR Characterisation, 8, 215, with permission from Elsevier Science.)
A resonance effect between the emission line of the laser at 10.6 µm and an infrared absorption
band of one of the reactant gases (silane, SiH4 or methylsilane, CH3 SiH3 ) causes the reaction
to occur. This laser-driven reaction leads to high temperatures (up to 1800◦ C) and a bright
flame. An argon flow prevents powder deposition on the windows and guides the products
into the collection chamber. The powders are collected and then stored in a glove-box under
argon atmosphere to avoid contamination by air or water vapour.
2.2.2 Synthesis results

Table 2.2 summarises the synthesis conditions of the different powder samples used in dif-
ferent parts of this book (Si, SiC, Si3 N4 and mixtures of SiC/Si3 N4 ) and also presents first
characterisation results. For all the experiments reported here, the cell pressure was kept
constant at 1 atmosphere (105 Pa). In Table 2.2, most of the results concern SiC and Si/C/N
synthesis, but some results shows the synthesis of Si from pure SiH4 (Si50), Si3 N4 from a mix-
ture of SiH4 and NH3 (SiN7). Structural investigations on both these powders are presented
in Chapter 5. SiC powders have been obtained from methylsilane (SiC151, SiC152) or from
mixtures of SiH4 and C2 H2 . In the run, SiC171 diborane was added in the silane/acetylene
mixture, as a boron source used for sintering aid in densification tests (Croix et al. 1991), and
after pressureless sintering at 2000◦ C, densities up to 0.95 were achieved. The last samples
presented in Table 2.2 are Si/C/N samples, obtained from a mixture of SiH4 , CH3 NH2 , and,
in some cases, NH3 has been added to the reactive mixture. In two runs (Si50, SiC163), an
inert gas (Ar, He) has been added to the reactive gases in order to increase the linear velocity.
After comparing the chemical composition of the gas phase with the chemical composition
of the powder, the C/Si and C/N ratios were obtained (see Table 2.2). In some cases, the
flame temperature was measured using an optical pyrometer. Specific surface area (S) was
determined from Brunauer–Emmet–Teller (BET) measurements and the equivalent diame-
ter (D) was calculated from these measurements. The time of residence in the laser beam
is calculated from the gas flow rates (2 mm nozzle diameter, 12 mm laser beam diameter)
assuming room temperature. From the results presented in Table 2.2, some information can
be obtained on the effect of experimental parameters.
Laser power
Increasing the laser power, and keeping all the other parameters constant, leads to an
increase in temperature, which is expected to have an influence on the powders produced.
In experiments SiC151 and SiC152, the laser power has been decreased by a factor of three
(600/220 W) and the measured temperature decreases from 1530◦ C to 1150◦ C. The same
crystalline structure is identified by X-ray diffraction (XRD). Therefore, in this temperature
range, the flame temperature does not influence the structure of the powder. In contrast, BET
measurements indicate a decrease in the powder size as the temperature decreases. Thus, the
temperature has a direct influence on the kinetics of the powder growth.
Flow rates
In runs SiC163–177, the flow rates have been changed keeping the laser power constant.
Increasing the flow rates leads to a decrease in the residence time as shown in Table 2.2.
Figure 2.2 presents the variation in the particle size of SiC powders with the residence time for
samples SiC163–177. Figure 2.2 also presents results (broken line) obtained five years before
Table 2.2 Gas phase synthesis conditions and characterisation results of the different samples
Samples Flow rates (cm3 / min) Atomic ratio Laser Temperature Residence BET results XRD
(gas phase) power (W) (◦ C) time (ms)
SiH 4 C2 H2 He, Ar CH 3 NH 2 NH 3 C/N C/Si S (m2 /g) D (nm)
Si50 120 0 480 (Ar) 0 0 600 930 4.3 29 89 Si

SiC151 CH3 SiH3 : 600 1530 13.0 34 55 β-SiC
200
SiC152 CH3 SiH3 : 220 1150 13.0 52 36 β-SiC
200
SiC163 540 300 1000 (He) 0 0 1.1 600 1.2 117 16
SiC171a 1080 600 0 0 0 1.1 600 1.3 135 14
SiC173 200 110 0 0 0 1.1 600 7.3 61 31
SiC174 350 192 0 0 0 1.1 600 4.2 74 25
SiC177 120 66 0 0 0 1.1 600 12.1 36 52
SiC212 596 306 0 0 0 1.0 640 2.5 70 27
SiN7 120 0 0 0 480 600 1250 4.3 71 26
SiCN12 340 0 0 200 0 600 1550 4.8 47 40 α, β-Si3 N4 ,
β-SiC
SiCN27 280 0 0 70 250 600 1615 4.3 26 72 α, β-Si3 N4
SiCN29 360 0 0 90 320 0.22 0.25 400 2.9 40 49
SiCN35 350 0 0 200 0 1 0.57 600 4.1 48 39
Note
a 40 cm3 /min of diborane B2 H6 added as boron source which acts as sintering aid for the densification of SiC.
50 SiC177
BET diameter (nm)
SiC173
25
SiC174
SiC163
0
5 10 15
Residence time (ms)
Figure 2.2 SiC particle size v. the residence time in the laser beam (laser power, 600 W; cell
pressure, 1 atm). Similar results have already been observed previously (– – –) with
a laser power of 640 W. (Reprinted from Tougne et al. (1993) Diamond and Related
Materials, Evolution of the Structure of Ultrafine SiC-Laser-formed Powders with
Synthesis Conditions, 2, 486–490, with permission from Elsevier Science.)
the present results, with a higher laser power (640 W) (Tougne et al. 1993). It must be noted
that the value obtained for the SiC212 (640 W) experiment (not plotted) is in good agreement
with these early results. Figure 2.2 clearly shows a linear decrease in the size of the particles
as the residence time decreases. Figure 2.3 presents the XRD diagrams of the SiC163–177
samples. The lines become sharper and the full width at half maximum (FWHM) decreases
as residence time increases, which indicates an increasing size of crystallites, parallel to the
increasing particle size (BET measurements).
TEM observations also confirm the BET and XRD results. Sample SiC163 (Figure 2.4(a))
presents fine spherical particles with a mean diameter of 20 nm (BET measurement: 16 nm)
and with a unimodal distribution. They are not fully crystallised and appear as fine crystallites
in an amorphous matrix. It clearly shows that the size of the particles (BET) and the size of
the crystallites (XRD) must be distinguished. Sample SiC177 (Figure 2.4(b)) also presents
fine spherical particles with an increased mean diameter of 60 nm (BET measurement:
52 nm). They are well crystallised with some black streaks. In correlation with the chemical
composition C/Si = 1.1, some fine filaments of turbostratic carbon (C) can be noticed.
In conclusion, it must be noted that both laser power and flow rates have a noticeable effect
on the size of the particles. A good control of these experimental parameters allows a good
control of the size and the structure of powders. Some other points which are relevant for
materials applications must be noted:
• The amount of synthesised powders is significant. For example, in the run SiC171, a
production rate of about 100 g/h indicates that the process can be easily scalable. The
3C
Polytypes
3C
3C
Intensity (a.u.)
3C
SiC177 3C
SiC173
SiC174
SiC163
20 40 60 80
2 (CuKα)
Figure 2.3 XRD patterns of the as-synthesised SiC powders (arbitrary units (a.u.)). (Reprinted
from Tougne et al. (1993) Diamond and Related Materials, Evolution of the Structure
of Ultrafine SiC-Laser-formed Powders with Synthesis Conditions, 2, 486–490, with
permission from Elsevier Science.)
duration of the experiment can be 3 h or more in order to collect powder quantities in

the 150–200 g range for the elaboration of materials.
• Also, a very good reproducibility of the experiments can be achieved; for example,
Table 2.2 shows BET results for the runs SiCN12 and SiCN35 undertaken after a delay
of 4 years.
• Another interesting point is the good yield of the reaction. For example, in the SiC212
run, and supposing 100% conversion of SiH4 and C2 H2 to the solid phase, the maximum
calculated production rate is 64 g of SiC per hour and the experimental result is 59 g/h –
this reaction yield (almost 100%) is very good.
2.2.3 Chemical analyses of the as-formed powders

The chemical composition in stoichiometric compounds (Si3 N4 , SiC, SiO2 , Si, C) has been
calculated from elemental analysis results, with the classical assumption that all O is in the
form of SiO2 , then all N forms Si3 N4 and the remaining Si is in the form of SiC. Free C
(or Si) is the difference between total C (or Si) and C (or Si) bonded to Si (or C) in SiC.
Such a calculation is useful to evaluate the composition of future sintered materials, or to
compare several powders but it is obvious that it is only an approximation, especially when
the powders are not fully crystallised.
(a)
100 nm
(b)
100 nm
Figure 2.4 TEMs of two as-formed powders: (a) SiC163; (b) SiC177.
SiC powders
In order to avoid the presence of free Si in the powders which makes the powder very sensitive
to oxygen contamination, most of the SiC samples were synthesised with a gaseous mixture
containing excess C (C/Si = 1.1 in the gaseous mixture). In Table 2.3, two examples show that
this ratio is also found in the powders produced. In agreement with the chemical composition,
XRD patterns (similar to Figure 2.3) correspond to the β-SiC phase. The O and free C
contents are low and correspond to the values usually encountered for commercial powders.
Table 2.3 also presents the chemical composition calculated in stoichiometric compounds
which indicates, in good agreement with the XRD pattern, that the powders are mostly
composed of SiC.
Si/C/N powders
For the synthesis of Si/C/N composite powders, two gaseous mixtures were investigated:
a binary mixture SiH4 + CH3 NH2 (SiCN35) and a ternary mixture: SiH4 + CH3 NH2 + NH3
Table 2.3 Chemical characterisations of gas phase synthesised powders
Powder Samples
Chemical analysis (wt%) Atomic ratio Chemical composition (wt%)
Si C N O C/Si C/N Si3 N4 SiO2 SiC C Si
SiC173 68.3 30.2 0 0.9 1.03 0 1.5 96 2.0 0

SiC212 68.3 30.3 0 1.4 1.03 0 2.7 95.7 1.6 0
SiCN29 58.3 6.5 34.6 0.6 0.27 0.22 86.6 1.1 8.3 4.0 0
SiCN35 66.9 13.6 18.2 2.3 0.47 0.87 45.1 4.3 45.1 0 5.5
Si3N4 SiC
Si3N4 Si
Intensity (a.u.)
SiCN35
SiCN29
10 20 30 40 50 60 70 80 90
Angle (2 degrees)
Figure 2.5 XRD patterns of as-formed SiCN nanopowders used in material elaboration.
(Reprinted from Mayne 1997.)
(SiCN29) (Table 2.2). In the case of SiCN29, the presence of NH3 is known to make the
nitriding introduce an increase in the nitrogen (N) content. For SiCN35 a similar content in
C and N is expected in the resulting powder due to the C/N initial atomic ratio of 1 in the
formula of monomethylamine. Tables 2.2 and 2.3 show a very good correlation between C/Si
and C/N ratios in the gas phase and in the powder for SiCN29, but the correlation is not so
good for SiCN35 probably due to evolution of carbonaceous gas of C in the gas phase during
the synthesis.
Chemical composition calculations show that the powder SiCN35, containing free Si is
the most sensitive to oxygen contamination. XRD patterns (Mayne 1997) are reported in
Figure 2.5 and confirm the calculated compositions. The SiCN29 sample contains mainly
α- and β-Si3 N4 ; the quantity of SiC is too small and is not detectable. The SiCN35 sample
presents the characteristic lines of Si and β-SiC and a broad peak between 2θ = 30◦ and
40◦ , which can be attributed to an amorphous phase of silicon carbonitride.
From the results presented in this section, it appears that the decomposition in stoichiomet-
ric compounds is a good representation of the powder and also that the chemical composition
of the powders produced is most often well controlled by the chemical composition of the
gaseous reactants. Together with the possibility of controlling the size and the structure of
the powder, it makes this synthesis technique attractive. But, as explained before, in order
to increase the safety and decrease the cost, it has been applied to the liquid precursors
containing Si, C and N elements.
2.3 Synthesis of silicon carbonitride (Si/C/N) powders using

hexamethyldisilazane as Si precursor
2.3.1 Experimental
Choice of the precursor

As noted before, investigations based on costs of various silicon precursors for the delivery
of large quantities have shown that silane remains too expensive for use in ceramic powder
synthesis (Cauchetier et al. 1994). In our case [(CH3 )3 Si]2 NH or HMDS with a Si cost very
low compared to the Si cost of SiH4 (43 US$/kgSi in HMDS and 343 US$/kgSi in SiH4 ) was
chosen as a model of the liquid precursor in order to demonstrate the possibility of using liquid
wastes of the organosilicon compound chemistry for the synthesis of nanometric Si-based
powders. Indeed, HMDS has a strong IR absorption band at 10.6 µm due to the Si N bond,
which was, therefore selected. It is a common liquid Si compound (boiling point of 125◦ C,
density of 0.76, and a viscosity of 0.69 cP at 25◦ C) largely used for the silylation of a wide
range of functional groups and it was the precursor used by Niihara and co-workers in the
synthesis of Si/C/N powders leading to non-oxide superplastic ceramics (Wakai et al. 1990).
The first experiments using HMDS in the vapour phase as Si precursor for Si/C/N powder
synthesis by CO2 -laser pyrolysis were performed by Rice (1986). A conversion efficiency
(liquid → powder) of about 60% has been obtained but with low flow rates of HMDS (7 g/h)
and with a low-powered CO2 laser (135 W). Higher production rates have been attained
(80–120 g/h) when the laser power has been increased to the 500–1000 W range (Li et al.
1994b).
The experimental device

The apparatus is shown in Figure 2.6. Liquid HMDS is placed in a special glass jar containing
a piezoelectric transducer (Pyrosol 7901 type from RBI, Meylan, France, apparatus developed
in collaboration with the CEA (Spitz and Viguié 1970)). The focusing of the intense beam
of ultrasonic energy delivered by the transducer near the surface of the liquid yields uniform
droplets whose diameter d is given by

πσ
d= 3
4ρf 2
where σ and ρ are the surface tension and the density of the liquid, respectively, and f the
frequency of the transducer (here 850 kHz). In order to increase the mass of the displaced
liquid, the glass jar is heated near 90–100◦ C with a heating ribbon. The aerosol droplets
and vapour are injected into an irradiation cell very similar to those presented in Figure 2.1.
The reaction cell is maintained at a regulated pressure of 105 Pa using a flow of argon or an
argon–ammonia mixture through a glass inlet tubing (inner diameter of 13 mm). The laser
beam diameter is increased from 12 to 24 mm with a beam expander in order to cover the
reactant flow entirely. The initial laser power is in the range 480–520 W.
Powder collector
Filter
Heating wires
Vacuum pump or
IR spectrometer
KCl window
Laser
CO2
Argon Argon
Chimney gas
Gas for the propulsion

of the aerosol
Piezoelectric
ceramic
Precursor
RF power supply
PYROSOL system
Figure 2.6 Schematic of the aerosol generator with the irradiation cell and the powder collector.
2.3.2 Synthesis results

Table 2.4 compares the influence of two parameters, the nature of the carrier gas (argon and
nitrogen) and heating of the liquid precursor (near 100◦ C), on the synthesis results. It can be
seen immediately that the yield of the reaction (expressed as the ratio between the mass of
powders produced and the mass of displaced liquid), does not appear to be as good as in the gas
phase. Both the amount of displaced liquid and production rate increase when the precursor
is heated. The effect of the heating is to combine the enrichment of the gaseous phase in
HMDS vapour and decrease the viscosity of the liquid. In order to work with significant
amounts of powders, most of the experiments were carried out with liquid heating. The yield
seems independent of the heating of the precursor, but is strongly dependent on the nature of
the gas. It is 46–49% for Ar carrier gas flow and 38–39% for N2 carrier gas flow.
2.3.3 Effect of experimental parameters
Effect of carrier gas (Ar or N2 )

Table 2.4 shows that the chemical composition of the powder does not depend on the nature
of the carrier gas flow (Ar or N2 ) and the C/N atomic ratio remains stable in the 2.5–2.9 range.
The activity of atomic N (N2 ↔ 2N) is low at the measured flame temperature: 1260 ± 20◦ C.
Table 2.4 also shows that all powders are sensitive to pollution by oxygen, but the powders
obtained from the heated precursor seem the most sensitive to pollution. It must be noted
that the chemical analysis presented in this section is not complete due to the presence of
hydrogen in the powder and due to the uncertainty of the measurements.
Effect of chemical evolution of the reactive mixture

Table 2.5 presents the synthesis parameters of all the samples studied in the different parts
of this book. Only samples HMDS40–45 where the effect of chemical composition has been
Table 2.4 Effect of the carrier gas nature and precursor heating
Run Carrier gas flow Displaced Powder Yield SBET Chemical analysis C/N
rate (cm3 /min) liquid production (wt%) (m2 /g) (wt%) (Atomic
Ar N (cm3 /h) rate (g/h)
Si C N O
ratio)
2
a
HMDS28 2430 — 108 38 46 88 49.8 30.3 12.3 5.6 2.9
HMDS36b 2500 — 164 61 49 82 45.8 28.0 11.7 9.7 2.8
HMDS38b — 2500 166 48 38 125 47.2 28.4 12.8 11.6 2.6
HMDS39a — 2500 95 28 39 79 49.9 29.7 14.1 5.2 2.5
Notes
a Liquid precursor at room temperature.
b Liquid precursor heated near 100◦ C.
Table 2.5 Synthesis conditions and chemical analysis of HMDS samples (chemical analyses were always
performed after several weeks of exposure to air)
Run Carrier gas flow Displaced Powder Yield SBET Chemical analysis C/N
rate (cm3 /mn) liquid production (wt%) (m2 /g) (wt%) (Atomic
(cm3 /h) rate (g/h) ratio)
Ar N2 Total Si C N O
HMDS40 1935 205 2140 182 59 43 110 46.7 25.3 21.8 6.1 1.35
HMDS41 1770 410 2180 160 61 50 93 46.1 20.5 25.2 6.7 0.95
HMDS42 1570 600 2170 175 75 56 98 44.4 18.5 29.7 7.7 0.73
HMDS43 1370 800 2170 179 74 53 95 48.3 15.5 26.8 8.0 0.67
HMDS44 1150 1040 2190 210 81 51 95 47.1 13.1 26.7 10.9 0.57
HMDS45 830 1346 2180 167 66 52 106 47.6 8.3 28.9 13.4 0.34
HMDS35 1600 1000 2600 87 21 32 144 47.3 6.6 33.4 9.8 0.23
HMDS66 1920 1920 114 32 36 66 51.2 31.9 15.1 1.8
HMDS67a 1440 1920 115 31 35 66 52.0 30.8 14.8 2.4
HMDS73a 862 207 1920 56 14 32 115 51.9 12.6 25.3 10.1
Note
a H2 in the carrier gas.
3.0
HMDS28
2.5
22
C/N atomic ratio (powder)
2.0
1.5
40
1.0
41
43
42
0.5 44
35 45
1 2 3 4 5 6
C/N atomic ratio (gas + aerosol)
Figure 2.7 C/N atomic ratio in as-formed HMDS powders v. C/N atomic ratio in the precursors
(liquid + ammonia). (Reprinted from Musset et al. 1997 with the permission of the
Belgian Ceramic Society, Mons, Belgium.)
closely studied will be commented on in this section; the main part of the results appear in the
PhD thesis of Emmanuel Musset (Musset 1995). For this set of six experiments, the liquid
temperature is about 100◦ C, the total flow rate of the carrier gas mixture remains constant
and the corresponding residence time of the precursor in the laser beam is about 0.1 ms.
Table 2.5 shows the influence of the addition of ammonia in the argon used as carrier
gas, namely, on the chemical composition of the resulting powders (samples HMDS40–45).
Figure 2.7 shows a good correlation between the C/N ratio in the as-formed powder and in the
reactive mixture; the C/N atomic ratio decreases from 1.35 to 0.36 when the ammonia volume
ratio increases from 10% to 60%. This correlation confirms the possibility of controlling the
chemical composition of the powders. Table 2.5 shows that the contamination by oxygen
becomes more and more important when the N content in the powder increases, because NH
bonds are easily hydrolysed.
2.3.4 First characterisations
Specific surface area

The specific surface area is always high, about 100 m2 /g and taking into account the mean
value of the density i.e. 2.00 (pycnometry measurement), the corresponding mean value for
the diameter is 30 nm, in agreement with TEM observations.
Si9N9Si Si9C
N9H
N9H
O9H
Si9CH3
C9H (CH3) Si9N
HMDS45 Si9H
KBr
HMDS44
Absorbance (a.u.)
HMDS43
HMDS42
HMDS41
HMDS40
3500 3000 2500 2000 1500 1000 500

Wavenumber (cm–1)
Figure 2.8 IR spectra of the as-formed HMDS powders. (Reprinted from Musset 1995.)
Infrared spectroscopy
IR spectra of the samples HMDS40–45 are shown in Figure 2.8. They present a broad absorp-
tion band between 750 and 1250 cm−1 with a maximum at 920–940 cm−1 due to a Si/C/N
amorphous phase, corresponding to a flat XRD diagram. A weak band at 550 cm−1 is due to
the Si N bond. Other bands are related to hydrogenous species: N H at 1180 cm−1 , Si H
at 2050 cm−1 and Si CH3 at 1250 cm−1 , indicating an incomplete pyrolysis of the precursor
or absorption of volatile species obtained from the pyrolysis. The presence of hydrogen is in
good agreement with the chemical analysis, which is often less than 100% (Table 2.4).
The results presented in this section show that it is possible to produce Si/C/N nanopowders
with controlled chemical composition from a liquid precursor. The powders are obtained in
significant quantities for materials applications. The main differences compared to powders
obtained from the gas phase are the amorphous character and high hydrogen content of the
powders obtained from the liquid phase.
2.4 Silicon carbonitride (Si/C/N) powders containing in situ

the elements of the sintering aids (Al, Y): pre-mixed
powders
2.4.1 Introduction: elaboration of SiC–Si3 N4 nanocomposite materials

Materials in the SiC/Si3 N4 system are elaborated by heat treatment of powders in the presence
of liquid-forming sintering aids such as Y2 O3 , MgO, Al2 O3 , etc. singly or in combination.
Such processes need a previous mixing step of all powders having different natures and
sometimes different sizes. Recently, some studies report the incorporation of metal elements
(Al, Y, etc.), necessary for the sintering step, into silicon nitride or carbonitride systems, most
of them being focused on chemical processing routes using organometallic precursors (Soraru
et al. 1992; Iwamoto et al. 1998; Koyama et al. 1998). A few other publications concern
physico-chemical processes: laser irradiation of gaseous mixtures (SiH4 , NH3 , (CH3 )3 Al)
allows the formation of nanosized powders with Al in a Si3 N4 matrix (Borsella et al. 1993b).
Aerosol of Si/C/N particles with yttrium and aluminium compounds were prepared under dual
irradiation of CO2 and excimer laser beams of a SiH4 , C2 H4 and NH3 mixture, aluminium
being incorporated in the form of alumina powder in the reactant flow and yttrium being intro-
duced as a low volatile organometallic compound in the reaction zone (Yamada et al. 1997).
2.4.2 Synthesis of pre-mixed powders

In order to prepare Si/C/N powders containing uniformly dispersed sintering aids inves-
tigations were undertaken to set up a laser spray synthesis process of Si/C/N/O/Al(Y)
nanopowders using solutions of a liquid organosilicon precursor – HMDS – with solid
metallic alcoxides, namely aluminium and yttrium isopropoxides [(CH3 )2 CHO]3 Al and
[(CH3 )2 CHO]3 Y.
Table 2.6 summarises the synthesis conditions of 14 runs which can be divided into
3 groups:
• Group I includes experiments carried out with solutions having different Al (+Y)/Si
atomic ratio.
• Group II includes experiments carried out with solutions having the same Al (+Y)/Si
atomic ratio. All runs are realised with a binary mixture of carrier gases (Ar + NH3 ).
• The third is composed of experiments made with the same solutions as in group II, but
the carrier gas is composed of Ar + NH3 + H2 in order to see if the chemical composition
of the powders is modified by the presence of H2 .
Some changes occur compared to the experiments described above in Section 2.3. The
initial laser power is in the range 300–330 W, but, here, with an unfocused laser beam
(diameter = 13 mm) which covers the aerosol flow sufficiently. For comparison, an
experiment with pure HMDS carried out under similar conditions is also reported (HMDS66).
2.4.3 Effect of experimental parameters
Effect of the solutions of precursors

In Table 2.6, most of the experiments were carried out with metallic isopropoxides in HMDS
but, in two cases (HSAl04 and HSAlY05), isopropanol was added to the reactive solution in
order to increase the solubility of the alcoxides and to decrease the viscosity of the solutions.
In these experiments, more liquid is displaced than in other experiments but the production
rate remains at the same level (≈30 g/h). Also, the amount of oxygen incorporated in the
as-formed powders is very high (>10%). In conclusion, isopropanol does not improve the
production or quality of the powders and this solution was not developed.
Precursor solutions are characterised by their atomic ratios: [Al(+Y)]/Si. For the first
experiments, the Al/Si ratio in the precursor solution was adjusted to 0.069 (e.g. HSAl03);
this value corresponds to 6 wt% Al2 O3 content in a final SiC/Si3 N4 material according to the
different oxide contents reported in the literature from about 10 (Kennedy et al. 1996) to 1 wt%
Table 2.6 Synthesis conditions and results of pre-mixed Si/C/N powders
Run Carrier gas flow rates Displaced Powder SBET Chemical analysis (wt%) Atomic ratio
(cm3 /min) liquid (g/h) production (m2 /g)
rate (g/h)
Ar NH 3 H2 Si C N O Al Y Al + Y /Si Al/Y
HSAl03 1900 0 0 87 34 66 46.5 33.9 12.9 5.7 2.5 0

HSAl04 1900 0 0 119 32 81 43.5 33.7 10.7 13.2 2.4 0
HSAl07 1900 0 0 88 24 110 47.1 29.1 12.8 8.6 2.5 0 0.05
HSAl08 0 0 1900 49 11 280 48.7 26.6 14.1 8.9 1.6 0
HSAlY05 1900 0 0 115 30 79 43.7 33.4 11.2 11.5 1.7 1.4
HSAl09 1140 760 0 71 23 112 49.5 6.8 36.0 6.1 1.5 0 0.03
HSAl12 1520 380 0 87 28 96 47.2 14.8 29.0 7.5 1.5 0 0.03
HSAl13 1710 190 0 87 30 83 49.8 23.0 19.2 5.9 2.0 0 0.04
HSAl11 475 570 855 64 27 134 49.8 5.8 37.2 5.7 1.5 0
HSAl14 855 190 855 74 26 89 48.8 17.3 24.5 7.7 1.6 0
HSAl15 665 380 855 75 22 99 50.9 11.7 26.8 8.8 1.8 0
HSAlY16 1140 760 0 81 26 100 53.0 7.5 30.3 8.2 0.4 0.4 0.01 3.0
HSAlY17 1520 380 0 89 25 91 50.7 16.9 25.4 5.4 0.9 0.7 0.02 4.2
HSAlY18 1710 190 0 79 28 77 49.3 21.9 22.4 5.1 0.5 0.7 0.01 2.5
alumina and yttria (Burger et al. 1997). The first result is that it is possible to incorporate Al
and Y additives in the powders, but Table 2.6 clearly shows that the ratio Al/Si, in this range
of experimental conditions, does not reach the 0.069 ratio. This is due to the preferential
pulverisation of the most volatile compound of the mixture, that is, HMDS.
So, in the following experiments, the initial Al/Si and (Al + Y)/Si ratios were decreased to
0.04 (HSAl09, 12, 13) and 0.02 respectively (HSAlY16, 17, 18). The similarity of the Al/Si
atomic ratio in the starting solution (0.04) and in the as-formed HSAl powders (0.03–0.04)
suggests that the nebulisation of the mixture of precursors is homogeneous. In the case of
HSAlY powders, the Al/Y atomic ratios are different in as-formed powders (2.5–4.2) and
in the starting solution (1.1), though (Al + Y)/Si atomic ratios remain similar (0.01–0.02)
to the starting solution. This is due to the incomplete dissolution of yttrium isopropoxide in
HMDS and probably to an inhomogeneous nebulisation of the mixture of precursors.
Effect of carrier gas

The nature and composition of the carrier gas mixture play a significant role in the chemical
composition of powders. Whatever the powder (HSAl or HSAlY), an increase of ammonia
relative flow rate induces a decrease in C content and C/N atomic ratio as obtained for powders
without sintering aids (Musset 1995).
Table 2.6 also shows that when hydrogen is added partially in the place of argon in
argon–ammonia mixtures, the C content decreases. This seems to indicate that more volatile
hydrocarbon species are formed during the synthesis. For example, the C content varies from
14.8 to 11.7 wt% in a 80% argon–20% ammonia mixture (HSAl12 and 15 samples) and from
23.0 to 17.3 wt% in a 90% argon–10% ammonia mixture (HSAl13 and 14 samples). It must
be noticed that a large quantity of free C (10–14%) remains in powders when the ammonia
relative flow rate increases from 0 to 20.
2.4.4 First characterisations
Specific surface area

Powder production rates in the 22–34 g/h range and specific surface area values in
66–134 m2 /g range are very similar to the values obtained for powders without metallic
additives.
Infrared spectroscopy and X-ray diffraction

As for powders without metallic additives, XRD patterns show a large background without
any distinct peak indicating an amorphous structure. This is confirmed by infrared spectra
showing a large band around 900 cm−1 . This one is essentially composed of Si C bonds
when powders are synthesised with argon-rich carrier gas while Si N bonds in an amorphous
environment (large band at 400 cm−1 ) appear with ammonia-rich carrier gas. Moreover,
Si CH3 bonds are present (1250 cm−1 ) in all powders.
2.5 Conclusion
In this chapter, it has been shown that laser pyrolysis is a versatile method well suited for the
production of significant amounts of Si-based nanopowders. Due to their properties (purity
limited only by the purity of the reactants, low size dispersion, etc.), the nanopowders are
good candidates for applications in ceramics. Nanopowders can be obtained from gaseous or
liquid precursors. The powders obtained from the gas phase are crystallised while the powders
obtained from the liquid phase are amorphous. In both cases, the chemical composition of the
powders is controlled by the chemical composition of the reactive mixture. Finally, an interest-
ing result is the incorporation of the elements of sintering aids (Al, Y, O) during the synthesis.
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3 Thermal behaviour of as-formed
silicon-based nanopowders
General introduction
This chapter presents the effects of thermal treatments on Si-based nanopowders obtained as
described in the previous chapter from the gas phase or from the liquid phase. It is mainly
focused on the behaviour of Si/C/N and Si/C/N/Al/Y/O powders (0.2 < C/N(at) < 2.6)
because such nanopowders may be used to obtain Si3 N4 /SiC materials after thermal treatment.
This chapter is divided into two parts. The first part is devoted to thermal treatment in a
high-temperature graphite furnace in order to know the evolution of the physico-chemical
characteristics. The second part reports the study of the thermal behaviour using TGA/MS
in order to determine the chemical reactions and mechanisms involved during annealing.
3.1 Thermal behaviour in a
high-temperature graphite furnace
Emmanuel Musset, Martine Mayne, Michel Cauchetier,
Xavier Armand, Michel Luce and Nathalie Herlin-Boime
3.1.1 Introduction
The aim of the first part of this study is to determine the influence of the annealing treatments
performed in a high-temperature graphite furnace both on the weight of samples and on
different physico-chemical properties of nanopowders such as the chemical composition,
structure, reactivity and size. It is mainly focused on Si/C/N samples obtained from the liquid
phase using the aerosol method. The results of annealing treatments and the consequences
of these treatments on the chemical composition, size, organisation, etc. of silicon-based
powders are presented with the intent of showing the similarities and the differences between
the different powders, to correlate these properties to the synthesis conditions, etc., and to
begin to compare the properties of these powders with the necessary properties for ceramic
applications.
3.1.2 Weight evolution of SiC, Si/C/N and Si/C/N/Al/Y/O

nanopowders
The as-formed powders are annealed at atmospheric pressure in a high-temperature graphite
furnace under argon or nitrogen (N) atmospheres. The temperature generally varies in the
range 1000–1700◦ C, and the dwell time is 1 or 4 h.
3.1.2.1 Weight evolution under inert atmosphere

Thermal treatments were performed on SiC or Si/C/N nanopowders in an argon atmosphere
for temperatures up to 1600◦ C. SiC powders exhibit a weight loss whatever the temperature.
The maximum weight loss, observed near 1500◦ C, remains low (usually <5 wt%) and is
mainly related to the carboreduction of the silica by the free carbon (C), both present in the
powders (1–3 wt%, Table 2.3) (Croix et al. 1991):
3C + SiO2 → SiC + 2CO (3.1.1)
For Si/C/N powders obtained from the gas phase (SiCN29 and 35 in Table 2.2), a low
weight loss (<10%) also occurs. This weight loss suggests a decomposition of the Si/C/N
system. SiCN35 nanopowder exhibits a higher weight loss than SiCN29, which could be
related to a stronger decomposition. It can also be partially explained by the carboreduction
of silica, because of a higher amount of silica in the SiCN35 as-formed powder (Table 2.3).
For Si/C/N nanopowders synthesised from HMDS, annealing experiments in argon at
1600◦ C lead to the formation of free silicon (Si) (Cauchetier et al. 1994) and the weight
Thermal behaviour in a high-temperature graphite furnace 27
loss is high (>20%). This also suggests the decomposition of the Si/C/N chemical system,
which appears to be more important than in the case of Si/C/N obtained from the gas phase.
Detailed mechanisms will be proposed and discussed in the TG–MS section.
The decomposition of the Si/C/N chemical system under an inert atmosphere could be
partially related to the degradation of the nitrogen-containing species inducing an evolution
of nitrogen during the thermal treatment. Usually, the elaboration of silicon nitride based
materials is achieved by sintering powders under a nitrogen atmosphere in order to limit the
weight loss and the degradation of the silicon nitride based system. That is why a nitrogen
atmosphere is used for heat treatment in the following sections.
3.1.2.2 Weight evolution under nitrogen atmosphere

The aim of the use of nitrogen is to limit the weight loss by preserving the N content in the
as-formed powders in order to further obtain dense silicon nitride based ceramic materials.
Heat treatment was performed at 1000◦ C and then in steps of 100◦ C between 1300◦ C
and 1700◦ C with a heating rate of 10◦ C/min. Most often, the dwell time is 4 h, unless
otherwise indicated in the text. Previously, the as-formed Si/C/N powders (about 2 g) are
slightly pressed in a Teflon mould to form pellets (diameter = 20 mm; height ≈ 10 mm)
which are then placed in graphite crucibles located inside the graphite furnace.
For Si/C/N nanopowders synthesised from the gas phase (SiCN29 and SiCN35), a signifi-
cant mass change (+8 wt%) is obtained for the SiCN35 sample between 1200◦ C and 1400◦ C
suggesting the nitridation of the free Si present in the powder. Contrary to the SiCN35 sam-
ple, the SiCN29 sample exhibits a relative mass stability up to 1600◦ C (Mayne 1997). This
can be related to the high N content and to the absence of Si that cannot enable a nitridation
process (Mayne 1997; Mayne et al. 1998). X-ray diffraction (XRD) patterns of the annealed
powders show the presence of crystalline phases (α- and β-Si3 N4 for SiCN29 sample and a
mixture of α- and β-Si3 N4 with β-SiC for SiCN35 sample).
In contrast to Si/C/N nanopowders obtained from the gas phase, Si/C/N and Si/C/N/Al/Y/O
powders obtained from the liquid phase (HMDS or mixtures of HMDS with organic com-
pounds) exhibit weight losses that are of the same order of magnitude (20–30% at 1600◦ C).
Therefore, the weight evolution of Si/C/N/Al/Y/O powders (Cauchetier et al. 1999; Mayne
et al. 1999), will not be specifically presented in this chapter. Such weight losses suggest a
decomposition of the Si/C/N chemical system even under nitrogen atmosphere. In Table 3.1.1,
the weight losses and chemical compositions of six HMDS samples are given. It shows that
the weight loss is dependent on the chemical composition of the as-formed powder. After
annealing at 1600◦ C, the weight loss is the highest for the samples with the highest C/N
ratio. This difference could be related to different chemical mechanisms involved in the
decomposition process and interpretations will be suggested in the TG–MS section.
This study on the weight evolution of Si-based samples during heat treatment enables us
to show the following:
• a strong difference in the behaviour of powders obtained from the gas phase or from the
liquid phase using the aerosol method especially under a nitrogen atmosphere. Nanopow-
ders obtained from the gas phase are more stable than those obtained from the liquid
phase, which suggests that they are more suitable for ceramic conversion than those
obtained from the liquid phase;
• that the thermal behaviour of powders obtained from the liquid changes as a function of
the chemical composition of the powder, suggesting different mechanisms.
Table 3.1.1 Results of chemical analyses for HMDS40 to HMDS45
b
Heating Mass Si C N O N/Si C/Si C/N
treatment (◦ C) loss (%)
HMDS40
AFa — 46.7 25.0 21.8 6.1 99.6 0.93 1.24 1.33
1000 5.9 48.4 23.6 20.9 5.0 97.9 0.86 1.14 1.31
1300 5.7 51.3 23.7 23.7 2.2 100.9 0.92 1.07 1.16
1400 6.0 51.5 23.7 22.5 1.5 99.2 0.87 1.07 1.23
1500 19.4 59.6 26.8 12.6 0.7 99.6 0.42 1.05 2.47
1550 27.0 65.7 28.2 4.7 0.8 99.4 0.14 1.00 7.02
1600 27.9 68.6 29.1 2.9 0.5 101.1 0.08 1.00 11.15
HMDS41
AFa — 46.1 20.6 25.2 6.7 98.6 1.09 1.04 0.95
1000 4.4 50.4 19.3 23.5 4.6 97.8 0.93 0.89 0.95
1300 5.8 51.4 19.2 27.3 2.4 100.3 1.06 0.87 0.82
1400 7.4 52.5 18.7 27.0 1.7 99.9 1.03 0.83 0.81
1500 17.2 59.2 21.0 19.6 1.1 100.9 0.66 0.83 1.25
1550 28.6 61.6 23.1 11.8 1.1 97.6 0.38 0.87 2.28
1600 28.2 67.4 25.2 8.5 1.4 102.4 0.25 0.87 3.50
HMDS42
AFa — 44.4 18.7 29.7 7.7 100.5 1.34 0.98 0.73
1000 4.0 48.9 17.9 27.1 4.4 98.3 1.11 0.85 0.77
1300 5.9 51.6 18.3 29.5 1.5 100.9 1.14 0.83 0.72
1400 8.0 52.6 18.0 29.8 1.6 102.0 1.13 0.80 0.70
1500 14.6 55.8 18.4 22.1 0.8 97.1 0.79 0.77 0.97
1550 23.4 65.2 20.9 13.1 1.0 100.2 0.40 0.75 1.85
1600 27.0 67.2 22.5 11.5 1.0 102.2 0.34 0.78 2.27
1700 28.8 66.6 23.3 9.7 0.3 99.9 0.29 0.81 2.80
HMDS43
AFa — 48.3 15.5 26.8 8.0 98.6 1.11 0.75 0.67
1000 4.7 50.2 13.8 30.3 5.9 100.2 1.21 0.64 0.53
1300 8.0 53.2 14.0 31.5 3.8 102.5 1.18 0.61 0.52
1400 10.8 54.3 14.4 28.2 2.9 99.8 1.04 0.62 0.60
1500 18.0 58.3 13.0 26.9 1.4 99.6 0.92 0.52 0.56
1550 25.3 58.8 13.2 27.3 0.7 100.0 0.93 0.52 0.56
1600 25.2 65.4 16.7 19.3 1.0 102.4 0.59 0.60 1.01
1700 28.8 64.2 19.4 17.1 0.4 101.0 0.53 0.71 1.33
HMDS44
AFa — 47.1 13.0 26.7 10.9 97.7 1.13 0.64 0.57
1000 6.2 49.8 11.1 32.5 7.4 100.8 1.30 0.52 0.40
1300 9.7 53.3 11.1 32.4 4.5 101.3 1.21 0.48 0.40
1400 12.7 52.6 10.5 32.4 3.4 98.9 1.23 0.46 0.38
1500 19.1 59.0 9.8 29.7 2.0 100.5 1.01 0.39 0.38
1550 27.7 56.9 10.4 31.2 0.5 99.0 1.10 0.42 0.39
1600 24.4 62.4 12.1 23.3 1.1 99.0 0.75 0.45 0.61
1700 25.7 62.6 13.7 25.6 0.5 102.4 0.82 0.51 0.62
HMDS45
AFa — 47.6 8.3 28.9 13.4 98.2 1.21 0.41 0.33
1000 7.4 51.8 6.1 34.2 9.7 101.8 1.32 0.27 0.21
1300 11.6 55.4 5.7 32.4 5.9 99.4 1.17 0.24 0.20
1400 14.1 52.9 4.7 35.8 4.9 98.3 1.35 0.21 0.15
1500 17.0 58.5 3.6 35.9 0.9 99.0 1.23 0.14 0.12
1550 23.4 54.7 1.6 34.4 0.6 92.3 1.26 0.07 0.05
1600 20.4 60.3 4.2 33.8 1.3 99.6 1.12 0.16 0.14
Notes
a As-formed powder.
b The sum of the different element masses from 100% due to the uncertainty of the chemical
analyses and the hydrogen is not taken into account, namely for the as-formed powders.
The as-formed powders obtained from the gas phase are at least partially organised, and
the weight changes occurring during thermal treatments are much less noticeable than for
the powders obtained by the aerosol method from the liquid phase that are amorphous.
3.1.3 Chemical evolution during annealing in a

nitrogen atmosphere
As in the previous chapter, the chemical composition in stoichiometric compounds of the
different samples annealed under a N2 atmosphere has been calculated from chemical analy-
sis obtained from CNRS analysis laboratory (Vernaison, France). The knowledge of the
composition in stoichiometric compounds (Si3 N4 , SiC, SiO2 , Y2 O3 , Al2 O3 ), especially for
annealed powders is important, because it enables us to evaluate roughly the composition of
future sintered materials. Moreover, this allows a more precise choice of the adapted powders
to obtain the desired material with specific properties.
The determination of the chemical composition in stoichiometric compounds for the dif-
ferent samples is as follows: for Si/C/N/Al/Y samples, all Al and Y are assumed to be in
the form of Al2 O3 and Y2 O3 , the remaining O being in the form of SiO2 , then all N forms
Si3 N4 and the remaining Si is in the form of SiC. Free C is the difference between total
C and C bonded to Si in SiC. The rules are the same for Si/C/N samples apart from Al
and Y that are not present. It must be noted that such a calculation is approximate both for
as-formed and annealed powders. Effectively, in the case of amorphous as-formed powders,
compounds such as Si3 N4 , SiC, Y2 O3 , Al2 O3 do not really exist as crystalline compounds. In
annealed Si/C/N powders, crystalline compounds Si3 N4 and SiC exist but the crystallisation
is not always complete, depending on the annealing temperature (as shown by XRD mea-
surements). In Si/C/N/Al/Y/O powders, Al and Y are not only bonded to O (Y2 O3 , Al2 O3 )
but may also be combined in SiAlON or YSiAlON amorphous phases (see Chapter 5), as
for classical sintering of silicon nitride compounds in the presence of sintering aids (Y2 O3 ,
Al2 O3 ) (Ekström and Persson 1990; Hoffmann and Petzow 1993). Note that the calculated
Si3 N4 and SiC contents should be very similar to that which exists in materials because of
the low quantity of Y and Al bonded to N. Furthermore, H present in as-formed powders has
not been taken into account for these chemical measurements. The chemical composition in
stoichiometric compounds is presented for Si/C/N and Si/C/N/Al/Y powders, both obtained
from the liquid phase in Tables 3.1.2 and 3.1.3. Tables 3.1.2 and 3.1.3 also give the C/N
ratios in the as-formed powders, because they are often used in the following sections to
characterise a sample.
3.1.3.1 Si/C/N samples

The samples studied in this section have an initial C/N ratio in the range 0.2–2.6 (HMDS40–45
and HMDS36, 66 and 67). The chemical composition in atomic ratio (C/Si, N/Si and C/N) and
its evolution as a function of annealing treatment between 1000◦ C and 1600◦ C is presented
in Table 3.1.1 for samples HMDS40–45. The results for stoichiometric compounds after
annealing at 1600◦ C, are reported in Table 3.1.2 for HMDS40–45 and HMDS36, 66 and 67.
Part of these results appear in the PhD thesis of Emmanuel Musset (Musset 1995).
Up to 1400◦ C, the chemical composition of Si/C/N samples presented in Table 3.1.1 shows
no significant changes in the different atomic ratio values. Meanwhile, at higher temperatures
30 Emmanuel Musset et al.
Table 3.1.2 Chemical composition (wt%) of various HMDS samples after
annealing 1600◦ C assuming stoichiometric composition
Samples Si3 N4 SiC SiO2 C C/N (at)

initial ratio
HMDS36a 5.3 91.5 1.9 1.3 2.8

HMDS40 7.7 87.6 2.1 2.6 1.3
HMDS41 19.1 75.1 3.3 2.6 0.9
HMDS42 28.6 67.4 3.0 1.0 0.7
HMDS43 56.4 37.7 3.0 2.9 0.7
HMDS44 65.9 29.9 2.8 1.4 0.6
HMDS45 88.9 8.4 2.5 0.3 0.3
HMDS66 6.2 83.0 1.5 9.9 1.8
HMDS67 6.3 82.4 1.5 9.8 2.4
Note
a Without ammonia in the carrier gas during synthesis.
Table 3.1.3 Chemical composition of Si/C/N/Al/Y/O pre-mixed powders after annealing under N
(1 h, 1600◦ C) assuming stoichiometric composition
Powder Chemical composition (wt%) (Al + Y )/Si Al/Y C/N initial

sample ratio
Y2 O3 Al2 O3 SiO2 Si3 N4 SiC C
HSAl03 2.8 0 17.8 70.2 10.4 3.1

HSAl04 7.1 0 18.3 66.7 8.1 3.7
HSAl07 3.1 0 17.6 72.2 5.9 0.04 2.7
HSAl09 3.3 1.7 92.3 0.2 2.5 0.03 0.2
HSAl12 2.6 0.4 52.7 44.0 0.2 0.02 0.6
HSAl13 3.3 0.8 17.0 78.5 0.4 0.03 1.4
HSAl14 3.5 0.5 46.5 48.1 1.4 0.03 0.8
HSAl15 3.9 0 77.5 16.1 2.4 0.04 0.5
HSAlY05 1.3 3.8 0 19.3 64.1 9.0 3.5
HSAlY16 0.1 0.3 1.9 92.4 3.1 2.1 0.01 14.8 0.3
HSAlY17 0.6 0.9 1.4 51.9 43.7 1.5 0.01 3.2 0.8
HSAlY18 1.1 1.1 1.5 14.5 80.9 0.8 0.01 2.3 1.1
different evolutions occur depending on the initial C/N ratio (Tables 3.1.1 and 3.1.2):
• For the C-rich samples (HMDS36, 66, 67 and HMDS40), the C/N atomic ratios compared
to the as-formed powders increase and the powders are converted essentially towards SiC
(between 80% and 90%) during annealing (C/Si atomic ratio near 1, see Table 3.1.1).
Free C is always present in these samples after annealing at 1600◦ C (Table 3.1.2).
• For the N-rich samples (HMDS44 and 45), the C/N atomic ratios decrease with a sta-
bilisation of the N content and the powders are converted essentially towards Si3 N4
(between 66% and 89%).
• For the two samples with intermediate composition (HMDS42 and 43, initial ratio C/N =
0.7), the C/N atomic ratios remain relatively stable with a stabilisation or a slight decrease
of the C/Si atomic ratios and a conversion of the powder towards a composite powder
containing both SiC and Si3 N4 .
Whatever the composition of the initial powders, annealing induces a decrease in silica
and in free C content because of the carbonitridation of this compound which involves CO
evolution.
For C-rich powders, the change in composition (Table 3.1.2) to SiC-rich compounds, during
annealing at 1600◦ C under a N2 atmosphere, can be essentially linked to the decomposition of
nitrogenous species (Si/C/N, Si3 N4 ) occurring from 1450◦ C. Such decomposition is impor-
tant because of the high C content in as-formed powders (C/N > 0.75) (Musset 1995; Musset
et al. 1997). Effectively, extended X-ray absorption fine structure (EXAFS) (Chapter 5.4)
and nuclear magnetic resonance (NMR) (Chapter 5.1) analysis of C-rich powders synthesised
from HMDS have shown that the atomic local arrangement of Si is essentially composed of
mixed SiC3 N tetrahedra and of SiC4 tetrahedra which are already close to the SiC structure.
This suggests the decomposition of slightly nitrogenous compounds (SiC3 N) during anneal-
ing in order to reach the SiC structure. Moreover, annealing induces a decrease in silica
and in free C content because of the carbonitridation of this compound which involves CO
evolution.
For N-rich powders, EXAFS and NMR analysis have shown that the atomic local arrange-
ment is essentially composed of SiN4 tetrahedra which are the local environment of crystalline
Si3 N4 . Therefore, the evolution towards a major phase of Si3 N4 after annealing is not
surprising.
The drastic change between the evolution of Si/C/N towards SiC or Si3 N4 compounds is
observed for the initial C/N atomic ratio in the as-formed powders near the 0.75 value and
corresponding to a 3SiC–Si3 N4 mixture (Figure 3.1.1).
3.1.3.2 Si/C/N/Al/Y/O samples

For samples obtained from a mixture of organometallic compounds as precursors, the com-
ments are mainly focused on the aspects specific to the presence of Al and/or Y in the powders.
Table 3.1.2 presents the results in stoichiometric compounds after annealing at 1600◦ C for
1 h under a N2 atmosphere for Si/C/N/Al/Y/O samples with an initial C/N ratio in the same
range as HMDS samples (0.2–2.6).
The most important difference between Si/C/N samples obtained from only HMDS and
Si/C/N/Al/Y samples obtained from a mixture of organometallic precursors is the incorpora-
tion of Al and Y metallic elements into the Si/C/N system, which could modify the evolution
of the chemical composition of the Si/C/N system during annealing. That is why a comparison
between Si/C/N and Si/C/N/Al/Y samples with a similar C/N ratio is presented below.
Tables 2.6 and 3.1.3 clearly show that, in the Si/C/N/Al/(Y) systems, the Al+(Y)/Si ratios
remain similar to those of the corresponding as-formed powders. This attests that the thermal
treatment under a nitrogen atmosphere (1600◦ C) does not induce the degradation of all Al
and Y containing species. Thus, Al and/or Y additives remain in the powder after annealing,
which is important for the future sintering process, in which sintering aids (Y2 O3 , Al2 O3 )
are necessary in order to obtain dense nanomaterials.
By comparing, after heat treatment, HSAl or HSAlY samples (Table 3.1.3) with HMDS
samples (Table 3.1.2), one can see that the evolution of the chemical composition in
Si/C/N/Al(Y) system as a function of the C/N ratio is comparable to that in HMDS samples
previously discussed. In this way, C-rich Si/C/N/Al/Y samples (initial C/N ratio between
1.1 and 2.7) are converted essentially to SiC (content between 64% and 81%, see samples
HSAl03, 04, 07 and HSAlY05) while N-rich samples (C/N ratio between 0.2 and 0.3) are
100
45
80
44 Si3N4
60 SiC
43 SiO2
Mass content (%)
40
42
41
20
40
36
0.0 0.5 1.0 1.5 2.0 2.5 3.0

C/N atomic ratio (as-formed powder)
Figure 3.1.1 Change in phase content (SiC, Si3 N4 , SiO2 and C) in HMDS powders after 4 h
annealing under nitrogen at 1600◦ C. (Reprinted from Musset 1995.)
converted essentially to Si3 N4 (content of 92%, see samples HSAl12 and HSAlY17). Sam-
ples exhibiting an intermediate composition (C/N ratio between 0.6 and 0.8) are converted
to a mixture containing both SiC and Si3 N4 (SiC around 44 wt%, Si3 N4 between 52% and
53%, see HSAl12 and HSAlY17 samples). Note that C-rich samples also contain a noticeable
quantity of free C (between 6% and 10%). Meanwhile, even if the evolution of the chemical
composition is similar between Si/C/N and Si/C/N/Al(Y)O samples, noticeable differences
appear where the C/N values and also the Si3 N4 and SiC contents are concerned, especially
for Si/C/N and Si/C/N/Al/Y C-rich samples (C/N = 2.6). Figure 3.1.2 shows the evolu-
tion of the C/N ratio after a 1 h annealing treatment at 1600◦ C under a N2 atmosphere for
some C-rich samples (HMDS66, HSAl03, 04 and HSAlY05). In this figure, the C/N ratio
is around 15 for HMDS powders while it is only of 4.3–5.1 for HSAl(Y) powders. These
results indicate that the loss of N is lower for powders containing Al and Y additives and
exhibiting high C/N ratio. The SiC content is then lower and the Si3 N4 content is higher in
these Si/C/N/Al/(Y)O samples than those in Si/C/N samples (see Tables 3.1.2 and 3.1.3). This
suggests that the decomposition of N containing species (Si/C/N, Si3 N4 ) is limited during
heat treatment of Si/C/N/Al/Y powders, probably due to the formation of a liquid phase in the
HMDS66
HSAl03
HSAl04
C/N (at. ratio)
HSAlY05
10
0
0 500 1000 1500
Temperature (°C)
Figure 3.1.2 Evolution of the C/N atomic ratio with annealing temperature. (Reprinted from
Cauchetier et al. 1999 with permission from Kluwer Academic/Plenum Publishers.)
quaternary Si–Al–O–N or in the quinary Y–Si–Al–O–N diagram preventing the degradation

of nitrogenous compounds.
3.1.4 Structural changes

XRD and infrared (IR) measurements were carried out in order to obtain information about
the nature of the different phases present and the evolution of structure and of the different
chemical bonding after heat treatment. They were carried out on both Si/C/N and Si/C/N/Al/Y
samples obtained from the liquid phase.

For annealing temperatures below 1500◦ C, the XRD diagrams of Si/C/N nanopowders
(HMDS samples) are flat indicating that the powders are still amorphous. The IR spectra
are very similar to the spectra of as-formed powders (see for example Figure 2.8), apart
from the absorption bands at 1170, 2950 and 1255 cm−1 involving hydrogenated bonds that
disappeared.
At 1500◦ C, peaks are present on the XRD diagram (Figure 3.1.3), indicating the pres-
ence of crystallised β-SiC in HMDS40, 41 and 42 samples and α- and β-Si3 N4 phases in
HMDS45. For HMDS43 and 44, the peaks are small and broad indicating a lower degree of
crystallisation. Figure 3.1.4 presents IR spectra for three samples (C/N = 0.73, 0.67 and 0.57,
respectively for HMDS42, 43 and 44) at the same temperature (1500◦ C). It shows two broad
peaks centred near 900 and 500 cm−1 indicating the presence of an amorphous material and
corresponding to Si C N and Si N bonds, respectively. These results, together with the
XRD result, indicate that crystallisation is not complete at this temperature, especially for
samples with an ‘intermediate’ C/N ratio (HMDS43 and 44). This late crystallisation will be
discussed in more detail in Chapter 5.5.
Between 1500◦ C and 1600◦ C, noticeable changes occur both in the XRD diagram and in
the IR spectra (Figures 3.1.4 and 3.1.5). Figure 3.1.5 presents the XRD diagrams of samples
annealed at 1600◦ C. C-rich powders (HMDS41 sample) lead preferentially to the β-SiC
phase, as was already noticed at 1500◦ C. N-rich powders (HMDS45 sample) mainly show
-Si3N4
HMDS45
-Si3N4

Al Support

Al Al Al
Al

HMDS44
-SiC
-SiC
HMDS43
-SiC -SiC
-SiC
-SiC
Al Al Al -SiC
HMDS42 Al
-SiC
HMDS41 -SiC
-SiC
-SiC
HMDS40 -SiC -SiC
20 30 40 50 60 70 80
Angle (2)
Figure 3.1.3 XRD patterns of HMDS powders after annealing at 1500◦ C. (Reprinted from Musset
1995.)
the presence of α- and β-Si3 N4 phases and very small β-SiC peaks. Samples exhibiting
intermediate composition (HMDS43 and 44) lead to a mixture of SiC and Si3 N4 . In the
IR spectra (Figure 3.1.4), the broad peak centred near 900 cm−1 becomes sharper between
1500◦ C and 1600◦ C. The shape becomes similar to the signature of crystallised SiC nanopow-
ders obtained from the gas phase. The fine absorption bands present in the 800–400 cm−1
range indicate the crystallisation of N-rich powders only present in HMDS43 and 44 samples
(α- and β-Si3 N4 phases, Luongo 1983). These results (XRD and IR) are in good agreement
with the calculated chemical compositions given in Table 3.1.2.
1700°C
1700°C
1700°C
1600°C 1600°C
Absorbance (a.u.)
Absorbance (a.u.)
Absorbance (a.u.)
1600°C
1550°C
1550°C 1550°C
1500°C 1500°C
1500°C
1500 1000 500 1500 1000 500 1500 1000 500

Wavenumber (cm–1) Wavenumber (cm–1) Wavenumber (cm–1)
HMDS42 HMDS43 HMDS44
Figure 3.1.4 Change in IR spectra during annealing under nitrogen between 1500◦ C and 1700◦ C.
(Reprinted from Musset 1995.)

As mentioned above for Si/C/N samples, annealing treatment under a nitrogen atmosphere
also induces a drastic change in the structure of Si/C/N/Al/Y powders. From amorphous,
in their as-formed state, they become crystallised or at least partially crystallised after a 1 h
treatment at 1600◦ C under nitrogen atmosphere. Figure 3.1.6 shows XRD diagrams of Si/C/N
samples (0.2 < C/N < 1.7) annealed under nitrogen at 1600◦ C for 1 h. The nature and the
crystallographic variety of the phases that crystallise during heat treatment are very similar to
those obtained from Si/C/N powders (HMDS samples). Thus, for a C-rich Si/C/N/Al powder
(HSAl13), the XRD diagram shows an evolution towards α- and β-SiC compounds while for a
N-rich Si/C/N/Al powder (HSAl09), α- and β-Si3 N4 are formed with a higher quantity of the
α phase compared to the β phase. For samples having intermediate composition (HSAl12), α-
and β-Si3 N4 and β-SiC phases are formed. The IR spectra of the same samples (Figure 3.1.7)
are in good agreement with the XRD diagram, that is to say that SiC bonds (around 900 cm−1 )
are detectable in a C-rich system, while Si N bonds in a Si3 N4 structure are detectable in
a N-rich system. The sample with intermediate composition contains the Si N bonds in
the Si3 N4 structure and also Si C bonds. IR and XRD results are very consistent with the
chemical composition mentioned above.
For C-rich samples (C/N = 2.6, HSAlY05 and HMDS66 samples), a comparison between
the XRD diagrams of Si/C/N and Si/C/N/Al/Y powders annealed at 1600◦ C is presented
(Figure 3.1.8). Moreover, the evolution of the IR spectra as a function of the temperature is
presented for the same samples (Figure 3.1.9).
XRD patterns of HSAlY05 and HMDS66 annealed at 1600◦ C are shown in Figure 3.1.8.
The Si/C/N/Al/Y powder annealed for 1 h (HSAlY05 sample) presents broad diffraction
-Si3N4
HMDS45
Al -Si3N4

-SiC
Al Al Support

Al Al

-SiC

-SiC
HMDS44
-SiC
-SiC
-SiC

+
-SiC -SiC

-SiC
HMDS43

-SiC

-SiC
-SiC

HMDS42

-SiC -SiC
-SiC
-SiC

-SiC
HMDS41
-SiC
-SiC
-SiC Al
-SiC Al Al
Al
20 30 40 50 60 70 80
Angle (2)
Figure 3.1.5 XRD patterns of HMDS powders after annealing at 1600◦ C. (Reprinted from Musset
1995.)
lines of β-SiC that are indicative of a low degree of crystallisation (Figure 3.1.8(a)). There
is also evidence for the presence of the α-SiC phase (2H polytype). When annealing time
is increased, well-crystallised α-SiC (2H polytype) and β-SiC are present (Figure 3.1.8(b)).
In contrast, for the Si/C/N powder (HMDS66 sample) there is evidence of α- and β-SiC
even after only 1 h of annealing and no difference can be noticed in the diffractogram for an
annealing duration of 1 or 4 h (Figure 3.1.8(c) and (d)). These results suggest that for C-rich
powders, the presence of Al and Y either limits the crystallisation or enables the formation
of an amorphous phase initiated in the Y–Si–Al–O–N quinary system.
-Si3N4 >> -Si3N4
HSAI09
Intensity (a.u.)
( + ) Si3N4 + -SiC
HSAI12
-SiC + -SiC
HSAI13
10 20 30 40 50 60 70 80 90
Angle (2 degrees)
Figure 3.1.6 XRD analysis of annealed HSAl powder. (Reprinted from Mayne et al. 1999.)
Si-N in -Si3N4
KBr
Absorbance (a.u.)
HSAI09
Si-N in -Si3N4
Si-C
HSAI12
HSAI13 Si-C
2000 1800 1600 1400 1200 1000 800 600 400

Wavenumber (cm–1)
Figure 3.1.7 IR spectra of annealed HSAl powder. (Reprinted from Mayne et al. 1999.)
Figure 3.1.9 presents examples of IR spectra of the as-formed and annealed Si/C/N and
Si/C/N/Al/Y/O powders (high C/N ratio). Up to 1400◦ C, the spectra of Si/C/N/Al/Y/O
powder are very similar to the spectra obtained for Si/C/N powder. The only difference
seems to be a flat base line for the powders containing Al(+Y) additives whereas a pro-
nounced dip appears near 1000 cm−1 in the IR spectrum of powders without additives
(a) HSAIY05/1 h (b) HSAIY05/4 h

Counts (a.u.)
(c) HSDS66/1 h (d) HSDS66/4 h
20 40 60 80 20 40 60 80
2 (CuK) 2 (CuK)
Figure 3.1.8 XRD patterns of samples (a) and (b) HSAlY05 and (c) and (d) HMDS66 after 1
and 4 h annealing under N at 1600◦ C. (Reprinted from Cauchetier et al. 1999 with
permission Kluwer Academic/Plenum Publishers.)
HMDS66 HSAI03 HSAIY05
Si-N Si-C Si-N Si-C Si-N Si-C
Si-CH3 Si-CH3
Si-CH3
As-formed As-formed As-formed

Absorbance (a.u.)
Absorbance (a.u.)
Absorbance (a.u.)
1000°C/1 hr
1000°C/1 hr
1400°C/1 hr 1000°C/1 hr
1400°C/1 hr
1400°C/1 hr
1600°C/1 hr
1600°C/1 hr 1600°C/1 hr
1600°C/4 hr
1600°C/4 hr 1600°C/4 hr
1500 1000 500 1500 1000 500 1500 1000 500

Wavenumber (cm–1) Wavenumber (cm–1) Wavenumber (cm–1)
Figure 3.1.9 Changes in IR spectra with annealing temperature. (Reprinted from Cauchetier et al.
1999 with permission Kluwer Academic/Plenum Publishers.)
indicating crystallisation or grain growth as observed previously in the annealing of SiC

powders obtained by a laser gas-phase driven reaction (Tougne et al. 1993) or from pyrolysis
of a polycarbosilane (Sasaki et al. 1989). No significant change is observed when the dwell
time increases from 1 to 4 h and no signature characteristic of Al or Y is observed.
This study of chemical and structural changes during annealing of Si/C/N and
Si/C/N/Al/Y/O samples under nitrogen atmosphere has shown a comparable evolution of
Si/C/N and Si/C/N/Al/Y/O samples with comparable C/N ratio. A more detailed comparison
seems to indicate that the presence of elements of sintering aids limits the degradation of
the nitride phase during heat treatment of Si/C/N/Al/Y/O samples. Another point is that the
elements Al, Y and O aids remain present in the powder after thermal treatment, which is
encouraging for future elaboration of materials.
3.1.5 Information about changes in the grain sizes
BET measurements were carried out in order to measure the specific surface area, which
enables determination of the changes in reactivity and grain size after heat treatment. These
measurements should be related to transmission electron microscopy (TEM) analysis (see
Chapter 4).

Figure 3.1.10 shows the variation of only two Si/C/N samples (HMDS41 and HMDS44).
Below 1000◦ C, the SBET decrease can be explained by the smoothing of the particles due
to the reticulation reactions, which occur during the ceramisation of the powders. Then the
SBET value remains constant up to 1400–1500◦ C and the decrease at 1600◦ C is due to the
crystallisation and growth of the particles, as confirmed by TEM (Chapter 4).

Annealing (nitrogen atmosphere, 1600◦ C, 1 h) of Si/C/N/Al/Y/O powders induces a decrease
of the specific surface area compared with that of initial powders attesting to a structural and
morphological change during heat treatment such as crystallisation, structural modification of
free C and particle growth. The difference between the specific surface areas of as-formed and
annealed powders increase when the C/N atomic ratio decreases. Thus for C-rich Si/C/N/Al/O
powders (HSAl07 sample), the specific surface area varies from 110 m2 /g (as-formed) to
54 m2 /g (annealed) while for N-rich Si/C/N/Al/O powders (HSAl09 sample), the decrease
of the specific surface area is more important (112–12 m2 /g). A similar evolution is also
true for the series of Si/C/N/Al/Y/O samples. This phenomenon could suggest a different
grain growth process in C-rich powders compared to N-rich powders, that is to say that the
grain growth could be more pronounced in N-rich samples. Apart from a low grain growth,
100
HMDS41
HMDS44
BET surface area (m2 g–1)
80
60
40
20
0
0 200 400 600 800 1000 1200 1400 1600
Temperature (°C)
Figure 3.1.10 Change in specific surface area during annealing under N for a C-rich HMDS powder
(HMDS41 sample) and a N-rich HMDS powder (HMDS44 sample). (Reprinted
from Musset 1995.)
this could also be related to the low crystallisation degree (see XRD patterns above) and to
a structural modification of free C giving rise to some C ribbons as was already observed
(Musset 1995) and as is usually formed from the heat treatment of amorphous C between
1500◦ C and 2000◦ C (Dresselhauss et al. 1988).
These interpretations must be checked by TEM observations in order to determine the
main phenomenon responsible for the surface area results.
3.1.6 Conclusion
From the first section of this chapter devoted to thermal behaviour, several interesting points
can be noted:
• The thermal behaviour of Si/C/N powders can be related to synthesis conditions; powders
obtained from the gas phase appear more stable than powders obtained from the liquid
phase using the aerosol method.
• Heat treatment under nitrogen allows one to obtain crystallised powders with a chemical
composition varying from a major phase SiC to a major phase Si3 N4 with intermediate
mixtures of SiC + Si3 N4 .
• The Al, Y and O elements of sintering aids remain present in the Si/C/N/Al/Y/O powders
after thermal treatment under N atmosphere. The behaviour of these powders is qualita-
tively comparable to the behaviour of Si/C/N powders with comparable C/N ratio. The
presence of these in situ sintering aids can be very helpful to obtain homogeneous dense
materials – their influence is presented in Chapter 7.
References
Cauchetier, M., Croix, O., Herlin, N. and Luce, M. (1994) Journal of the American Ceramic Society,
77, 993.
Cauchetier, M., Armand, X., Herlin, N., Mayne, M., Fusil, S. and Lefevre, E. (1999) Journal of
Materials Science, 34, 1.
Croix, O., Gounot, M., Bergez, P., Luce, M. and Cauchetier, M. (1991) Ceramics Today: Tomorrow’s
Ceramics, Elsevier Science Publishers, Amsterdam, p. 1447.
Dresselhaus, M. S., Dresselhaus, G., Sugihara, K., Spain, I. L., Golbert, H. A., Cardona, M. (1988)
Graphite Fibers and Filaments, Springer Verlag.
Ekström, T. and Persson, J. (1990) Journal of the American Ceramic Society, 73, 2834.
Hoffmann, M. J. and Petzow, G. (1993) Materials Research Symposium Proceedings, 287, 3–14
Luongo, J. P. (1983) Journal of the Electrochemical Society, 130, 1560.
Mayne, Martine (May 1997) Ph.D. Thesis, Limoges University, 97LIMO0021; http://thesenet.abes.fr
Mayne, M., Balhoul-Hourlier, D., Doucey, B., Goursat, P., Cauchetier, M. and Herlin, N. (1998) J. Eur.
Ceram. Soc., 18, 1187.
Mayne, M., Armand, X., Cauchetier, M., Doucey, B., Bahloul-Hourlier, D. and Goursat, P. (1999)
Ceramics: Getting in the 2000’s, Part B (Ed. P. Vincezini) Techna, Faenza, pp. 211–218
Musset, Emmanuel (Nov. 1995) Ph.D. Thesis, Paris-Sud Orsay University, 95PA112537;
http://thesenet.abes.fr
Musset, E., Herlin, N., Cauchetier, M. and Luce, M. (1997) Silicates Industriels, 62, 111.
Sasaki, Y., Nishima, Y., Sato, M. and Okamura, K. (1989) Physical Review B: Condensed Materials,
40, 1762.
Tougne, P., Hommel, H., Legrand, A. P., Herlin, N., Luce, M. and Cauchetier, M. (1993) Diamond and
Related Materials, 2, 486.
3.2 Thermal reactivity of silicon-based
nanopowders
Djamila Bahloul-Hourlier, Benoît Doucey,
Jean-Louis Besson and Paul Goursat
3.2.1 Introduction
Si/C/N nanopowders may be converted into Si3 N4 /SiC bulk materials by consolidation and
hot pressing. Several studies have been devoted to the synthesis of Si/C/N nanopowders and
their sintering. However, only a few studies on the thermal decomposition of these preceramic
nanopowders have been reported (Giorgi et al. 1996; Suzuki et al. 1995; Borsella et al.
1997; Mayne et al. 1998; Pan et al. 1999), in contrast to the situation with organometallic
polymer precursors of Si/C/N ceramics (Burns et al. 1987; Blum et al. 1989; Han et al.
1992; Corriu et al. 1992; Schmidt et al. 1992; Lavedrine et al. 1991; Bahloul et al. 1993,
1997). It is well known that ultrafine powders can undergo structural changes when they are
heated at specific temperatures. This is due to their high surface energy and non-equilibrium
phases. A good knowledge of adsorbed species on the surface, the nature of chemical groups
present in nanopowders and their reactivity during annealing may be used to further improve
the colloidal processing, shaping and forming techniques and also to optimise sintering
conditions and thus mechanical properties.
The aim of the present work is to further clarify the effects synthesis conditions and
chemical composition of the preceramic Si/C/N nanopowders have on their thermal stability
while under different atmospheres.
The synthesis conditions and chemical composition of the studied powders as well as their
corresponding designation are reported in Table 3.2.1. The studied samples have a C/N ratio
varying from 0.2 to 2.6.
Various experimental techniques: thermogravimetric analysis coupled with mass spec-
trometry (TGA/MS), elemental analysis and X-ray diffraction (XRD) were used to follow
the evolution of annealing in preceramic nanopowders.
Table 3.2.1 Nanopowders chemical composition

Powder %NH3 Chemical analysis (wt%) Atomic Chemical composition (at %)
(cm3 /min) ratio
Si C N O Al C/N Al2 O3 SiO2 Si3 N4 SiC Si C N
SiCN29 40 58 6 35 1 — 0.2 — 1 87 8 — 4 —
SiCN35 0 67 13 18 2 — 0.8 — 4 45 45 6 — —
HMDS35 40 51 6 38 5 — 0.2 — 9 77 — — 6 8
HMDS66 0 51 32 15 2 — 2.4 — 5 37 39 — 19 —
HMDS73 10 52 13 25 10 — 0.6 — 19 63 7 — 11 —
HSAl07 0 47 29 13 9 2 2.6 4 12 32 33 — 19 —
HSAl09 40 49 7 36 4 2 0.2 4 9 76 — — 7 6
42 Djamila Bahloul-Hourlier et al.
3.2.2 Results and discussions
3.2.2.1 TG/MS analysis

Figure 3.2.1 shows a comparison of the measured weight losses during the decomposition
of the as-received Si/C/N preceramic nanopowders in flowing helium (He). At first sight,
the results indicate a direct dependence of the ceramic yields on the synthesis conditions.
Obviously, the overall weight loss is greater for the family of nanopowders produced from
liquid precursor (HMDS) than for that obtained from gas reactant SiH4 (gas). The major
weight loss variations basically evolve at high temperature (T > 1300◦ C), where extensive
degradation of the preceramic nanopowders occurs (Figure 3.2.1).
A combined TGA/MS study was then used to determine the identity of the evolved species
at each step. On account of the large number of powders produced by particular synthesis
conditions, it is not possible to illustrate here all the mass spectra. Only the data corresponding
to the sample that exhibited the highest weight loss (HMDS35) will be given in detail.
However, when differences exist, they will be compared with the other samples. The TG/MS
analysis of HMDS35 under He is given in Figure 3.2.2.
On heating from room temperature to 300◦ C, the weight loss of 1% corresponds to the
simultaneous escape of water (M/z = 18, 17) and ammonia (M/z = 17, 16, 14). The inten-
sity of water progressively diminishes with increasing temperature up to approximately
300◦ C, while ammonia seems to stabilise between 400◦ C and 600◦ C and then diminishes
with further heating. The appearance of two shoulders at M/z = 17 is evidence for the
occurrence of at least two different reactions.
Temperature (°C)
0 300 600 900 1200 1500 Dwell time 1h00
0
–5
∆M/M O (%)
–10
–15
–20
0 50 100 150 200
Time (min)
SiCN29, SiCN35, HMDS66, HMDS35, HSA109
Figure 3.2.1 TG profiles of different nanopowders pyrolysed under He flow.

Thermal reactivity of silicon-based nanopowders 43
Temperature (°C)
0 300 600 900 1200 1500 Dwell time 1h00
0
–5
Intensity (a.u.)
∆M/Mo (%)
–10
–15
–20
0 50 100 150 200
Time (min)
M/z = 2, M/z = 12, M/z = 14, M/z = 16, M/z = 17,

M/z = 18, M/z = 27, M/z = 28, M/z = 41, ∆M/Mo (%)
Figure 3.2.2 TG–MS analyses of HMDS35 nanopowder pyrolysed under He flow.
The escape of H2 O and NH3 at low temperatures (less than 300◦ C) may be a consequence
of the higher latent reactivity induced by the presence of the condensable Si NH2 and
Si OH groups on the preceramic nanopowders (Equations 3.2.1, 3.2.2a,b).
Si NH2 + HO Si → Si NH Si + H2 O↑ (3.2.1)
Si NH2 + H2 N Si → Si NH Si + NH3 ↑ (3.2.2a)
Si NH2 + Si NH Si → Si N Si + NH3 ↑ (3.2.2b)
|
Si
While the nitrogen (N) bridging may take place at low temperatures, the reaction between
silanol surface groups to form oxygen bridges is known to take place above 350◦ C
(Equation 3.2.3).
−H2 O
Si OH + HO Si −−−→ (Si O Si) (T > 300◦ C) (3.2.3)
Nakamatsu et al. (1998) proposed the following reaction (Equation 3.2.4) to explain the
simultaneous desorption of both H2 O and NH3 at low temperatures (around 200◦ C).
SiONH4+ + SiOH → Si2 O + H2 O↑ + NH3 ↑ (3.2.4)
Besides NH3 and H2 O, some other fragment ions at M/z = 44, 30 are also detected below
400◦ C. The intensities of these peaks are very low and thus prevent a detailed characterisation
of the origin structures.
Between 300◦ C and 900◦ C, a second weight loss (3.8%) is attributed to the sec-
ond escape of ammonia (M/z = 17, 16), which indicates the occurrence of the
transamination/condensation reactions (Equation 3.2.5) which are known to occur during
the thermal conversion of polysilazanes (Bahloul 1993).
2 ( Si NH Si ) + Si NH Si → 2( Si N Si ) + NH3 ↑ (3.2.5)
|
Si
Concomitant with the evolution of NH3 is the loss of other gases with M/z varying from 42
to 12 atomic mass units (AMU) (Figure 3.2.3). It is noteworthy that compounds with molec-
ular weights higher than M/z = 42 were not detected. Looking at these peak fragments, one
would attempt to assign them to light hydrocarbons containing up to three carbon (C) atoms
at most, like alcyne, olefin and alkane compounds. However, it should be remembered that
the synthesis of this powder was made with NH3 as a reactant gas, being very reactive over
Si H, Si C and C C bonds. Consequently, the probability of formation of hydrocarboned
species having two or three carbons in their structure seems very weak (Van Dijen and Plui-
jmakers 1989). Moreover, it is seen from the comparison of the intensities of the obtained
peaks that the most intense peak at M/z = 41 is followed, by descending order in intensity, by
the peak at M/z = 40, then M/z = 39, and finally M/z = 42. No hydrocarbon combination
with two or three carbons leads to such an evolution. It is, therefore, believed that these frag-
ments may be assigned to R C N species such as CH3 CN (M/z = 41, 40, 39, 38), HCN
(M/z = 26, 27) and also to less protonated species such as carbo-imines like CH3 CH NH
(M/z = 42, 28). Further data that confirms the assignment of such species will be presented
during the analysis of the exhaust gas at high temperatures (T > 900◦ C).
Intensity (a.u.)
200 400 600 800

Temperature (°C)
M/z = 27, M/z = 39, M/z = 40, M/z = 41, M/z = 42
Figure 3.2.3 MS analysis of HMDS40 nanopowder pyrolysed under He flow.

The maximum desorption of these species is situated at 600◦ C, whereas in the temperature
range (600–900◦ C) the major volatile products detected are methane (M/z = 16, 15, 14)
and H2 (M/z = 2). Methane continues to evolve up to 1000◦ C, whereas hydrogen evolution
occurs in a wider temperature range up to 1500◦ C with a maximum loss at about 900◦ C.
Some of these gaseous emissions are classical during the thermal conversion of polycarbo-
silane and polycarbosilazane polymers and were described by several authors whereas others
are more specific to this type of laser-driven powders.
Considering this temperature range, the reactions that describe the thermal decomposi-
tion of these materials are those that most probably involve radical mechanisms. There are
several potential sources of radical species that can explain the above exhausted molecules
(Equation 3.2.6–3.2.12).
Si CN → Si• +•CN (3.2.6)

N H→ N• +•H (3.2.7)
• •
Si CH2 Si → Si + CH2 Si (3.2.8)
• •
Si CH2 CN → Si + CH2 C N (3.2.9)
Si CH2 CN → SiCH2• +C N•
(3.2.10)
• •
Si CH2 CH NH → Si + CH2 CH NH (3.2.11)
• •
Si CH3 → Si + CH3 (3.2.12)
For example, the formation of CH3 C N arises from radical cleavage of Si CH2 C N
leading to the • CH2 C N radical, followed by H abstraction and/or radical combination
reactions. The formation of the other species can also be explained using this approach.
The C N groups do not appear in the initial structure of HMDS precursors, and seem
to have been formed during the synthesis process. This is confirmed by Rice’s studies (1986)
on the laser induced dissociation of the molecule of HMDS in the gas phase under argon.
Analysis of gases of the processing chamber indicated the presence of, amongst other species,
HCN and hydrocarbons, in particular.
Thus, it is not surprising to think that, in our case, as the synthesis is being carried out in
the presence of NH3 , the concentration of C N or amine groups giving HCN and RCN
species, should increase at the expense of C C groups yielding to light hydrocarbon species.
Indeed, the reaction of C or hydrocarbon compounds with ammonia has been well described
elsewhere and the resulting product is HCN while no hydrocarbons are formed (Corriu et al.
1992; Bahloul et al. 1993).
Above 900◦ C, a significant weight loss is observed. This is accompanied by the increased
evolution of the shape of the TGA curve. Between 900◦ C and 1400◦ C, besides H2 , the major
gaseous decomposition product is unambiguously ascribed to HCN at M/z = 26, 27. This
exhaust gas gives credence to the description given above concerning the attribution to HCN
and amine species of the signals at M/z between 42 and 12 AMU. This result is in good
agreement with the chemical analysis of the as-received HMDS35 (Table 3.2.1) from which
an excess of N and C are obtained assuming that only the equilibrium phases SiO2 , SiC, Si3 N4
and C, are present in the as-prepared powders (rule of mixture calculations). Furthermore, the
short-range atomic structure description of the same Si C N nanopowders by XAS reveals
the presence of C N bonds in the amorphous network (Ténégal et al. 1996). A structural
model has been proposed (Ténégal et al. 1996), where mixed tetrahedral SiCx N4−x are
randomly linked through C N bonds. The release of HCN at high temperature is further
proof that CN groups are not only pendant groups X CN as observed for temperature T <
900◦ C, or radical scavenger/quencher groups under the experimental conditions employed
in the synthesis process, but the branching groups to probably a mixed tetrahedra SiCx Ny .
Homolytic cleavages of C N bonds between two mixed tetrahedra of silicon need more
energy in comparison with those at chain-ends.
Parallel to the evolution of HCN gas is the loss of N2 at M/z = 28, 14 up to the temperature
limits of the experiment (1500◦ C) whereas the CO loss at M/z = 28, 12 begins at 1450◦ C in
minor amounts (comparison of ions at M/z = 12 for CO and M/z = 14 for N2 ). At 1500◦ C,
despite the important weight loss, the intensity of N2 diminishes rapidly, some traces of CO
are still detected by MS during the isothermal holding.
Interestingly, at 1500◦ C, during the holding time, we observe that the mass continues
to decrease with increasing time, whereas any species cannot be detected by MS in large
enough quantities to account for this continued weight loss. It is believed that this weight
loss in the TGA curve is due to compounds such as SiO which condense rapidly in cold parts
of the apparatus and may not be detected by MS. Evidence for this proposal comes from the
deposition of SiO as a wool-like product on many parts of the apparatus, which consequently
leads to the breaking of the thermocouple based on platinum.
The most probable chemical reactions in the Si/C/N/O system, that involve the evolution
of volatile species and which produce a significant weight loss, can be described in two steps.
Primarily, decomposition of the quaternary SiCx Ny Oz phase leads to the formation of an
intermediate ternary oxynitride solid phase Six Ny Oz and the simultaneous release of SiO
and CO, N2 , in which N2 is the gas detected in the greatest quantity by MS.
Then, in the second step, which occurs during holding at 1500◦ C, the oxynitride phase
Six Ny Oz undergoes a decomposition in which gaseous N2 , Si(l, g), SiO and a solid phase
are produced according to the following reactions:
SiNx Oy Cz → Si3 N4 + SiO↑ + N2 ↑ + Si(1, v)

⇓ ⇑ (3.2.13)
Six Ny Oz + N2 ↑ + CO↑ + SiO↑
The most known ternary oxynitride phase is Si2 N2 O. Although several investigators have
reported on the thermal decomposition of Si2 N2 O, no mechanism has yet been clearly estab-
lished. This is due to some of the following experimental difficulties: (a) the reproducibility
of experiments, (b) the error in the determination of the weight loss, which is sometimes not
representative of the real value of mass loss due to the condensation of the SiO species on
the rod attaching the crucible to the balance, (c) progressive clogging of the aperture of the
tube furnace and capillary for admission of gas to the mass spectrometer, by the deposit of
SiO, and (d) the rupture of the thermocouple, stopping subsequent treatment. The majority
of decomposition reactions of Si2 N2 O suppose the simultaneous escape of volatile species
SiO(g) and N2 (g). Our analyses revealed that, after 10 min at 1500◦ C, no gas species are
detected by MS, despite the continued weight loss as observed by TGA. It may be assumed
that as the powder HMDS35 has been synthesised with ammonia as a reactant, a noticeable
number of SiN4 sites are present and the amount of C in this powder is low. Taking into
account our previous observations, it is thus hypothesised that the oxynitride SiNx Oy result-
ing from the decomposition of oxycarbonitride phase SiNx Oy Cz coexists with SiN4 sites
initially present in the material. Hence when the duration of heating is increased, the oxyni-
tride phase degrades to give SiO evolution in greater quantity, while the two other species
HMDS35
He – 1500°C –1 h
20%N2/He – 1500° C –1 h
Intensity (a.u.)
As-formed
HMDS66
He – 1500°C –1 h
20%N2/He – 1500°C–1 h
As-formed
10 20 30 40 50 60 70 80
2 (degrees)
-Si3N4, -Si3N4, -SiC, -SiC
Figure 3.2.4 XRD patterns of nanopowders pyrolysed under a reactive (20%N2 /He) and inert
(He) atmosphere.
Si(l, g) and N2 interact on the SiN4 sites to give better organised Si3 N4 as supported by XRD
illustrated in Figure 3.2.4.
Rocabois et al. (1996) used Knudsen effusion MS to study the thermal degradation of
several systems based on Si like binary, tertiary and even quaternary ones containing Si/C/N/O
(Rocabois 1993).
They stressed that the thermal degradation of Si-based materials is much less pronounced
than what is predicted by thermodynamics and that their vaporisation is hindered and related
to the different evaporation coefficients of each species. Moreover, the grain size, chemical
composition, surface of contacts or interfaces during vaporisation would play an important
role in the degradation of various phases. In our case, the nanopowder is initially amorphous
as shown by XRD (Figure 3.2.4) and we can postulate that the number of surface contacts is
high and the degradation of material is more homogeneous. By admitting, as suggested by
Rocabois et al. (1996), that the evaporation coefficient of N2 is low in comparison with that
of SiO, the two concomitant reactions, decomposition of oxynitride phase with release of
SiO, Si(l, v), and N2 , and the reaction of the two latter gaseous species on SiN4 sites initially
present leading to new Si3 N4 by epitaxial growth, is expected.
3.2.2.2 Major differences in thermal behaviour

of the preceramic nanopowders
The results pointed out major differences between the nanopowders synthesised from the
same HMDS precursor with NH3 (HMDS35 and HMDS73) or without (HMDS66). Elemental
NH3 HMDS35
H 2O
HMDS73
Intensity (a.u.)
HMDS66
100 200 300 400 500 600 700 800

Temperature (°C)
M/z = 17, M/z = 18
Figure 3.2.5 MS analysis of HMDS nanopowders pyrolysed under He flow.
analysis of these powders confirmed that when NH3 is used during synthesis, the C/N ratio
decreases. This diminution of C also depends on the concentration of NH3 in the reactant
gas mixture. Moreover, during the heat treatment of these powders, the MS analysis also
confirmed that the powders synthesised in the presence of NH3 contain more N X bonds
(X = H, C, Si). Indeed, the evolution of NH3 at M/z = 17 (Figure 3.2.5) occurs over a wide
temperature range and is characterised by two waves for HMDS35 and HMDS73, whereas
for HMDS66, it exhibits only one narrow wave up to 300◦ C.
In the case of HMDS66 between 400◦ C and 700◦ C, the MS spectra (Figure 3.2.6) reveal
the loss of Si-containing species at M/z = 73, 59, 45, 44, 30, which suggests the formation
of (CH3 )x≤4 Si, whereas for HMDS35 and HMDS73, species with M/z greater than 42 AMU
were not detected. In view of the abundance of such organosilicon species, it seems that
under the experimental conditions used during synthesis, the laser interaction with HMDS
does not induce the total atomisation (bursting) of the molecular structure since NH3 is more
reactive toward Si C, which implies the amination of Si and C sites. This is the first, chief
origin of the formation of N-rich powders.
Above 800◦ C, it can be seen that for preceramic powders prepared in the presence of NH3
during the laser synthesis process, HCN evolves in larger quantities compared to the powders
prepared without NH3 .
HMDS35
Intensity (a.u.)
HMDS66
200 400 600 800 1000

Temperature (°C)
M/z = 26, M/z = 27, M/z = 39,

M/z = 40, M/z = 41, M/z = 42,
M/z = 43, M/z = 45, M/z = 73
Figure 3.2.6 MS analysis of HMDS nanopowders pyrolysed under a He flow.
It can also be observed, that as the temperature increases (T > 1200◦ C) the release of N2
and CO illustrated in Figure 3.2.6 for the C-rich powder HMDS66 and the N-rich powder
HMDS35 is different. Indeed, the release of N2 and CO takes place during the entire thermal
cycle for HMDS66, whereas no gas is detected after 10 min at 1500◦ C for HMDS35 N-
rich powder. This suggests that the thermal degradation of these two nanopowders proceeds
according to different reaction paths and depends on the chemical composition as well as on
the microstructure of the materials.
The CO response for C-rich powder HMDS66 was not monomodal indicating that the
process involves more than one reaction. The oxynitride intermediate phase suggested for
a N-rich powder in reaction (3.2.13) would not be formed, since an excess of C is present.
Regarding previously discussed thermal decomposition of silicon carbonitride material con-
taining free-carbon phase obtained from polysilazane precursors, degradation of C-rich
nanopowders may be related to the following reaction (Bahloul 1993):
SiNy Cx Oz + Cfree → SiC + CO↑ + N2 ↑

⇓ ⇑ (3.2.14)
Si(1, v)
The loss of CO starts at about 1150◦ C, whereas the escape of N2 is observed from 1300◦ C.
This can be explained in analogy to the reaction (Equation 3.2.15) observed in the solid phase
by the carboreduction of Si O bonds by excess C.
SiO2 + 3C → SiC + 2CO↑ (3.2.15)
In an analogous fashion, the large amount of N2 evolved during the holding time at 1500◦ C
can be explained by the reaction of Si N and C:
Si3 N4 + 3C → 3SiC + 2N2 ↑ (3.2.16)
Several authors (Rocabois et al. 1996; Lee and Jacobson 1992) have suggested that this
reaction is inhibited when a SiC layer is formed on the surface of the C. This causes the system
to shift to the equivalent SiC/Si3 N4 system and the excess loss of N2 would be suspected
from the direct decomposition of Si3 N4 as shown in the following equation:
Si3 N4 → 2N2 ↑ + 3Si (3.2.17)
It was supposed that, as the experimental procedure of heat treatment is the same for
all powders, we should expect that N-enriched powders generate more N2 than C-enriched
powders, since they contain more Si3 N4 phase. This was not the case. Consequently, the
decomposition of Si3 N4 is not able to offer an explanation for the evolution of N observed.
Furthermore, powder samples after heat treatment showed no evidence for the presence of
metallic silicon when examined by XRD (Figure 3.2.4). SiC is one of the main compounds
in the samples obtained from C-rich powder HMDS66 heated at 1500◦ C under He. The low
emission of CO during holding time can be attributed to the following reactions:
SiO2 + SiC → SiO↑ + CO↑ (3.2.18)

SiO + C → 2SiC + CO↑ (3.2.19)
We, therefore, suggest that in our system the SiC obtained from the reaction of Si3 N4 with
C (3.2.16) may be consumed by SiO2 following reaction (3.2.18), which in turn releases C
particles and consequently allows reaction (3.2.16) to continue producing gaseous N2 .
3.2.2.3 Thermal behaviour of nanopowders under a nitrogen

atmosphere
The reason for studying the heat treatment under N was to answer the question: could
the decomposition of silicon carbonitride, occurring under He, be stopped by using N
environmental gas?
The structural evolution of various nanopowders was thus followed as a function of heat
treatment temperature and time whilst under a N atmosphere.
The resulting curves in Figure 3.2.7, which represent the sole nanopowders that have
the same ratio C/N = 0.2, show that below 1300◦ C the weight losses are nearly identical
regardless of the nature of the atmosphere (nitrogen or He for the same kind of powder). The
main gases detected by MS are attributed to the same species as those detected under He.
In contrast, above 1400◦ C, comparison of the variation of mass is noticeably lower under
N than He, as is shown for the HMDS35 sample. These differences are more pronounced for
SiCN nanopowders obtained from only gaseous reactants (SiH4 + CH3 NH2 + NH3 + Ar),
as shown in the data in Table 3.2.2.
The volatile species which evolve are similar to those obtained under He with a majority
of CO but of a lesser degree. Furthermore, it can be seen from Figure 3.2.8 that the variation
Temperature (°C)
1050 1200 1350 1500 Dwell time 1h00
HMDS35 N2
HCN
CO
Intensity (a.u.)
N2
HMDS66
CO
100 120 140 160 180 200

Time (min)
M/z = 17, M/z = 18
Figure 3.2.7 MS analysis of HMDS nanopowders pyrolysed under He flow.
Table 3.2.2 Nanopowders weight loss changes according to atmosphere heat

treatment
Atmosphere Weight loss !M/Mo (%)

heat treatment
SiCN35 SiCN29 HMDS66 HMDS35 HSAl07 HSAl09
He −7.7 −6.8 −16.3 −19.3 −20.6 −19.8

20%N2 /He +6.1 +1.3 −6.2 −15.5 −14.6 −13.1
of mass is remarkably decreased with increasing partial pressure of N. These results suggest
that carbothermal nitridation reactions take place at high temperatures under N according to
the following reactions (Mayne et al. 1998):
SiNx Oy Cz + N2 → Si3 N4 + gaseous species (SiO↑ + N2 ↑ + Si(1, v)) (3.2.20)

Temperature (°C)
0 300 600 900 1200 1500 Dwell time 1h00
–4
∆M/Mo (%)
–8
–12
–16
–20
0 50 100 150 200
Time (min)
SiCN29 (20%N2/He), HSA109 (20%N2/He), HMDS35 (20%N2/He), HMDS35 (He)
Figure 3.2.8 TG profiles of different nanopowders pyrolysed under a 20%N2 /He flow.
For C-enriched powders that contain more SiC phase, the nitriding process is also possible
via the following reaction:
3SiC + 2N2 ↑ −→ Si3 N4 + 3C (3.2.21)
The weight gain observed, particularly for SiCN synthesised from gaseous reactants, can be
attributed to the nitridation reaction of excess metallic silicon detected by XRD (Mayne et al.
1998). According to the α- or β-Si3 N4 content calculated from XRD patterns of heat treated
powders, the nitridation reaction leads to the preferential formation of the α phase. This could
be explained by an oversaturation in nitrogen coming from the nitrogen atmosphere, which
results in the crystallisation of the less ordered α phase. Meanwhile, the β silicon nitride
phase that is more ordered and stable, is preferentially formed during annealing under the
inert He atmosphere.
3.2.2.4 Influence of the nature of the precursors’ source of silicon on

the chemical composition and thermal stability
It is observed that the aluminium doped powders (HSAl), synthesised under the same condi-
tions as that of HMDS powders, except that only aluminium isopropoxide precursor is added,
exhibit similar behaviour. Likewise, the differences observed between HMDS nanopowders
and their conditions of synthesis, in particular the NH3 pressure in the reactive mixture of
synthesis, seem to be reproduced for the HSAl powders. The role of aluminium isopropoxide
introduced during the synthesis on the thermal behaviour is being studied.
The use of a gas source of Si such as SiH4 has led to nanopowders of a more stable nature
in terms of temperature, without doubt, due to their crystallisation state as revealed by XRD.
The formation of CN bonds does not seem to be favoured when SiH4 is used. However,
contrary to the HMDS and HSAl powders, the use of silane (SiH4 ) generates an excess of
metallic silicon within the powders, which will be used profitably during sintering under N.
3.2.3 Conclusion
These studies indicate that the relative atomic concentrations of Si, C, N and H are primar-
ily influenced by the types of carrier gases used for the synthesis laser process. Residual
functionalities C H, N H and Si H bonds will still be present as supported by the
identification of volatile species by MS. The study of heat treatment of such systems based on
Si indicates that thermal degradation is not an individual reaction but the net result of many
reactions. The difference in thermal behaviour is attributed to variations in the preceramic
structure. Taking into consideration the gases detected during our investigation and compar-
ing them with similar results found by other research groups (9, 7), we are able to put forward
the suggestion that by analysing preceramic nanopowders by thermal decomposition, it is
possible to identify the processes by which they were synthesised.
A potential advantage of laser-driven synthesis of refractory materials over gaseous reac-
tants is the ability to include additives and co-reactants (e.g. sintering aids) (Cauchetier et al.
1999) in a truly homogeneous fashion.
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P. H. and Vioux, A. (1991) J. Eur. Ceram. Soc., 8, 221.
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Cer Soc, 18(9), 1187.
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4 Structure of some nanopowders and
micro/nano composites by transmission
electron microscopy
Marc Monthioux, Catherine Béraud and Nahida El Horr
4.1 As-prepared and heat-treated nanopowders

Some of both the raw and heat-treated powders were investigated by transmission electron
microscopy (TEM). Sample preparation prior to TEM investigations and TEM operating
conditions are reported in Section 4.3, together with a brief reminder of the principles for the
various TEM modes used in the study.
4.1.1 Synthesis from gaseous precursors

Starting from a mixture of silane (SiH4 ) and ethylene (C2 H2 ) as gaseous precursors, a serie
of SiC-based powders was obtained. Likewise, still using silane as Si source but replacing
ethylene by ammonia (NH3 ) and/or CH3 NH2 allowed Si/C/N-based powders to be obtained.
Si/C-based powders
Materials were investigated either as-prepared or after various treatments. Related preparation
conditions and elemental analysis of the as-prepared materials are reported in Tables 2.2
and 2.3, respectively.
Some of the samples reported in Table 2.2 were investigated after various treatments,
including SiC173, SiC177 and SiC212. Various annealing in argon atmosphere were carried
out, in order to check structural and textural changes in both the SiC and C phase.
Also, SiC173 and SiC212/1200 were investigated after thermal treatment at 450◦ C per-
formed in air (1–3 h isothermal), in order to eliminate the carbon (C) phase when present.
Finally, further heat-treatment experiments in inert atmosphere were also performed at
1800◦ C on sample SiC173 oxidised.
Special precautions were taken for the 1800◦ C heat-treatment experiments (Laanani 1997)
to prevent any possible oxidation reaction due to oxygen traces in the gas phase, that is, a non-
dynamic, high purity argon atmosphere (N56 grade from Air Liquide) and an all-graphite
furnace were used.
SIC173, AS-FORMED
Daylight colour of the as-prepared powder is dark grey, somewhat related to the polyaro-
matic C content, as already expected from the elemental analysis (see Section 3.1.1) and as
supported in the following by the direct evidence from TEM investigation. Grains exhibit
round and isometric shapes (Figure 4.1).
Micro/nano composite structure by TEM 55
50 nm
Figure 4.1 TEM bright-field image from SiC173. Arrows show stripes on SiC crystals indicating
polytypes as stacking faults.
SiC
SiC
2 nm
Figure 4.2 TEM lattice fringe image from SiC173. Note how two adjacent SiC crystals are able
to accommodate a slight mismatch in orientation of their respective lattices, making
both the 111 lattice fringes connected to each other without interruption.
Grain sizes range according to a two-mode distribution. Large grains (10–60 nm) are
prevalent, each being a single crystal, sometimes faulted (Figure 4.1, arrows). Grains are
associated into aggregates, most often chain-like, due to both weak forces (electrostatic) or
stronger ones, that is, structural. Figure 4.2 illustrates the latter, showing two grains whose
lattices are connected despite a misorientation of 10◦ , obviously inducing a strong (covalent)
bonding between grains. They are SiC crystals, β structure mainly, but some stacking faults
56 Marc Monthioux et al.
(indicating the local occurrence of polytypes) are revealed in electron diffraction patterns as
additional aligned spots (Figure 4.3), as a probable consequence of the rapid growth. Grains
are coated with a thin (∼1 nm) layer of an amorphous phase, assumed to be a silicon oxide,
as supported by X-photon energy dispersive spectroscopy (X-EDS) measurement, whose
spectra show the presence of the element O, in addition to Si and C as expected (Figure 4.4).
4 nm–1
Figure 4.3 Electron diffraction of SiC crystals from SiC173. The structure is mainly β-SiC (see
Figure 4.7 for diffraction ring identification). However, arrows show some aligned
spots indicating stacking fault sequences. The occurrence of an amorphous coating at
the grain surface (thickness ∼1 nm) is probable, though confusion with overfocusing
Fresnel fringes is possible.
Si
O
I 0.50 1.00 1.50 2.00

11 CNT 0.00 keV 10 eV/ch A EDAX
Figure 4.4 X-EDS spectrum of SiC crystals from SiC173. The presence of O attests the occurrence
of an amorphous silica layer associated to the SiC grains.
The minor occurrence of a silica phase is consistent with the results from elemental analysis
(Table 2.3).
On the other hand, small grains are a very minor phase, whose sizes (3–10 nm) are difficult
to estimate from regular bright-field images. Dark-field images help in more easily appreciat-
ing the occurrence and size distribution of it, as compared to the major phase (Figure 4.5(c),
arrows). They are not Si3 N4 but possibly SiC crystals too, since they appear in Figure 4.5(c)
while not in Figures 4.5(a) or (b). However, other small, minor crystals are also found,
despite that the amount of it is too small to appear in the diffraction pattern, from which high-
resolution images reveal fringes whose spacing is too large to match the SiC lattice distances
(not illustrated). Rarity and concentration of this minor phase are such that identification was
not possible.
A third phase is found associated with the major (SiC) phase, more or less coating the
grain surface, and identified as polyaromatic C. Its low proportion is such as it does not
appear in the electron diffraction patterns when exposure times are appropriately chosen to
reveal the SiC phase (Figure 4.3). However, its structure is most probably turbostratic (i.e.
not having the three-dimensional structure of graphite), as assumed from its morphology and
nanotextural characteristics. Lattice fringe imaging mode illustrates the latter (Figure 4.2).
The C phase appears as thin, somewhat buckling and polygonal, ribbon-like graphene stacks.
Using the parameters N (number of graphenes per stack) and L2 (length of the continuous,
though distorted, d002 lattice fringe) to characterise the nanotexture of the C phase, as pro-
posed by Oberlin (1989), the latter exhibits a rather low N values (N ∼ 2–5) with respect to
(a) (b) (c)
50 nm
Figure 4.5 TEM dark-field image sequence from SiC173. (a) and (b) correspond to ‘polyaromatic
C-specific’ (DF1) dark-field imaging conditions for two selected orientations. The selected
orientation direction is indicated by the ‘=’ sign, that is, only graphene stacks displayed
parallel to the ‘=’ sign are imaged. Graphene stacks appear as small bright rims between
SiC crystals. (c) corresponds to ‘SiC-specific’ (DF2) dark-field imaging conditions. Arrows
show the occurrence of the minor phase (probably SiC) as small size grains among the larger
SiC crystals.
a rather high L2 value (up to 20–30 nm). As far as the existence of free edges of graphenes
is unlikely, since inducing improbable dangling bonds, and since the so-called ribbons never
appear twisted as genuine ribbons might be, the graphene stacks are believed to be walls of
three-dimensional, somewhat polyhedral, polyaromatic C shells. These shells are likely to
form under mechanisms related to the thermal and/or catalytic decomposition of a carbide
phase for instance (Badami 1965; Oberlin and Rouchy 1971; Audier et al. 1981). Similar
textures, whose nanotexture parameters are fairly consistent with those measured here, were
also found in oxygen-free SiC-based materials obtained from heat-treated polycarbosilane
(Delverdier et al. 1991; Laanani 1997). Low magnification, specific (i.e. using an objective
aperture selecting some diffracted polyaromatic 002 beams) dark-field images (Figures 4.5(a)
and (b)) illustrate the proportion and location of the C phase relative to the SiC grains, as the
latter appear as round-shaped, grey to pale white objects while the former appears as bright,
elongated, tiny spots (arrows) in which graphenes are oriented parallel to the elongation
direction. Though not systematic, graphene stacks are often found oriented parallel to the
grain surface.
SIC177, 1200◦ C ANNEALED
The daylight colour of the starting powder is dark grey. The material is very similar to
SiC173/as-prepared. Slight discrepancies concern the distribution of grain size (one-mode
instead of two-mode), and the size range (slightly larger: 10–100 instead of 10–60 nm).
Another difference lies in the probable absence of the non-identified, crystallised, minor phase
of SiC173. Instead, another minor phase is found, mainly amorphous since specific dark-
field images show that it does not contain any crystallised phases, neither Si3 N4 nor SiC (not
illustrated). Considering the high diffusion contrast of this phase in dark-field images when
the beam tilt angle corresponds to the Bragg angle for the 002 reflection of polyaromatic C, it is
believed that this amorphous phase is enriched in poorly organised, turbostratic C, as expected
from the transformation of a formerly amorphous C phase due to the annealing temperature
(1200◦ C is actually far above the minimal carbonisation temperature – ∼500–600◦ C – i.e. the
temperature sufficient to transform any kind of non-gaseous C precursor into polyaromatic
solids). This phase is distinct from the better organised, polyaromatic, turbostratic C phase
associated with the SiC phase (Figure 4.6). Figure 4.6 exhibits a C shell still partially filled
with a SiC crystal (arrow), which strongly supports that the porous C phase originates from
a carbide decomposition process.
The daylight colour of the starting powder is dark grey. The sample is mainly made of
agglomerated SiC grains with round shapes (see Figure 4.1 for reference). Grain size range
is 3–40 nm, that SiC-specific dark-field images show with a probable two-mode distribution
similar to that of SiC177/as-formed (see Figure 4.5(c) for reference). The structure is strictly
β since only diffraction rings corresponding to 111, 200, 220 and 311 reflections of β-SiC
appear (Figure 4.7). SiC crystals are coated with amorphous silicon oxide, ∼1.5 nm thick
(Figure 4.8). The coating may help the SiC crystals to link to each other (Figure 4.8). However,
although confusion with an amorphous or poorly organised C coating was unlikely due to the
annealing temperature, an oxidation experiment was performed to ascertain the oxide nature
of the coating (see below).
Unlike SiC173/as-formed or SiC177/1200◦ C, the relatively well-organised, turbostratic,
polyaromatic C phase associated to the SiC phase (see Figures 4.2 or 4.6 for reference) is not
C
SiC
SiC
5 nm
Figure 4.6 TEM lattice fringe image from SiC177/1200. Arrow shows a small SiC crystal filling
incompletely a polyaromatic C shell, supporting the hypothesis that the polyaromatic
C phase between SiC grains originates from the early decomposition of some primary
SiC crystals.
220 311
200 111
4 nm–1
Figure 4.7 Electron diffraction of SiC crystals from SiC212/1200. The structure is exclusively
β-SiC.
found. Instead, a poorly organised, turbostratic, polyaromatic C phase is found, concentrated

into a minor phase consequently exhibiting a nanoporous texture (Figure 4.9), assumed to be
similar to that found in sample SiC177/1200.
The thermal treatment did not induce any change but the average SiC grain size, which
has increased mainly due to a coalescence mechanism by impingement according to
2 nm
Figure 4.8 TEM lattice fringe image of SiC crystals from SiC212/1200. The amorphous, about
2 nm wide silica coating is imaged, somewhat bonding crystals together.
5 nm
Figure 4.9 TEM bright-field image from SiC212/1200. The left part of the image illustrates the minor,
poorly organised, polyaromatic C phase.
Le Coustumer et al. (1993), Monthioux and Delverdier (1996) and Laanani (1997). The
smallest grains are now about 30–40 nm, many are in the range of ∼100 nm, and the largest
diameters are difficult to measure by TEM due to the chances of overlapping for crystals whose
large dimensions make them no longer electron transparent. In addition, an amorphous oxide
layer about 2 nm thick at the grain surface is still found, quite similar to that of Figure 4.8.
Nevertheless, the C phase associated to SiC crystals is also still found, though less abundant,
with about the same textural and structural features than that found in Figures 4.2 or 4.6. Elec-
tron diffraction patterns show that β is the most frequent SiC structure, but the occurrence of
diffraction spots located besides the regular 111, 200, 220 and 311 diffraction rings for the
3C polytype indicates that other polytypes (α structures) are present (Figure 4.10).
The main effect of such a high heat-treatment temperature is the development of the polyaro-
matic C phase, either as SiC-free porous material or shells around SiC crystals (Figure 4.11).
Though still turbostratic as ascertained by electron diffraction patterns, since only 00l reflec-
tions and hk bands are present (Figure 4.12(a)), the nanotextural state of the C phase is very
good, that is, exhibiting perfect graphene stacks at long range (Figure 4.13), which is consis-
tent with a probable origin from the partial SiC decomposition (Oberlin et al. 1976; Iijima
4 nm–1
Figure 4.10 Electron diffraction of the SiC phase from SiC177/1500. The 3C (β structure)
polytype is prevalent, but some other polytypes are found.
SiC
10 nm
Figure 4.11 TEM bright-field image from SiC173/1800. The partial decomposition of SiC crystals
induces the secondary formation of empty or crystal-filled C shells.
(a) (b)
11
10
002
4 nm–1
Figure 4.12 Electron diffraction patterns from SiC173/1800. (a) On the C phase: the structure is tur-
bostratic, since only hk reflections are found in addition to the 002 reflection. (b) On SiC
crystals (+C). The 3C polytype of SiC is no longer prevalent.
2 nm
Figure 4.13 TEM lattice fringe image from SiC173/1800. Walls of the C shells seen edge-on.
The nanotexture (i.e. graphene perfection) is very good, though the structure is not
graphitic but turbostratic according to electron diffraction patterns.
1982). Indeed, though the decomposition of SiC might sound doubtful since 1800◦ C is still
early regarding the theoretical sublimation temperature of SiC (2700◦ C), the SiC crystals
are the only C source available to explain the increase in the C phase amount. Beside, the
average SiC grain size increased dramatically (more than two to four times larger than in the
starting material), which is consistent with the similar effect observed in the SiC177/1500◦ C
sample (but in a lesser extent). Meanwhile, the diffraction patterns now exhibit many diffrac-
tion spots other than that of the 3C polytype, indicating the occurrence of other polytypes
(Figure 4.12(b) as compared to Figure 4.3).
SIC173, 450◦ C OXIDISED
As a result of the oxidising treatment, the daylight colour of the powder has turned from
dark grey to green-grey. The treatment was successful in removing the primary polyaromatic
C phase without altering the SiC grains (Figure 4.14), as compared to the non-oxidised,
as-prepared powder (Figure 4.15). Every other feature was kept unchanged.
SIC173, 450◦ C OXIDISED, 1800◦ C ANNEALED
A secondary polyaromatic C phase has appeared again, abundant, as C shells systematically

surrounding the SiC grains (see Figure 4.11 for reference). This experiment definitely ascer-
tains that SiC crystals start to decompose at temperatures as low as 1800◦ C (but beyond
20 nm
Figure 4.14 TEM bright-field image from SiC173/450 O2 . The oxidation treatment was successful
in removing the C phase without oxidising the SiC crystals.
20 nm
Figure 4.15 TEM bright-field image from SiC173. Arrows show the polyaromatic C phase
associated to the SiC crystals. To be compared with Figure 4.16.
1500◦ C, as shown by the 1500◦ C annealing experiment of sample SiC177, where only the
primary C phase was found), although the average grain diameter increases. The fact that
this temperature is far below the theoretical sublimation temperature for SiC (2700◦ C) may
be explained by the small sizes of the SiC grains. Generally speaking, physical constants of
a given phase are likely to be lowered when finely partitioned into nanocrystals as compared
to macrocrystals, due to a higher contribution of surface atoms relative to core atoms (Buffat
and Borel 1976).
SIC212, 1200◦ C ANNEALED, 450◦ C OXIDISED
Like for sample SiC173, the daylight colour of the sample has turned from dark grey to
green-grey. This is the only change observable. Specifically, the amorphous coating on the
SiC grains is still found (not illustrated), ascertaining that the coating is silicon oxide, since
amorphous C should have burnt into CO2 during the oxidation experiment.
Si/C/N-based powders
Two materials were investigated as-prepared, labelled SiCN29 and SiCN35. Related prepara-
tion conditions and elemental analysis of the as-prepared materials are reported in Tables 2.2
and 2.3, respectively. Though the amount of silane is similar, they mainly differ from each
other both by the amount of nitrogen (N) supplied (twice for the former), and the N-containing
gaseous precursors used (CH3 NH2 only for the latter, as compared to CH3 NH2 + NH3 for
the former). This induces a higher supply in C for SiCN35.
SICN29, AS-FORMED
Daylight colour of the material is light grey-green. As often, the sample exhibits two kinds
of morphologies. The major phase is made of large grains, in the range of 20–150 nm, with
frequent round shapes (Figure 4.16), sometimes polyhedral (Figure 4.17). According to the
50 nm
Figure 4.16 TEM bright-field image from SiCN29.

20 nm
Figure 4.17 Low magnification TEM lattice fringe image of some crystals from SiCN29.
dark-field images, each grain is a single crystal (Figure 4.18(b)). Grains are associated to each
other into aggregates or chains both by covalent bonding, since lattice fringe imaging suggests
structural continuity between adjacent crystals through grain boundaries (Figure 4.19), or by
weak forces. They are identified as α-Si3 N4 crystals by electron diffraction (Figure 4.20),
as supported by the occurrence of the specific reflection 101 at 0.432 nm. However, the
concomitant occurrence of the β structure is possible. Indeed, from the point of view of
selected area electron diffraction mode, diffraction patterns from α- and β-Si3 N4 structures
are difficult to distinguish from each other, due to the high amount of reflections many of
which are present in both structures on one hand, and due to the frequent absence of either
complete diffraction patterns or complete diffraction rings on the other hand.
Although lattice fringe images reveal some distorted fringes at the Si3 N4 crystal surface
looking like turbostratic C stacks (Figure 4.19), it is believed that, unlike in the SiC-based
powders, they do not correspond to a polyaromatic C phase. Indeed, the X-EDS spectra
(Figure 4.21) do not show any presence of C (either sp2 or sp3 ), neither associated to the
Si3 N4 major phase nor to the SiOx Ny minor phase (see below). Also, considering the chemical
balance for a SiC-based sample like SiC173 (Table 2.3) shows that 2 wt% only of calculated
excess C are enough to provide obvious evidence of polyaromatic C stacks in the lattice fringe
or dark-field images (Figures 4.2 or 4.5(a) and (b), respectively). On the contrary, twice a
calculated amount of excess C in SiCN29 would barely correspond to the few distorted
stacks (in lattice fringe mode, Figure 4.19) or bright rims (in dark-field mode, Figure 4.18(a),
open arrow) shown in the TEM images. The absence of a polyaromatic C phase is therefore
suggested, and the phase found at the crystal surface is more likely a silicon oxinitride phase.
Actually, previous studies combining both TEM and XPS investigations and performed on
various Si3 N4 powders have shown that silicon oxinitride is able to exhibit the same kind of
distorted fringes as turbostratic C (Madigou et al. 1990a,b; Madigou 1991). However, since
the chemical balance indicates the presence of C atoms, they could possibly be incorporated
into the amorphous silicon oxinitride phase with such a low proportion that would make C non-
detectable. Such amorphous silicon oxicarbonitride phases do actually exist, as synthesised
from the thermal curing under gaseous oxygen or air of polycarbosilazane polymers (Okamura
et al. 1984; Mocaer et al. 1993).
(a) (b)
50 nm
Figure 4.18 TEM dark-field image sequence from SiCN29. (a) ‘C-specific’ (DF1) imaging
conditions. Actually, crystals appearing bright are not C but Si3 N4 crystals. They
are imaged in the selected imaging conditions because the crystals exhibit lattice dis-
tances close to that of C002 . Likewise, the white arrow shows bright rims which are
more likely an organised Si O N phase rather than a polyaromatic phase, according
to X-EDS spectra (see text). The black arrow shows a polyaromatic C-rich phase.
(b) ‘SiC-specific’ (DF2) imaging conditions. Crystals appearing bright are actually
not SiC but Si3 N4 . They are imaged in the selected imaging conditions because the
crystals exhibit lattice distances close to that of SiC111 . The fact that the crystals
are thus able to be imaged in both dark-field imaging conditions allow them to be
identified as Si3 N4 instead of C or SiC.
2 nm
Figure 4.19 TEM lattice fringe image on Si3 N4 crystals from SiCN29. Evidence of a coating layer,
∼1 nm thick, at the crystal surface, whose distorted fringes are oriented parallel to
the grain surface.
4 nm–1
Figure 4.20 Electron diffraction from SiCN29. Si3 N4 crystals typically exhibit a lot of lattice
distances at small scattering angles.
Si
I 0.50 1.00 1.50 2.00

Figure 4.21 X-EDS spectrum on some Si3 N4 crystals from SiCN29. The occurrence of O and the
absence of C suggests that the phase coating the crystals is actually Si O N-type.
The minor phase is made of grains whose size range is often lower than for the major
phase, with round shapes. Since always faintly scattering the electron beam in dark-field
imaging mode whatever the position of the objective aperture (Figures 4.18(a) and (b)) –
though decreasingly as the tilt angle increases – the structure of this phase is amorphous.
The chemical composition is qualitatively given by X-EDS measurements (not illustrated),
which indicate an enrichment in oxygen and a depletion in N relative to the Si3 N4 phase
(Figure 4.21), in addition to the presence of Si. It is therefore believed that this minor phase
is amorphous silicon oxinitride or oxicarbonitride.
SICN35, AS-FORMED
Daylight colour of the material is dark grey-green. As sample SiCN29, two morphologies are
again observed. The major phase exhibits large grains with irregular and polyhedral shapes
associated into compact aggregates (Figure 4.22). Size range cannot be ascertained due to
the superimposition effects which make the grain contours difficult to determine. Dark-field
imaging reveals that each grain is itself an aggregate containing crystals with various sizes up
to about 40 nm (Figure 4.23(c)). These crystals were identified as pure β-SiC (=3C polytype
only) by electron diffraction (Figure 4.24). Both dark-field (Figure 4.23(a)) and lattice fringe
(Figure 4.25) images reveal that the SiC crystals are associated with an amorphous phase
somewhat embedding them. According to the X-EDS analysis which shows the presence of
N and O in addition to Si and C (not illustrated), this amorphous phase is probably a silicon
oxinitride or oxicarbonitride. No turbostratic C phase was revealed.
The minor phase exhibits much smaller grain sizes, in the range of 10–30 nm, with
round shapes, associated into elongated chains (Figure 4.22, arrow). Dark-field imaging
(Figure 4.23(b), arrow) supported by lattice fringe imaging (Figure 4.26) both reveal that
each grain is itself an aggregate of tiny crystals, few nanometres large. They were identified
as Si crystals (CFC structure) by means of electron diffraction (Figure 4.27). Correspond-
ingly, lattice fringe images show lattice distances consistent with the (111) planes of Si
(Figure 4.26). These images also reveal that Si crystals are associated with an amorphous
phase, located at their outer surface as a coating, about 2 nm thick (Figure 4.26). According
to the X-EDS analysis which barely shows another light element than O (in addition to the
prevalent Si peak – not illustrated), this amorphous phase is probably a silicon oxide phase,
which is likely considering the sensitivity of pure Si to oxidation.
50 nm
Figure 4.22 TEM bright-field image from SiCN35. Arrows show chain-like aggregate of small
grains.
(a) (b) (c)
50 nm
Figure 4.23 TEM dark-field image sequence from SiCN35. (a) ‘C-specific’ (DF1) imaging condi-
tions. No crystals appear, indicating that no Si3 N4 crystals are present (see Figure 4.20
caption for further explanation). (b) Dark-field imaging conditions selected are inter-
mediate between (a) and (c), therefore admitting both C002 and SiC111 distances. Both
SiC crystals and another phase (arrowed) are imaged. (c) ‘SiC-specific’ (DF2) imag-
ing conditions. The azimuthal angle is same as for (b). Correspondingly, the same
SiC crystals as in (b) are imaged, but the crystals arrowed in (b) no longer appear,
attesting that they are not SiC, but Si crystals (see Figures 4.26 and 4.27).
4 nm–1
Figure 4.24 Electron diffraction on a SiC-rich area from SiCN35. Crystals are pure β-SiC crystals.
2 nm
Figure 4.25 TEM lattice fringe image from the SiC phase from SiCN35. SiC crystals are
embedded in an amorphous phase.
2 nm
Figure 4.26 TEM lattice fringe image from the Si phase from SiCN35. Si crystals are coated with
an ∼1–2 nm thick amorphous phase, very probably silica.
Conclusion regarding ceramic nanopowders from gaseous precursors
SI/C-BASED MATERIALS
Though SiC173 was the only material investigated as-prepared, it is believed that comparing
SiC173 with SiC177/1200 and SiC212/1200 is possible since the annealing temperature is
rather low. Since the ethylene/silane ratio is about the same (∼0.5) for all the samples, the
main difference in preparation conditions lies in the total flow rate. It increases from SiC177
to SiC173 to SiC212 for a similar C/Si ratio in the precursor gases, inducing a decrease in
the residence time from 12.1 to 7.3 then 2.5 ms, respectively (Table 2.2). Correspondingly,
4 nm–1
Figure 4.27 Electron diffraction on a Si phase-rich area from SiCN35. Crystals are pure Si, CFC
structure.
the grain size range decreases, and SiC polytypes other than the primary form 3C (β struc-
ture), though present in the two former samples, do not have the time to develop in the latter.
Likewise, the organisation of the polyaromatic C phase tends to decrease. Conditions for the
preparation of SiC212 prevent the occurrence of a primary polyaromatic C phase. One expla-
nation could be that long residence times used for SiC173 and SiC177 allow a Si C (H)
solid solution enriched in C (relative to the 1 : 1 stoichiometry of SiC) to form in the reaction
zone. The subsequent crystallisation of the SiC phase makes the excess C to be expelled as
a polyaromatic C phase associated to the SiC crystals.
Heat treatments in inert atmosphere provoke the increase in the average SiC grain size
due to a coalescence mechanism (i.e. growth from coalescence) by impingements, while the
primary C phase, when any, remains unchanged up to 1500◦ C. Beyond 1500◦ C (at least
from 1800◦ C), the latter mechanism competes with an early decomposition mechanism,
due to the nanometric size of the SiC phase. The partial decomposition of SiC induces
the formation of a secondary polyaromatic C phase. Meanwhile, the SiC structure tends to
increasingly change from a majority of 3C (cubic) polytype to a mixture of various polytypes
(except 2H which is irreversibly unstable beyond ∼1600◦ C – Inoue and Kourachi 1983),
probably mostly as stacking fault sequences within the same grains. An explanation is that
the coalescence mechanism involves solid crystals, that does not allow single crystals with
defect-free, homogeneous structure to be obtained.
SI/C/N-BASED MATERIALS
Correspondingly to the higher N content in the precursor gas phase for SiCN29 (twice that
of SiCN35), Si3 N4 crystals only develop in the former. A SiC phase develops in SiCN35
instead, further enhanced by a higher amount of C supply. The fact that no Si3 N4 phase is
able to form in SiCN35 is amazing since, consistently with the theoretical phase content
calculated from the elemental composition (Table 2.3), the N supply should be sufficient.
This is not merely due to a lower formation kinetic for Si3 N4 relative to SiC, since Si3 N4 is
able to form in SiCN29 while the residence time is lower. The main parameter is therefore
believed to be the nature of the primary gases, and possibly the presence of C specifically.
Thus, when combined with silane and ethylene, a C-free precursor like NH3 is more likely
to induce the Si3 N4 formation than a C-containing precursor like CH3 NH2 . The reason is
probably that the former precursor gas combination only provides C H, Si H and N H
bonds which are easier to thermally break than the pre-existing C N bonds in the latter.
Si N bonds are therefore allowed to form more easily and early in the former than in the
latter.
4.1.2 Synthesis from liquid precursors

Nebulisation of liquid precursors such as hexamethyldisilazane (Si2 C6 NH18 ) produced other
Si/C/N-based powders. Adding an increasing amount of NH3 allowed the C/N atomic ratio
of the as-prepared material to be controlled. The various experiments result in a whole series
of samples listed in Table 2.5, and characterised by a continuous decrease in their C/N atomic
ratio.
On the other hand, the same principle of using an increasing NH3 /Ar ratio for a constant
total flow rate was applied to a nebulised liquid precursor made of a mixture of HMDS and
aluminium isopropoxide (see Section 2.4.2) in order to prepare Si/Al/C/N-based powders.
Materials obtained and relative preparation conditions are reported in Table 2.6.
Si/C/N-based powders
Among the whole series of samples listed in Table 2.5, HMDS42 and HMDS44 were
investigated by TEM. They correspond to a slope change in the variation trend of the C/N ratio
value measured in the starting materials v. the SiC/Si3 N4 content in the 1600◦ C-annealed
materials (see Figure 3.9). HMDS42 and HMDS44 exhibit C/N ratios of 0.73 and 0.56,
respectively. Since amorphous at the as-prepared state, they were investigated after increas-
ing annealing heat treatments under pure N atmosphere at temperatures ranging from 1000◦ C
to 1600◦ C.
HMDS42, 1000◦ C ANNEALED
The bulk structural evolution of the sample with increasing annealing temperature from
1000◦ C and beyond is illustrated by electron diffraction, whose patterns are gathered on
Figure 4.28.
After 1000◦ C annealing, the daylight colour of the material is black. Though all the grains
exhibit a rather round and isometric morphology (Figure 4.29(a)), a two-mode distribution
of grain size is observed, with small grains (20–60 nm) being prevalent, and the subsidiary
occurrence of large grains (80–60 nm). Small grains exhibit a nanometric porosity revealed by
a Fresnel contrast effect when unfocused. Grains are associated into aggregates (often chain-
like) either by strong, structural bonds (illustrated by the chain-like aggregate made of three
large grains at the centre of Figure 4.29(a)), or by weak (electrostatic) forces (as illustrated by
the small grain aggregate at the top of Figure 4.29(a)). It is worth noting that isolated grains
look isometric, but aggregates are not. Considering one morphology (isometric) or the other
(chain-like for instance) will provide very different shape factors, which is likely to explain
possible mismatches between actual and calculated surface area of the powder.
Electron diffraction patterns indicate an overall amorphous structural state, both for large
and small grains (Figures 4.28(a) and (b)). However, patterns from small grains exhibit
an additional modulation (white arrow) whose location suggests the early occurrence of
Small grains Large grains
(a) (b)
1000°C
(c) (d)
1300°C
(e)
4 nm–1
1400°C
(f) (g)
1500°C
Figure 4.28 Electron diffraction from HMDS42 on large grain and small grain phases respectively
after increasing annealing treatment. From (a) to (g) the arrows show the occurrence
of a faint C002 reflection.
(a) (b) (c)
50 nm
Figure 4.29 TEM bright-field image and dark-field image sequence from HMDS42/1000. (a) illustrates
the differentiation into two phases with different grain size range. (b) ‘C-specific’ dark-field
imaging conditions. The polyaromatic C phase appears as tiny bright dots representing
primary graphene stack entities ∼1 nm large. (c) ‘SiC-specific’ dark-field conditions. No
phase has crystallised yet.
very small (<1 nm) C (polyaromatic) entities. The stacking distance (∼0.37 nm) is larger
than for usual turbostratic C (0.344 nm) but similar to that found in immature organic pre-
cursors (Oberlin et al. 1980, 1986). These nanometric C entities are expected to appear
as small bright dots in C-specific dark-field imaging mode (see Annexe) as illustrated in
Figure 4.29(b). However, due to the limited resolution in dark-field imaging conditions
(δ ∼ 0.7 nm), bright dots from the small polyaromatic entities cannot be distinguished
from the background of dots originating from each atom pairs from the surrounding
amorphous material. No other crystallised, nanometric phase like SiC is found, since SiC-
specific dark-field images only exhibit the regular scattered intensity of amorphous material
(Figure 4.29(c)).
A polyaromatic C phase is, therefore, present in the small grains, whose graphenes are
at the very beginning of their face-to-face association (Monthioux 1998). This should prob-
ably be related to the nanoporous texture of the grains. Otherwise, no other difference is
detected between large and small grains, which exhibit the same bulk chemical composition,
with the respective X-EDS spectra similar to that of Figure 4.21, however with a higher
contribution of C.
Important structural changes occur in both grain types. The modulation attributed to the
002 reflection of a polyaromatic, turbostratic C phase in small grains becomes stronger in
diffraction patterns (Figure 4.28(c), white arrow). The C phase is now evidenced at the grain
surface, where it now appears as bright rims in dark-field images (Figure 4.30(a)), and as
small fringe stacks in high-resolution images, mostly oriented parallel to the grain surface,
either at small grain surface (Figure 4.31) or large grain surface (though C is systemati-
cally less abundant than for small grains, not illustrated). Such a preferred occurrence of
the polyaromatic stacks at the grain surface in C-rich amorphous ceramics with increasing
annealing temperature is a common observation (Monthioux et al. 1990; Delverdier et al.
1992a,b, 1993, 1994). It is probably due to easier atomic movements at the grain surface,
allowing C segregation on one hand and a graphene display more or less parallel to the grain
surface on the other hand. The proportion of the C phase is obviously much higher in small
grains than in large grains. It is still poorly organised, since it is made of distorted graphenes
about 1–2 nm wide (L2 ) only, stacked by N = 2–4 only.
Also, the occurrence of some brighter dots irregularly disseminated in SiC-specific
dark-field images (Figure 4.30(b)) indicates the very beginning of crystallised SiC-phase
segregation as nanometric crystals, possibly clusters. Such an early crystallisation step was
hardly guessed from the related diffraction patterns (Figures 4.28(c) and (d)) due, on one
hand to the relative amount of scattering volumes for the amorphous and the crystallising
parts of the material respectively, on the other hand to the overlapping of the SiC reflec-
tions, which are very faint and broad as a consequence of the tiny sizes of the SiC crystals
involved.
(a) (b)
50 nm
Figure 4.30 TEM dark-field image sequence from HMDS42/1300. (a) ‘C-specific’ (DF1) imaging
conditions. Graphene stack entities parallel to the ‘=’ sign are selected, showing that they
tend to align parallel to the grain surface. (b) ‘SiC-specific’ (DF2) imaging conditions.
Nanometric dots appear, indicating the early stage of overall SiC nucleation.
2 nm
Figure 4.31 TEM lattice fringe image from HMDS42/1300 (small grains). Poorly organised
graphene stacks at the grain surface are imaged.
Same features as above (Figure 4.28(e)), but the occurrence of the C phase becomes higher
and higher, while its organisation improves, mainly by increasing L2 more than increasing
N (not illustrated).
In both small and large grains, the overall crystallisation of a β-SiC phase is now obvious, as
revealed by the evidence of an intense, though broad, 111 reflection (black arrow in diffraction
patterns, Figures 4.28(f) and (g) for small and large grains, respectively). Crystal sizes are
still very small, nanometric, inducing wide reflections so that 220 and 311 overlap. This is
verified in SiC-specific dark-field images, where crystals as large as ∼5 nm are very seldom,
most of them being in the 1 nm range (Figure 4.32(b)).
It is worth noting that the 002 reflection of the turbostratic C phase, now close to 0.344 nm,
still appears for small grains only (Figure 4.28(f)). The C phase is now obviously present at the
small grain surface and possibly within them (Figure 4.32(a)). It is responsible for an apparent
nanometric porosity (Figure 4.33). High-resolution images illustrate the improvement in the
abundance and organisation of the polyaromatic C phase associated with small (Figure 4.34)
and large (see Figure 4.19 as reference for the abundance and organisation of the surface C
exclusively) grains, respectively.
Compared to the chemical composition of the grains in the material annealed at 1000◦ C as
seen by X-EDS (see Figure 4.21 for reference), the chemical composition given by X-EDS
analysis of the 1500◦ C-annealed material reveals a depletion in oxygen content indicated
by a lower O/N ratio in both small and large grains (Figure 4.35). This suggests that oxygen
atoms were initially not involved in SiO4 tetrahedra from silica since the latter is stable
at 1500◦ C, but possibly in SiOx Cy Nz tetrahedra similar to that formed in polymer-derived
Si/C/N-based ceramics (Delverdier et al. 1994). This is consistent with the fact that no
other crystallised phase but polyaromatic C and SiC is evidenced, indicating the necessary
occurrence of an amorphous silicon oxi(carbo)nitride phase as an intergranular phase between
(a) (b)
50 nm
Figure 4.32 TEM dark-field image sequence from HMDS42/1500 (small grains). (a) ‘C-specific’
(DF1) imaging conditions. As the contrast between the bright dots and the background
increases, the organisation of the graphene stacks improves. (b) ‘SiC-specific’ (DF2)
imaging conditions. SiC growth has started.
20 nm
Figure 4.33 TEM bright-field image from HMDS42/1500 (small grains). The development of the C
phase provides a textured aspect to the grains. Superimposition effects of the projected
image do not allow to ascertain whether most of the C is inside or outside the grains.
2 nm
Figure 4.34 TEM lattice fringe image from HMDS42/1500 (small grains), illustrating the
improvement of the polyaromatic C phase organisation and development with
temperature (compare with Figure 4.31).
Si
N
I 0.50 1.00 1.50 2.00

Figure 4.35 X-EDS spectrum from HMDS42/1500. Valid for large or small grain phases.
SiC grains. The partial removal of oxygen atoms from this amorphous phase due to the
annealing temperature should probably be related to the crystallisation of the SiC phase, as
a cause or a consequence of it for thermodynamic reasons.
As determined by means of electron diffraction, dark-field, bright-field, and lattice fringe

imaging modes, its features are very similar to that of sample HMDS42 annealed at the same
5 nm
Figure 4.36 TEM bright-field image from HMDS44/1400. The extensive development of a
polyaromatic C phase at the grain surface is obvious.
temperature, and will therefore not be extensively illustrated again. However, one discrepancy
is a slightly smaller grain size range, that is, 20–50 nm. Another is that crystallisation of SiC
phase has not even started yet. The average polyaromatic C content is difficult to estimate
since the material appears again heterogeneous, with both grains associated with an abundant
C phase (Figure 4.36), and grains associated with few C phase (see Figure 4.19 as reference
for the abundance and organisation of the surface C) or none. At least, there is no obvious
contradiction with the result from the bulk elemental analysis, which reveals a continuous
decrease in the C content from sample HMDS40 to HMDS45 (Table 2.5). Qualitatively, it is
worth noting that the occurrence of polyaromatic C is also ascertained by other investigation
methods like electron spin resonance (ESR) and X-photon spectroscopy (XPS) (Chapters 5.2
and 5.3).
Features are identical to that of the 1400◦ C-annealed sample described above. The interesting
observation is that, contrarily to what happened in sample HMDS42 in which a widespread
β-SiC phase is found after annealing at this temperature, no crystallisation of a Si-based
phase has occurred yet. The bulk material is still amorphous, and still contains Si, C and N,
as identified by electron energy loss spectroscopy (EELS) (Figure 4.37). It is worth noting
that no oxygen is detected.
An extended EELS study in a VG STEM microscope was specifically performed by N.
Brun (Laboratoire de Physique du Solide, Paris, France) on some grains from this sample
in order to tentatively characterise further the C content, using a very fine electron probe
combined with scanning facility. Quantitative exploitation of the EELS spectra led to a bulk
Si L2,3 edge
C K edge
N K edge
Figure 4.37 EELS spectrum (large probe) from HMDS44/1500. Si, C and N are revealed.
atomic C content estimated at ∼16–20%, most of it being segregated at the grain surface
(Figure 4.38(a)) as sp2 C atoms, that is, as a polyaromatic C phase (Figure 4.38(b)). On
the contrary, the grain core was found to contain ∼4% of sp2 -type C atoms (Figure 4.38(b)),
giving an inner C/N atomic ratio of ∼0.2 (together with an inner N/Si atomic ratio of ∼1.3). All
these values strongly support the previous observations on the C phase occurrence, type and
location, and are fairly consistent with the quantitative data obtained otherwise. In addition,
the Si amount in the bulk is more that twice that of the C amount corresponding to the sum
of the inner and outer C (Figure 4.38(a)). This and the occurrence of an abundant N content
(∼45%) show that an Si (C) N amorphous phase is also present in the grain in addition to
the SiC crystals.
The SiC phase crystallises first, exhibiting peculiar polyhedral morphologies, most often
triangular (sometimes rectangular) corresponding to the primary crystalline form of the cubic
(hemihedral) structure of SiC (Figure 4.39).
Overall crystallisation of both Si3 N4 and SiC has occurred. It is likely that the location where
Si3 N4 and SiC phases crystallise is correlated to the previous occurrence of polyaromatic-
carbon-depleted and polyaromatic-carbon-rich grains, respectively. Grain sizes are in the
50–200 nm range (Figure 4.39). Electron diffraction shows that the cubic (3C) structure is
probably no longer prevalent, and a lot of other polytypes are found since additional diffraction
spots other than 111, 200, 220 and 311 of β-SiC are present, often as stacking faults as
indicated by the specific occurrence of aligned spots (Figure 4.40, arrow). The triangular
shape of the SiC crystal projection suggests that the growth has occurred in conditions of
saturation (i.e. no limitation in the C and Si atom supply) or, at least, in conditions such that
feeding atoms have equal access opportunity to the various crystal faces, since the relative
growth speeds of the various faces were respected. In such conditions, ‘slow’ faces (like
(111)) are actually favoured relative to ‘fast’ faces (like (100)) since the latter require less
atoms than the former to be completed.
(a) 100
%N
%C
80 % Si
60
Atom (%)
40
20
0
0 10 20 30 40 50
Distance (nm)
(b)
1.4 Mod 7–10
Mod 2–5
Carbon atom content quantification
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0 10 20 30 40 50
Distance (nm)
Figure 4.38 Data obtained from scanning nanoprobe EELS performed on single grains from
HMDS44/1500. (a) EELS quantification of Si, C and N (in at% along y axis) within
half a grain (grain radius along x axis) showing that most of the C content is at the
grain surface. (b) sp2 (solid symbols) and sp3 (open symbols) C atom content quan-
tification within a grain about 50 nm large, indicating that the surface C is exclusively
polyaromatic (sp2 ). Data from N. Brun, Laboratoire de Physique du Solide, Paris,
France.
50 nm
Figure 4.39 TEM bright-field image from HMDS42/1600 (SiC phase). Most of the SiC crystals
exhibit a triangular projection.
Figure 4.40 Electron diffraction from HMDS42/1600 (SiC phase). A lot of polytypes other than
3C are present, including as stacking faults (arrows).
On the other hand, the Si3 N4 phase was not investigated, due to the very large size
range of the crystals (several micrometers) making them not transparent to the TEM elec-
tron probe. However, crystallised Si3 N4 was otherwise undoubtedly revealed by X-ray
diffraction (XRD).
Finally, it is worth noting that the polyaromatic C phase is no longer found, suggesting an
oxidation into CO (rather than CO2 , because of the high temperature) due to the release of
oxygen consequently to the crystallisation of SiC and Si3 N4 .
Si/C/N/Al-based powders
Among the various samples prepared following this route, three were specifically investi-
gated by TEM, as-prepared first, then after a 1600◦ C (1 h isothermal) annealing under N
atmosphere. Samples labelled HSAl07, HSAl12 and HSAl09 thus respectively correspond
to 0/100, 20/80 and 40/60 NH3 /Ar proportions in the gas phase.
HSAL07, AS-FORMED
The colour of the macroscopic powder at natural light is grey. In TEM, electron diffrac-
tion shows that the bulk sample is amorphous (Figure 4.41). Grain size range from ∼20
to ∼130 nm, with a tendency to a two-mode distribution (Figure 4.42). The overall grain
morphology is round, although the smallest grains may tend to be more or less slightly poly-
hedral. Another difference between small (i.e. in the range ∼20–60 nm) and large grains (i.e.
in the range 50–130 nm) is that the former exhibit some nanometric porosity (Figure 4.43),
suggesting some primary difference in chemical composition. No polyaromatic C phase was
revealed at the grain surface either by means of dark-field (not illustrated) or lattice fringe
imaging (Figure 4.44). However, some primary, nanometric graphene stack entities are pos-
sibly imaged (Figure 4.44, arrows). Also, some poorly organised polyaromatic C particle
(∼15–30 nm) aggregates similar to C blacks (not illustrated) were found as a seldom phase
apart from the amorphous phase.
HSAL12, AS-FORMED
The natural light colour of the macroscopic powder is black. The material differs from
HSAl07 by the grain size range, which is more obviously shared into two sub-size ranges
4 nm–1
Figure 4.41 Electron diffraction from HSAl07. The whole material is amorphous.
50 nm
Figure 4.42 TEM bright-field image from HSAl07. The two-mode grain size distribution is
shown.
5 nm
Figure 4.43 High magnification TEM bright-field image from HSAl07. Small grains (bottom) exhibit
a nanotexture while large grains (top) do not.
(see Figure 4.42 for reference). The most prevalent one is ∼10–30 nm, whose grains are
more or less polyhedral and exhibit a nanometric porosity (see Figure 4.43 for reference).
The minor one is ∼50–100 nm, with grains having round contours and no obvious porosity.
The main difference with HSAl07 is that the early crystallisation of a widespread, poorly
organised, turbostratic, polyaromatic phase is suggested by a faint C002 halo in electron
diffraction patterns (Figure 4.45, arrow), further supported by the occurrence of tiny brighter
2 nm
Figure 4.44 TEM lattice fringe image from HSAl07. Primary nanometric graphene stacks are
probably showed.
4 nm–1
Figure 4.45 Electron diffraction from HSAl12. The whole material seems amorphous.
spots into the grains and some bright rims at the grain surface in the related dark-field images
(Figure 4.46, arrow).
Likewise, the early crystallisation of SiC has also started in the small grains, as revealed
by the SiC-specific dark-field images (left side in Figure 4.47, arrows) while large grains
remain amorphous (right side in Figure 4.47). Indeed, the fact that no such crystals appear in
‘C-specific’ dark-field images (Figure 4.46) ascertain that crystals are actually SiC, not Si3 N4
(see Section 4.3). It is worth noting that, unlike what was found for SiCxxx- or HMDSxx-
type materials, the SiC crystallisation does not start according to an overall, widespread
germination mechanism resulting in a homogeneous dissemination of nanometric crystals in
50 nm
Figure 4.46 TEM dark-field image from HSAl12. ‘C-specific’ (DF1) imaging conditions. Bright
dots within small grains and bright rims at grain surface appear, indicating the
occurrence of a poorly organised, polyaromatic C phase.
the material, but rather corresponds to the local occurrence of the appropriate nucleation-
then-growth conditions, resulting in the random but seldom occurrence of SiC crystals. The
amount of crystals is not enough to appear in the diffraction patterns (Figure 4.45), but the
β structure can be ascertained from the dark-field data.
HSAL09, AS-FORMED
The natural light colour of the macroscopic powder is heterogeneous with grey to light brown
areas. The overall TEM features of the sample are very similar to HSAl12 regarding the two-
class grain size distribution (see Figures 4.42 or 4.47 for reference), the early occurrence of
seldom SiC crystals in the small grains, the absence of Si3 N4 , and the possible occurrence of
a widespread, poorly organised, polyaromatic phase. However, the latter is less ascertained
since no C rims at the grain surface were found. Some C black type aggregates are also found
(not illustrated).
50 nm
Figure 4.47 TEM dark-field image from HSAl12. ‘SiC-specific’ (DF2) imaging conditions. SiC
crystals are found locally in small grains, already several nanometres large.
HSAL07, 1600◦ C ANNEALED
The macroscopic natural light colour of the sample has turned from grey to black. The material
is quite homogeneous, and a single morphology of round or slightly polyhedral grains was
found in TEM images (see Figure 4.22 for close enough reference). The grain size range is
∼30 to ∼60 nm, therefore, significantly narrower than in the as-prepared materials, which
has to be related to some weight loss during the ceramisation process. Appropriate dark-
field imaging (not illustrated) shows that each grain is actually an aggregate of round single
crystals (∼2–25 nm) with a non-symmetrical grain size distribution since a majority of them
are less than ∼10 nm. Electron diffraction identifies the crystals as SiC with the prevalent
β (3C) structure since reflections 111, 220 and 311 are the only ones being revealed as
diffraction rings, although some diffraction spots beside these rings appear, showing the
seldom occurrence of other polytypes (see Figure 4.8 for reference). Correspondingly, some
crystals exhibit stripes in dark-field images, revealing polytype sequence as stacking faults.
The association of the SiC crystals into larger grains implies the occurrence of a binder, that
is, an intergranular amorphous phase to ensure the grain cohesion, obviously containing N
and Al, in addition to some Si and possibly C.
A polyaromatic C phase is now revealed at the grain surface (though not systematically),
either by dark-field (not illustrated) or lattice fringe imaging (see Figure 4.37 for reference),
which is responsible for most of the polyhedral contours of the grains.
The cohesion of the aggregates is ensured by an intergranular amorphous phase, that
X-EDS reveals to contain at least Al and O, in addition to probably Si and possibly C. Also,
traces of K, Ca and Na are found (Figure 4.48).
Al
Si
C
O K
Ca
I 1.00 2.00 3.00 4.00

768CNT 3.48 keV 10 eV/ch A EDAX
Figure 4.48 X-EDS spectrum of the SiC-containing grains from HSAl07/1600. The occurrence
of Al and O in addition to Si and C suggests that these elements are present in the
composition of an intergranular amorphous phase.
No N-containing amorphous or crystallised phases are found, while N is more abundant

than O in the material according to the bulk chemical composition (Table 2.6). This empha-
sises the fact that the qualitative comments about the respective proportions of the various
phases are only valid for the material once prepared for TEM investigation. Actually, when
a phase is present as very large grains (i.e. micrometric) together with another phase with
smaller grains (sub-micrometric), the suspension method used to prepare an electron trans-
parent aliquot of the materials favours the prevalence of the latter relative to the former, with
no respect to the original proportions. It is therefore possible that large grains of Si3 N4 (or
SiAlON) were present in the material, though not found in the TEM preparation.
The natural light colour of the macroscopic powder has turned from dark to light grey-green.
The whole material is crystallised. The SiC phase is the most frequent (in the TEM preparation
of the material, see the end remark of previous section) and appears as grains ∼20–100 nm
large, exhibiting systematic triangular projections (see Figure 4.39 for reference). Electron
diffraction shows that the cubic (3C) structure is not prevalent since the related 220 and
311 reflections barely form complete rings in the diffraction patterns (see Figure 4.40 for
reference). Many other diffraction spots corresponding to other lattice distances are found
instead, therefore, revealing the occurrence of other polytypes. Crystals are frequently coated
with an amorphous phase, few nanometres thick (not shown), believed to be different from
mere silica since containing at least Al and O (in addition to possibly Si and C) according to
X-EDS spectra (see Figure 4.48 for reference), which helps in bonding the crystals to each
other (not shown, similar to Figure 4.8).
Large, somewhat elongated, micrometric crystals, therefore, not electron transparent, were
also found (Figure 4.49). They are free of any amorphous coating, and provide only Si and N
with a small contribution of Al and traces of O in X-EDS spectra (Figure 4.50), suggesting
a SiAlON-type composition. Other crystals exhibit a needle-like morphology (Figure 4.51).
Some observations suggest that they somehow originate from cleavages of the larger, massive
0.5 µm
Figure 4.49 TEM bright-field image from HSAl12/1600. Large, dark grains are SiAlON crystals, while
needle-like grains are Si3 N4 crystals according to X-EDS spectra. Arrow shows that the
latter probably originates from the former by cleavages.
Si
Al
N
I 1.00 2.00 3.00 4.00

Figure 4.50 X-EDS spectrum from large, dark crystals from HSAl12/1600. Al is shown, probably
together with O as a shoulder at the right side of the N peak, suggesting a SiAlON
composition.
crystals (Figure 4.49, arrow). Correspondingly, X-EDS spectra similarly exhibit Si and N,
however with the systematic absence of Al and the probable absence of O (Figure 4.52)
suggesting that they are genuine Si3 N4 crystals, while the needle-like morphology would
indicate a structural transformation from α to β. Quantitative mismatches with the phase
proportions estimated from XRD (Table 4.1) originate from the segregation effect mentioned
at the end of the previous section.
50 nm
Figure 4.51 TEM bright-field image from HSAl12/1600. Arrow shows that even needle-like
crystals are cleaved into smaller needle-like crystals.
Si
I 1.00 2.00 3.00 4.00

Figure 4.52 X-EDS spectrum from needle-like crystals from HSAl12/1600. The absence of Al
(and O) indicates a Si3 N4 composition.
Again, like for material HMDS44/1600, evidence for a polyaromatic C phase was no longer
found, suggesting an oxidation into CO (rather than CO2 , because of the high temperature)
due to the release of oxygen consequently to the crystallisation from the primary O-containing
amorphous phase.
Table 4.1 Phase proportions as determined from XRD
spectra in 1600◦ C annealed HSAlxx-type
samples
Sample reference Results from XRD
HSAl07/1600◦ C β-SiC + α-SiC(ε)

HSAl09/1600◦ C α-Si3 N4 + β-Si3 N4 (ε)
HSAl11/1600◦ C α-Si3 N4 + β-Si3 N4
HSAl12/1600◦ C α-Si3 N4 + β-Si3 N4 + β-SiC
HSAl13/1600◦ C β-SiC + α-SiC
HSAl16/1600◦ C α-Si3 N4 + β-Si3 N4
HSAl17/1600◦ C α-Si3 N4 + β-SiC + β-Si3 N4 (ε)
HSAl18/1600◦ C β-SiC + α-SiC
Note
Underlined = most abundant.
(ε) = less than ∼5%.
The natural light colour of the macroscopic powder has turned from light grey-brown to light
brown. The same phases (i.e. SiC, and Si3 N4 or SiAlON) as in HSAl12/1600 are found,
however with different proportions. In addition, some of the primary amorphous phase(s)
remain(s), as minor small and large round grains (see Figure 4.42 for reference), whose
chemical composition contains Si, N (and O) according to X-EDS spectra (not illustrated).
The most prevalent morphology is made of aggregates of polyhedral crystals about
20–60 nm large, whose projection are often triangular (Figure 4.53), identified as β-SiC
by electron diffraction (Figure 4.54). Some but few polytypes are also present. This SiC
phase is associated with an amorphous phase coating the crystals and somewhat acting as
an intergranular phase and ensuring the aggregate cohesion. As for the other HSAlxx mate-
rials investigated though with various element proportions, the chemical composition of the
amorphous phase at least includes Al and O, in addition to possibly Si and C according to
X-EDS spectra (see Figure 4.48 for reference).
Massive, large, therefore, non-transparent crystals are also found as in material
HSAl12/1600 (see Figure 4.49 for reference). A difference is that the morphological trans-
formation into needle-like crystals has barely occurred yet (Figure 4.55) and the latter are
seldom, possibly indicating that the α to β transformation has just started. Another difference
is that either massive or needle-like crystals exhibit Al and O in addition to Si and N according
to X-EDS spectra (Figure 4.56) suggesting a SiAlON-type composition. Mismatches with
the phase composition estimated from X-rays originate from the sample preparation for TEM
investigation.
Conclusion regarding ceramic nanopowders from liquid precursors
SI/C/N-BASED MATERIALS
Due to their high hydrogen content which makes the materials behave like Si-based polymer-
derived ceramics, the as-prepared materials remain mainly amorphous up to annealing
temperatures as high as ∼1500◦ C. Such a thermal stability is induced by the complexity
50 nm
Figure 4.53 TEM dark-field image (‘SiC-specific’ (DF2) imaging conditions) from HSAl09/1600.
Many of the crystals exhibit a triangular projection.
4 nm–1
Figure 4.54 Electron diffraction from the SiC phase from HSAl09/1600. The 3C polytype is
highly prevalent.
0.5 µm
Figure 4.55 TEM bright-field image from HSAl09/1600. Large, dark grains are SIALON crystals
according to X-EDS spectra.
Si
Al
I 1.00 2.00 3.00 4.00

Figure 4.56 X-EDS spectrum from large crystals from HSAl09/1600 (also valid for the needle-like
crystals). The occurrence of Al and O indicate a SiAlON composition.
of the chemical system (Si C N O (H)) which tends to unfavour the atomic rearrange-
ments at the solid state. Indeed, the previous formation and segregation of tetrahedra with
appropriate compositions (like SiC4 ) is necessary to subsequently allow the various phases
(like SiC) to crystallise.
The C/N atomic ratio of the as-prepared materials appears to be the leading parame-
ter to determine whether SiC and/or Si3 N4 will finally crystallise at some point of the
annealing treatment. Starting from a nearly similar Si content, a high C/N content favours
the early formation of a SiC phase within a surrounding amorphous matrix, in which
heteroatoms (O, N) are subsequently concentrated as an amorphous Si (carbo)oxinitride
phase. On the contrary, a low C/N content helps in maintaining the amorphous structure
of the bulk at a higher annealing temperature, lately inducing a dramatic nucleation-
then-growth of both SiC and Si3 N4 phases (Si3 N4 only for the lowest C/N ratios).
Because nucleation occurs at higher temperatures (>1500◦ C) with low or no tempera-
ture gradient, growth mechanisms (and kinetics) are different, possibly due to a higher
mobility of atoms allowing crystals to grow freely, therefore, giving rise to primary crystal
morphologies instead of the round, isometric morphology (like that resulting from the flash-
temperature nucleation-then-growth mechanism occurring for the gaseous-precursor-based
nanopowders).
Whatever, polyaromatic C is always the first phase to crystallise, though with a low-
dimensionality – turbostratic – structure, according to a common behaviour of Si-based
polymer-derived ceramics (Monthioux and Delverdier 1996). Consequently, the amount of
it is directly related to the C content of the as-prepared material.
SI/C/N/AL-BASED MATERIALS
Whether NH3 is present or not in the gas phase, all the as-prepared materials investigated are
nearly all amorphous but tend to a two-morphology differentiation with small, nanoporous
grains, and larger, non-porous grains, which could be related to the subsequent SiC/Si3 N4
phase differentiation.
Effect of the 1600◦ C annealing

• Average grain sizes decrease, revealing a weight loss subsequent to the ceramisation
process. The crystallised phases mainly depend on the N content of the chemical system.
• Not mentioning the polyaromatic C phase, which is not systematic, the SiC phase
crystallises prior to the Si3 N4 /SiAlON phase.
• SiC crystals are always coated with an amorphous (Si?) Al O phase which is an
interesting feature for subsequent attempts of high-temperature sintering.
• Correspondingly to the high annealing temperature, the SiC structure is always a mixture
of various polytypes (though with various proportions from a material to the other),
present as stacking faults rather than as single crystals.
Effect of the presence of NH3 in the precursor gas phase

• After annealing, N-depleted chemical system, induced by the absence of NH3 in the
precursor gas phase, on one hand allows the occurrence of a polyaromatic C phase and
on the other hand allows the formation of a crystallised SiC phase only (i.e. no Si3 N4 ).
• Adding NH3 in the precursor gas phase induces the early crystallisation of SiC. How-
ever, the nucleation step does not occur as a widespread germination but occurs locally.
Such a heterogeneous behaviour has to be related to a heterogeneity in chemical com-
position, possibly originating in the non-homogeneous incorporation of N and/or H
into the material. On the contrary, the absence of NH3 provides a quite amorphous
material.
• Adding NH3 in the precursor gas phase allows the required stoichiometry to be reached,
resulting in the rapid crystallisation of a SiAlON-type phase after annealing. Meanwhile,
the high temperature at which the overall SiC crystallisation occurs induce such an
atom mobility than the respective intrinsic growth rates of the various crystal faces are
respected.
Effect of varying the NH 3 concentration in the precursor gas phase

• For the lowest and the highest supply in NH3 , the prevalent polytype of the resulting
crystallised SiC phase after annealing is 3C, corresponding to the β-cubic structure.
An intermediate NH3 supply results in a more rapid growth of the SiC phase, for
which the other polytypes are correspondingly prevalent. Such a non-monotonous effect
of the increasing N content of the chemical system regarding the behaviour of the
material during annealing was already observed for Si-based polymer-derived ceramics
and originates from the competition between antagonist mechanisms (Delverdier et al.
1992a).
• Increasing the N proportion slows down the kinetics of structural rearrangement; induc-
ing the highest amount of remnant amorphous phases in the N-richest system after
annealing. Another reason is also the early crystallisation of SiC prior to Si3 N4 , which
induces a local excess of N atoms relative to the Si atoms left with respect to the required
Si3 N4 stoichiometry, which then gather into an amorphous phase.
• The crystallisation of a nitride phase occurs for a 20% and 40% input of NH3 in the
precursor gas phase. In both materials, the high annealing temperature tends to induce
the overall crystallisation of massive SiAlON-type crystals rather than Si3 N4 . In addition,
seldom SiAlON needle-like crystals are found in the latter sample (40% NH3 ), while
numerous Si3 N4 needle-like crystals are found in the former (20% NH3 ). Assuming that
the massive and needle-like morphologies correspond to α and β structures respectively,
these data suggest that the structure change might be somehow controlled by the N content
of the chemical system, independently from the extent of Al Si and O N substitution.
4.2 As-prepared sintered composites

Some of the as-prepared, sintered, micro–nano-type composites, whose detailed process-
ing conditions and mechanical properties are described in Chapter 7, were investigated by
TEM to investigate further the structural and textural relationships between the composite
components. Related sample preparation prior to TEM investigations and TEM operating
conditions are reported in Section 4.3. Sintering temperature was 1650◦ C for all the compos-
ites (1600◦ C for the bulk Si3 N4 material). All the materials (i.e. bulk Si3 N4 and composites)
are added with the regular sintering aids, Al2 O3 and Y2 O3 , added in the proportions of 3% and
6%, respectively. For technical reasons, all the materials but the bulk Si3 N4 were sectioned,
thinned and observed in a direction parallel to the hot pressing direction. In the following,
after describing the monolithic Si3 N4 material, composites will be presented according to
the decreasing amount of theoretical SiC content (Table 7.1).
4.2.1 Bulk Si3 N4

Monolithic sintered Si3 N4 – that is, not added with any nanopowder – was studied as a ref-
erence material. The sintering temperature at 1600◦ C provides the highest densification rate
200 nm
Figure 4.57 TEM bright-field image from the SiAlON monolithic material.
(see Figure 7.6(b)). The sample was investigated in a plane perpendicular to the hot-pressing
direction. This plane also contains the direction of mechanical testing.
The material appears highly densified (Figure 4.57). Due to the high sintering temperature
and the presence of oxides, a dramatic chemical and structural transformation has occurred,
inducing a high β-SiAlON (Si6−z Alz Oz N8−z ) crystal content (see Section 7.2), about 70%
according to calculations based on XRD data (Rossignol 1995), as compared to 100% of
α structure in the starting powder (see Section 7.4.1). Correspondingly, a majority of the
grains are more or less elongated, some exhibiting an obvious needle-like morphology. This
is consistent with previous TEM observations which demonstrated that oriented pressure
sintering is able to statistically induce a preferred orientation perpendicular to the pressing
direction as far as non-isometric crystals – like high-temperature β-SiAlON or β-Si3 N4 –
are concerned (Champion et al. 1992). Of course, aspect ratios revealed by TEM are just
apparent, since depending on the crystal orientation relative to the sectioning direction for the
non-isometric grains. Actually, many of the nearly isometric crystal morphologies are likely
to also derive from β-type crystals, that is, about 250–300 nm, while the maximal value
observed for the elongated crystal dimension is about 2 µm. Crystals most often exhibit
a uniform grey contrast, indicating that they are mainly free of stacking faults.
4.2.2 Si3 N4 /SiC173 composites

The composites investigated were initially prepared with 20% and 40% of SiC173 nanopow-
der, respectively (Table 7.1). Considering that the starting SiC173 nanopowder is made of
quasi pure SiC (with some content of polyaromatic C, see section on Si/C-based powders),
such proportions also correspond to the theoretical proportions of the SiC phase in the final
composites (Table 7.1).
No obvious discrepancy was found between composite Si3 N4 /SiC(20) and composite
Si3 N4 /SiC(40) as observed in TEM. The following comments are therefore valid for both
materials.
Low magnification TEM images are consistent with the theoretical SiC phase proportions
(Figure 4.58), and emphasise the size difference between the SiAlON and SiC phases. SiAlON
crystals appear as large, polyhedral grains, quite similar to that of the monolithic material
(Section 4.2.1). Although diffraction patterns indicate a majority of β structure consistent
with the high-temperature sintering (Figure 4.59(a)), a reflection specific of the α phase
(at 0.432 nm) is still found sometimes (Figure 4.59(b)), indicating that the structural α to
β transformation rate is not 100%, which is consistent with the theoretical calculations
(Table 7.3). However, considering that XRD was not able to reveal any α structure, the actual
amount of α crystals is surely less than the 11% predicted from calculations (and probably
less than 7%, the lowest percentage determined by X-ray in composite Si3 N4 /SiCN35(22.2)).
Most of the crystal facets appear as straight lines, as for single crystals when allowed to grow
freely (Figure 4.58). However, crystal facets of SiAlON crystals at the contact of SiC grains
often appear notched (see Figure 4.66 for reference) due to the presence of SiC grains at the
interface, confirming that SiC grains were not allowed to melt or soften during the sintering
process, unlike the growing SiAlON crystals. It is worth noting that only few elongated
crystals are found. Calculating an average apparent crystal size is therefore possible: ∼470 nm
100 nm
Figure 4.58 TEM bright-field image from composite Si3 N4 /SiC(20). The SiC crystals (small,
round grains) are gathered into aggregates.
(a) (b)
4 nm–1
Figure 4.59 Electron diffraction from composite Si3 N4 /SiC(20). (a) Most of the diffraction spots are
characteristic from the β-SiAlON phase. (b) However, some specific diffraction spots
(arrow) reveal the minor occurrence of the α structure as well.
for composite Si3 N4 /SiC(40). The slightly lower value for Si3 N4 /SiC(20) is not significant.
Comparison with the monolithic Si3 N4 material regarding the evolution of the grain size is
limited since it was not investigated along the same section plane.
SiC crystals appear as small, round crystals, most often gathered into agglomerates instead
of being randomly dispersed all around the SiAlON crystals (Figures 4.58). Contrarily to the
latter, SiC crystals exhibit numerous, non-periodical, dark contrasts revealing the occurrence
of polytypes as stacking faults. Indeed, the β to α (i.e. polytypes other than β) SiC transfor-
mation has slightly progressed, as ascertained by the more frequent occurrence of specific
features in the diffraction patterns, like the occurrence of diffraction spots aside the regular
diffraction rings for the β structure, and of some aligned spots corresponding to the presence
of stacking faults (Figure 4.60 to be compared with Figure 4.3). On the contrary, the average
SiC grain size has not progressed significantly compared to the starting powder (see section
on Si/C-based powders). This indicates that the growth mechanism by coalescence, though
an usual process at such temperatures (Monthioux and Delverdier 1996), was prevented,
probably because of the presence of the intergranular phase (Figure 4.62), as opposed to the
starting nanopowder (see Section 4.1.1). Some SiC grains are also found possibly enclosed
into SiAlON crystals (Figure 4.61). However, high magnification images are not sufficient to
ascertain if the SiC crystals are actually enclosed into the SiAlON crystals or if they merely
are superimposed to them in the projected image as allowed by the thickness value of the
TEM preparation (∼100 nm). Proofs of enclosing of SiC crystals into SiAlON crystals will
be brought using dark-field imaging (see Figure 4.66 to come).
The polyaromatic C phase associated with SiC grains revealed in the starting powder is no
longer found, suggesting that it might have burnt into CO during the sintering process.
An amorphous, intergranular phase is found, gathering the whole yttrium content of the
composite (in addition to some content in the other elements present, Si, Al, O, N) as revealed
4 nm–1
Figure 4.60 Electron diffraction from a SiC grain agglomerate in composite Si3 N4 /SiC(40).
Though reflections from the β structure are still prevalent, many other polytypes
are present.
5 nm
Figure 4.61 High magnification TEM image from composite Si3 N4 /SiC(20). A SiC grain (faulted)
seems to be enclosed in the SiAlON crystal.
by the darkness of the grey contrast associated to this phase, originating from the intense
electron inelastic scattering induced by the high Z value for yttrium (Z = 39). However,
most of the intergranular phase is found within SiC grain agglomerates either filling the voids
between grains (Figure 4.62) or at the grain interfaces (Figure 4.62, arrows). On the contrary,
the intergranular phase is absent between SiAlON crystals (Figure 4.63) or might eventually
SiAION
SiC
SiC
SiC
5 nm
Figure 4.62 High magnification TEM image from composite Si3 N4 /SiC(20). Spaces between
SiC grains or at the SiC/SiAlON interface appear dark due to the presence of the
yttrium-containing amorphous intergranular phase.
be present as some very thin – <1 nm – films only, therefore not visible on lattice fringe
images due to the slight tilt angle of the interface relative to the electron beam. It is assumed
that such a preferred location of the intergranular phase is due to the faceted morphologies
for the SiAlON crystals, whose face-to-face contacts of the respective crystal facets during
the hot pressing is likely to expel and reject the intergranular phase into intergranular voids
between SiC crystals (Figure 4.62). The latter are numerous in SiC crystal agglomerates due
to the round morphology of the grains.
4.2.3 Si3 N4 /SiCN35 composites

The following two composites were prepared with 44.4% and 11.1% of SiCN35 nanopowder,
providing a theoretical SiC content of 20% and 5%, respectively (Table 7.1).
2 nm
Figure 4.63 TEM lattice fringe image from composite Si3 N4 /SiC(20). The interface between SiAlON
crystals is free of interfacial phase.
Si3 N4 /SiCN35(44.4) composite

Many of the morphological, textural and structural features described above for the
Si3 N4 /SiC173 composites are valid for this composite. One discrepancy, however, con-
cerns the SiC phase, which now exhibits two kinds of morphology. In addition to the
regular, round, major morphology previously described (with about the same grain size
range, though slightly lower, 10–60 nm), polyhedral crystals whose sizes range from ∼50
to ∼150 nm are found as a minor phase (Figure 4.64). Correspondingly to this larger
average size, the β to α transformation is more pronounced for this second morphol-
ogy (see Figure 4.40 for reference, to be compared with Figure 4.60 for the major SiC
phase morphology, and with Figure 4.24 for the structural state of the SiC phase in the
as-prepared SiCN35 nanopowder). This morphological differentiation indicates at least
two distinct sources for the SiC phase, one originating from the pre-existing SiC crys-
tals, the other possibly originating from the crystallisation of the pre-existing Si C O N
amorphous phase and/or the reaction of the pre-existing Si phase with any dispersed C
atoms.
Another discrepancy concerns the SiAlON phase, whose average apparent crystal size is
∼360 nm, that is, smaller than for composite Si3 N4 /SiC173(40).
Si3 N4 /SiCN35(11.1) composite

A major difference with the three composites described so far is brought by the SiC phase,
which is now more often located between the SiAlON crystals, that is, clearly located in
intergranular position (Figure 4.65). Beside, in this sample as in all the other SiC-containing
composites described in this chapter, SiC crystals structurally enclosed into SiAlON crystals
are found, as clearly demonstrated by the example of the bright-field/dark-field comparison
of Figures 4.66(a) and (b). Two SiC crystals supposedly enclosed into a SiAlON crystal are
60 nm
Figure 4.64 TEM dark-field image (DF2 position) from composite Si3 N4 /SiCN35(44.4). Exam-
ple of the minor SiC morphology, exhibiting larger sizes and polyhedral contours,
found in addition to the major, regular, round morphology.
arrowed in the bright-field image of Figure 4.66(a), to be compared with the specific dark-field
image of Figure 4.66(b), whose objective aperture position is adequately chosen so that none
of the possible diffracted beams from crystallised SiC are allowed to participate in the image,
while the diffracted beam from the SiAlON crystal selected is allowed (see Section 4.3). On
Figure 4.66(b), the SiAlON crystal appears dark at the very place of one of the SiC crystal
(solid arrow on Figure 4.66(a)), while it appears bright at the very place of the other SiC
crystal (open arrow on Figure 4.66(a)) making the latter invisible. The former SiC crystal
(solid arrow) is therefore really enclosed into the SiAlON crystal, while the latter SiC crystal
(open arrow) is merely superimposed to it in the thickness of the TEM preparation. Contacts
between enclosed SiC and surrounding SiAlON crystals were always found direct, that is,
with no interfacial phase. Though enclosing of SiC crystals into SiAlON crystals is thus
ascertained and supported by the literature (Niihara et al. 1990; Sasaki et al. 1993), examples
are actually few in our materials, making doubtful that such nanometric SiC crystals are able
to play a substantial role in the germination or phase transformation of the SiAlON crystals
in the composites investigated.
Meanwhile, Figure 4.66(b) also illustrates how the development of the crystal faces is
hindered by the presence of SiC grains in interfacial position, inducing a highly indented
topology of the related crystal facets.
Decreasing the SiC content in the Si3 N4 /SiCN35 composites help the SiAlON crystals to
develop further, since the average apparent SiAlON crystal size is ∼395 nm (as opposed to
∼360 nm in composite Si3 N4 /SiCN35(44.4)).
60 nm
Figure 4.65 TEM bright-field image from composite Si3 N4 /SiCN35(11.1). Light grey contrast-
free areas are SiAlON crystals. SiC grains are in interfacial position between SiAlON
crystals.
(a) (b)
30 nm
Figure 4.66 Composite Si3 N4 /SiCN35(11.1). (a) TEM bright-field image. SiC grains are gathered
into aggregates. Arrows show examples of SiC grains possibly enclosed in a SiAlON
crystal. (b) TEM dark-field image. Imaging conditions (DF1) are adequately chosen
to image SiAlON crystals (bright area), while SiC is excluded. One of the SiC grain
(solid arrow) is still visible and is therefore really enclosed into the SiAlON crystal,
while two other SiC grains (open arrows) have vanished and are therefore merely
superimposed to the SiAlON crystal in the projected image. Note how the SiAlON
crystal facets are notched due to the contact with SiC grains which have hindered the
normal growth. The amorphous intergranular phase is revealed between SiC grains
as a slightly scattering phase.
200 nm
Figure 4.67 TEM bright-field image from composite Si3 N4 /SiCN29(20). Many elongated crystals
are found.
4.2.4 Si3 N4 /SiCN29(20) composite

This composite was prepared with 20% of SiCN29 nanopowder, providing a theoretical SiC
phase content of 1.7% only. The textural description of the composite is basically similar
to that of composite Si3 N4 /SiCN35(11.1) described above. SiC grains are again often dis-
seminated in intergranular position between SiAlON crystals. However, SiC crystals are
found to exhibit a single morphology, which is consistent with the fact that the SiC source
is unique, since no pre-existing SiC nor Si phases were present in the starting nanopowder
(see Section 4.1.2). Also, SiC crystals are less numerous, consistently with the calculation,
allowing SiAlON crystals to grow and develop more freely than in other composites. Cor-
respondingly, SiAlON crystals very frequently exhibit elongated sections, as opposed to the
other composites (Figure 4.67), making an average apparent crystal size difficult to calculate.
Grain section range is wide, up to several micrometers for maximal lengths, and 200–400 nm
for maximal widths. Although the direct comparison is not allowed with the monolithic Si3 N4
material due to the fact that TEM preparations were not performed following the same direc-
tion (i.e. perpendicular and parallel to the hot-pressing direction for the monolithic and the
composite materials, respectively), the overall impression is that the average crystal size is
smaller for the composite (Figure 4.67) than for the monolithic material (Figure 4.57), which
is consistent with results from SEM investigations (see Figures 7.8(b) and 7.10, respectively
for comparison).
4.2.5 Conclusion regarding as-prepared sintered materials

An overall statement is the elimination of the pre-existing polyaromatic C phase – if any –
during the sintering process, due the carbo-thermal reduction reaction with the oxide phases
added (or pre-existing). This is likely to induce some gas release (CO) possibly responsible
for some of the remaining porosity.
Pre-existing SiC grains are stable in the material being sintered, more or less preventing
the SiAlON crystals to develop freely. Specifically, SiAlON crystal facets appear flat at the
SiAlON/SiAlON contacts, while they appear notched at the SiAlON/SiC contact. When in
high proportions (>5% according to the theoretical calculations), the SiC phase tends to gather
into agglomerates apart of the SiAlON phase, instead of being dispersed in intergranular
position. Agglomeration could be caused by the occurrence of the surrounding minor phase
(polyaromatic C in case of SiC173 nanopowder, and an amorphous silicon oxycarbide phase
in case of SiCN35 nanopowder), preventing a convenient dispersion during the mixing step
prior to making the green bodies (see Chapter 7). Such agglomerates, because they are made
of small, round grains having limited surfaces of contact, exhibit a high intergranular porosity
allowing to somehow trap most of the yttrium-containing amorphous phase, which is then no
longer available to form interfacial films between SiAlON crystal facets. A poor superplastic
behaviour is therefore expected for these composites.
On the contrary, a low content in SiC nanograins is favourable to a better dispersion in
intergranular position between SiAlON crystals. However, SiAlON crystal faces are then
prevented to grow freely, the hindering presence of the SiC grains at the SiAlON crystal
interfaces while developing from the liquid phase inducing indentations in the related crystal
faces. SiC grains thus act as ‘keystones’ between SiAlON grains, which is also detrimental
to a superplastic behaviour. Nano/nano composites are therefore expected to be preferable to
micro/nano composites regarding the ability to creep without developing cracks.
Further and extended comments will be found in Chapter 7.
4.3 TEM sample preparation prior to investigations and

operating conditions
4.3.1 Preparation of samples

In order to be electron transparent at 120 kV acceleration voltage, materials investigated
should exhibit a thickness ideally lower than 100 nm in the direction parallel to the electron
beam. Ceramic nanopowders therefore require limited efforts for TEM preparation, consider-
ing the convenient initial grain sizes. On the contrary, composites require a specific thinning
process.
Powders
Aliquots of each ceramic nanopowder were dispersed into ethanol under sonication for several
minutes in order to make a suspension from which a drop was then deposited on a regular
(3 mm) 200 mesh copper microgrid previously coated with a holey or a lacey amorphous
C film. For samples suspected to be possibly hydrolysable, dry preparation – that is, direct
deposition of the nanopowder onto the microgrid – were sometimes also made for double
checking. When large powder agglomerates were formed unable to be dismantled by the wet
sonication step, gentle grinding using a boron carbide mortar was previously made (use of
a silica mortar should be avoided, due to its lower hardness relative to SiC, which is likely to
provoke some input of silica into the sample being prepared).
The main limitation of such a preparation procedure is the possibility to induce a gravimet-
ric discrimination – the phases exhibiting much higher density, or much larger grains being
likely to sink to the bottom of the flask.
Sintered materials
A slice about 100 µm thick of each sintered materials was obtained using a diamond-coated
slow circular-saw (preferably to a diamond-coated tungsten-wire saw, whose efficiency was
limited in this specific case). The slice dimensions was then adjusted to fit in a 3-mm wide
copper aperture, then glued on a stainless steel support using a thermofusible resin. Then
the thickness of the slice was decreased down to ∼50 µm using a mechanical polishing
procedure involving submicrometric diamond powders. The slice was then reversed upside
down in order to complete the polishing/thinning process through the other side of the slice,
hopefully down to ∼20 µm. The slice was then glued onto a 3-mm copper aperture, then
ion-milled both sides for several hours. Acceleration voltage for the argon ions was ∼4 kV,
and ion gun direction angles with respect to the sample surface were 12–15◦ . A hole was
created, whose edges were suitable for the TEM investigation.
All the micro/nano composites investigated (specifically those with a high SiC content)
were more or less found to specifically exhibit a very high hardness making them unusu-
ally difficult to slice during the first step of the procedure (diamond-enhanced sawing), as
opposed to the behaviour of regular micro/micro-type composites (such as in Champion et al.
1992). On the contrary, the micro/nano composites were found to dismantle more easily than
regular micro/micro composites at the end of the polishing/thinning procedure. A possible
explanation is that the primary specifically high hardness is due to the lack of amorphous
intergranular phase at the SiAlON crystal interfaces, making the crystals collectively sup-
porting the shearing stresses developed during the sawing procedure as a monolithic single
crystal would do. On the other hand, the removal of SiC grain agglomerates is easier during
the next polishing/thinning step due to their high content in amorphous phase. This is likely
to promote the earlier dismantling of the composite with respect to micro/micro composites,
as soon as a critical limit (∼50 µm) for the slice thickness is reached.
4.3.2 TEM operating procedure

We do not intend to describe all about the principle of electron imaging. The goal of this
section is merely to provide to the non-microscopist reader the keys needed to understand
the comments reported in this chapter. Basics and more about the principles of TEM can be
found in Williams and Carter (1996).
About dark-field mode imaging

Contrasted bright field and lattice fringe are two regular imaging modes involving the use of
apertures with suitable opening diameters placed in the back focal plane of the objective lens.
For the non-microscopist reader, considering the electron microscope as a powerful, high-
resolution magnifying lens able to image down to the lattice planes of crystals is enough to
understand the kind of comments made in this chapter. Likewise for the selected area electron
diffraction, whose principles are similar to that of XRD. However, further explanation might
be useful to fully understand the data brought by the dark-field imaging mode.
Although a TEM may contain seven or more electromagnetic lenses, its main quality and
mode abilities depend on the objective lens. As for regular, optical glass lenses, electromag-
netic lenses are characterised by three planes: the focalisation plane (where the specimen
should be located for its image to be focused on the image plane), the focal plane (specifi-
cally the back focal plane, which contains the electron diffraction patterns in the case of the
objective lens), and the image plane, where the enlarged image of the specimen is formed
(a) e– (b) e–
Specimen
Objective lens
Back focal plane

Objective
aperture
Image plane
Figure 4.68 Sketch of the electron beam paths in the objective lens of a microscope. (a) Bright-field
image, (b) dark-field image.
1 A
DF1 DF2
1 1/d (nm–1)
SiC C
002
200 SiC
+ 111
C
10
SiC
SiC 220
311
Figure 4.69 Examples of various positions of the objective aperture relative to the diffraction
pattern of a multiphase material (β-SiC + turbostratic C) used to perform specific
dark-field imaging.
(Figure 4.68(a)). Placing an aperture (so-called objective aperture) in the back focal plane
of the objective, therefore, allows specific electron beams to be selected, that is, the image
is built with some electron beams only (Figure 4.68(b)). For instance, selecting a specific
diffracted beam with the objective aperture results in an image whose bright parts indicate the
regions of the specimen from which the selected diffracted beam is emitted, while everywhere
else, in or around, the specimen appears dark (or nearly).
It is then already quite clear that, by successively selecting adequately various positions for
the objective aperture, sequential dark-field images can be formed which can be specific of
different orientations for a single crystallised phase, or of different phases within a multiphase
material, or both. This principle is illustrated in Figure 4.69, with the example of a material
containing both β-SiC and polyaromatic, turbostratic C. The related theoretical diffraction
patterns are both represented. Positioning the aperture in DF1 allows part of the C002 diffracted
beams to go through, and to build the image of polyaromatic entities – if any – whose (001)
lattice planes are oriented both parallel to the electron beam (i.e. graphenes are seen edge-on)
and parallel to the E–W direction (or nearly, since the width of the aperture is such that it
admits an arc instead of a single dot). Then, positioning the aperture at 90◦ along the same
diffraction ring (position DF1⊥) will image other polyaromatic entities – if any – oriented
S N, that is, perpendicularly to the former. The related two images are exclusive from SiC
crystals and are therefore specific of the C phase. SiC crystals will in turn be able to be imaged
by using position DF2. In that case, rotating the aperture relative to the diffraction pattern
all along the SiC111 diffraction ring (meanwhile also rotating along the SiC200 ring, which
is very close) will successively reveal any SiC crystal oriented so that they present (111) or
(100) reticular planes parallel to the electron beam. It is worth noting that the DF2 position
is not really specific of a SiC phase, strictly speaking, since the aperture width is such that
the 10 diffraction band of turbostratic C is also admitted, allowing the related electrons to
participate in building the image (using smaller apertures would be too much detrimental to
the resolution). Graphene stack entities oriented perpendicularly to the electron beam (i.e.
lying flat on the specimen support grid) are thus supposed to be imaged together with the SiC
crystals. Practically, due to the intensity of the SiC111 reflection, by far much higher than for
the C10 , DF2 images are considered specific of a SiC phase in most cases.
Because the objective aperture is placed in various positions relative to the diffraction
pattern, such dark-field imaging sequences are said to correspond to a radial and azimuthal
exploration of the reciprocal space. For this reason, the objective aperture apparent widths
are given in nm−1 .
TEM operating conditions

Bright-field, dark-field, lattice fringe and selected area diffraction mode images were obtained
using a Philips EM400 microscope operating at 120 kV and equipped with a high-resolution
stage providing a point resolution better than 3 Å, with a tungsten wire as electron source.
The width of the aperture used for the contrasted bright-field and lattice fringe imaging was
8 nm−1 , while that used for dark-field imaging was 2 nm−1 . According to the Abbe relation
ρ = 0.61 × λ/a
where λ is the wavelength and a the half-width of the aperture (in radians) using an objective
aperture as small as 2 nm−1 reduces the resolution ρ to ∼6 Å. Dark-field imaging was car-
ried out most often using DF1 (aperture centred at 2.2 nm−1 ) and DF2 (aperture centred at
4.3 nm−1 ) positions described in the previous section. Considering the width of the aperture
opening, the radial tolerance regarding the frequency range admitted for both positions are
1.3–3.3 nm−1 and 3.3–5.3 nm−1 , respectively. Likewise, the azimuthal deviations relative to
the centring position due to the aperture opening are ±24◦ and ±15◦ , respectively. Attention
has to be paid that, depending on the phases present in the material investigated, the speci-
ficity of the positions may vary. For instance, the powder diffraction pattern for a Si3 N4 phase
exhibits numerous diffraction rings (Figure 4.20 for instance), making Si3 N4 crystals likely
to be imaged in any possible position for the objective aperture, including DF1 and DF2.
Also, other aperture positions were sometimes used, for specific purposes. Finally, though
they do not provide diffracted beams strictly speaking, but are anyway able to scatter elec-
trons in some specific directions because of short-range structural periodicities (often around
the most intense diffracted beam for the related crystallised material), so-called amorphous
materials are likely to also appear in dark-field images. For instance, amorphous silica may
be revealed in DF1 position, providing an intense halo at 0.44 nm−1 (Chaudhari et al. 1972),
while the most intense reflection for any form of crystallised silica is located at ∼0.41 nm−1 .
X-EDS spectroscopy was performed using a Philips CM20 microscope equipped with
a high-resolution goniometric stage (super-twin stage) and an EDAX detector (Li-doped
silicon diode), protected by an ultra-thin window allowing the detection of chemical elements
including light elements down to C.
References
Audier, M., Oberlin, A., Oberlin, M., Coulon, M. and Bonnetain, L. (1981) Carbon, 19, 217.
Badami, D. V. (1965) Carbon, 3, 53.
Buffat, P. and Borel, J.-P. (1976) Phys. Rev. A, 13, 2287.
Champion, E., Goursat, P., Besson, J. L., Madigou, V., Monthioux, M. and Lespade, P. (1992) Ceram.
Eng. Sci. Proc., American Ceramic Society, USA, p. 732.
Chaudhari, P., Graczyk, J. F. and Herd, R. (1972) Phys. Stat. Sol., 51, 801.
Delverdier, O., Monthioux, M., Mocaer, D. and Pailler, R. (1992a) Proc. 5th Eur. Conf. Compos.
Mater., (eds A. R. Bunsell, J. F. Jamet and A. Massiah), Bordeaux, France, p. 691.
Delverdier, O., Monthioux, M., Oberlin, A., Lavedrine, A., Bahloul, D. and Goursat, P. (1992b) High
Temp. Chem. Proc., 1, 139.
Delverdier, O., Monthioux, M., Mocaer, D. and Pailler, R. (1993) J. Eur. Ceram. Soc., 12, 27.
Delverdier, O., Monthioux, M., Mocaer, D. and Pailler, R. (1994) J. Eur. Ceram. Soc., 14, 313.
Iijima, S. (1982) Solid State Chem., 42, 101.
Inoue, Z. and Kourachi, Y. (1983) Proc. Int. Symp. Ceram. Components Engines, Japan, p. 519.
Laanani, Fadéla (1997) Thèse de Doctorat, no 2707, Université Paul Sabatier, Toulouse, France.
Le Coustumer, P., Monthioux, M. and Oberlin, A. (1993) J. Eur. Ceram. Soc., 11, 95.
Madigou, Véronique, Monthioux, M. and Oberlin, A. (1990a) Proceedings of Matériaux Composites
pour Applications à Hautes Températures (eds R. Naslain et al.), AMAC-CODEMAC, Bordeaux,
France, p. 221.
Madigou, Véronique, Monthioux, M. and Guimon, C. (1990b) Proc. XX Int. Conf. Carbon, GFEC,
Paris, France, p. 220.
Madigou, Véronique (1991) Thèse de Doctorat, n◦ 116, Université de Pau et des Pays de l’Adour,
France.
Mocaer, D., Pailler, R., Naslain, R., Richard, C., Pillot, J.-P., Dunoguès, J., Delverdier, O. and
Monthioux, M. (1993) J. Mater. Sci., 28, 2639.
Monthioux, M. and Delverdier, O. (1996) J. Eur. Ceram. Soc., 16, 721.
Monthioux, M., Oberlin, A. and Bouillon, E. (1990) Compos. Sci. Technol., 37, 21.
Niihara, K., Suganuma, K., Nakahira, A. and Izaki, K. (1990) J. Mater. Sci. Lett., 9, 598.
Oberlin, A. (1989) Chemistry and Physics of Carbon, vol. 22 (ed. P. A. Thrower), Marcel Dekker,
New York, p. 1.
Oberlin, A. and Rouchy, J.-P. (1971) Carbon, 9, 39.
Oberlin, A., Oberlin, M. and Comte-Trotet, J. R. (1976) J. Microsc. Spectrosc. Electron., 1, 391.
Oberlin, A., Boulmier, J. L. and Villey, M. (1980) Kerogen (ed. B. Durand), Technip, Paris, p. 191.
Oberlin, A., Bonnamy, S., Bourrat, X., Monthioux, M. and Rouzaud, J.-N. (1986) Petroleum Derived
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Okamura, K., Sato, M., Hasegawa, Y. and Amano, T. (1984) Chem. Lett., 2059.
Rossignol (1995) Thèse de Doctorat, Université de Limoges, France.
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287, 335.
Williams, D. B. and Carter, C. B. (1996) Transmission Electron Microscopy. A Textbook for Materials
Science, Plenum Press, New York.
5 From short- to long-range order
Structural organisation of silicon-based
nanopowders
5.1 Chemical order studied by solid-state
nuclear magnetic resonance
André Pierre Legrand, Jean-Baptiste d’Espinose de la
Caillerie and Youssef El Kortobi
Native or heat-treated ceramics contain different atoms, the nuclei of which can be used, if
provided with a magnetic moment, as NMR probes. Among them 1 H,13 C,27 Al and 29 Si are
of particular interest. Different information can be obtained, depending on the method of
observation and on the nature of the nucleus under analysis.
Each proton has a magnetic moment (1 H) and is relatively easy to observe. Nevertheless,
it physically interacts through dipole–dipole interactions. This induces a line broadening of
the spectrum, which can hide the chemical information concerning the different chemical
species on, and inside ceramics (hydroxyls, water, etc.). So different approaches are possible
by taking advantage of this dipolar interaction or on the contrary by suppressing it.
Silicon nucleus (29 Si), on the contrary to 1 H, is an isotope with a low natural abundance
of 4.7%. The same is true for 13 C (1.1%). For as-formed ceramics, these diluted species are
in dipolar interaction with the abundant proton (1 H) species. To observe the nature of the
different chemical species in the material, it is necessary to suppress this dipolar interaction.
This is obtained through specific techniques.
Aluminium nucleus (27 Al) has a natural abundance of 100%. Contrarily to the previous
nuclei, 27 Al is not a spin 21 . Its quantum number is 5/2. This has positive and negative
effects. A positive one is that the nucleus is sensitive to the local electric field gradient and
consequently this gives an important information on the symmetry of the aluminium sites. The
negative one is that if the electric field gradient from one site to another site is different, for
example, tetrahedral to octahedral, the quantitative determination of the relative proportions
could be questionable.
5.1.1 Nuclear magnetic methods

As mentioned above, the as-formed amorphous ceramics may contain hydrogen atoms
belonging to different chemical species such as hydroxyls and adsorbed water molecules.
They constitute a set of 1 H spins which, by dipolar interaction, produce a line broadening
hiding the chemical information. This harmful effect disappears by heat treatment, with the
expulsion of protonated species.
5.1.1.1 Rare spin half spectroscopy (29 Si, 13 C)

Considering the low abundance of 29 Si,13 C isotopes, the dipolar interaction responsible for
line broadening is mainly due to neighbouring protons, for as-formed ceramics. To determine
112 André Pierre Legrand et al.
the nature of the different functionalities of such nuclei in ceramics, it is necessary to use
specific techniques.
High power decoupling (HPD)

To suppress the unwanted proton-rare spin dipolar interaction, the following method can be
used. It requires application of a strong radio frequency field at the Larmor frequency of the
abundant spins. Through this operation, the populations of spins in the low and high Zeeman
energy levels are made equal and the resulting magnetisation falls to zero, leaving only the
chemical shift interaction to be studied (Bloch 1958).
Averaging the chemical shift anisotropy (CSA) – Magic angle spinning (MAS)
The method involves putting the sample into a rotor, the axis of rotation of which is at
an angle of rotation of 54.73◦ with the external magnetic field. This method is efficient
not only to average the dipolar interaction, when MAS speed is high enough, but also the
CSA (Engelhardt and Michel 1987). The chemical shift has a theoretical expression that is
mathematically similar to that of the dipolar interaction. It is composed of an isotropic value,
similar to that observed in liquid state, and an anisotropic part. In consequence, for a powder,
this term produces a line broadening, due to the superposition of all possible orientations
of the chemical species studied. This requires that the speed of rotation be high enough
relatively to the CSA. If not, a more complex spectrum appears which is composed of the
mere spectrum, flanked on either side with more or less intense replicas of this one. These
satellites are separated by multiples of the rotation frequency. The different isotropic lines are
characterised by a position in frequency with respect to a given reference, tetramethylsilane
(TMS) in this book, and consequently can be identified. Numerous experiments in solids
have demonstrated that the observed chemical shifts are near what is observed in liquids,
if the environment is the same. Data already collected for species in solution can therefore
be used to analyse solid-state spectra (Lippmaa et al. 1982; Lippmaa and Samoson 1982;
Engelhardt and Michel 1987; Fyfe 1983; Marsmann 1981).
As the technology has improved, allowing in particular to increase the MAS speed, it is
possible to achieve such measurements using higher magnetic fields than previously, which
enables increasing resolution and sensitivity.
Cross-polarisation (CP)
For as-formed ceramics containing an important amount of hydrogen, this method is jointly
used with MAS to enhance the signal of carbon (C) or silicon (Si) bonded to protons. First,
it involves cooling down the proton reservoir through a sequence shown in Figure 5.1.1.
Second is the time to transfer the low temperature of the proton reservoir to that of rare
spins. Last is to observe the signal of the rare spin while at the same time using the HPD.
The method is consequently denominated CP/MAS. The complete sequence is represented
in Figure 5.1.2.
Model compound example

Role and interest of the different methods mentioned above are summarised in Figure 5.1.3.
29 Si NMR spectra of a powdered sample of pure cubic octamer silicic trimethylsilyl ester
Chemical order studied by solid-state NMR 113
x y
Abundant
spins Time
/2
Spin lock Measurement
(a) M1H (b) M1H B1 (c) M1H B1

y y y
Relaxation
in the rotating frame
90° phase shift

B1
x x x
Observation in the rotating frame
Figure 5.1.1 Setting of a spin temperature for the abundant spins (observation in a plane perpen-
dicular to the director field B0 ): (a) the magnetisation is brought in the perpendicular
plane after a 90◦ pulse; (b) the radio frequency field B1 is phase shifted by a 90◦
angle, bringing it parallel to the magnetisation; (c) after a certain time, the magneti-
sation decreases slowly in the B1 field and is measured after switching this field off,
on the free induction decay. The upper part of the figure represents schematically the
application of radio frequency pulses along the Ox and Oy axis in the rotating frame.
(Reproduced with permission of John Wiley & Sons from Legrand et al. 1998.)
x y
Abundant Time
spins
/2
Spin lock Decoupling Waiting time
Time
Rare spins
Contact Measurement
Figure 5.1.2 Complete sequence of CP for abundant spins (e.g. protons 1 H) in interaction with
less abundant spins (e.g. silicon 29 Si). (Reproduced with permission of John Wiley
& Sons from Legrand et al. 1998.)
(d)
(c)
a.u.
(b)
(a)
60 40 20 0 –20 –40 –60 –80 –100 –120 –140 –160

ppm
(d) Q8M8 spin rotation 5 kHz
13 12 11 10 –107 –108 –109 –110 –111

ppm
Figure 5.1.3 Rare spin 29 Si solid state NMR spectra at 59.6 MHz of a powdered pure cubic octamer
silicic trimethylsilyl ester (Q8 M8 ) as model compound, showing the influence of dif-
ferent types of NMR measurements: (a) static or broadband spectrum with no high
power decoupling of the protons. Only a broad line is observed: no chemical infor-
mation is available; (b) static or broadband spectrum with high power decoupling
of protons. Two bands, due to chemical anisotropy, corresponding to two Si are
observed: no clear chemical identification available; (c) HPD with CP (contact time
1 ms) and MAS with a speed or rotation not high enough (567 Hz). Chemical infor-
mation partially available; (d) CP/MAS + HPD. Chemical information available.
(Courtesy of P. Tougne.)
(Q8 M8 ) present the following aspects:
1 With static or broadband method, only broad lines mainly due to the dipolar interaction
1H 29 Si are observed. No chemical information is available.
2 As above, with HPD of the protons, CSA of two Si types are observed.
3 CP/MAS method, but with MAS speed of 560 Hz. Side bands with the mere spectrum
are observable.
4 CP/MAS method, with MAS speed high enough. Side bands are suppressed and the
spectrum shows a triplet and a quadruplet.
5.1.1.2 Aluminium 27 Al NMR spectroscopy
Unlike 29 Si or 13 C, 27 Al has an I = 5/2 spin and therefore a nuclear quadrupole moment. This
implies that not only this nucleus is sensitive to the chemical shift and dipolar interactions
but also to the quadrupolar one. The six energy levels (2I + 1) of the 27 Al due to the Zeeman
effect are modified, assuming a first-order perturbation effect, which results in five different
transition frequencies. The corresponding Hamiltonian is:
eQ eq ˆ2 η ˆ2
ĤQ = 3Iz − I (I + 1) + I+ + Iˆ−2 (5.1)
4I (2I − 1) 2
where eQ is the nuclear quadrupolar moment and Vzz = eq, the main electric field gradient
(|Vzz | > |Vyy | > |Vxx |); η = (Vyy − Vxx )/Vzz is the asymmetrical parameter. Oxyz are
principal axes of the tensor that describe the electric field gradient. All transitions except the
central one ( 21 ↔ − 21 ) are subject to a first-order quadrupolar interaction depending on the
orientation of the electric field gradient tensor with respect to the external magnetic field.
Since in powder samples there is a random distribution of such orientations, it results in a large
spreading of the line which prevents its observation. On the contrary, the central line is only
sensitive to the second-order perturbation effect, which causes a line spreading proportional
2
to e2 Qq/ h /νL = νQ , where νL is the Larmor frequency of the 27 Al nucleus. Contrarily
to spin half, the observation is not obtained with a 90◦ pulse, although this one is obtained
with a solution of aluminium salt, in which the Brownian motion averages the quadrupolar
effect. Samoson and Lippmaa (1983) proved that the signal intensities are independent of the
magnitude of νQ only if the pulse length is short enough. For an error less than 5% in the
signal intensity for the centre band of the central transition ( 21 , − 21 ), the spin flip angle ω1 τ
must satisfy the condition ω1 τ (I + 1/2) ≤ π/6, with I = 5/2 for 27 Al.
An example of the influence of the pulse duration on the relative intensities of the lines is
given in Figure 5.1.4 for 23 Na (spin 3/2).
Such quadrupolar and line shifts render more difficult the interpretation of the line structure
but are able to provide additional information of the charge distribution (Figure 5.1.5).
5.1.1.3 Interest of the method

The chemical shift of the nuclear resonance provides an incredibly delicate fingerprint of the
chemical functionality of an element in a compound. NMR has provided chemists with one
of the most powerful qualitative and quantitative analytical tools available to the chemist,
material scientist and medical technician. The advent of high-resolution techniques appro-
priate to nuclei in solids supplied further dimensions to do qualitative analysis of chemical
functionalities. Moreover, some information concerning structure and local organisation of
clusters can be obtained. Such a method had been largely used for ceramic characterisation
(Müller 1999; Templin et al. 1999).
5.1.2 SiC powders analysis

In Figure 5.1.6, the 29 Si spectrum for sample as-formed SiC163 is shown. Like previously
published spectra of silicon carbide powders (Table 5.1.1), it consists of a superposition of two
kinds of line: a single line at −16.0 ppm can be attributed to the β-SiC type, whereas the triplet
consisting of lines at −15.6, −20.5 and −24.9 ppm can be attributed to α-SiC polytypes.
(a)
NaCl
NaNO2
10 5 0 –5 –10 –15 –20 –25 –30 –35 –40 –45 –50

ppm
(b)
Integral 2,925 17,590
10 6 2 –2 –6 –10 –14 –18 –22 –26 –30 –34 –38

ppm
Figure 5.1.4 2D solid state 23 Na MAS–NMR spectra at 79.39 MHz of sodium chlorine and nitrite
salts. (a) Influence of the pulse length (from 0.25 to 5 µs, by step of 0.25 µs) on
the relative intensities of the two sodium sites; (b) Relative proportion has to be
evaluated at short pulse length (here 1 : 6). (Courtesy of P. Tougne.)
As the experimental high-resolution solid-state NMR technique involves only MAS, the
spectra can be decomposed and the amount of each type, α-SiC or β-SiC, is proportional
to the respective areas of the different lines, if the repetition time for accumulation is long
enough relatively to the spin-lattice relaxation times. The 29 Si spectrum of SiC174 is very
similar to the previous spectrum except that the amount of α-SiC has decreased a little.
Altet Aloct
Gibbsite
Saponite
a.u.
90 80 70 60 50 10 5 0 –5 –10
ppm
Figure 5.1.5 Solid state 27 Al MAS–NMR spectrum at 130.32 MHz of gibbsite and saponite. MAS
speed: 12 kHz. Clear distinction between four- and sixfold coordinated aluminium
in AlO4 and AlO6 units is observed. 27 Al chemical shifts are between +50 and
+80 ppm for AlO4 and about −10 to +20 ppm for AlO6 .
SiC163 SiC174 SiC173 SiC177
0 –40 0 –40 0 –40 0 –40

ppm ppm ppm ppm
Figure 5.1.6 Solid state 29 Si MAS–NMR spectra at 59.6 MHz of as-formed silicon carbide (duty
cycle, 500 s; 90◦ pulse, 5 µs; number of scans, 161, 100, 164 and 60). Spectra
are classified as function of decreasing residence time into the laser irradiation cell
(Table 2.1). (Reprinted from Tougne et al. (1993) Diamond Relat. Mater., Evolution
of the structure of ultrafine SiC-laser-formed powders with synthesis conditions, 2,
486–490, with permission from Elsevier Science.)
29
Table 5.1.1 Si chemical shift in ppm/TMS for silicon carbides
Authors Polytype
3C(C) 6H (A B C) 15R (A B C) 4H(B C) 2H (D)
Finlay et al. −18.3 −13.9 −20.2 −24.2

1985
Guth et al. 1987 −18.4 −16.1 −14.3 −20.4 −24.9 −14.6 −20.5 −24.1
Hartman et al. −18.3 −13.9 −2.02 −24.5 −14.9 −20.8 −24.4
1987
Wagner et al. −18.4 −16.1a
1989
Dando and −16 −14.4 −20.5 −25 −15.2 −20.2 −24
Tadayyoui
1990
Apperley et al. −18.4 −14.7 −20.9 −25.4 −19.7 −22.5 −20
1991
Schmidt et al. −18 −14 −20 −25
1991–2
Richarson et al. −14.5 −20.4 −25.1
1992
Dybowski et al. −16 −22 −27
1996
Tateyama et al. −18.4 −14.7 −19.7 −25.4 −20.9 −22.5 −20
1997
Note
a Depends on the crystalline structure of the sample (−16.1 for small single crystals).
No quantitative accurate decomposition has been performed but it is qualitatively apparent

from the spectra. Moreover, on comparing the figure which shows the spectrum for sample as-
formed SiC173 with the figure which shows the spectrum for sample SiC177 the trend follows
the same line. Increasing the residence time into the hot region of the cell where the synthesis
takes place results in a decreasing amount of α-SiC phase. To assess this evolution, samples as-
formed SiC163 and SiC177 were annealed in a furnace at 1600◦ C for 24 h. Figure 5.1.7 shows
the spectra of the annealed samples SiC163 and SiC177. One single line at −16.0 ppm now
appears which can unambiguously be attributed to a pure β-SiC phase, it appears therefore
rather surprisingly that the β-SiC phase is the high temperature stable phase.
By comparing the evolution of samples SiC163 and SiC171, one can study the effect of heat
treatment. Table 5.1.2 shows that the grain growth occurs at a higher temperature for sample
SiC171 than for sample SiC163. At 2000◦ C, the densification of sample SiC171 is 94% but
the grain size has become comparable to the grain size of a commercial powder. The problem
is then to achieve good densification and conserving a fine structure. A good knowledge of
the local structure evolution would be very helpful. Figure 5.1.8 presents the NMR spectra of
samples SiC163 and SiC171 after heat treatment between 1600◦ C and 2050◦ C. One can see
that the α-phase is always present in sample SiC171, while it almost disappears in sample
SiC163 between 1700◦ C and 1900◦ C. At 2050◦ C, β-phase is transformed into α polytypes.
6H, 15R and 4H polytypes are unambiguously identified in sample SiC171 while only the 6 H
environment is in sample SiC163. It seems then that there is a relation between the annealing
and the presence of the α-SiC polytypes.
SiC163 SiC177
0 –40 0 –40
ppm ppm
Figure 5.1.7 Solid state 29 Si MAS–NMR spectra at 59.6 MHz of 1600◦ C (24 h) annealed silicon
carbide (duty cycle, 500 s; 90 ◦ pulse, 5 µs; number of scans, 69 and 57). (Reprinted
from Tougne et al. (1993) Diamond Relat. Mater., Evolution of the structure of
ultrafine SiC-laser-formed powders with synthesis conditions, 2, 486–490, with
permission from Elsevier Science.)
Table 5.1.2 Surface of different silicon carbide

batches as a function of temperature
dwell (dwell duration: 1 h)
Temperature (◦ C) SBET (m2 /g)

SiC171 SiC163 SiC177
1600 24.9 13.2 8.1

1800 3.7 7.3 3.3
2000 0.09 5.3 2.3
5.1.3 Si/C/N powders analysis
5.1.3.1 29 Si and 13 C solid-state MAS–NMR measurements

Well-crystallised silicon nitrides have been analysed and 29 Si chemical shifts of the two main
α and β structures had been determined (Table 5.1.3). Average chemical shift identification
of different Si environments in Si/C/N compounds has been done by comparison between
pure silanes and pure silicon carbide or silicon nitride. Analysis of the results is given in
Table 5.1.4.
Besides, different authors have estimated the presence in less organised compounds of Si
environments as SiCN3 , SiC2 N2 and SiC3 N (Seitz et al. 1996; Gérardin et al. 1997; Verdecia
SiC171 9SiC
SiC163
9SiC 15R 15R
6H 15R 6H 4H 6H
2050°C
6H
2050°C 2000°C
1900°C
1900°C 1800°C
1700°C
1700°C 1600°C
–10 –20 –30 –10 –20 –30

ppm ppm
Figure 5.1.8 Evolution of 29 Si MAS–NMR spectra of sample 163 and 171 as a function of
the temperature (dwell duration 1 h). Top of β-SiC peak had been cut to observe
polytypes signal.
Table 5.1.3 Chemical shift of 29 Si in ppm/TMS for crystallised amorphous silicon nitrides. Values
within parentheses are full-width at half-height of each peak
Authors β-Si3 N4 (singlet) α-Si3 N4 (doublet) equal intensities Amorphous
Carduner et al. 1987, 1990 −48.7 (2.5) −46.8 (1.8) −48.9 (1.8) −46.4 (27)
Harris et al. 1990 −48.5 (1.3) −47.1 −49
29
Table 5.1.4 Si average chemical shift of different silicon nitrides. Chemi-
cal shift measurements done on silane series (upper part) exhibit
an average shift of −20 ppm comparatively to pure silicon car-
bide and silicon nitride. Consequently interpolation is done for
intermediary environment of the Si (lower part)
Silane Chemical shift (ppm/TMS)
(CH3 )4 Si 0
(CH3 )3 SiN(CH3 )2 6.9 to 5.0
(CH3 )2 Si(N(CH3 )2 )2 −1.3 to 1.85
(CH3 )Si(N(CH3 )2 )3 −16.3 to −17.5
Si(N(CH3 )2 )4 −28.1 to −28.6
Silicon environment in solid state Average chemical shift (ppm/TMS)
SiC4 −20
SiC3 N −13 to −14
SiC2 N2 −21 to −22
SiCN3 −36 to −37
SiN4 −46 to −49
Seitz (1996)
0
–5
Gérardin (1997)
–10
–15
–20
(ppm/TMS)
–25
Carduner (1987, 1090)

–30
–35
–40 Verdecia (1998)
–45 α
–50
β
200 400 600 800 1000 1200 1400 1600 1800 2000
Temperature (°C)
Figure 5.1.9 Chemical shift of 29 Si in ppm/TMS for crystallised SiCx N4−x compounds as a func-
tion of the HTT of different ceramics from Seitz et al. (1996), Gérardin et al. (1997)
and Verdecia et al. (1998). Symbols are SiN4 , • SiCN3 and SiC2 N2 ; highest
temperature is for well-crystallised silicon nitrides (Carduner et al. 1987, 1990).
et al. 1998). Chemical shifts of such Si environments are dependent on the first and second
sphere of coordinence. This one is able to contain hydrogen atoms for as-formed or low
heat-treated materials and consequently the chemical shift is susceptible to modifications.
Figure 5.1.9 summarises different observations.
Series HMDS41 to HMDS44, heat-treated from 1000◦ C to 1600◦ C in N atmosphere during
1 h, have been analysed using 29 Si MAS–NMR. This method enables us to distinguish,
through previous mentioned observations given in Figure 5.1.9, the evolution of the local
structure around Si. Figures 5.1.10 and 5.1.11 give the general results of the survey.
They are classified as a function of the initial C/Nini composition or of the heat-treatment
temperature (HTT). Some remarks have to be made:
• At HTT 1000◦ C, no important differences are observable. A broad massif centred around
−50 ppm demonstrates an amorphous silicon nitride environment. Besides, a shoulder
near −35 ppm can be attributed to SiCN3 , the importance of which decreases with initial
C/N ratio. A small peak at −110 ppm corresponds to silica.
(a) (b)
1600°C/N2/1 h
1600°C/N2/1 h
1550°C
1500°C
1500°C
1400°C
1400°C
1000°C
1000°C
40 20 0 –20 –40 –60 –80 –100 –120 40 20 0 –20 –40 –60 –80 –100 –120
ppm ppm
(c) (d)
1600°C/N2/1 h
1600°C/N2/1 h
1550°C
1500°C
1500°C
1400°C
1400°C
1000°C
1000°C
40 20 0 –20 –40 –60 –80 –100 –120 40 20 0 –20 –40 –60 –80 –100 –120
ppm ppm
Figure 5.1.10 Solid state 29 Si MAS–NMR spectra at 99.36 MHz, rotation frequency of 5 kHz, of
HMDS powders heat-treated during 1 h in N atmosphere, as a function of the initial
C/N (atomic number) composition, at increasing temperature. (a) HMDS41 (duty cycle,
500 s; 90◦ pulse, 5 µs; number of scans, 160, 160, 160, 12, 84); (C/N)ini = 0.95; (b)
HMDS42 (duty cycle, 500 s; 90◦ pulse, 5 µs; number of scans, 160, 103, 160, 75);
(C/N)ini = 0.73; (c) HMDS43 (duty cycle, 500 s; 90◦ pulse, 5 µs; number of scans,
144, 125, 140, 120, 81); (C/N)ini = 0.67; (d) HMDS44 (duty cycle, 500 s; 90◦ pulse,
5 µs; number of scans, 150, 160, 102, 40); (C/N)ini = 0.57.
(a) (b)
HMDS44 HMDS44
HMDS43 HMDS43
HMDS42 HMDS42
HMDS41 HMDS41
40 20 0 –20 –40 –60 –80 –100 –120 40 20 0 –20 –40 –60 –80 –100 –120
ppm ppm
(c) (d)
HMDS44 HMDS44
HMDS43 HMDS43
HMDS42 HMDS42
HMDS41 HMDS41
40 20 0 –20 –40 –60 –80 –100 –120 40 20 0 –20 –40 –60 –80 –100 –120
ppm ppm
Figure 5.1.11 Solid state 29 Si MAS–NMR spectra of HMDS powders. Experimental condi-
tions are given in Figure 5.1.10 caption. (a) 1000◦ C/N2 /1 h; (b) 1400◦ C/N2 /1 h;
(c) 1500◦ C/N2 /1 h; (d) 1600◦ C/N2 /1 h.
• At HTT 1400◦ C, a silicon nitride broad peak (SiN4 and SiCN3 ) emerges from the massif.
It appears as a shoulder near −20 ppm (SiC2 N2 ). X-ray diffraction patterns do not provide
similar information, owing to the amorphous organisation of the material.
• At HTT 1500◦ C, the structure of the massif is more evident. Three more or less
well-resolved peaks are observed which are respectively attributed to SiN4 , SiCN3 and
SiC2 N2 . A shoulder near −18 ppm seems to appear which can be silicon carbide.
• At HTT 1600◦ C, crystallised silicon nitride (α and β) are observed, the proportion
of which increases as initial C/N decreases. A silicon carbide massif (SiC4 , SiC3 N) is
clearly separated from this one.
Two significant samples, HMDS42 and HMDS44, are analysed in more detail using least
square decomposition method, assuming different occupations sites as given in Figure 5.1.9.
Results are shown on Figures 5.1.12 and 5.1.13. Table 5.1.5 gives the relative proportions of
the different sites.
Neither SiC4 nor SiC2 N2 are observed till HTT is 1000◦ C. A mixture of such sites is
observed at a higher temperature. From HTT 1550◦ C, crystallised SiN4 (α and β) sites
are clearly identified. In the silicon carbide broad line, SiC4 and SiC3 N sites are present.
The relative proportions of crystallised silicon nitride clearly depend on the initial C/Nini
composition (C/Nini = 0.73 and 0.57, respectively, for HMDS42 and HMDS44). Such
different evolutions are shown on the chemical composition (Figure 5.1.14).
An important remark concerns the duty cycle, that is, the time between two accumulations,
to obtain reliable spectra. This time has to be of the order of five times that of the spin-lattice
(a) (b)
SiN4
SiN4
SiCN3 SiCN3
1000°C 1000°C
SiCN3 SiN4 SiCN3 SiN4

SiC2N2
SiC2N2
1400°C 1400°C
SiCN3
SiCN3 SiN4
SiC2N2 & SiC4 SiN4 SiC2N2 & SiC4
1500°C
1500°C
20 0 –20 –40 –60 –80 20 0 –20 –40 –60 –80

ppm (TMS) ppm (TMS)
(a) HMDS42 and (b) HMDS44 heat-treated at 1000◦ C, 1400◦ C and 1500◦ C during 1 h
in N atmosphere and decomposition, using a least square method, into different assumed
Si environments (El Kortobi 1998).
(a) (b)
SiC SiC2N2
SiC
SiC3N SiC3N SiC2N2
1550°C
1550°C
Si3N4 (, )
SiC
SiC
SiC3N Si3N4 (, )
SiC3N SiC2N2
1600°C 1600°C
SiC
SiC
SiC3N SiC2N2
SiC3N
1700°C 1700°C
20 0 –20 –40 –60 20 0 –20 –40 –60

ppm (TMS) ppm (TMS)
(a) HMDS42 and (b) HMDS44 heat-treated at 1550◦ C, 1600◦ C and 1700◦ C during
1 h in N atmosphere and decomposition, using a least square method, into different
assumed Si environments (El Kortobi 1998).
relaxation times of the species to observe. Figure 5.1.15 shows spectra obtained for different
values of such time. One notices that the relative apparent proportion of silicon nitride is
only significant for temperatures higher than 1550◦ C, which shows that the two massifs
are associated with relatively short and long spin-lattice relaxation times. Different authors,
using MAS–NMR, had similarly used duty cycle as long as 30 mn to obtain reliable spectra
(Dybowski et al. 1996). In the case considered here, it is necessary to reach 8000 s to estimate
the relative proportion of silicon nitride in the different specimens. Amorphous silicon carbide
massif relaxes more rapidly as shown in Figure 5.1.16.
In Chapter 5.2, electron paramagnetic resonance (EPR) measurements show that the
materials contain an important amount of paramagnetic centres. Besides, the study of the
magnetisation as a function of the temperature as in the example on HMDS44 heat-treated at
1550◦ C, shows a Curie law dependence. This is in favour of localised paramagnetic centre
organisation. As the above observation concerning the difference of spin-lattice relaxation
times between silicon nitride and other species, it is obvious to consider that such centres are
inside the amorphous silicon carbide structure.
Same samples, HMDS42 and HMDS44, have been analysed using 13 C MAS–NMR
(Figure 5.1.17). The useful CP/MAS–NMR is useless in that temperature range, due to
the lack of proton in the material. The difficulty in acquiring a good signal over noise spec-
tra is related to the low-frequency measurement. This had been done to prevent side bands
coming from a large CSA of the aromatic carbons. Different comments have to be made:
• At HTT 1000◦ C, some differences are observable. A broad massif centred around
−130 ppm is attributed to aromatic sp2 and oxygenated carbons. This is generally
29
Table 5.1.5 Si chemical shift δ in ppm/TMS, obtained using a least square fitting method for HMDS42 and HMDS44 samples. Gaussian fit shape assumed
for a theoretical decomposition of the experimental spectra. ! is the Gaussian quadratic square deviation of each specie assumed
H T T (◦ C) SiN4 SiCN3 SiC2 N2 SiC3 N SiC4

δ (ppm) ! (ppm) % δ (ppm) ! (ppm) % δ (ppm) ! (ppm) % δ (ppm) ! (ppm) % δ (ppm) ! (ppm) %
HMDS42
1000 −53.6 18 67 −35 20 33 / / / / / / / / /
1400 −50 14 54 −34.6 13 30 −21 14 16 / / / / / /
1500 −48 14 34 −32 15 31 / / / / / / −14.5 15 35
1550 / / 9 / / / −21 8 26 −9 10 34.5 −17 8 31.5
1600 / / 13 / / / / / / −6 13 31.1 −18 10 56.5
1700 / / 10 / / / / / / −11 5 12.6 −17 6 74.4
HMDS44
1000 −53.6 17 80 −37 17 20 / / / / / / / / /
1400 −50 14 67 −36 14 16 −23 14 17 / / / / / /
1500 −53 12 40 −37 14 36 / / / / / / −20 13 24
1550 / / 48 / / / −22 7 5.5 −7 9 12.3 −17 10 34.2
1600 / / 40 / / / −23 5 6 −10 8.5 11.4 −17 8 42.6
1700 / / 42 / / / −21 6 3.2 −9 8 14.1 −17 6 40.8
HMDS40
N HMDS42
0.0 1.0 HMDS44
0.1 HMDS45
0.9 Wakai (1990)
0.2 0.8 −−−−> HTT increase
0.3 0.7
en
0.4 0.6
rog
0.5
Nit
0.5
0.6 0.4
0.7 45 44 42 40 0.3
0.8 0.2
0.9 0.1
1.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
C Si
Carbon
Figure 5.1.14 Atomic chemical composition Siy Cx Nz (x + y + z = 1) of HMDS42 and

HMDS44 as a function of heat treatment temperature. Arrows indicate evolution
from as-formed to highest treatment temperature.
considered as ‘free carbon’. Besides, for HMDS42, a small peak near −20 ppm can
be attributed to sp3 Si bonded C.
• From HTT 1400◦ C, the amount of Si bonded C increases, which is in accordance with
the 29 Si MAS–NMR observation. Besides, the existence of other environments such as
CSix Ny are possible.
• At HTT 1550◦ C, the line around −20 ppm, related to silicon carbide, is more important
for both samples. Although the difference is noticeable concerning the ‘free carbon’ still
present in the richer C HMDS42 sample than in HMDS44, were it is now absent.
More generally, similar determinations are of interest to characterise silicon carbide fibres
and consequently their mechanical properties (Hommel et al. 1990; Laffon et al. 1989).
Some comparisons can be done between the atomic chemical compositions and 29 Si NMR
determinations. From Table 5.1.5, with the relative proportions of SiN4 (p), SiCN3 (q),
SiC2 N2 (r), SiC3 N(s) and SiC4 (t), it is possible to calculate the average atomic compo-
sitions Siy Cx Nz (x + y + z = 1) as a function of HTT and to plot Figure 5.1.18, using the
following formula:
x 1 2 3 4
=q +r +s +t
y 4 4 4 4
(5.2)
z 4 3 2 1
=p +q +r +s
y 3 3 3 3
The above values are listed in Table 5.1.6.

Such obtained plots show a convergence of the two types of analysis at high heat tem-
perature treatment of both samples. The divergence observed at low HTT originates from
HMDS44 1550°C HMDS44 1600°C HMDS44 1700°C
D1 = 8000 s
D1 = 8000 s D1 = 8000 s
D1 = 500 s
D1 = 500 s D1 = 500 s
20 10 0 –10 –20 –30 –40 –50 –60 –70 –80 20 10 0 –10 –20 –30 –40 –50 –60 20 10 0 –10 –20 –30 –40 –50 –60
ppm ppm ppm
HMDS42 1600°C HMDS42 1700°C

20 10 0 –10 –20 –30 –40 –50 –60 20 10 0 –10 –20 –30 –40 –50 –60
D1 = 8000 s D1 = 8000 s
D1 = 500 s
D1 = 500 s
20 10 0 –10 –20 –30 –40 –50 –60 20 10 0 –10 –20 –30 –40 –50 –60
ppm ppm
Figure 5.1.15 Solid state 29 Si MAS–NMR spectra obtained at different duty cycle (D1) values on
HMDS44 and HMDS42, at different heat treatment temperatures. Spectra are adjusted
so that the maximum of each spectrum is similar to the others. Signal over noise depends
on the number of scans and consequently of the total time of accumulation, which is
different for some spectra (El Kortobi 1998).
an underestimation of C content. Those not being bonded to silicon C atoms are set in the
amorphous ‘free carbon’ as it had been discussed above (Figure 5.1.17). This effect is not
important for sample heat-treated at temperature higher than 1550◦ C, as it can be observed
on the points corresponding to NMR measurements. They are in the vicinity of those in the
chemical analysis. From the C content values obtained for chemical analysis and NMR, it is
possible to estimate the proportion of ‘free carbon’ in total C. This calculation is only valid,
within the experimental errors, in the temperature range 1000–1550◦ C (Figure 5.1.19).
5.1.3.2 Thermal evolution from NMR measurements

This evolution can be roughly decomposed in three steps as follows:
First step: HT T inferior to 1000◦ C This domain, from as-prepared powder till almost
end of mineralisation, is mainly discussed in Chapter 2. The most efficient methods of
HMDS44 1600°C
D1 = 8000 s
D1 = 4000 s
D1 = 1000 s
20 10 0 –10 –20 –30 –40 –50 –60

ppm
Figure 5.1.16 Solid state 29 Si MAS–NMR spectra obtained at different duty cycle (D1) values on
HMDS44 heat-treated at 1600◦ C (LB = 30 Hz, NS = 16) (El Kortobi 1998).
characterisation are in particular TGA and IR. It is characterised by emission of H2 O, NH3

and CH4 . It results in the formation of Si N with ammoniac (Gérardin et al. 1997; Bowen
1980) and Si C bonds with methane (Gérardin et al. 1997, Hasegawa and Okumura 1983)
emissions.
Second step: 1000–1500◦ C As seen from 29 Si MAS–NMR, it starts with a rich nitrogen
(N) to Si environment (SiN4 , SiCN3 ) depending on the initial C/Nini concentration. Besides,
13 C MAS–NMR demonstrate the presence of C not bonded to Si, named ‘free carbon’. The
proportion of such C decreases considerably till 1500◦ C. Parallelly, it is observed as an

increase of C to Si environment.
Third step: 1550–1700◦ C The crystallisation of the material is observed, with important
loss in weight due to the departure of N, consecutive to a carbo-reduction. Demixtion occurs
with the appearance of well-crystallised α − β SiN4 and of amorphous silicon carbides
(SiC4 , SiC3 N and SiC2 N2 ).
5.1.4 Pre-alloyed Si/C/N/Al/Y nanopowders

In Chapter 7 explanations are given on the interest to use additives for the sintering of
silicon nitride based materials. The objective here is to characterise nanosized ready-to-
sinter powders including additives. Two types of additives have been incorporated: alumina
(Al2 O3 ) and yttria (Y2 O3 ).
HMDS42 HMDS44
CSi4 CSi4
Carbon sp2
1550°C 1550°C
1500°C
1500°C
1400°C 1400°C
1000°C
1000°C
250 200 150 100 50 0 250 200 150 100 50 0

ppm (TMS) ppm (TMS)
Figure 5.1.17 Solid state 13 C MAS–NMR spectra at 25.15 MHz, rotation frequency of 5 kHz, of
HMDS42 and HMDS44 at different heat treatment temperatures.
HMDS44
N HMDS42
0.0 1.0 HTT increase
0.1 0.9 NMR HMDS44
NMR HMDS42
0.2 0.8
0.3 0.7
en
0.4 0.6
rog
Si
Nit
lic
0.5 0.5
on
0.6 0.4
0.7 0.3
0.8 0.2
0.9 0.1
1.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Si
C
Carbon
Figure 5.1.18 Atomic NMR and chemical compositions Siy Cx Nz (x + y + z = 1) of HMDS42

and HMDS44 as a function of heat-treated temperature. Arrows indicate evolution
from as-formed to highest treatment temperature.
Table 5.1.6 Atomic NMR composition Cx Siy Nz (x + y +
z = 1) of HMDS42 and HMDS44 as a function
of heat treatment temperature
H T T (◦ C) C Si N
HMDS42 1000 0.03896 0.4329 0.52814

1400 0.06987 0.43668 0.49345
1500 0.15315 0.45045 0.3964
1550 0.33175 0.47393 0.19431
1600 0.38462 0.48077 0.13462
1700 0.42157 0.4902 0.08824
HMDS44
1000 0.02155 0.43103 0.54741
1400 0.05652 0.43478 0.5087
1500 0.12796 0.47393 0.3981
1550 0.20354 0.44248 0.35398
1600 0.24658 0.45662 0.2968
1700 0.23767 0.44843 0.3139
1.0
0.8
Relative proportion
of ‘free carbon’
0.6
0.4
HMDS42
0.2 HMDS44
0.0
1000 1100 1200 1300 1400 1500 1600
HTT (°C)
Figure 5.1.19 ‘Free carbon’ evolution as a function of heat treatment temperature. Values are
obtained owing to the formula: (xCA − xNMR )/xCA where xCA , xNMR are those of
the chemical analysis and NMR, respectively.
5.1.4.1 Free carbon effect

Samples HSAl03 and HSAl05, heat-treated from 1000◦ C to 1600◦ C in N atmosphere during
1 h, have been analysed using 29 Si MAS–NMR (Figure 5.1.20). The following observations
can be made:
• From as-formed to HTT 1000◦ C, no important differences are observed. A broad peak
around −20 ppm shows different environments of Si (SiC3 N, SiC2 N2 and/or SiC4 ).
• At HTT 1400◦ C, a line narrowing is observed. Only SiC2 N2 and/or SiC4 environments
remain.
(a) (b)
SiC SiC
1600°C/N2 /1h 1600°C/N2 /1h
1400°C
1400°C
1000°C
1000°C
SiC3N SiCN3
SiC3N SiCN3
As-formed
SiC4 As-formed SiC4
SiC2N2 SiC2N2
100 50 0 –50 –100 100 50 0 –50 –100

ppm (TMS) ppm (TMS)
Figure 5.1.20 Solid state 29 Si MAS–NMR spectra at 99.36 MHz, MAS speed of 5 kHz, of
(a) HSAl03 and (b) HSAl05 at different heat treatment temperatures. At 1600◦ C,
no silicon nitride remains; compare to Table 3.1.3 (El Kortobi 1998).
• At HTT 1600◦ C, the narrowing is more important. A structure is perceptible, which can
be attributed to α and β silicon carbide.
13 C
MAS–NMR is able to improve such results. Only as-formed samples can be analysed
using CP and MAS. The sites are CH3 Si and Si CH2 Si in the range 0–5 ppm.
• At HTT 1000◦ C, as hydrogen is expulsed with heat treatment, 13 C MAS–NMR sp3 and
sp2 C are observed.
• From HTT 1400◦ C to 1600◦ C, the ‘free carbon’ massif disappears progressively. The
line around 24 ppm is proportionally improved. This confirms the presence of partially
crystallised silicon carbide (Figure 5.1.21).
27 Al
MAS–NMR shows three aluminium environments for as-formed materials. Tetra,
penta and octahedral environments are observed (Figure 5.1.22).
• At HTT 1000◦ C, such three sites are still observable, with a significant increase of the
octahedral environment.
• From HTT 1400◦ C to 1600◦ C, besides tetra and octahedral sites, there is a broad massif
at lower field, around 90 ppm. This can be attributed, owing to measurements done
on defined samples (AlON and SiAlON) (Figure 5.1.23), to aluminium oxynitrides
AlOx N4−x , with 0 < x < 4 (Smith 1992; Mackenzie et al. 1994; Fitzgerald et al.
1994). At HTT 1400◦ C, this massif contains AlO3 N and AlO2 N2 (96 ppm), AlON3
(106 ppm) and AlN4 (114 ppm). At HTT 1600◦ C, the peak corresponding to AlN4 is
easier to observe (Figure 5.1.24).
sp2 carbon sp3 carbon
(free carbon)
MAS 1600°C
MAS 24 1400°C
MAS 1000°C
130 2
CP/MAS As-formed
250 200 150 100 50 0 –50 –100

ppm (TMS)
Figure 5.1.21 Solid state 13 C MAS–NMR spectra at 25.15 MHz, rotation frequency of 5 kHz, of
HSAl03 at different heat treatment temperatures (El Kortobi 1998).
(a) (b)
AlN3O AlO6 AlN3O AlO6
AlN4 AlN4
1600°C/N2 /1 h
AlNO3 AlNO3
AlN2O2
1400°C/N2 /1 h
Al04
1000°C/N2 /1 h
AlO5
As-formed
200 100 0 –100 –200 200 100 0 –100 –200

ppm (Al(H2O)6 3+) ppm (Al(H2O)63+)
Figure 5.1.22 Solid state 27 Al MAS–NMR spectrum at 130.32 MHz of (a) HSAl03 and
(b) HSAl05. MAS speed 12 kHz, 1 µs pulse, duty cycle 1 s, number of scans 600
(El Kortobi 1998).
60–70
YSiAlON glass
YSiAlO glass
AlN4105
Conventional
sintered sample
γ-AlON
300 200 100 0 –100 –200 –300

ppm (Al(H2O)63+)
Figure 5.1.23 Solid state 27 Al MAS–NMR spectrum at 130.32 MHz of different reference sam-
ples. MAS speed 12 kHz, 1 µs pulse, duty cycle 1s, number of scans 600. At
1600◦ C, N is bonded to aluminium; compare to Table 3.1.3.
So, the following remarks can be made:
• Al O and A N bonds are observed.

• N, initially bonded to Si as SiC3 N and SiC2 N2, is finally bonded to aluminium oxynitrides
AlOx N4−x .
In conclusion, the study of the local environment of 13 C,27 Al and 29 Si nuclei, enables us
to understand why, within the proportions of reactants used for the synthesis, such powders
did not produce a compound suitable for sintering (Chapter 7). The large amount of ‘free
carbon’ favours the nitridation of aluminium owing to the reaction:
Al2 O3 + (3 − 2x)Cfree + 2 Si/C/N4−x → 2 AlOx N4−x + (3 − 2x)CO + 2 SiC
This aluminium nitridation is responsible for the N loss in the Si environment.

A new series of preparation is done with hydrogen and ammonia added on. This is to
obtain the trapping of reactive free radical • CH3 . The 27 Al spectra show that the aluminium
nitridation is noticeably decreased (Figure 5.1.24). It presents an intense line at 60 ppm,
attributed to AlO4 , sharper than that observed in a glass or conventional sintered sample.
This line corresponds to a well-organised tetrahedral specie, only surrounded by oxygen
atoms. This should be an aluminium solid solution in β-SiAlON. Similarly, the 29 Si spectra
demonstrate the presence of silicon nitride (Figure 5.1.25). The comparison between samples
prepared without (HSAl07) and with (HSAl09) ammonia (Figure 5.1.26) shows clearly this
AlO6
AlO4
HSAlY17 1600°C/N2 /1 h
HSAl15 1600°C
AlN4
HSAl14 1600°C
HSAl12 1600°C
HSAl09 1600°C
HSAl12 As-formed
200 150 100 50 0 –50 –100

ppm (Al(H2O)63+)
Figure 5.1.24 Solid state 27 Al MAS–NMR spectrum at 130.32 MHz of HSAl12 to HSAlY17.
MAS speed 12 kHz, 1 µs pulse, duty cycle 1 s, number of scans 600.
phenomenon not only for Si but also for aluminium. This support the analysis done above on
the role of ‘free carbon’ effect which is clearly observable on 13 C spectra (Figure 5.1.26).
5.1.4.2 Influence of hot pressing

A comparison can be done between hot pressed and heat-treated nanopowders. As examples
HSAl09 29 Si and 27 Al NMR measurements are shown in Figures 5.1.27 and 5.1.28.
As the hot pressing had been done at a higher temperature than that of the nanopowder,
silicon carbide has almost disappeared. The structured peak, corresponds to different silicon
nitrides. As mentioned in Table 5.1.3, α- and β-Si3 N4 respectively present a doublet and
a singlet lines. Carduner et al. (1987) measured line-width between 1.5 and 2.5 ppm (full-
width at half-height) for well-crystallised material. Although the spectra are in accordance
with these measurements, the decomposition, in order to have the relative proportion of
β/(α + β), is questionable. The powder heat treated at 1600◦ C is able to contain some
amorphous part, which explains the higher intensity at −47 ppm. For the sintered powder,
the β proportion estimation by X-ray diffraction is 30% (Table 7.6), which is qualitatively in
accordance with the 29 Si NMR observation.
27 Al NMR spectra (Figure 5.1.27) show the Al O N broad line with the typical peaks or
x y z
shoulder characteristics of AlN4 , AlO4 and AlO6 environments. A significant difference is
observed with the relative proportions of the different species from one sample to another.
This has to be compared with Figure 5.1.22 where alumina is bonded to variable environments
containing N.
Si3N4
Free carbon
SiC
SiC
HSAl15
HSAl15
HSAl14 HSAl14
20 10 0 –10 –20 –30 –40 –50 –60 –70 –80 200 180 160 140 120 100 80 60 40 20 0 –20
ppm ppm
Figure 5.1.25 Solid state 29 Si and 13 C MAS–NMR spectra at 99.36 MHz and 125.76 MHz of HSAl14,
HSAl15 heat treated at 1600◦ C/N2 /1 h. 29 Si MAS speed 5 kHz, 5.2 µs pulse, duty cycle
500 s, number of scans 38, 4; 13 C MAS speed 5 kHz, 5 µs pulse, duty cycle 500 s, number
of scans 244.
1600°C/N2 /1 h 1600°C/N2 /1 h
Si3N4
HSAl09 D1 = 8000 s
AlO4
HSAl09
HSAl09 D1 = 500 s SiC
AlN4 AlO6
HSAl07
HSAl07 D1 = 500 s
0 –20 –40 –60 –80 250 200 150 100 50 0 –50 –100 –150 –200
ppm ppm
Figure 5.1.26 Solid state 29 Si and 27 Al MAS–NMR spectra at 99.36 MHz and 130.32 MHz of HSAl07,
HSAl09 heat treated at 1600◦ C/N2 /1 h. 29 Si MAS speed 5 kHz, 5.2 µs pulse, duty cycle
500, 8000 s, number of scans 38, 121 and 4; 27 Al MAS speed 14 kHz. 1.2 and 1 µs pulse,
duty cycle 1 s, number of scans 3600. An underestimation of the amount silicon nitride
is observed when a too short duty cycle is used (see Figure 5.15).
HSAl09 D1 = 8000 s
Powder heat treated Sintered powder

1600°C/N2 /1 h 1700°C/35 Mpa/20°mn/N2
Si3N4
-and -Si3N4
− and -Si3N4
Sintered powder
1700°C/35 MPa/20°mn/N2
α-Si3N4 +
amorphous phase
α-Si3N4 +
amorphous phase
Powder heat treated Si3N4

1600°C/N2 /1h
SiC
–40 –42 –44 –46 –48 –50 –52 –54 –40 –42 –44 –46 –48 –50 –52 –54
ppm ppm
20 10 0 –10 –20 –30 –40 –50 –60 –70 –80

ppm
Figure 5.1.27 Solid state 29 Si MAS–NMR spectra at 99.36 MHz. MAS speed 5 kHz, 5.5 µs, duty
cycle 8000 s, number of scans 10. Comparison between sintered and heat treated
HSAl09 nanopowder.
HSAl09 Sintered powder

1700°C/35 MPa/20°mn/N2
AlO4
AlN4 AlO6
Powder heat treated

1600°C/N2 /1 h
200 100 0 –100 –200

ppm
Figure 5.1.28 Solid state 27 Al MAS–NMR spectrum at 130.32 MHz. MAS speed 14 kHz, 1.2 µs
pulse, duty cycle 1 s, number of scans 600. Comparison between sintered and heat
treated HSAl09 nanopowder.
5.1.5 Conclusion
The analyses of different nanopowders, as-prepared and heat treated at different temperature,
show the efficiency of the solid-state NMR, particularly for not well-crystallised samples.
The possibility of obtaining cross informations from different nuclei, as 13 C,27 Al and 29 Si
and eventually proton via CP will improve the structural analysis. This enables us to modify
synthesis conditions as demonstrated on pre-alloyed Si/C/N/Al/Y nanopowders.
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5.2 Paramagnetic defect states in
silicon-based nanopowders
Abdelhadi Kassiba and Stéphane Charpentier
5.2.1 Introduction
Electron paramagnetic resonance (EPR) technique is a suitable tool in characterising the
paramagnetic defects in the Si/C/N nanopowders. The EPR experiments are carried out both
following the annealing temperature (realised separately up to 1800◦ C) and the specimen
temperature (in situ from 4 to 1000 K). Different EPR frequency bands (4–95 GHz) and
numerical EPR spectrum analyses are needed for an understanding of the defect nature
and properties. However, when mixed compositions and structures coexist as in (Si/C/N)
networks, the overlapping of the resonance lines leads to structureless EPR spectra. In such
materials, it is possible to assess the concentration of paramagnetic defects and their properties
such as being localised or delocalised. More quantitative analyses can be achieved on more
homogeneous materials (Si/C) where structured EPR spectra are obtained. Precise insights
on the paramagnetic defects are made and correlated with the material composition, structure
and physical properties.
The first set of investigations is devoted to SiC nanopowders synthesised by a laser pyroly-
sis of a gaseous mixture (SiH4 , C2 H2 ). The batches, referred as SiC242, SiC163 and SiC177,
differ by the residence time of the reactants in the laser beam and by the gaseous precur-
sor flux rate [SiH4 ]/[C2 H2 ]. The defect concentration is relatively high in all the samples
(NS ≈ 1020 spin g−1 ) and their nature seems correlated with the coexisting SiC polytypes.
A consistent numerical analysis of the EPR spectra, over several EPR frequencies, was
developed in order to identify the paramagnetic centres. Whatever the annealing stage and
the EPR frequency band, three paramagnetic defects with well-defined (g̃, Ã) tensors coexist
with contributions dependent on the annealing stages. Delocalised centres, thermally induced
by varying the sample temperature, are also evidenced in these nanopowders. They would
contribute to the significant electric conduction induced by annealing at Ta ≥ 1500◦ C.
The second deals with Si/C/N materials (referred as HMDS40–45) where the coexisting
structures (SiC, Si3 N4 ) and the free carbon (C) content give rise to a large unpaired spin
concentration brought by two types of paramagnetic centres. Their contributions depend on
the synthesis conditions and on the annealing stages. We have shown that the rate of C on
nitrogen (N) monitors the defect concentration and the annealing under N partial pressure
(nitriding process) favours the creation of unpaired spins in the Si3 N4 -rich powders.
The forthcoming EPR investigations focus on these two classes of silicon-based
nanomaterials.
140 Abdelhadi Kassiba and Stéphane Charpentier
5.2.2 Theoretical background
Paramagnetic defects in these Si/C/N covalent networks, consist mainly in unpaired electrons.
Under an external magnetic field B0 , each paramagnetic defect is described by an effective
spin Hamiltonian which reads:

Ĥspin = β S · g̃ · B0 + S · Ãk · Ik
k
where β represents the Bohr magneton, k refers to an interacting nucleus (nuclear spin Ik )
with hyperfine diagonal tensor Ãk in a reference frame (xk , yk , zk ) centred on the (k) nuclei.
The g̃ tensor, has a diagonal form in its principal (magnetic) frame (XY Z), with components
in the order of ge = 2.0023 value; that is, the free electron Landé factor. In crystalline
powders, the magnetic field B0 is defined by angular variables (θ0 , ϕ0 ) with respect to the
magnetic axes (X, Y, Z). The local resonance fields Bres ; that is, the EPR line position, is
expressed as follows:
geff βBres = hνEPR = ge βBe

geff = gZ2 cos2 θ0 + gX
2 sin2 θ cos2 ϕ + g 2 sin2 θ sin2 ϕ
0 0 Y 0 0
where h is the Planck’s constant and νEPR = 9.5 GHz in X-band EPR measurements. Be is
the resonance position of a free electron. The EPR signal of paramagnetic defects would have
the shape of a continuous absorption background with singularities at the positions
ge
Bres (i) = Be
gi i=X,Y,Z
However, in current EPR experiments the derivative of the absorption line is recorded. The
small departure !gi = gi − ge , in a given (i = X, Y, Z) direction, results from a weak
through the perturbation formula:
· S)
spin–orbit coupling (λ · L

|ψ0 |Li |ψn |2
!gi = 2λ − n
E(0) − E(n)
where |ψ0 and |ψn represent respectively the ground and the excited electronic states of
energies E(0) and E(n) . Quantitative analysis of the g̃ tensor components cannot be undertaken
safely in these heterogeneous Si/C/N media. However, the evolution of !g shifts with partic-
ular thermal treatments that can be used to characterise the changes of the local environments
around the involved paramagnetic centres.
With regard to the hyperfine tensor components Aki , they are determined experimentally
from the hyperfine line positions. A brief theoretical justification of these parameters can
be established in the following simple case. When the electronic spin density on the nuclei
exhibits an axial symmetry around the zk -axis, the components of the Ãk tensor are:
A(k)
= Aiso + 2Aaniso and A(k)
⊥ = Aiso − Aaniso
with
8 (k) 2 3 cos2 θ − 1
Aiso = πge βgn βn ϕ(s) (0) and Aaniso = ge gn ββn
3 r3 (k)
|ϕ(p)
Paramagnetic defect states in Si-based nanopowders 141
Aiso represents the contact interaction parameter and Aaniso accounts for a dipolar interaction.
(k) (k)
ϕ(s) (r ) and ϕ(p) (r ) represent the orbital wave function of (s) and (p) types related to the (k) ion.
(r, θ) are the radial and azimuthal coordinates of the unpaired electron in the reference frame
centred on the nucleus. gn and βn represent respectively the nuclear g-factor and the nuclear
Bohr magneton.
The hyperfine lines are observed when the unpaired electron interacts with a nuclear
spin in its near environment. For Si/C/N materials, the nuclear spin (I ) is brought by 13 C
(I = 21 , natural abundance (na) = 1.1%), by 29 Si (I = 21 , na = 4.7%) or by 14 N (I =
1, na = 99.6%). The intensity and the number of the hyperfine lines can be used to determine
the nature of the interacting nuclei.
Moreover, the integrated intensity of the EPR signal is proportional to the paramagnetic
defect concentration (Ns ) and to their magnetic susceptibility (χ). The temperature depen-
dence of χ informs on the localised or delocalised nature of the paramagnetic species. Indeed,
when χ varies with temperature following the Curie law (χ = C/T ), the unpaired electrons
are localised in the host material sites. In the case of delocalised unpaired electrons, χ is
temperature independent and ‘Pauli-like’ paramagnetism is expected.
5.2.3 Experimental details

EPR experiments are carried out on Brucker spectrometer with different frequency bands
[S (4 GHz), X (10 GHz), K (24 GHz), Q (34 GHz) and W (95 GHz)]. Investigations at dif-
ferent temperatures (4–300 K) are conducted on an Oxford cryostat. The high unpaired spin
concentration in the samples limits the microwave power below 2 mW and the modulation
field to 0.5 G. Saturation phenomena and EPR line shape distortions are thus avoided. The
absolute concentration (Ns ) of paramagnetic species is determined by a comparison with
CuSO4 · 5H2 O single crystal (≈3·1021 spin g−1 ). This absolute Ns estimate is within a range
of four times more or less than the real value.
5.2.4 Si/C powders

Three Si/C batches (SiC163, SiC177 and SiC212) synthesised from gaseous precursors
(Table 2.2) are investigated. Whatever the nanopowder series are, the EPR spectra have
common features and similar electrical properties. So, the forthcoming report is limited to
the SiC212 batch referred below as SiC212 1200–1800◦ C according to annealing temp-
erature T = 1200–1800◦ C. The structural modifications, the powder composition and grain
morphology are well known (Charpentier 1997, 1999 and 1999a).
Figure 5.2.1(a) shows the room temperature EPR spectra at X-band in the SiC212 1200◦ C
and 1650◦ C samples. High temperature measurements in the SiC212 1200◦ C sample up
to 600◦ C under air did not show any change on the EPR spectrum features except for the
obvious intensity decrease. The reversible behaviour of the EPR spectra, that is, before and
after the oxidation rules out any influence of the oxidation process or thermal removal of
the paramagnetic species. Furthermore, it seems that the defects are not connected with
hydrogen which may be released by annealing at high temperatures. The defects are intrinsic
to the material mainly caused by vacancies in the C or silicon (Si) sites of the coexisting C
arrangements and SiC polytypes.
Low temperature measurements are needed in order to assess the localised or delocalised
nature of the defects. In the SiC212 1200◦ C sample, the X-band EPR spectrum is drastically
(a)
SiC212 T = 300 K ------ 1200°C
1650°C
Intensity (a.u.)
3380 3400 3420 3440 3460

Magnetic field (G)
(b)
SiC212 T = 7 K ------ 1200°C
1650°C
Intensity (a.u.)
3380 3400 3420 3440 3460

Magnetic field (G)
(c) Experimental
Fit
Intensity (a.u.)
DI
DII
DIII
33,460 33,480 33,500 33,520 33,540

Magnetic field (G)
Figure 5.2.1 (a) Typical X-band EPR spectra in SiC212 nanomaterials annealed at 1200◦ C and
1650◦ C. (b) Evolution of the SiC212 1200◦ C EPR spectrum with the temperature.
(c) Experimental and calculated W-band EPR spectra in the SiC212 1200◦ C sample.
The contributions from the different paramagnetic centres are also shown (relative
contributions to the EPR spectrum DI: 21%; DII 49%; DIII 30%).
(a) 1.00
SiC212 1200°C
0.95
0.90
I ×T (a.u.)
0.85
0.80
0.75
0.70
0 50 100 150 200 250 300
Temperature (K)
(b) 10
SiC212 1600°C
8
I × T (a.u.)
2
0 50 100 150 200 250 300
Temperature (K)
Figure 5.2.2 Evolution with the temperature of the EPR signal integrated intensity weighted by
T : (a) in the SiC212 1200◦ C sample and (b) in the SiC212 1600◦ C sample.
broadened by lowering the temperature (Figure 5.2.1(b)). This is understood by the possible
defect motion which is frozen at low temperature. A double integration of the EPR signal
allows the determination of the overall intensity which is proportional to the spin susceptibil-
ity χ (Figure 5.2.2). A departure of χ(T ) from the Curie law above 150 K, also observed in
the SiC212 1650◦ C sample (Figure 5.2.2), indicates the presence of delocalised paramagnetic
species. Furthermore, the peak-shaped behaviour of the product χ (T ) × T around 30 K is
consistent with a localisation of the defects and correlated unpaired spins.
Consistent numerical analyses of the EPR spectra are hereafter conducted in order to
determine the paramagnetic defect features in these SiC nanopowders. The paramagnetic
centres are S = 1/2-defects assumed to interact with p equivalent nuclei (nuclear spin
I = 21 ). Under an applied magnetic field B0 , the spin Hamiltonian is given by:
Ĥspin = β B0 g̃ S + SÃI
Ã represents the hyperfine coupling tensor between the electronic and nuclear spins.
The magnetic dipole transition intensities and their resonance positions are determined
numerically from Ĥspin . The basis is limited to |mS , mI states with mS , mI = ± 21 due
to the multiplicity of electronic and nuclear spins (S = I = 21 ) in SiC materials. On the
other hand, the na (=0.047) of the 29 Si and (na = 0.01) for 13 C, giving rise to a hyperfine
coupling, impose the EPR spectrum of a given paramagnetic defect to be a superposition of
the two contributions. One is related to a spectrum with a hyperfine interaction, weighted
by the p × na, superimposed to a spectrum without the hyperfine interaction as for 28 Si and
12 C nuclei weighted by (100 − p × na).
A homemade program for EPR spectrum adjustments in crystalline powders was devel-
oped. All the magnetic field orientations (θ0 , ϕ0 ) are allowed (0 ≤ θ0 ≤ π/2, 0 ≤ ϕ0 ≤ π)
due to the random orientations of the crystalline sites in the SiC powders. The calculated
resonance positions are used with suitable line widths in order to adjust the experimental
EPR spectra.
Whatever the annealing temperature or the operating νEPR frequency bands are, the EPR
spectra are accounted by using three paramagnetic defects with the spectroscopic data (g̃, Ã)
summarised below at room temperature:
• DI centres: gxI = 2.0044(2); gyI = gzI = 2.0024(1). Ax = Ay = Az = 1110−4 cm−1

• DII centres: gxII = 2.0036(1); gyII = 2.0026(1); gzII = 2.0030(1); Ax = Ay = Az =
11·10−4 cm−1
• DIII centres: gxIII = gyIII = gzIII = 2.0031(2), no hyperfine coupling.
Furthermore, the EPR spectra in X-band are characterised by individual resonance line
widths less than 2 G for DI and DII species and close to 8 G for DIII centres. The relevance of
the EPR signal adjustments is shown for the SiC212/1200◦ C sample in the W-band, highly
sensitive to the anisotropy of the defect g̃-tensors (Figure 5.2.1(c)). The hyperfine constants
are determined from the S-band measurements where the hyperfine lines are well resolved.
5.2.5 Assignment of the paramagnetic species in

Si/C nanopowders
The components of g̃ and Ã tensors, the behaviour with the sample temperature of the EPR
spectrum line width and integrated intensity are the relevant information in identifying the
paramagnetic species.
The anisotropic DI centres are characterised by a g̃ tensor with an axial symmetry along
X-direction (!gx = gx − ge = 0.0021 and !gy = !gz = 0). Qualitatively, such shifts are
not consistent with the assignment of the unpaired spins to dangling bonds (DB). Indeed,
taking the DB along X-direction, a symmetry argument implies that the shifts would be
!gx = 0 and !gy , !gz = 0. This conclusion is supported by the hyperfine coupling con-
stant (A = 11·10−4 cm−1 ) which is proportional to the residence probability of the unpaired
electron on the Si or C nucleus. The theoretical hyperfine constants for free ions are
(Luchsinger et al. 1997):
−4
Afree
iso ( Si) ≈ −1510·10
29
cm−1 Afree
aniso ( Si) ≈ −37·10
29 −4
cm−1
and
−4
Afree
iso ( C) ≈ 1260·10
13
cm−1 and Afree
aniso ( C) ≈ 33·10
13 −4
cm−1
From the above EPR spectrum analysis, the experimental isotropic hyperfine tensor for DI
and DII centres gives Aiso = 11·10−4 cm−1 . Then, the probability of the unpaired electron
exp
being in the s orbital of Si or C is:

exp
Aiso
ηs2 (29 Si) = ≈ 0.006 ≈ ηs2 (13 C)
Afree
iso 29 Si
No more than 1% of the spin density is accounted for by the localisation on one Si or C
nucleus. So, the paramagnetic defects DI and DII in these SiC nanopowders can be associated
to unpaired electrons delocalised inside the cubic and hexagonal crystalline sites of the
coexisting SiC polytypes (3C SiC and α-SiC). The possible origin of these paramagnetic
centres consists in charged vacancies in the SiC sites favoured by the initial C in excess in
these materials (Kityk 2000). The elimination of the DI centres by annealing above 1500◦ C
(Figure 5.2.3) seems correlated with the structural modification α-SiC → 3C SiC.
The paramagnetic centre DIII is characterised by an isotropic g̃ tensor with components
close to 2.0031(2), that is, close to the average value ((gx + gy + gz )/3) of DI or DII
defects. The EPR spectrum contribution from DIII centres consists of a broad and unstructured
resonance line (Figure 5.2.1(c)). Such features can result from defects involved in amorphous
or disordered regions. However, by varying νEPR , we have not observed any line broadening
1e20
Unpaired spin concentration (spin g–1)
DI
DII
DIII
1e19
1e18
1e17
1200 1300 1400 1500 1600 1700
Annealing temperature
Figure 5.2.3 Variation with annealing of the absolute contributions from DI, DII and DIII para-
magnetic centres. The vanishing of the DI contribution in the SiC212 1600◦ C sample
coincides with the structural change α → β-SiC.
70
DI
DII
60
Relative contribution (%)
DIII
50
40
30
20
10
0 20 40 60 80
Frequency (GHz)
Figure 5.2.4 Evolution with the EPR frequency band of the relative contributions of the different
paramagnetic species. DI exhibits a stationary variation while that of DII and DIII
indicates a conversion between these centres.
(!Hpp ) connected with a spread of the g̃ III components which may be caused by a structural
disorder around DIII defects. Indeed, !Hpp X = 8 G in X-band changes only to !H W = 13 G
pp
in W-band. If a spread of g-values works, the ratio between the line widths will be close to
!Hpp
W
νEPR
W
≈ ≈ 10
!Hpp
X νEPR
X
Such a criterion rules out the location of DIII defects in disordered regions.
On the other hand, when νEPR increases, that is, for short EPR characteristic times, the rel-
ative proportion of DII and DIII exhibits an opposite evolution (Figure 5.2.4). Similar behav-
iours are observed by varying the SiC212 1200◦ C and 1650◦ C sample temperature. As shown
in Figure 5.2.5, the relative contributions to the EPR spectrum from the paramagnetic centres
exhibit an anti-coincidence behaviour between the anisotropic (DI, DII) and the isotropic DIII
centres (Figure 5.2.5). These results are understood by a conversion between the localised
paramagnetic DII species and the DIII ones. The departure from the Curie law of the overall
spin susceptibility would result from the DIII centres being delocalised in the material. This
can be partly responsible for the significant macroscopic electric conduction which appears
in these nanopowders annealed above 1500◦ C (Kassiba 2000) as discussed in Chapter 6.
To sum up, EPR gives relevant information on the paramagnetic defects in SiC mat-
erials. Consistent analyses can be achieved when the EPR signal exhibits resolved details
depending on the operating conditions (νEPR , T , etc.). A correlation can be made between
the delocalised paramagnetic centres and the electrical properties in SiC nanopowders as
reported in Chapter 6.
5.2.6 Silicon carbonitride (Si/C/N) powders

X-band EPR spectra in HMDS series (Table 2.5) exhibit similar features in all the as-formed
powders. The spectra are composed of a broad Gaussian line (peak to peak line width
(a) 80
DI + DII
70 DIII
60
50
40
30
20
0 50 100 150 200 250 300
Temperature (K)
(b) 80
DII
70 DIII
60
50
40
30
20
0 50 100 150 200 250 300
Temperature (K)
Figure 5.2.5 Variation with the sample temperature of the relative contributions of the anisotropic
(DI, DII) and the isotropic (DIII) centres. A conversion between defects is evidenced
in the (a) SiC212 1200◦ C sample and in the (b) SiC212 1600◦ C sample.
!Hpp = 9 G) superimposed on a narrow Lorentzian line (!Hpp = 4 G). The resonance

position at g = 2.0030(2), is reported in a wide class of (Si, C, N) based materials where
dangling bonds (DBs) are attached to C or N atoms (Warren 1990; Demichelis 1991; Suzuki
1995 and Xingguo Li 1996).
Measurements down to 50 K in the as-formed HMDS40 powder did not show any resolved
hyperfine lines and any effect due to a slowing down of the paramagnetic centre motions. The
integrated EPR spectrum intensity varies with the temperature according to I (T ) = C/T +Ip
(Figure 5.2.6). This is supported by a coexistence of localised defects giving rise to the (C/T )
contribution and delocalised ones with a temperature-independent contribution (Ip ). The latter
is connected with Pauli-like paramagnetism which can originate from delocalised electrons
on the free C arrangement present in a high concentration in the as-formed powders.
1200
1150 HMDS45
HMDS40
1100
1050
I × T (a.u.)
1000
950
900
850
800
100 120 140 160 180 200 220 240
Temperature (K)
Figure 5.2.6 Evolution v. the temperature of the product I ∗ T , I represents the EPR signal inte-
grated intensity. (•) HMDS45 annealed at 1500◦ C in 50% Ar and 50% N partial
pressure. () HMDS40 as-formed powder. The slope of the curves is connected with
the importance of delocalised paramagnetic species.
HMDS45
HMDS44
Intensity (a.u.)
HMDS43
HMDS42
HMDS41
HMDS40
3310 3320 3330 3340 3350 3360 3370

Magnetic field (G)
Figure 5.2.7 Typical X-band EPR spectra in HMDS40–45 annealed at 1500◦ C in 50% Ar and
50% N partial pressure. In HMDS45, Si3 N4 -rich material, a creation of a large
defect concentration is induced by the annealing and nitriding process.
With regard to the behaviour with annealing of the paramagnetic centres in the HMDS
series, 1500◦ C is a critical annealing temperature. Indeed, while the EPR broad Gaussian
component exhibits an enhanced intensity only in the HMDS43–45 batches (Figure 5.2.7),
the sharp Lorentzian line is dramatically reduced in all the batches after annealing at 1500◦ C
(a) 4.0×1020
Broad line
3.5×1020 Sharp line
As-formed
3.0×1020
Number (spin g–1)
2.5×1020
2.0×1020
1.5×1020
1.0×1020
5.0×1019
0.0
40 41 42 43 44 45
HMDS
(b) 4.0×1020
Broad line
3.5×1020 Sharp line
HTT 1500°C/N2/1 h
3.0×1020
Number (spin g–1)
2.5×1020
2.0×1020
1.5×1020
1.0×1020
5.0×1019
0.0
40 41 42 43 44 45
HMDS
Figure 5.2.8 Paramagnetic centre concentrations: (a) in the as-formed HMDS40–45 powders and
(b) in the annealed powders at 1500◦ C. Black and white bars refer respectively to
the contribution from two types of defects involved in these materials.
HMDS44 HMDS42
1700°C 1700°C
1600°C
1600°C
1550°C 1550°C
1500°C 1500°C
1400°C
1400°C
1000°C 1000°C
As-formed As-formed
3300 3320 3340 3360 3380 3300 3320 3340 3360 3380
Magnetic field (G) Magnetic field (G)
Figure 5.2.9 EPR spectra in HMDS42–44 v. the annealing temperature.
(Figure 5.2.8(b)). A careful analysis of the EPR spectra in HMDS44–45, reveals that the
spectra consist of a sharp line and shoulders which undergo a better resolution after annealing
above 1500◦ C (Figure 5.2.9, El Kortobi 1998). Since these materials are N rich (a low
C/N atomic ratio), the observed EPR spectrum shoulders would originate from hyperfine
interactions between unpaired spins and 14 N nuclei. A crude EPR signal deconvolution in
HMDS44, annealed at 1600◦ C, is made in terms of a sharp central line and three equivalent
and equidistant lines with a separation of about 5 G (Figure 5.2.10).
According to EPR investigations of DB centres in amorphous Si nitride (Warren et al.
1991), Si DBs interacting with the nearest N neighbours are characterised by g̃ tensor
(g = 2.0028, g⊥ = 2.0032) and by 4.6 G as a hyperfine coupling constant. Furthermore,
(SiN3 )− are the most thermally stable DBs in SiC Si3 N4 networks heat treated above 1673 K
under partial N pressure (Li et al. 1996). So, in HMDS44–45 annealed above 1500◦ C, DBs
such as (SiN3 )− would probably bring the large concentration of the paramagnetic cen-
tres. Their magnetic susceptibility follows the Curie law in the temperature range (4–100 K)
(Figure 5.2.9, El Kortobi 1998) and indicates that the involved DBs are localised. Structural
reorganisations and composition changes of the HMDS networks after annealing at 1500◦ C
were noticed by NMR investigations (Chapter 5.1). The behaviour of the paramagnetic
Experimental
Intensity (a.u.)
Fit
C1
N1
N2
N3
3310 3320 3330 3340 3350 3360 3370

Magnetic field (G)
Figure 5.2.10 Comparison between the experimental EPR spectrum in HMDS44 annealed at
1600◦ C and the calculated ones by a superposition of a central line (C1) and triplet
lines (N1, N2, N3). (C1) is associated to paramagnetic centres implying C atoms.
(N1, N2, N3) lines are induced by hyperfine coupling of unpaired electrons on Si
atoms with equivalent N nuclei in centres such as (SiN3 )− .
centres seems intimately connected with these modifications. What can be addressed below
is the correlation between the characteristic EPR lines, that is, the paramagnetic species and
the sample composition.
On one hand, the narrow Lorentzian EPR line can be partially caused by delocalised
paramagnetic defects as suggested by the temperature variation of the EPR integrated intensity
(Figure 5.2.11). Motional narrowing and exchange between localised and delocalised spins
by a thermal activation were reported in C black particles embedded in a polymer matrix
(Adriaanse et al. 1997). Similarly, in C rich material (HMDS40–41–42), the importance of
the narrow Lorentzian lines would result from DBs and delocalised unpaired electrons on C
atoms.
On the other hand, the broad EPR line is consistent with paramagnetic species implying N
atoms. Indeed, when the material composition is 90% of Si3 N4 type (HMDS44 annealed at
1600◦ C), the experimental spectrum is characterised by an isotropic g tensor (2.0030(2)) and
hyperfine triplet lines due to the coupling of S = 21 defects with I (14 N) nuclear spins. The
large spin concentration created by annealing under N partial pressure can be explained by the
large rate of structural defects induced by the nitriding process and structured reorganisation.
These features are similar to those reported in ultrafine SiC Si3 N4 composite powders (Li
et al. 1996). According to these authors, annealing above 1500◦ C gives rise to different
behaviours of the EPR signal depending on the atmosphere used. Under argon, the defect
concentration decreases with annealing while the opposite behaviour is obtained for annealing
under Ar and 50% N2 .
We have shown that more homogeneous materials are obtained by annealing at 1500◦ C
and above, HMDS40–41–42 (SiC-rich materials) and HMDS43–44–45 (N-rich materials).
25
HMDS44 1600°C
20
Integrated intensity (a.u.)
15
10
0
0.0 0.1 0.2 0.3
1/T (°K–1)
Figure 5.2.11 Integrated EPR line intensity in HMDS44 annealed at 1600◦ C v. the inverse sample
temperature (1/T ). The Curie law is revealed and indicates the localised nature of
the coexisting paramagnetic centres.
A large concentration of paramagnetic defects is created in HMDS45–44–43 consecutive to

the annealing and the nitriding process. The opposite behaviour is observed in HMDS40–
41–42 where a dominant SiC structure is realised as well as the removal of the free C
content.
References
Adriaanse, L. J., Brom, H. B., Michels, M. A. J. and Brokken-Zijp, J. C. M. (1997) Phys. Rev. B55, 15,
9383.
Charpentier, S., Kassiba, A., Emery, J. and Cauchetier, M. (1999) J. Phys.: Condens. Matter, 11, 4887.
Charpentier, S., Kassiba, A., Bulou, A., Monthioux, M. and Cauchetier, M. (1999a) EPJ: AP, 8, 111.
Charpentier, S., Kassiba, A., Fusil, S., Armand, X., Cauchetier, M., Fayet, J. C. and Emery, J. (1997)
Appl. Magn. Reson., 12, 255.
Demichelis, F., Pirri, C. F., Tresso, E., Rigato, V. and DellaMea, G. (1991) J. Non-Cryst. Solids, 128,
133.
El Kortobi, Youssef (1998) Thesis, Université P. M. Curie, Paris, France. http://corail.sudoc.abes.fr80
& Sudoc-Catalogue no 053764552.
Kassiba, A., Tabellout, M., Charpentier, S., Herlin, N. and Emery, J. R. (2000) Solid State Commun.,
115, 389.
Kityk, I., Kassiba, A., Tuesu, K., Charpentier, S., Ling, Y. and Makowska-Janusik, M. (2000) Mater.
Sci. Eng. B, 77(2), 147.
Li, X., Chiba, A., Nakata, Y., Nagai, H. and Suzuki, M. (1996) Mater. Sci. Eng., A219 95.
Luchsinger, R. H., Yu Zhou and Meier, P. F. (1997) Phys. Rev. B55, 1, 6927.
Suzuki, M., Hasegawa, Y., Aizawa, M., Nakat, Y. and Okutani, T. (1995) J. Am. Ceram. Soc. 8, 1.
Warren, W. L., Lenahan, P. M. and Curry, S. E. (1990) Phys. Rev. Lett. 65, 2, 207.
5.3 Electronic structure studied
by X-ray photoemission (XPS) and
soft-X-ray (SXS) spectroscopies
Adriana Gheorghiu de La Rocque, Georges Dufour,
François Ténégal and Christiane Sénémaud
5.3.1 Principles
X-ray Photoemission Spectroscopy (XPS) provides the electronic distributions of the core
levels and valence band (VB) of solids. As concerned the VB states, energy distribution
curves (EDCs) correspond to the total density of states (DOS) modulated by appropriate
photoionisation cross-sections:
I (E) ∝ σS NS (E) + σP NP (E) + · · ·
σx being the cross-section and Nx (E) the partial DOS of x state.

Thus, in some cases, information concerning particular symmetry states can be arbitrar-
ily enhanced. Due to the small escape depth of emitted photoelectrons (0.5–10 nm), the
experiments are sensitive to the superficial layer of the samples.
X-ray spectroscopy probes separately the valence and the conduction DOS. In X-ray
Emission (XES), radiative transitions between the VB and a localised inner vacancy are inves-
tigated. Initial core holes are created by means of either electron impact or X-ray photons,
possibly synchrotron beam. The radiative de-excitations of the inner vacancy are governed by
dipole selection rules which imply that only valence states with particular angular momentum
are involved. Moreover, as the core level concerns a specific atomic site, the DOS around each
atomic species of a compound are investigated separately. The information obtained by XES
concerns the volume. The spectral intensity of an X-ray emission is, in first approximation:

I (hν) ∝ ν 3 Mif2 (E)Nocc 1±1
(E)L(hν–E) dE
where Mif (E) is the matrix element which does not affect the main features of an XES
spectrum over a limited spectral range; Nocc
1±1 (E) is the DOS with (1±1) symmetry; L(hν–E)
is the Lorentzian distribution of the core hole.

By X-ray absorption spectroscopy, transitions between a core level and the conduction
band states are analysed. In the spectral region close to an absorption edge: X-ray Absorption
Near Edge Structure (XANES), the photoabsorption coefficient µ is in first approximation
proportional to the density of the empty states Nunocc above the Fermi level (EF ), with
particular angular momentum around a specific site:

µ(hν) ∝ ν Mif2 (E)Nunocc 1±1
(E)L(hν–E) dE
By XANES either the volume or only the surface of the sample is concerned according to
the technique chosen (Total Electron Yield (TEY), transmission or Fluorescence Yield (FY)).
154 Adriana Gheorghiu et al.
For both XES and XANES spectra, the contribution of the Lorentzian profile of the core
hole induces a broadening of the spectra, which limits the resolution of the method and
implies to study only transitions involving a sufficiently sharp core level.
For a valuable comparison of XPS and SXS data, it is particularly important to set both
XPS–XES (or XPS–XANES) experimental curves in a common energy scale referring to the
Fermi level. This is directly obtained in XPS as EDCs are referred to EF . In the case of XES
and XANES spectra, the spectral curves are obtained in a transition energy scale (EVB –EX )
or (ECB –EX ) and the energy position of the Fermi level can be obtained by determining the
core level binding energy (BE) EX , provided that relaxation effects are neglected.
5.3.2 Experiments
5.3.2.1 X-ray Photoemission Spectroscopy (XPS)

XPS spectra were obtained by using Mg Kα incident radiation (hν = 1253.6 eV). An elec-
trostatic hemispherical analyser was used in the fixed analyser transmission mode (FAT)
with a pass energy equal to 40 eV. Under these conditions, the full-width at half-maximum
(FWHM) of the Ag 3d5/2 line is 1 eV. The core level spectra were scanned with a 0.1 eV step
and the XPS VB with a 0.2 eV step. In some cases, an energy shift of the photoelectron peak
due to a charging effect was observed (Shirley 1972; Jentoft et al. 1999). In order to take this
effect into account, we calibrate the BE scale with reference to the C 1s line observed from
hydrocarbonated species, which are always present at the surface of the sample. The C 1s
line is set at 285.0 eV. In our case, the corrections are more complicated because carbon (C)
is also present in the studied materials. The energy scale was then adjusted so that O 1s peak,
which corresponds essentially to silicon dioxide, coincides approximately for all spectra. In
this procedure, it is assumed that oxygen atoms are essentially present in silicon dioxide
bonding. Let us note that in our experimental work the oxygen proportion measured by XPS
is only a few percent in as-formed (AF) samples and slightly higher, 10–15%, in annealed
samples, due to surface contamination (Gheorghiu et al. 1997).
The interpretation of the core level lines is based on a decomposition of each spectral
distribution into Voigt functions; the spectra are superposed to a background due to the
inelastic electron scattering. For a mathematical treatment of core level spectra, a subtraction
of this background is performed by assuming that its variation is linear or polynomial. No
correction of background was made in the case of the VB spectra.
5.3.2.2 Soft X-ray Spectroscopies (XES–XANES)

In the case of Si/C/N powders, we measured the Si Kβ (3p → 1s) emission line which probes
the Si 3p VB states and Si K absorption line (1s → np) which provides the Si p conduction
band (CB) states.
The X-ray emission spectra Si Kβ were analysed with a bent-crystal vacuum spectro-
meter (Sénémaud et al. 1989) using as a monochromator either a quartz 101̄0 crystal (2d =
850.766 pm) in the first order of reflection, or a gypsum crystal (020) (2d = 1519.84 pm) in
the second order of reflection bent to a radius of 250 mm. The detector was a proportional
counter (500 mb Ar/CH4 90/10) with an entrance slit fixed to 50 µm. The spectra were
scanned with a 0.2 eV wide step. The total instrumental broadening, mainly due to the
monochromator itself, is estimated to be about 0.3 eV (Sénémaud and Ardelean 1990). The
emissive target was prepared by depositing a thin layer of laser synthetised powder onto
Electronic structure studied by XPS and SXS 155
a copper anode. The spectra were excited by electron bombardment with exciting conditions
5 kV, 5 mA. The thickness sampled is determined by the penetration of the incident electron
beam. In our experimental conditions, we estimate the thickness of the emitting layer to about
0.5 µm. Thus in this case the whole volume of the powder particles is concerned.
The near edge photoabsorption (XANES) measurements were carried out at Laboratoire
pour l’Utilisation du Rayonnement Electromagnétique – Orsay (LURE). The Super-Aco
storage ring was operating at 800 MeV, and the average current was approximately 200 mA.
A two-crystal monochromator equipped with InSb (111) crystals (2d = 748.06 pm) was
used. The photoabsorption spectra corresponding to the Si K-edge were obtained in the
transmission geometry and scanned with a 0.2 eV-wide step. The detector was a proportional
counter filled with a 300 mb Ar/CH4 (90/10) mixture. The absorbing screens were obtained
by depositing powders onto 5-µm-thick millipore polycarbonate membranes. The spectra
of the incident beam were obtained through a membrane without powder. The instrumental
resolution is evaluated to be approximately 0.4 eV (Bouisset et al. 1991).
5.3.3 Study by XPS–SXS of Si, Si/C, Si/N and Si/C/N laser

synthetised nanopowders produced from
gaseous precursors
The samples were prepared by laser pyrolysis of appropriate precursors in the same conditions
as reported previously (Gheorghiu et al. 1992), summarised in Table 2.2.
5.3.3.1 Core levels

The Si 2p spectrum of Si50 powder (Figure 5.3.1) exhibits a strong asymmetric line accompa-
nied on the high-BE side by a low intensity component due to SiO2 . This oxide contribution
has approximately the same relative intensity as that of a native oxide layer at the surface
of a monocrystalline Si wafer (Himpsel et al. 1988). The main peak, located at 99.3 eV,
Si 2p1/2
SiO2
Si 2p1/2
Si50
Si 2p
Intensity (au)
106 104 102 100 98

Binding energy (eV)
Figure 5.3.1 Si 2p core levels for Si50 sample.

(a) SiO2 SiC (b) SiO2 SiC
SiC151 SiC152a
Si 2p Si 2p
Intensity (au)
Intensity (au)
106 104 102 100 98 106 104 102 100 98
Binding energy (eV) Binding energy (eV)
Figure 5.3.2 Si 2p core levels for (a) SiC151 and (b) SiC152a samples.
corresponds to the 2p1/2,3/2 doublet from Si Si bonds and is well fitted by a sum of two
Voigt lines separated by 0.6 eV, with an intensity ratio 1/2 which accounts for the spin–orbit
splitting. The total width at half-maximum of the line is 1.2 eV, close to the value obtained with
a single-crystal wafer and in the same experimental conditions: 1.1 eV (Rochet et al. 1986).
The remaining intensity in between Si and SiO2 lines reveals probably the existence of an
intermediate oxide SiOX (Hollinger et al. 1988). A tailing could result from inhomogeneities
in the sample. For pure Si powders, the XPS results show that the sample is a well-organised
silicon (Si), which is in agreement with X-ray diffraction (XRD) results (Table 2.2).
In Si/C samples, SiC151 and SiC152a (Figures 5.3.2(a) and (b), the Si 2p spectra have
identical shapes: quasi-symmetric with a high BE tail. The decomposition achieved on the
basis of two components: one at the energy position of the maximum intensity, the second at
higher BE, corresponding to SiO2 (102.9 ± 0.1 eV), shows that the energy of the main line is
located at 101.3 and 101.2 eV for SiC151 and SiC152a, respectively. The Si 2p line is slightly
sharper in SiC151 than in SiC152a. Finally, a low proportion of SiO2 is present at the surface
for both samples. It is noteworthy that the intensity is negligible at the BE corresponding to
Si Si bonds. Thus in Si/C, heteropolar Si C bonds are present, without any segregation of
Si atoms. In SiC151, the local order is slightly better than in SiC152a and commercial β-SiC
(Driss-Khodja et al. 1992) (fewer bond angle and bond length fluctuations). Consequently,
XRD measurements led to the same conclusions (Cauchetier et al. 1988).
The C 1s BE from powders is close to the value that characterised the C Si bonds in β-SiC
(Driss-Khodja et al. 1992). The C 1s line is shifted towards high BE in powder samples as
compared to β-SiC. As the energy distance E(Si 2p) − E(C 1s) varies, this effect cannot be
interpreted in terms of a Fermi-level shift but rather by the presence of H atoms in the network,
in agreement with previous measurements (Fang and Ley 1989). This is in agreement with
the identification of Si Hn groups by infrared (IR) spectroscopy in samples prepared under
the same conditions (Cauchetier et al. 1990).
For Si/C powder materials, the XPS measurements reveal that only Si C bonds are present
in Si C4 and C Si4 groups and that there is no segregation of Si atoms in the network.
They reveal, moreover, that the samples contain a very low proportion of oxide. The atomic
(a) Si3N4 (b) SiO2 Si3N4

SiO2 Si
SiN7 α-Si3N4
Si 2p
Si 2p
Intensity (au)
Intensity (au)
106 104 102 100 98 106 104 102 100 98

Figure 5.3.3 Si 2p core levels for (a) SiN7 sample and (b) α-Si3 N4 powder.
structure and the long-range order of the material depend on the preparation conditions. Thus,
an increase of the laser power used for the powder synthesis from 220 to 600 W (Table 2.2)
induces an increase of the flame temperature and consequently of the local order; the Si 2p
becomes slightly sharper.
The Si 2p peaks observed from the SiN7 sample (Figure 5.3.3(a)) compared to commercial
α-Si3 N4 (Figure 5.3.3(b)) show that, in both cases, the spectrum consists of a wide, asymmet-
ric line, the high-binding energy tail resulting from the presence of SiO2 . The decomposition
of the α-Si3 N4 spectrum in two components presented in Figure 5.3.3(b) shows a main Si
2p component, 1.7 eV wide at 101.8 eV BE, accompanied by a contribution from SiO2 at
103.1 eV having an intensity of about 11%. In this case the spin–orbit splitting of Si 2p is not
observed due to the increase of Si 2p FWHM as compared to pure Si. The Si 2p spectrum from
SiN7 sample has a similar shape but is significantly broader than the commercial α-Si3 N4
one. The peak decomposition gives a main peak, 2.0 eV wide, located at 101.7 eV, and a SiO2
contribution with a relative intensity of about 12% (Figure 5.3.3(a)). Moreover, a low BE
feature is present at 99.0 eV which we interpret as due to the existence of a low proportion
(about 2%) of Si Si clusters. Thus, in the SiN7 powder, most Si atoms are bonded to N atoms
in Si N4 units which is characteristic of the silicon nitride network. The broadening of the
corresponding Si 2p component as compared to the α-Si3 N4 one (2.0 instead of 1.7 eV) can
be attributed to the existence of structural disorder in the network, introduced by fluctuations
in the bond lengths and/or bond angles as compared to their values in the crystalline phase.
The presence of H atoms in the material is possible and could contribute to such a disorder.
The N 1s line is observed at approximately the same BE value (397.7 eV) in both the
powders and the stoichiometric α-Si3 N4 samples indicating the N Si3 configuration, but
the width is significantly broader in the powder than in crystalline α-Si3 N4 (1.7 eV). This
result confirms the existence of a chemical order in the powder sample, the broadening of
the line being attributed to the local topological disorder, in agreement with the above results
concerning the Si 2p line. The existence of N H bonds can contribute to a broadening of the
N 1s line as previously observed in Si NX : H samples prepared by photo-chemical-vapour
deposition (PCVD) (Driss-Khodja et al. 1989).
Si3N4 Si3N4
(a) SiO2
(b) SiC
SiC Si SiO2 Si
SiCN12 SiCN27
Si 2p Si 2p
Intensity (au)
Intensity (au)
106 104 102 100 98 106 104 102 100 98

Figure 5.3.4 Si 2p core levels for (a) SiCN12 and (b) SiCN27 samples.
We conclude that the SiN7 powder contains mainly Si N4 groups, N atoms being sur-
rounded by three Si atoms. The local bonding is similar to that of silicon nitride α-Si3 N4 .
A few Si atoms are involved in Si Si bonds; the proportion of oxide is very low (12% in
the powder). The presence of Si Si bonds in the network, as well as the possible existence
of hydrogen in the sample, can contribute to the introduction of short-range disorder around
both Si and N atoms.
The Si 2p spectra from the two Si/C/N samples, SiCN12 and SiCN27 (Figures 5.3.4(a)
and (b)) consist of a rather broad asymmetric line with different FWHM: 2.2 and 1.7 eV,
respectively. According to the conditions of decomposition, we infer that, besides the small
SiO2 contribution around 103.3 eV, the SiCN12 spectrum results from the contribution of two
main lines, while SiCN27 spectrum corresponds to a single Voigt line. In the case of SiCN12
spectrum, the two Voigt curves, 1.5 and 1.7 eV wide, are located at 101.1 and 101.9 eV,
respectively; the intensity ratio of the components is about 0.7. These two components are
close to Si 2p lines from β-SiC and α-Si3 N4 , respectively. An additional line, lower in
intensity, at 99.6 eV can be attributed to Si Si. In contrast, the main peak of SiCN27 is
1.7 eV wide and is located at 101.6 eV. It is accompanied by two smaller components at
99.4 and 103.3 eV that we attribute to Si Si bonds and SiO2 , respectively. This result clearly
shows that the local bonding is quite different in the two Si/C/N samples under consideration.
In one case, SiCN27, for which C/N = 0.22, most Si atoms have the same local structure
SiCx N4−x , Si being mainly bonded to N atoms. The value of the FWHM is the same as in
the crystalline α-Si3 N4 and reveals that the network is well ordered. It is noteworthy that
the Si 2p line from this sample is sharper than that from the Si/N7 sample. Consequently,
the modifications of the gas mixture (addition of CH3 NH2 ), which leads to an increase
of temperature, contributes to give a better ordered material. In the SiCN12 sample, with
C/N = 0.93, our results show clearly that both Si N4 and Si C4 groups are present, with
approximately the same proportion.
The C 1s BE corresponding to C Si bonds is practically the same in both samples.
However, the FWHM increases significantly in mixed compounds as compared to Si/C,
indicating a loss of local order around C atoms induced by the presence of N atoms.
The N 1s BE value remains the same for all samples containing N atoms, revealing a pre-
ferential N Si3 arrangement in Si/C/N samples. A decrease of its FWHM is observed for
mixed compounds as compared to Si/N, which confirms the increase of local order induced
by C atoms.
In the case of composite Si/C/N, our results show that different materials can be prepared
depending on the preparation conditions, especially the initial gases concentration. The pow-
ders are formed either by a mixture of Si C4 and Si N4 units or by a single type of local
Si environment. For a C/N ratio of about 1 in the initial gas mixture, the existence of two
types of local Si bonding, Si C4 and Si N4 , with a proportion of about 0.7–1 is revealed
by our XPS measurements; a few Si atoms are involved in Si Si bonds. For an initial C/N
ratio in the gas mixture equal to 0.22, the XPS spectra reveal that most Si atoms are involved
in a single type of chemical environment; the Si 2p core level has a BE close to the value
corresponding to α-Si3 N4 ; the Si C bonds are also present, as revealed by the C 1s line.
Consequently our results suggest the existence of local C Si N3 arrangement around Si
atoms.
5.3.3.2 XPS valence band results

The VB spectra of powders Si/C (SiC151), Si/N (SiN7) and Si/C/N (SiCN12, SiCN27)
exhibit a broadband (Figure 5.3.5) noted A extending between 0 and about 13 eV, followed
by peaks B and C, at about 15 and 19 eV, respectively, which have different relative intensities
in the considered samples. The distances from these features to EF are given in Table 5.3.1.
The SiC151 VB spectrum is almost identical to a β-SiC spectrum, as already reported
(Driss-Khodja et al. 1992). Part A exhibits two peaks labelled A2 and A4 located at 5.7 and
9.5 eV, respectively. From a comparison with theoretical densities of states (Robertson 1992)
these peaks are attributed to C 2p states mixed with Si 3p and Si 3s, respectively; a wide
minimum separates A4 from peak B, located at 14.4 eV BE, which corresponds to C 2s states
mixed to Si 3p and Si 3s.
The SiN7 spectrum is very similar to the silicon nitride (Johnson Mattey, 99.99% powder)
XPS VB spectrum previously reported (Sénémaud et al. 1993). The upper part A exhibits
C B A
A⬙
A⬘ SiCN27
Intensity (au)
A5 SiCN12
A3
A4 A1
A2 SiN7
SiC151
20 15 10 5 EF
Binding energy (eV)
Figure 5.3.5 XPS VB spectra of laser-synthesised SiC151, SiN7, SiCN12 and SiCN27 samples.
Table 5.3.1 Energy positions of the XPS VB features (eV) for laser synthe-
sised samples
A1 A2 A A3 A4 A A5 B C
SiC151 5.7 9.5 14.4

SiN7 3.3 7.5 11.4 18.9
SiCN12 7.0 10.8 14.9 19.3
SiCN27 3.9 7.6 11.4 19.0
three structures labelled A1 , A3 and A5 located at 3.3, 7.5 and 11.4 eV, respectively. From
the previous study of Si3 N4 XPS and SXS spectra (Sénémaud et al. 1993), in agreement with
theoretical DOS (Robertson 1992), peak A1 is unambiguously attributed to N 2pπ lone pair,
peaks A3 , A5 are associated respectively to N 2p–Si 3p states and N 2p–Si 3s states. Peak C,
well separated from the A band, is due to N 2s states mixed with Si 3s–Si 3p states.
The VB spectra from SiCN12 and SiCN27 are quite different in shape (Driss-Khodja
1993). The spectrum from sample (SiCN12) with C/N = 0.93 exhibits only two structures
A and A at 7.0 and 10.8 eV. The energy position of A is intermediate between that of
A2 from SiC151 and A3 from SiN7. Similarly, A is located between A4 (SiC151) and A5
(SiN7) (Table 5.3.1). The low BE edge of the spectrum is more contrasted than in the SiN7
spectrum; however, it is less abrupt than in SiC151. It is noteworthy that both peaks B and C
are observed in this spectrum at 14.9 and 19.3 eV. Their energy positions correspond to those
of peaks B from SiC151 and C from SiN7 suggesting that both C 2s and N 2s mixed to Si
3s, 3p states are present.
For SiN27, which corresponds to C/N = 0.22, the spectrum is rather similar to the SiN7
one. The upper band A exhibits three structures (see Table 5.3.1); it is followed by a sharp peak
C located at 19.0 eV, well separated from band A; consequently, the VB states correspond
essentially to those of Si N bonds found in silicon nitride. Let us note that the minimum
between A and C is not so marked as in SiN7 spectrum and that a shoulder is clearly observed
around 15 eV.
5.3.3.3 SXS-XPS results

In Figures 5.3.6–5.3.9, we have plotted, in the same BE scale with EF as origin, the XES
Si Kβ, the XPS VB and the XANES spectra for powders SiC151, SiN7 and SiCN12 and
SiCN27. Let us recall that the XES Si Kβ curves give the Si 3p VB states distribution and
the XANES curves the unoccupied Si p states distribution.
Si Kβ from SiC151 powder (Figure 5.3.6) is very similar to silicon carbide Si Kβ spectrum
observed previously (Driss-Khodja et al. 1992; Zahorowski et al. 1989). The maximum
intensity located at 5.3 eV from EF corresponds to peak A2 of XPS VB spectrum, the decrease
of intensity towards EF is rather abrupt; its inflection point coincides with that of the low BE
edge of XPS VB spectrum. The high BE edge is less steep and shows a shoulder at about
half-maximum, that is at an energy corresponding approximately to the energy of peak A4 .
Finally a small intensity peak, well resolved from the main band, is observed at 15 eV from
EF , showing that Si 3p states are present deeper in the VB. This small peak coincides with
peak B of XPS VB spectrum. The XANES spectrum of SiC151 presents a two-step edge
extending from about 0 to 5.3 eV, where a sharp maximum occurs. A secondary maximum
occurs at 11.5–12 eV and a strong peak at 19 eV from EF .
SiC151
A4
XPS B
A2
Intensity (au)
XAS
XES
30 20 10 EF
Binding energy (eV)
Figure 5.3.6 XPS VB, XES and XAS spectra from SiC151 sample adjusted in a common energy
scale with EF as origin.
C SiN7
XPS A5
A3
Intensity (au)
A1
XAS
XES
30 20 10 EF
Binding energy (eV)
Figure 5.3.7 XPS VB, XES and XAS spectra from SiN7 sample adjusted in a common energy
Si Kβ from SiN7 (Figure 5.3.7) is a quasi-symetric band; its overall shape is close to that
of silicon nitride Kβ emission band previously reported (Sénémaud et al. 1993); however, its
FWHM is wider, 6.5 instead of 5.5 eV. The energy position of the maximum, 8.4 eV from EF
gives the mean BE of the Si 3p states; it is the same as in the nitride. This maximum coincides
approximately with peak A3 of XPS VB spectrum. Consequently, this result confirms that
the peak A1 of XPS VB spectrum corresponds to pure N states. We note that the decrease of
intensity on the low BE tail of Si Kβ is not steep but exhibits some tailing; we attribute this
effect to the presence of a few Si Si bonds in this sample. Let us recall that these like-atom
bonds had already been revealed by the study of Si 2p core level from the same sample
(Figure 5.3.3(a)). The low intensity peak located at 19.5 eV is in coincidence with peak C of
XPS VB spectrum and reflects the presence of Si 3p states mixed to N 2s ones in this part
of the VB. The XANES spectrum of SiN7 consists of a steep edge whose inflection point is
located 1 eV above EF , followed by a maximum at 3.8 eV from EF . A second maximum is
observed around 22 eV from EF .
In SiCN12 and SiCN27, the Si Kβ emission band is a quasi-symmetric band with FWHM
7.7 and 6.5 eV, respectively (Figures 5.3.8 and 5.3.9) (Driss-Khodja 1993). In SiCN12 sample,
the main peak is accompanied by a shoulder at 8.5 eV, in coincidence with SiN7 Kβ maximum;
a faint feature around 5 eV could be a signature of SiC151 Si Kβ maximum. The distance
from EF of the low BE edge, measured at half amplitude, is about the same as in SiC151. The
Si Kβ spectrum is broader than in binary compounds and can be considered approximately as
a sum of both the SiC151 and the SiN7 spectral distributions. It is noteworthy that, in the high
BE range, a small feature is observed at the energy positions of B. The photoabsorption edge
of SiCN12 has a continuous slope, slightly less abrupt than in SiN7 spectrum. Beyond the first
maximum, two peaks are observed at about 3.8 and 5.3 eV from EF , that is, at approximately
SiCN12
C A4
XPS B A2
Intensity (au)
XAS
XES
30 20 10 EF
Binding energy (eV)
Figure 5.3.8 XPS VB, XES and XAS spectra from SiCN12 sample adjusted in a common energy
SiCN27
B
A5
XPS A3
A1
Intensity (au)
XAS
XES
30 20 10 EF
Binding energy (eV)
Figure 5.3.9 XPS VB, XES and XAS spectra from SiCN27 sample adjusted in a common energy
the same position as in SiC151 and SiN7 photoabsorption curves, respectively. Beyond this
energy range, a slight feature is noted at 11.5 eV from EF and a strong maximum at 19.6 eV
from EF .
In SiCN27, the Si Kβ spectrum is narrower than in SiCN12; its shape is rather similar
to SiN7 Si Kβ. The maximum is approximately in coincidence with peak A3 of the XPS
VB curve, while no feature appears at the energy position of A1 . The photoabsorption curve
exhibits a strong maximum at 3.6 eV from EF , that is, close to that observed in SiN7 photo-
absorption, giving the appearance of a ‘white line’. A shoulder is observed at 7 eV and a wide
maximum at 21 eV from EF .
5.3.3.4 Discussion
Complementary information on the valence and conduction states of solids can be obtained
by using both SXS and XPS spectroscopies. XES and XANES spectra correspond in first
approximation to the convolution of the Si p occupied or unoccupied state distributions
by the Lorentzian distribution of the Si 1s core-level distribution, which is about 0.5 eV
wide (Sénémaud et al. 1993). The XPS spectra correspond to the total valence distribution
modulated by the photoionisation cross-sections which, in our case, emphasises s states as
compared to p states.
For binary systems Si/C and Si/N, the experimental XPS and XES–XAS spectral curves
are qualitatively well reproduced by the DOS calculations performed by J. Robertson in
the tight-binding formalism for crystalline β-SiC (Robertson 1992) and α-Si3 N4 crystalline
phases (Robertson 1991). Differences in relative intensities of the peaks are due to differences
in photoionisation cross-sections (Driss-Khodja et al. 1996). These conclusions are in total
agreement with those obtained for the same sample from the XPS core levels and EXAFS
studies (Gheorghiu et al. 1992).
In Si/C, our results confirm unambiguously the existence in the powder material of chem-
ically ordered sp3 bonded network with Si C heteropolar bonds. The Si 3p states whose
position corresponds to Si Kβ emission are mainly located at the top of the VB, in coinci-
dence with peak A2 of XPS. The sharp XPS peak A4 at 9.5 eV, at the same energy as a low
feature of Si Kβ, can be associated to sp states. From Robertson’s calculations, we have
deduced that this peak is due to mixed Si 3s and C 2p states; from our results Si 3p states
are also involved in this energy range. A sharp minimum, corresponding to the ionicity gap,
separates the maximum A4 from peak B; this energy gap is characteristic of Si C bonds in
a crystalline network. The minimum is expected to be partially filled in the case of amorphous
SiC, as predicted from a theoretical study of α-SiC density of states performed by Finocchi
et al. (1993). Peak B is largely C 2s in character, with a small, but non-negligible Si 3p
contribution as clearly revealed by our XES data, in excellent agreement with theoretical
predictions. As concerned the conduction band, an overall agreement is found between the
photoabsorption curve and the theoretical DOS, for which the absorption edge is followed
by two peaks attributed to antibonding Si 3p–C 2s and Si 3p–C 2p states distant by about
3 eV ; the non-resolution of these features in the experimental curve is probably due to the
core-level broadening. Beyond the first peak, the experimental photoabsorption curve shows
well-resolved peaks that reveal the existence of a well-organised network. This is in agree-
ment with the EXAFS results (Gheorghiu et al. 1992) we have obtained for this powder,
which clearly revealed the existence of Si C4 groups.
The influence of hydrogen incorporation in SiC matrix has been recently studied in a the-
oretical simulation by Finocchi and Gattia (1994). For a-SiC : H alloys at stoichiometric
composition, containing 20% hydrogen, these authors predict that hydrogen atoms are bonded
to both C and Si atoms and that the presence of H favours the formation of a tetrahedral net-
work and thus enhances the chemical order in the material. This is well supported by our
results.
In Si/N powder, the VB distribution observed experimentally is very close to the Si3 N4
one. Our results confirm that the top of the VB corresponds to an N 2pπ lone pair orbital, in
agreement with theoretical results (Robertson 1991). The lone pair orbital is characteristic of
the planar configuration of N atoms surrounded by three Si atoms. This feature is followed
by mixed Si 3p–N 2p and Si 3s–N 2p states; N 2s states, mixed to Si 3s–3p states appear as
a well-resolved peak. A broadening of the Si 3p distribution, when going from Si3 N4 (Séné-
maud et al. 1993) to Si/N powders is noted. Two effects can contribute to this broadening.
The first effect is due to a loss of long-range order as compared to well-crystallised silicon
nitride; a topological disorder attributed to fluctuation of bond lengths and bond angles has
been evidenced in this material from a previous study (Gheorghiu et al. 1992). Let us note
that this effect does not modify the overall shape of the VB distribution, which is essentially
determined by the short-range order (Kärcher et al. 1984). The second effect is the presence
of like-atoms bonds Si Si in a low, but not negligible proportion, as already revealed by the
Si 2p core level study. Thus Si/N powders are characterised by both structural and chemical
disorder. The presence of hydrogen in the network is possible, according to the preparation
conditions. In a previous study of a-SiNX : H alloys, we had shown that hydrogen atoms are
preferentially bonded to N atoms (Driss-Khodja et al. 1989). In this case, the Si states distrib-
ution should not be significantly modified. From the results obtained by Ley for hydrogenated
a-Si NX samples (Kärcher et al. 1984), hydrogen incorporation involves a recession of the
VB maximum, which remains probably small for the low H concentration corresponding to
our samples. Moreover, due to the low value of H 1s cross-section under our experimental
conditions (hν = 1253 6 eV), the effect of hydrogen on XPS VB spectrum remains probably
quite negligible.
The first photoabsorption peak gives the distribution of the unoccupied Si p states;
its shape corresponds to a disordered network and supports the previous EXAFS results
on the same samples (Gheorghiu et al. 1992). In this energy range, the DOS calcula-
tions for silicon nitride (Robertson 1991), which covers an energy range of about 12 eV
from EF , predicts the existence of a broad maximum between 5 and 10 eV from EF ; the
shift between the experimental and the calculated data that we have already mentioned
(Gheorghiu et al. 1992) can be explained by the experimental gap value introduced in the
calculation.
It is interesting to note that the presence of hydrogen in the network favours a higher chem-
ical and structural order in the case of Si/C systems; on the contrary, it involves a tendency for
more disorder in the case of Si/N powder; in both cases the laser power used for the synthesis
is 600 W (Table 2.2).
In Si/C/N powders, the valence and conduction band distributions are quite different
according to the composition. For C/N value equal to 0.93 (SiCN12), our results indicate
clearly that Si atoms are involved in both carbide and nitride configurations. This is evidenced
from XPS VB spectrum which reveals that both C 2s and N 2s states, mixed to Si sp states,
are present; on the XES Si Kβ spectrum, we observe a small peak at the energy position
of B (Si 3p–C 2s states). Moreover, these results are well supported by the photoabsorption
spectrum of SiCN12, which shows two features close to the edge in coincidence with the first
absorption maximum of SiN7 and SiC151, respectively, next features being close to those
observed in SiC151 spectrum.
In SiCN27 with C/N = 0.22, the spectral distributions are rather close to SiN7 ones, but
slight differences are noted which clearly indicate that the network is not identical to silicon
nitride: (i) the XES Si Kβ spectrum (Figure 5.3.9) shows that the Si 3p maximum is slightly
shifted towards low BE as compared to SiN7 Si 3p, without broadening; this result shows
that additional Si C bonds are present in the network, a few Si N bonds being replaced
by Si C bonds; (ii) the minimum between A5 and B on the XPS VB spectrum is slightly
enhanced as compared to SiN7 one. The energy position of this minimum corresponds to that
of peak B of Si151C spectrum and consequently this additional shoulder reveals that C 2s
states due to a few Si C bonds are present in the network.
On the photoabsorption curve, the sharp maximum following the photoabsorption edge
corresponds to the SiN7 first maximum; it is characteristic of a crystalline Si3 N4 network.
A maximum is located at about 20 eV, close to both SiN7 and SiC151 maxima. The presence
of a shoulder at about 7 eV from EF could result from Si C bonds.
Consequently, for sample SiCN27, our experimental results are consistent with the exis-
tence of a single type of chemical environment of Si atoms with both Si N and a few Si C
bonds in the network. This is in quite good agreement with our previous results obtained
from XPS core levels and EXAFS studies (Gheorghiu et al. 1992).
Therefore, our results reveal that in ternary systems the local environment of Si atoms
depends essentially on the preparation conditions of the powder. For C/N ratio close to 1, Si
atoms are involved in both Si C4 and Si N4 configurations. EXAFS data for these samples
(Gheorghiu et al. 1992) indicated that atomic distances Si C and Si N are close to the
corresponding crystalline values. Moreover, they clearly revealed the presence of β-SiC
microcrystallites in the material; we suggested that the microcrystals could be contained in
an amorphous phase of SiN4 units, H atoms being present in NHX , CHX or SiHX groups. For
an initial ratio C/N equal to 0.22, we confirm a local atomic arrangement with both C and N
atoms surrounding the same Si atom, in agreement with XPS core levels and EXAFS results
(Gheorghiu et al. 1992).
5.3.4 Effect of heat treatment on the electronic structure of

nanometric Si/C/N ex-HMDS and pre-alloyed
Si/C/N/Al/Y powders studied by XPS spectroscopy
5.3.4.1 HMDS nanopowders

The samples were prepared by laser pyrolysis of hexamethyldisilazane. The experimental
method, already described (Cauchetier et al. 1994; Martinengo et al. 1996), is based on
the resonance between the emission of a continuous-wave CO2 laser, at 10.6 µm, and the
IR absorption of the liquid precursor, in the form of an aerosol produced by an ultrasonic
generator. The Si/C/N ex-HMDS powders have an average grain size in the nanometric range
(20–40 nm). Their composition, determined by chemical analysis, is adjusted by varying the
partial pressure of the carrier gas (NH3 ). Two series of powders in the intermediate range
were studied, namely HMDS43 and HMDS44, which correspond to chemical composition
C/N equal to 0.67 and 0.58, respectively, for AF samples. The XPS measurements were
performed on AF powders and after heat treatment at Ta = 1500◦ C and 1600◦ C during 4 h
under N2 . The AF powders were stored under inert atmosphere. The analysed samples were
pressed pellets prepared from pure laser synthetised powders.
Core levels
The Si 2p, C 1s and N 1s core levels spectra from HMDS43 and HMDS44 powders are
reported in Figures 5.3.10–5.3.12 for AF samples and for powders after heat treatment at
1500◦ C and 1600◦ C for 4 h.
The Si 2p spectra (Figures 5.3.10(a) and (b)) are broad and asymmetric peaks which reveal
the presence of several contributions in each spectrum. A decomposition of the spectra into
Voigt functions is achieved, by assuming that each contribution corresponds to stoichiometric
species: pure Si (99.5 eV), SiC (101.1 eV), silicon nitride Si3 N4 (101.8 eV), or silicon dioxide
SiO2 (103.2 eV) and no intermediate bonds such as Si CX N4−X are considered (Sénémaud
et al. 1998).
For AF samples (Figures 5.3.10(a) and (b)), the maximum of the peak is close to the BE of
Si3 N4 . The overall shape of the spectrum is significantly wider in HMDS43 than in HMDS44,
for which a marked asymmetry towards low BE is observed. The Si 2p peaks can be fitted
with a sum of two Voigt functions, the energy separation of which is close to the energy
distance SiC Si3 N4 and, consequently, are attributed to a sum of silicon carbide and silicon
nitride contributions, respectively. In agreement with the results of chemical analysis of the
samples, the relative proportion Si3 N4 /SiC (noted G) is much higher in HMDS44 than in
HMDS43; G is respectively 2.2 and 4.2 for HMDS43 and HMDS44. The two components
are broad (about 2 eV) and their energy position is not well defined (within ± 0.5 eV). This
result reveals that the AF powders exhibit a high degree of chemical disorder. The existence
of mixed tetrahedra with C and N atoms around a same Si atom, which would correspond
to peaks located at intermediate energy positions, is likely (Gheorghiu et al. 1997, 1998b).
Hydrogen is present in AF powders (Musset et al. 1994) and the presence of H bonds in the
network can contribute to increase the chemical disorder and consequently the width of the
lines.
After a heat treatment of powders at 1500◦ C, the Si 2p line from both samples exhibits
a high BE tail which can be attributed to the presence of silicon dioxide. Besides this SiO2
(a) Si3N4 (b) Si3N4

SiO2 SiC SiO2 SiC
Si 2p HMDS43 Si 2p HMDS44
1600°C 1600°C
Intensity (au)
Intensity (au)
1500°C 1500°C
AF AF
104 100 104 100

Figure 5.3.10 Si 2p core levels for AF samples and for 1500 ◦ C and 1600◦ C annealed samples
(a) HMDS43 and (b) HMDS44.
contribution, a shift of the maximum of the line towards higher BE is observed in HMDS44
as compared to HMDS43. The decomposition of the lines into peaks from silicon carbide and
silicon nitride shows that the apparent shift is due to the variation of the relative proportion of
the Si3 N4 to SiC contributions (G ratio) which is respectively 1.1 and 2.1. In HMDS43, the
relative proportion of nitride and carbide is approximately the same whereas in HMDS44,
Si N bonds are dominant. Moreover, the widths of the components are significantly lower
in HMDS43 than in HMDS44 (about 1.6–1.7 instead of 1.9 eV).
In 1600◦ C annealed samples, the presence of SiO2 is still noted with about the same propor-
tion as in 1500◦ C annealed sample. It is noteworthy that the factor G decreases considerably
from AF samples to 1500◦ C and 1600◦ C samples: G is respectively 0.4 and 0.8 for 1600◦ C
annealed HMDS43 and HMDS44 samples. The contribution from SiC is dominant for both
samples; it is higher for HMDS43 than for HMDS44; once again, this result is in good agree-
ment with the chemical analysis results. The energy positions of SiC and Si3 N4 contributions
are obtained, in this case, close to the reference binding energy values; their energy widths
are significantly narrower than in AF samples. It is noteworthy that Si 2p lines from SiC are
only 1.6 and 1.5 eV wide respectively in 1600◦ C annealed HMDS43 and HMDS44 samples;
these values correspond to a perfectly well-ordered SiC network. The nitride contribution
is narrower in HMDS43 (1.6 eV) than in HMDS44 (1.8 eV); in both cases the result reveals
a well organised network.
C 1s spectra observed from HMDS43 and HMDS44 samples (Figures 5.3.11(a) and (b))
exhibit quite different shapes according to the composition and to the heat treatment. In
HMDS43 AF sample, C 1s consists of a quasi-symmetric broad line; in HMDS44, the peak
is split into two components. The decomposition into Voigt functions reveals in both cases the
existence of two peaks. In HMDS43 and HMDS44 the high BE component corresponds to
C N (285.9 eV) (Dufour et al. 1994), possibly mixed to C H (285.0 eV) bonds; the low BE
component is clearly resolved from the high BE one in HMDS44 and thus it can be associated
(a) C9N C9C (b) C9N C9C

C9O C9Si C9O C9Si
C9H HMDS43 C9H HMDS44

C 1s C 1s
1600°C 1600°C
Intensity (au)
Intensity (au)
1500°C 1500°C
AF
AF
286 282 286 282
Figure 5.3.11 C 1s core levels for AF samples and for 1500◦ C and 1600◦ C annealed samples
to C Si (283.2 eV) (Driss-Khodja et al. 1992). In HMDS43, the low BE component is closer
to the high BE component and reveals more probably the presence of C C bonds (sp2 ).
After a 1500◦ C annealing of sample HMDS43, the C 1s line is strikingly sharp and the
energy maximum of the narrow peak corresponds to C C bonds (284.3 eV) (Diaz et al.
1996). The small width of this peak (only 1.2 eV) reveals unambiguously the presence of
small crystallites. This sharp peak is accompanied by a low BE shoulder corresponding to
C Si bonds in small proportion and by a tailing towards high BE which reveals the presence
of C N bonds (or C H). A 1500◦ C annealing of HMDS44 sample gives quite a different
shape for C 1s spectra. The line is well fitted by both C C and C N contributions; a low
proportion of C Si bonds is present as revealed by the low BE component. The high BE
tailing of the spectrum can be interpreted by the existence of a few C O species at the surface
of the sample. After a 1600◦ C annealing, the most intense line is attributed to C Si (carbide)
for both HMDS43 and HMDS44 samples. Towards higher BE, the tailing is interpreted by
the presence of C N bonds. The presence of C C bonds, the energy position of which is
intermediate between those of C N and C Si contributions, is not excluded.
N 1s spectra from HMDS43 and HMDS44 samples are reported in Figures 5.3.12(a)
and (b). In AF HMDS43 powder, a broad line is observed which can be fitted with a sum
of two Voigt functions having approximately the same intensity. The low BE peak can be
associated to N Si3 group (398.0 eV) (Gheorghiu et al. 1992); the higher energy component
can be associated to N H and N C bonds; these two contributions are only separated by
0.5 eV and located at respectively 400.1 and 399.5 eV (Bischoff et al. 1987; Rossi et al.
1994). In fact, AF powders contain a non-negligible proportion of H atoms (Musset et al.
1994) which are essentially present in N Hn groups. For HMDS44, the width of the observed
line is noticeably lower than in HMDS43. A tailing of the line on the low BE side is noted.
The decomposition reveals the existence of a strong peak attributed to N H and N C bonds
and a lower intensity peak associated to N Si bonds. Consequently, the significant decrease
of the total width of the line is due to an appreciable decrease of the low BE contribution.
(a) N9C (b) N9C

N9H N9Si N9H N9Si
HMDS43 HMDS44
N 1s N 1s
1600°C 1600°C
Intensity (au)
Intensity (au)
1500°C 1500°C
AF AF
400 396 400 396

Figure 5.3.12 N 1s core levels for AF samples and for 1500 ◦ C and 1600◦ C annealed samples
After a 1500◦ C
annealing of the sample, most H atoms are eliminated and, consequently,
the proportion of N H bonds is much lower. In this case, the N 1s peak is asymmetric and
reveals the existence, in both samples, of two components that we attribute to N Si and N C
bonds, respectively. In HMDS43, the low BE (N Si) peak is more intense than the high BE
(N C) one. On the contrary, in HMDS44, the high BE component dominates. After a 1600◦ C
annealing, both HMDS43 and HMDS44 spectra exhibit contributions at approximately the
same energies. In HMDS43, the relative intensities are about the same as at 1500◦ C. In
HMDS44, the relative intensities are completely modified, as compared to 1500◦ C, and the
N Si contribution becomes the most important. The splitting of the peak is well observed in
1600◦ C annealed samples. This effect is principally due to a narrowing of N Si component
in both samples.
XPS valence band spectra

The VB distributions from HMDS43 and HMDS44 powders in AF samples and in samples
annealed at 1500◦ C and 1600◦ C are reported in Figures 5.3.13(a) and (b).
The VB of the AF samples consists, for both spectra, of a wide band A in the range 0–14 eV;
the maximum of this band is located at about 12 eV BE. This first band is followed by a deep
minimum around 15 eV; an intense peak D is observed at 20 eV, and a lower structure E at
about 26 eV.
For 1500◦ C annealed samples, the overall shape of the spectral curves remains
approximately the same and only small modifications are observed as compared to AF pow-
ders. The maximum A is not significantly shifted but it becomes slightly broader, especially
in HMDS43. The minimum between A and D is broader and slightly filled up; in HMDS43,
the sharp minimum is replaced by a 1 eV wide step. Peak D is noticeably narrower; the
energy position of features D and E are not modified. The minimum between D and E is
more pronounced. These modifications are approximately the same in both samples.
Striking changes of the VB distributions are observed after the annealing at 1600◦ C, in
both HMDS43 and HMDS44 samples. The maximum of peak A is shifted by 2 eV towards
(a) E (b) E
A HMDS43 A HMDS44
D B D B
1600°C 1600°C
Intensity (au)
Intensity (au)
1500°C 1500°C
AF AF
30 20 10 EF 30 20 10 EF
Figure 5.3.13 XPS VB spectra for AF, 1500◦ C and 1600◦ C annealed samples (a) HMDS43 and
(b) HMDS44.
lower BE for both samples; it becomes sharper and a shoulder at about 7.5 eV BE is clearly
observed. The most striking modification, as going from Ta = 1500–1600◦ C, consists of
a dramatic decrease of peak D intensity and the appearance of an additional peak labelled
B at about 15 eV. It is noteworthy that peak B is well resolved from A and from D, and that
wide minima occur between A, B and D. The intensity of B is slightly higher than that of
D for both HMDS43 and HMDS44 samples. As far as peak E is concerned, its intensity is
strongly enhanced for 1600◦ C annealed samples as compared to 1500◦ C annealed ones.
The modifications of the spectral distributions observed as Ta increases from 1500◦ C to
1600◦ C can be discussed by reference to VB distributions of the stoichiometric compounds
SiC (Driss-Khodja et al. 1992) and Si3 N4 (Sénémaud et al. 1993), which are reported in
Figures 5.3.14 and 5.3.15. The energy positions of features A, B and D are given in Table 5.3.2
for HMDS43 and HMDS44 powders (AF, Ta = 1500◦ C and 1600◦ C), comparatively to
stoichiometric compounds SiC and Si3 N4 . Let us recall that in SiC, peak A corresponds to
C 2p states mixed to Si 3s and Si 3p states and peak B to C 2s states mixed to Si 3s and Si
3p states (Driss-Khodja et al. 1992) In Si3 N4 , peak A is attributed to N 2p states mixed to Si
3s and Si 3p states, the lower BE feature being attributed to the N 2pπ lone pair; peak D is
associated to N 2s states mixed to Si 3s and Si 3p states (Sénémaud et al. 1993). For HMDS43
and HMDS44 nanopowders annealed at 1600◦ C, the shape of band A is intermediate between
those of SiC and Si3 N4 : the maximum of the peak is located between the maximum of A
in SiC and in Si3 N4 . Both peaks B and C are observed for the samples annealed at 1600◦ C;
they correspond to Si 3s, 3p states mixed to C 2s states (B) and respectively N 2s states (D);
they reveal unambiguously the existence of both Si C4 and Si N4 groups in these systems.
The results obtained from the analysis of the N 1s core level have shown (see Section 4.1.1)
that in 1500◦ C annealed samples, N atoms are bonded to both Si (N Si bonds) and to C atoms
(N C bonds). The contributions of these bonds in the VB are located in the energy range
corresponding to peak D (about 20 eV BE). For these samples annealed at 1500◦ C, the study
of C 1s core level has shown that C atoms are essentially bonded to C atoms (C C bonds)
or to N atoms (C N bonds); the contribution of C Si bonds is very low (even negligible),
as revealed by the very low intensity in the energy range concerned. The presence of C C
bonds (either sp2 or sp3 ) induces VB states around 17 eV BE, accompanied by a sharp peak
at 11.5 eV in diamond (Mac Feely et al. 1974). These states are located well apart from
A SiC
B
E
Intensity (au)
30 20 10 EF
Binding energy (eV)
Figure 5.3.14 XPS VB spectrum for stoichiometric SiC.

D
Si3N4
E
A
Intensity (au)
30 20 10 EF
Binding energy (eV)
Figure 5.3.15 XPS VB spectrum for stoichiometric Si3 N4 .
Table 5.3.2 BE referred to the Fermi level EF for HMDS43

and HMDS44
HMDS43 and HMDS44 A (eV) B (eV) D (eV)
AF 12.0 — 20.0
Ta = 1500◦ C 12.0 — 20.0
Ta = 1600◦ C 10.0 14.5 20.0
SiC (5.7) 9.5 14.4 —
Si3 N4 (3.9 7.6) 11.4 — 18.9
C Si(Si C4 ) contribution which occurs at 14.4 eV. As a consequence, the contribution of

C C bonds induces in the VB a broadening of peak D and a filling up of the minimum
between peak D and peak A; no separate peak is expected. Consequently, the great intensity
of peak D, in AF and 1500◦ C annealed samples, is consistent with an associate contribution
of N C and C C bonds in the VB. The slight filling up of the VB distribution in the energy
range of peak B reveals the low contribution of C Si bonds to the VB. After annealing
at 1600◦ C, there is a complete reorganisation of bonds around C and N atoms which are
involved mainly in Si C4 and Si N4 groups. It is to be noted that some effects may be due
to rehybridisation of orbitals (e.g. C sp2 –C sp3 ).
The data obtained for the VB distribution, as a function of heat treatment, are in good
agreement with the results observed for the Si 2p, N 1s and C 1s core levels. In particular,
after a 1500◦ C annealing, the presence of the strong peak at about 20 eV BE observed in the
VB spectrum can be interpreted by the fact that N atoms are involved in both N Si and N C
bonds; the existence of both types of bonds involving a broadening of the corresponding N 2s
peak of the VB around BE = 20 eV. In these samples, C atoms are essentially involved in
C N and C C bonds, as revealed by the analysis of core levels spectra, and this can explain
why the VB distribution exhibits no contribution in the BE range corresponding to C 2s states
from C Si bonds.
Our results are in quite good agreement with a structural model composed of SiN3 C
tetrahedra linked through C N bonds obtained from EXAFS measurements on the AF SiCN-
HMDS samples (Ténégal et al. 1996).
5.3.4.2 Si/C/N/Al/Y nanopowders

The samples were prepared by laser pyrolysis of a liquid mixture of hexamethyldisi-
lazane (HMDS) and dissolved solid Al,Y-isopropoxides. This method is already described
in Section 5.3.4.1 (HMDS powders). Amorphous ultrafine (20–40 nm) nanopowders are
produced by laser pyrolysis of a liquid precursor. As for the SiCN-HMDS powders, the
Si/C/N/Al/Y nanopowders may have variable N contents depending on the proportion of
NH3 in the carrier gas (which is a mixture of argon and ammoniac). The powders were
annealed at 1600◦ C for 1 h under N2 atmosphere. The atomic compositions of the studied
powders (amorphous and annealed) as well as their designation are reported Table 5.3.3. The
Al + Y content does not exceed 1 at% in the AF powders.
Evolution of the Al and Y content in the superficial layers with

annealing treatment
CORE LEVELS
In order to get information about atomic concentrations in the superficial layers of the powder
grains and about their evolutions with annealing treatment, the intensities of the photoemis-
sion peaks (core levels) were compared. The core levels were normalised with respect to the
number of measured scans. Figure 5.3.16 gives the Al 2p and Si 2p core levels for the interme-
diate composition (C/N = 0.78) for the AF and annealed sample and one can observe a strong
increase of the Al 2p/Si 2p intensities ratio with annealing. From the measurements of the
peak intensities and from the values given by Scofield (Scofield 1976) for the photoionisation
cross-sections, we deduced the Al/Si atomic ratio in the superficial layers:
Al IAl2p σSi2p
= (5.3.1)
Si ISi2p σAl2p
where IAl2p and ISi2p are the intensities of the Al 2p and Si 2p photoemission peaks, σAl2p
and σSi2p the photoionisation cross-sections given by Scofield (Scofield 1976). Table 5.3.4
reports the results of the intermediate composition. Al/Si atomic bulk (global) ratios are also
given. The comparison between bulk and superficial ratio (from superficial layers) underline
a strong increase of the Al/Si superficial ratio with annealing, whereas the bulk ratio tends
Table 5.3.3 Atomic composition of the studied Si/C/N/Al/Y/O nanopowders

Powders Si N C O C/N Al Y
(at%) (at%) (at%) (at%) (at%) (at%)
HSAlY17, AF 33.5 33.5 26 6.2 0.78 0.57 0.14

HSAlY16, 1600◦ C/1 h/N2 41.3 52.1 4.9 1.5 0.09 0.14 0.02
HSAlY17, 1600◦ C/1 h/N2 44.4 29.5 24.1 1.6 0.82 0.34 0.11
HSAlY18, 1600◦ C/1 h/N2 47.3 8.3 41.9 1.9 5.05 0.41 0.18
(a)
1 eV HSAIY17
AF (C/N = 0.78)
1600°C (C/N = 0.82)
Al 2p
60
Intensity (au)
81 78 75 72
Binding energy (eV)
(b)
0.5 eV HSA117
AF (C/N = 0.78)
4000 1600°C (C/N = 0.82)
Si 2p
Intensity (au)
2000
0
108 105 102 99
Binding energy (eV)
Figure 5.3.16 Al 2p and Si 2p core levels for a powder with an intermediate C/N ratio (HSAlY17).
(a) For the AF sample (C/N = 0.78) and (b) for the annealed one (1600◦ C, C/N =
0.82).
Table 5.3.4 Surface ratios deduced from XPS analysis compared

to bulk ratios from atomic global compositions for
HSAlY17
IAI2p /ISi2p AP/Si surface AP/Si bulk ratio

ratio (XPS)
AF 0.004 0.01 0.02

1600◦ C/1 h/N2 0.022 0.03 0.01
to decrease. This result shows that Al atoms move towards the surface of the grains, when
annealing is performed, and chemical shifts of the Al 2p and Si 2p peak by 1 and 0.5 eV
(Figure 5.3.16) reveal that the chemical environment of Si and Al atoms changes as they
reach the surface.
As we want to evaluate in which proportions aluminium content increases in the superficial
area of the grains, the atomic ratio of Al (1600◦ C/AF) is deduced from the measurements of the
Al 2p peak intensities for the AF sample and for the annealed one (1600◦ C). As we compare
ratio of the same atomic species (Al or Si) in two different samples, then equation (5.3.1) is no
longer valid and differences of densities, textures (amorphous or crystalline powders) which
modify λ (the elastic mean free path for the measured electron kinetic energies), and of the size
of the grains, must be taken into account in the evaluation of the atomic surface ratio. For the
crystalline sample (1600◦ C), the density is about 1.5 times more than the one found in the AF
sample (amorphous powder) and then the elastic mean free path is reduced in the crystalline
sample. In a first approximation, the number of atoms probed by XPS for the two samples is
almost the same: in the annealed sample, the distances covered by the electrons are shorter
than in the AF sample but the number of atoms per unit of volume is increased. In the crys-
talline sample (1600◦ C), the increase of the average size of the grains (by 30–40%) induces a
reduction of the atomic fraction seen by XPS: sensitivity to superficial layers is increased for
the annealed sample. Table 5.3.5 reports the intensities ratio for Al 2p and Si 2p core levels as
well as the atomic ratios given for the bulk. Collectively, Si content increases slightly (ratio
of 0.75) when annealing is performed whereas the Al content (ratio of 1.68) decreases. The
analysis of superficial ratios (relative to superficial layers) peak intensities confirms a strong
increase of the Al content in the superficial layers after annealing: for the annealed powder
(Figure 5.3.16(a), Table 5.3.6), the intensity for the Al 2p peak is five times greater than that
found in the AF sample. The strong difference between atomic compositions and measured
Table 5.3.5 Ratios of the atomic concentration between the AF

sample and the annealed one (1600◦ C) for Al and
Si. Measurements were performed in the same experi-
mental conditions for both samples (same preparation,
same detection angle). Samples HSAl16-17-18
IAF/I 1600◦ C AF/1600◦ C AF/1600◦ C

surface (XPS) bulk
A1 2p 0.17 0.17 1.68

Si 2p 1 1 0.75
Table 5.3.6 Results of the simulations with Voigt functions of the Al 2p and Y 3d core levels
Powders Al 2p Y 3d
AlO4 + AlO6 AlN4 3/2 5/2
E(eV) A(eV) E(eV) A(eV) E(eV) A(eV) E(eV) A(eV)
HSAlY17, AF 75.7 2.6 — — — — — —

HSALY16, 1600◦ C/1 h/N2 75 1.8 73.8 1.8 160.9 1.7 159.0 1.8
HSALY17, 1600◦ C/1 h/N2 74.9 1.9 73.8 1.6 160.9 2.0 159.0 1.8
HSALY18, 1600◦ C/1 h/N2 74.8 1.5 73.8 1.5 160.7 1.9 158.6 1.8
References:
YSiAlON 74.9 1.8 73.8 1.7 160.7 2.1 158.6 2.2
Sintered sample 74.9 2.2 73.8 2.1 160.0 1.8 158.2 1.7
AF (C/N = 0.78)
1600°C (C/N = 0.82)
HSAl17
Intensity (au)
Si 2s
Y 3d
170 165 160 155

Binding energy (eV)
Figure 5.3.17 Y 3d core levels (3/2 and 5/2) for the intermediate powder (HSAlY16, HSAlY17,
HSAlY18) (AF and the annealed sample).
AIO4+
AlN4
(1600˚C) AIO6
AI 2p
HSAIY18
(C/N = 5.05)
Intensity (au)
HSAIY17
(C/N = 0.82)
HSAIY16
(C/N = 0.09)
78 75 72
Binding energy (eV)
Figure 5.3.18 Al 2p core levels for the annealed samples (1600◦ C (HSAlY16, HSAlY17,
HSAlY18) and results of the simulations with Voigt functions.
values for Al 2p confirms the increase of Al concentration at the surface of the grain. The
same result is obtained for yttrium. Measurements performed on the as-prepared sample show
that Y 3d core levels are not detected (Figure 5.3.17). On the other hand, XPS spectra display
a clear Y 3d signal for the annealed sample (Figure 5.3.17), whereas yttrium global con-
tent does not change. As the temperature increases until 1600◦ C, SiC and Si3 N4 crystallites
appear and Al and Y atoms are totally or partially rejected at the surface of the crystallites.
AIO4
+AIO6 AlN4
AI 2p
Sintered
sample
Intensity (au)
YSiAION
78 75 72
Binding energy (eV)
Figure 5.3.19 Al 2p core levels for the references compounds (sintered sample and YsiAlON) as
well as the reconstructions.
Figure 5.3.16 shows that the Si 2p and Al 2p XPS peaks move towards lower BE when
annealing is performed, indicating that Al and Si atoms are bonded to less electronegative
atoms at 1600◦ C than in the AF powder. The Al 2p peak is located at 75.8 eV in the AF
sample and its large width at half maximum (2.6 eV) indicates that Al atoms are embedded in
a disordered network. This energetic position indicates the presence of voids in the network.
After annealing, the peak position is between 75 and 74 eV depending on the C/N atomic ratio
of the sample (Figure 5.3.18). Figure 5.3.18 presents the results of the simulations performed
on Al 2p core levels for the annealed samples. Three compositions were analysed: a rich C
powder (C/N = 5.05), an intermediate one (C/N = 0.82) and a rich N powder (C/N = 0.09).
The results obtained for the reference compounds (YSiAlON vitreous phase and a sintered
sample) are also given (Figure 5.3.19). The solid sintered sample is a mixture of silicon nitride
(Si3 N4 ), SiC, β-SiAlON (crystalline phase) and YSiAlON. First of all, the width of the Al
2p peaks is quite similar in the nanopowders (1600◦ C) and in the reference compounds.
The results of the simulations show that Al 2p peaks can be simulated using two Voigt
functions, the energetic position of which is that found for aluminium in AlN and Al2 O3
(Muilenberg 1979; Briggs and Seah 1996): AlN4 and AlO4 + AlO6 sites are detected in
the annealed powders. The proportion of Al N bonds increases with the C/N atomic ratio.
Concerning reference compounds, one finds the same contributions to Al 2p core levels but
the proportion of AlN4 sites is lower than that found in the powders. These results are in
excellent agreement with those found by XAS analysis by Flank et al. (1999) on the same
powders, (see part XAS): EXAFS results show that crystalline AlN is present in the powders
at 1600◦ C. The XANES study revealed also that Al atoms are embedded in an amorphous
phase in the as-prepared powders. The results of our simulations are given in Table 5.3.6. The
FWHM of the contributions is quite similar for all the compounds. However, we observed
the lowest width for the rich C powder, which is in agreement with a preferential formation
of crystalline AlN in that powder.
Y 3d core levels (3/2 and 5/2) for the rich C powder are presented in Figure 5.3.20 (annealed
powder) as well as those from the YSiAlON phase. The position and width of the peaks are
similar for both compounds. The results of the simulations, given in Table 5.3.4 for the
nanopowders and for the references, show that the chemical environment for yttrium atoms
in the nanopowders is close to that found in the YSiAlON vitreous phase. The comparison
of the simulations for the YSiAlON reference phase and for the sintered compound reveals a
slight difference of the final parameters (E and A), due to differences in composition between
the YSiAlON reference and the YSiAlON phase inside the sintered composite.
The results of the decompositions (annealed samples) are given in Figure 5.3.21 for Si
2p core levels, in Figure 5.3.22 for N 1s core levels and in Figure 5.3.23 for C 1s ones.
Si 2p core levels are modelised with four components relative to Si Si4 , Si C4 , Si N4
and Si O4 sites in crystalline compounds (Si, SiC, Si3 N4 and SiO2 ). As the content of
C increases, the proportion of crystalline SiC increases and the proportion of Si C4 sites
increases (Figure 5.3.21). A weak contribution from Si Si bonds is observed for the rich N
powder. The study of Si 2p core levels confirms the results of XRD analysis, which revealed
the existence of Si3 N4 and SiC crystalline phases with an increasing proportion of SiC when
the C content of the powder increases. These results are in agreement with those of the
previous structural studies performed on SiCN nanopowders (Sénémaud et al. 1998; Musset
et al. 1994; El Kortobi et al. 1996; Ténégal et al. 1996, 1998) with different C/N ratios.
The study of the N1s core levels (Figure 5.3.22) confirms the existence of N Si bonds (near
398 eV), N Al bonds (396.8 eV) and N C bonds (399–399.5 eV) in the annealed powders.
The main contribution to the N 1s core level comes from N Si bonds (even for the rich C
powder). The proportion of N C bonds is more important in the powder with intermediate
C/N ratio. Contribution at higher BE (near 401 eV) is attributed to N O bonds. The existence
of crystalline AlN at the surface of the grains is confirmed by analysis of the N 1s core levels.
(1600°C) 3/2 5/2
Y 3d
YSiAION
Intensity (au)
HSAIY18
HSAIY17
HSAIY16
165 162 159 156

Binding energy (eV)
Figure 5.3.20 Y 3d core levels for annealed HSAlY16, HSAlY17, HSAlY18 as well as the results
of the simulations with Voigt functions.
Si9O4 Si9C4
Si9N4 Si9Si4
Si 2p
C/N = 5.05 HSAIY18

Intensity (au)
C/N = 0.82 HSAIY17
C/N = 0.09 HSAIY16
105 102 99
Binding energy (eV)
Figure 5.3.21 Si 2p core levels for the annealed samples HSAlY16, HSAlY17, HSAlY18. One
can observe the increase of the SiC content with the increase of the C/N ratio.
N9C N9Al4
N9O N9Si3
N 1s
HSAIY18
C/N = 5.05
Intensity (au)
HSAIY17
C/N = 0.82
HSAIY16
C/N = 0.09
402 399 396

Binding energy (eV)
Figure 5.3.22 N 1s core levels for annealed HSAlY16, HSAlY17, HSAlY18. The simulations
confirm the existence of an AlN crystalline phase at the surface of the grains. N C
bonds are also detected.
The study of C 1s core levels confirms the existence of C N bonds (286 eV), while C H
bonds from surface contamination are also detected as well as contributions from C Si bonds
in silicon carbide. Contrary to the case of N 1s core levels, the N and C rich powders display
very different shapes for C 1s core levels. Indeed, for the C rich powder, the main contribution
to the core level comes from C Si bonds in silicon carbide, the shoulder at 285–286 eV is
expected to come from C H and C N bonds, but for the rich N powder, the intensity of
the C Si contribution strongly decreases and the main contribution to the C 1s core level
is that from C N bonds. These results show that C N bonds are stable through annealing
treatments. These results are in good agreement with the previously detailed structural study
of Si/C/N nanopowders produced by laser pyrolysis of hexamethyldisilazane (Ténégal et al.
1996, 1998, see the XAS part) which underline the existence of homogeneous amorphous C
substituted Si3 N4 -type structures (1–2 nm) for annealing temperatures below 1500◦ C. Mixed
tetrahedra SiCX N4−X and C N bonds were detected by XPS, RMN and XAS (Sénémaud
et al. 1998; El Kortobi et al. 1996; Ténégal et al. 1996). When the annealing temperature
increases beyond 1500◦ C, the N departure allows the local formation of SiC germs and
powders crystallise in a mixture of Si3 N4 and SiC, the proportions of which are dependent on
the initial C/N ratio (in the AF powder). Our results show that when the C content decreases,
the stable phase for C atoms is no longer a silicon carbide phase but a C substituted silicon
nitride one.
XPS VALENCE BAND SPECTRA
VB spectra are given in Figure 5.3.24 for the three powders annealed at 1600◦ C. For the
intermediate composition (HSAlY17), the corresponding spectra for powders without Al
and Y is that of HMDS43 or HMDS44 given in Section 4.1 (Figures 5.3.13 and 5.3.14). The
overall shape of the VB spectra for HSAlY17 (Figure 5.3.24) is similar to that obtained for
HMDS43 and HMDS44 (Figures 5.3.13, 5.3.14 in Section 4.1.2). In SiC, peaks A and B are
C9H
C9N C9Si4
C 1s
HSAIY18
C/N = 5.05
Intensity (au)
HSAIY17
C/N = 0.82
HSAIY16
C/N = 0.09
288 285 282

Binding energy (eV)
Figure 5.3.23 C 1s core levels for annealed HSAlY16, HSAlY17, HSAlY18. C N bonds are
dominant in the rich N sample at 1600◦ C.
HSAIY18
Intensity (au)
E
A
D B
HSAIY17
HSAIY16
30 20 10 EF
Binding energy (eV)
Figure 5.3.24 VB distributions in the pre-alloyed HSAlY16, HSAlY17, HSAlY18 powders

annealed at 1600◦ C.
respectively attributed to mixtures of C 2p states with Si 3s–Si 3p states and C 2s states with
Si 3s–Si 3p states. In silicon nitride, A and D are respectively attributed to mixtures of N
2p states with Si 3s–Si 3p states and N 2s with Si 3s–Si 3p states (see Section 4.1.2). The
incorporation during the laser synthesis of Al and Y atoms does not change the shape of the
VB. However, a slight decrease of the D peak (N 2s states mixed with Si 3s–Si 3p states)
in the pre-alloyed powder (HSAlY17) is observed. The VB spectra for the rich N powder
(HSAlY16) is quite different from that found for the silicon nitride reference (Figure 5.3.15
in Section 4.1.2). Modulations from 12 eV to the Fermi level observed on the silicon nitride
VB spectra are not detected on the VB of HSAlY16. We expect to explain this difference by
the presence of C and Al atoms in the network of silicon nitride which leads to a smoothing of
the structures near the top of the VB. The presence of Al atoms in superficial layers either in
AlN or SiAlON(C) crystalline phases at 1600◦ C can explain the VB smoothing from 12 eV
to the Fermi edge. The VB distribution for HSAlY18 is close to that found in crystalline SiC
(Figure 5.3.14, Section 4.1.2).
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5.4 Local order in Si/C/N nanopowders
studied by X-ray absorption
spectroscopy
Study at the Si K edge
François Ténégal, Anne-Marie Flank, Adriana
Gheorghiu-de La Rocque and Christiane Sénémaud
5.4.1 X-ray absorption principles and data analysis
5.4.1.1 Principles
X-ray absorption spectroscopy (XAS) refers to the measurement of the X-ray absorption
coefficient µ as a function of photon energy E. µ is given by the Beer–Lambert law:
I0
µx = ln
I
where I0 and I are the intensities of the incident and transmitted beams, respectively and
x is the sample thickness. µ is a measurement of the absorption cross-section σ which is
given by the Fermi golden rule formula. As the energy of the incident X-ray beam reaches the
binding energy of a core level, one can observe a strong increase of the absorption coefficient,
corresponding to the excitation of an electron from its core level to bounded vacant states
or to the conduction band. The edge position depends on the chemical environment of the
absorbing atom. Transitions occur within the dipolar approximation for the absorbing atom.
For a K-shell absorption (1 s electron), due to the dipole selection rules, only transitions to
p-states are allowed (!l = ±1) and the X-ray absorption spectrum reflects the local partial
unoccupied p-density of state (DOS) around absorbing atoms.
As the energy gradually increases, if the absorbing atoms are isolated, the absorption
coefficient decreases monotonically and its shape can be evaluated by a Victoreen function. If
the atoms are embedded in a condensed phase (liquid or solid), then one observes modulations
which have been shown to depend on the local environment around the absorbing atom
(Figure 5.4.1). The photoelectron which has a variable kinetic energy (depending on the
photon energy) is scattered by the neighbours of the excited atom, and builds up interference
patterns that contain structural information. In the early 1970s, Lytle et al. (1975) showed
that a subsequent Fourier transform (FT) of the extended X-ray absorption fine structure
(EXAFS) oscillations yields a pseudo-radial distribution function. As the mean free path
of the photoelectron depends on its kinetic energy (Figure 5.4.2), one will distinguish two
regimes. In the EXAFS regime (Ec > 50 eV) (Figure 5.4.1), the interaction is in a first
approximation calculated using the single scattering approach. The initial state for the electron
is the localised core level corresponding to the absorption edge (K, LI, LII, LIII, . . .).
The final state is that of the ejected electron, which can be represented as an outgoing
spherical wave originating from the X-ray absorbing atom which is backscattered by the
neighbouring atoms. The final state is the sum of the outgoing and incoming waves that gives
Local order in Si/C/N nanopowders studied by XAS 183
XANES
EXAFS
(au)
E0
1800 2000 2200 2400
E (eV)
CB
VB
..
h . LII (2p1/2), LIII (2P3/2)
LI (2s)
Core levels
K (1s)
Figure 5.4.1 Absorption coefficient (background was subtracted) for β-SiC (cubic). When the
energy of the X-ray beam reaches the binding energy of a core level (E0 = 1841 eV),
then an abrupt increase of µ is observed. As the energy increases (E > 1841 eV),
modulations of the coefficient are clearly evidenced.
100 Au
Al
Ag Au Au
Escape depth (Å)
Au
Mo
Be W
10 Ag C C
Mo
Ag Be
Ag Be W Mo
Fe Ni
Ag
1
1 10 100 1000 10000
Electron energy (eV)
Figure 5.4.2 Mean free path for the electron as a function of its kinetic energy.
rise to the sinusoidal variation of µ known as EXAFS. For an unoriented sample with small
or approximately Gaussian disorder, the EXAFS oscillations are given by (Teo 1986)
µ(k) − µ0 (k)
χ (k) =
µ0 (k)
Fj (π, k, Rj ) (−2Rj / λj (k)) −2σj2 k 2
= S02 (k)(N)j e e sin[2kRj + φj (k, Rj ) + 2δc ]
j
kRj2
(5.4.1)
184 François Ténégal et al.
k is given by
√
2m(E − E0 )
k = 4π 2
h2
where E0 is the threshold energy, µ0 (k) is the atomic absorption (for isolated atoms) and
µ(k) the absorption coefficient. The summation is made over the concentric coordination
shell j around the absorbing atom at a distance Rj . Nj is the number of atoms of the same
kind inside the coordination shell j . Nj and Rj are structural parameters. The electronic
parameters Fj (π, k, Rj ) (the backscattering amplitude for the shell j ) and φj (k, Rj ) + 2δc
(the phase function) were calculated for each kind of atomic pairs and tabulated by Teo and Lee
(1979), McKale et al. (1986) and Rehr and Albers (1990). They can be extracted from model
compounds. S02 (k) is an amplitude reduction factor which accounts for the intrinsic inelastic
loss (concerning the absorbing atom), exp(−2Rj /λj (k)) is a reduction factor accounting for
extrinsic inelastic process (concerning neighbouring atoms) and exp(−2σj2 k 2 ) is a reduction
factor accounting for thermal and structural disorder, where σj is the Debye–Waller factor.
The EXAFS formula (5.4.1) neglects multiple scattering events which were introduced
in the EXAFS theory by Lee and Pendry (1975). Later on, Rehr and Albers (1990) gave
a formulation of the EXAFS signal as a sum of the contributions from each possible scattering
path A (single or multiple scattering path) for the photoelectron:

χ (k) = χA
A
S 2 (k)
A
(k) sin[2kR + φ A (k) + 2δc (k)]e−2σA k e−2R/λ(k)
2 2
= 0
feff (5.4.2)
kR 2
A
R is the effective path radius (the total length of the path A is 2R). σA is the DW factor
A (k) is its effective scattering amplitude and φ A (k) + 2δ (k) its effective
for the A path, feff c
phase shift. The second formulation of the EXAFS signal accounts for multiple scattering
events which must sometimes be included in the EXAFS analysis (Figure 5.4.3). The FEFF
code developed by Rehr and Albers calculates the EXAFS signal using the second expression
(5.4.2) (Rehr and Albers 1990). The calculation requires an atomic coordinate file from which
a muffin-tin potential is calculated. The paths are numbered and selected using amplitude
Figure 5.4.3 Representation of a single scattering process (1) for the photoelectron and a multiple
scattering process (2) for the photoelectron.
filter paths importance criteria (Zabinsky et al. 1995). All the contributions A are individually
calculated and gathered to give the EXAFS signal.
Multiple scattering events become fundamental in the ‘low kinetic energy’ regime
(Ec < 50 eV) where the mean free path of the photoelectron can be large. In that region,
the photoabsorption spectrum is very sensitive to the medium-range order, as it is illustrated
in Figure 5.4.4, where the XANES part of the XAS spectra for SiC in the crystalline beta
form and in the amorphous phase are compared. The loss of medium-range order in the
amorphous material washes out the structures in the near edge area. As well, some features
of the near-edge structures may appear as fingerprints of the crystalline phases present in the
sample (Figure 5.4.5).
E0
XANES
EXAFS
(au)
c-SiC
a-SixCy
1830 1860 1890 1920

E (eV)
Figure 5.4.4 XANES part for β-SiC and amorphous silicon carbide (a-SiC) prepared by RF
sputtering. XANES features are strongly smoothed in the case of a-SiC.
-Si3N4
-Si3N4
Absorption (au)
-SiC
B C
0
1840 1850 1860 1820
E (eV)
Figure 5.4.5 Comparison of Si K edge XANES spectra for β-SiC, α-Si3 N4 , β-Si3 N4 .
5.4.1.2 Experimental
An X-ray absorption experiment requires a white X-ray source of reasonable intensity to
collect data. One fundamental reason for the development of the technique, in the 1970s, was
the advent of the synchrotron radiation X-ray sources of high brilliance and intensity, which
were improved since then.
The photoabsorption measurements (HMDS powders) were carried out on the SA32 beam-
line (Super-ACO, LURE-Orsay) equipped with a double-crystal (InSb (111)) monochromator
which allows an energy resolution of 0.7 eV. The incident beam was monitored by measuring
the total electron drain current of an aluminium foil located downstream the monochromator.
The photoabsorption EXAFS spectra at the Si K edge were recorded at 298 K, were collected
in the transmission mode as a function of the incident photon energy, in the 1800–2500 eV
energy range and with a 1 eV step. The transmitted beam was measured with an ionisation
chamber filled by a low pressure of air (200 Torr). Measurements for the powders produced
from gaseous precursor were carried out on the SB3 beamline which was equipped with
a two crystal InSb (111) monochromator. The photoabsorption spectra were recorded at
room temperature, in the transmission mode as a function of the incident photon energy,
in the 1750–2550 eV range with a 2 eV step. The transmitted beam was measured with
a proportional counter filled with a 220 Torr Ar/CH4 (90/10) mixture.
More accurate measurements were done in the near edge region (1830–1910 eV, 0.2 eV
step), as the XANES part of the absorption spectra has been shown to be a good fingerprint
of the degree of crystallinity and of the nature of the silicon phases present in the compound
(Sainctavit et al. 1991). As a good approximation very near the edge, which is sufficient
to draw qualitative inferences, a constant background was subtracted in the pre-edge region
from the as-recorded spectra. They were then normalised far from the edge (at 1910 eV).
As an example, Figure 5.4.5 presents the XANES spectra of β-SiC, α-Si3 N4 , and β-Si3 N4 .
All the XANES spectra were recorded during the same shift, and references were checked
before and after the measurements, as well as crystalline Si and crystalline and amorphous
SiO2 already reported in the literature (Lagarde and Flank 1986; Lagarde et al. 1992, 1993).
5.4.1.3 EXAFS data analysis

The first step is the extraction of the oscillatory part χ(k) from the absorption coefficient µ.
The atomic absorption µ0 is modelised by a polynomial (4th or 5th order) fit of the modu-
lations. The spectra are normalised using the Lengeler–Eisenberger (1980) approximation.
The normalisation coefficient is given by the Heitler formula:

8(E − E0 )
µ1 (E) − µ0 (E) = [µ1 (E0 ) − µ0 (E0 )] 1 − (5.4.3)
3E0
where µ1 (E0 ) − µ0 (E0 ) is the experimental value of the jump at the threshold (E0 ). µ0 (E)
is the atomic absorption given by the polynomial fit. Once the oscillatory part is extracted,
FT in R space of the k 2 or k 3 weighted oscillations χ(k) is performed. A Kaiser (τ = 2.5)
or Hanning window is applied to the k n χ(k) oscillation. FTs are calculated over the same
energy range (2–10 Å−1 ) for all the samples and references compounds. Extraction of the
oscillatory part and FT calculations must be executed using the same parameters for all
the compounds that will be compared. FT calculations give according to the expression (I)
a pseudo-radial distribution function (uncorrected from the phase shift) of the coordination
shells surrounding the absorbing Si atoms (Figure 5.4.6). The sorted and back transformed
12 Si
-SiC
2
4C
|FT| (au)
1 A
0
0 2 4 6
R (Å)
Figure 5.4.6 Modulus of the FT of k 2 χ (k) for β-SiC(2–10 Å−1 ). The first peak corresponds to
the first coordination shell around Si atoms (4 C atoms at 1.89 Å), the second to the
second coordination shell (12 Si atoms at 3.07 Å). Peak A is a multiple scattering
structure known as a fingerprint of the cfc structure. It is a focusing effect due to the
alignment of 3 Si atoms. Phases shift are not corrected and the peaks do not appear
at the real distances.
in the k space peak, corresponding to a given coordination shell, is at first fitted using the
electronic parameters (amplitude and phase functions) extracted from model compounds in
which bonding configurations similar to those being investigated are present: β-SiC for Si C
pairs (4 at 1.89 Å) and Si Si second neighbour pairs (12 at 3.08 Å), α-Si3 N4 for Si N pairs
(4 atoms at an average distance of 1.74 Å), and α-SiO2 for Si O pairs (4 at 1.61 Å) (Wyckoff
1963). The experimental signal extracted for the first shell is fitted using the single scattering
formula (5.4.1) for EXAFS. For the first shell, given the available energy range of the EXAFS
spectra !k equal to about 8 Å−1 , and the !R equal to 1.4 Å used in the back-FT, the number
of free parameters (2 · !R · !k/π) turns out to be seven. The free parameters during fitting
process were the coordination number and the interatomic bond length. A three-shell fit
deals with six free parameters. The description of the other contributions (beyond the closest
neighbours) must include multiple scattering events and formula (5.4.2) must be used.
5.4.2 Study by EXAFS at the Si K edge of Si, SiN, SiC and

Si/C/N laser-synthetised nanopowders produced from
gaseous precursors
Six as-formed nanopowders (Si, SiC151, SiC152a, SiN7, SiCN12 and SiCN27) were mea-
sured. The Si nanopowder was formed from a SiH4 Ar gas mixture. XRD measurements
revealed the existence of c-Si in the as-formed nanopowder. Two SiC (SiC151 and SiC152a)
powders were synthetised from CH3 SiH3 gaseous precursor. They were differentiated by
the temperature reaction which induces changes in X-ray diffraction (XRD) patterns, as
observed previously in the case of the SiH4 C2 H2+n mixtures (Luce 1990). The XRD
measurements performed on SiC151 and SiC152a revealed the existence of β-SiC crystallites
in the nanopowders. The SiN7 powder was formed from a SiH4 NH3 mixture and the two
SiCN powders (SiCN12 and SiCN27) from SiH4 CH3 NH2 NH3 mixture in variable pro-
portions. Thus, NH3 was only used for the synthesis of SiCN27 and allowed the increase of
the N content in SiCN27 (C/N at. = 0.22) compared to SiCN12 (C/N at. = 0.93). XRD
measurements revealed the existence of α and β-Si3 N4 crystallites in SiN7, SiCN12 and
SiCN27 powders and of β-SiC crystallites in SiCN12. Note that a small proportion of c-Si
was also detected in the SiN7 powder.
5.4.2.1 Si, SiN7, SiC151 and SiC152a nanopowders

Figure 5.4.7 presents the FT of the Si nanopowder. The first peak (A) located near 2 Å
corresponds to the first coordination shell surrounding the Si atoms. It is related to the four Si
atoms which build the tetrahedral environment of the absorbing Si atom (RSi Si = 2.35 Å).
Beyond this first intense peak (R > 3 Å), one finds a set of small peaks, related to the
intermediate-range organisation in the material, which are characteristic of that of crystalline
Si (Lagarde and Flank 1986). These results are in good agreement with those found by XRD
which revealed the existence of c-Si.
The FT curves obtained for SiN7 and α-Si3 N4 are displayed in Figure 5.4.8 and one can
take qualitative information of their comparisons. First, one can observe a strong decrease
in the amplitude of the peaks located at R > 2 Å for SiN7 compared to α-Si3 N4 . This
reduction is an effect of the static disorder. A reduction in the amplitude of the first peak
(A) is also observed in SiN7. An attempt was made to simulate the contribution of this
peak on the basis of a one-shell model. The only parameters which were varied are the
interatomic bond lengths and the coordination number. The DW factor was not allowed to
vary during the fitting procedure, which means that we considered this factor equal to that
found in the crystalline compound α-Si3 N4 for the Si N bond. A slight variation (<2 eV)
9
Si
A
6
|FT| (au)
0
0 2 4 6
R (Å)
Figure 5.4.7 FT of the k 3 weighted EXAFS signal (χ (k)) for the Si nanopowder.
9 A
α-Si3N4
SiN7
6
|FT| (au)
0
0 2 4 6
R (Å)
Figure 5.4.8 FTs of k 3 χ (k) for α-Si3 N4 and the SiN7 nanopowder.
Table 5.4.1 First-shell structural parameters obtained for the different

samples. !N/N = 10%, !R = 0.02 Å
Sample Si C Si N NSi C+Si N
NSi C RSi C (Å) NSi N RSi N (Å)
SiN7 — — 3.1 1.73 3.1

SiC152a 3.4 1.88 — — 3.4
SiCN12 2 1.89 1.7 1.74 3.7
SiCN27 1 1.87 2.9 1.73 3.9
of the energy edge shift was allowed. The result of the simulation, given in Table 5.4.1,
indicates that the coordination number is close to three which is lower than in α-Si3 N4 . The
interatomic distance does not change compared to α-Si3 N4 . The reduction of the coordi-
nation number can be explained by Si H bonds. Indeed, H with its single electron shows
no measurable scattering and the main effect of its presence in the neighbourhood of Si
atoms is a reduction in the effective measured coordination number. We expect that an
effect of static disorder on the Si N bond length is excluded. Indeed, the DW factor of
the Si N bonds in α-Si3 N4 is strong (the bond length distribution spreads from 1.70 to
1.79 Å) and no change of its value was observed in amorphous SiNx compounds in previous
studies.
The FT curves of SiC151 and SiC152a are displayed in Figure 5.4.9. SiC151 exhibits
the well-known structures of the crystalline β-SiC phase (Laffon 1986). Particularly, the
peak labelled D is characteristic of the fcc structure of the Si subnetwork in β-SiC. This
is the ‘focusing effect’ peak which is related to the alignment of three Si atoms distant to
each other of 3.08 Å in the β-SiC structure. SiC151 is fully crystallised in the β-SiC phase.
The spectrum of SiC152a presents the structures of the β-SiC phase too, but a strong reduction
of the amplitude of the peaks located at R > 2 Å is observed. The first shell contribution to the
12
SiC151
9
SiC152a
|FT| (au)
D
3
0
0 2 4 6
R (Å)
Figure 5.4.9 FTs of k 3 χ (k) for SiC151 and SiC152a.
FT of SiC152a was simulated using the electronic parameters extracted from SiC151 (4 C at
1.89 Å). The result given in Table 5.4.1 is the decrease of the coordination number. One finds
3.4 C atoms around one Si atom. This result gives evidence of the presence of crystallite of
β-SiC in SiC152a. The reduction of the coordination number may have several explanations.
First, the H content is higher in the SiC152a sample, than in the SiC151 sample, and induces
a decrease of the coordination numbers and so, the H effusion during the pyrolysis process
is less important in SiC152a. We expect that, the existence of Si H bonds in the as-formed
powder is responsible for this decrease, since the gaseous precursor contains SiH3 groups.
Second, the structural disorder is more important in SiC152a than in SiC151 due to bond
length and/or angular fluctuations. Smaller crystallites (1–2 nm) of silicon carbide in SiC152a
would also lead to a decrease of the coordination number around Si atoms. For SiC151, the
proportion and/or the size of the β-SiC clusters are more important and the features of the
EXAFS spectra are those of the crystalline β-SiC phase.
5.4.2.2 SiCN12 and SiCN27

FTs of SiCN12 and SiCN27 are given in Figure 5.4.10. The two compounds exhibit the
features of ordered structures. Beyond the first peaks of the FT, one finds a set of peaks
related to the intermediate-medium-range organisation in the material. The presence of the
focusing effect peak in SiCN12 indicates that, contrary to SiCN27 for which the peak is
absent, this powder is crystallised partially in a β-SiC phase. This result is in agreement with
the XRD measurements which detect α, β-Si3 N4 phases for 1 and SiCN27 and the β-SiC
phase only for SiCN12. The analysis of the other peaks is difficult because of the multiplicity
of the possible configurations for Si atoms, in such SiCN compounds, and because a fine
analysis of this part of the pseudo-radial distribution function requires the introduction of
multiple scattering contributions. Concerning the first peak related to the first coordination
shell, a two-shell fit (Si N + Si C) was realised using electronic parameters extracted
from model compounds (SiC151 and α-Si3 N4 ). The results are given in Table 5.4.1. One
9
SiCN12
SiCN27
6
|F T| (au)
0
0 2 4 6
R (Å)
Figure 5.4.10 FTs of k 3 χ (k) for SiCN12 and SiCN27.
Table 5.4.2 Influence of the flame temperature T during the pyroly-

sis process on the proportion of Si H remaining bonds
in the as-formed nanopowders assuming that the reduc-
tion of the coordination number is completely due to
Si H bonds (!N/N = ±10%)
SiN7 SiC152a SiC151 SiCN12 SiCN27
T (◦ C) 1250 1150 1530 1550 1615

NSi−H 0.9 0.6 0 0.3 0.1
finds that the NSi C /NSi N ratio follows the C/N ratio. For SiCN12 (C/N = 0.93), the
first coordination shell of one Si atom is composed of 2 C atoms and 1.7 N atoms, whereas
for SiCN27 (C/N = 0.22), it is composed of 2.9 N atoms and 1 C atom. The coordination
numbers are close to 4 for the two compounds which indicate that, as for SiC151, there
is not much H bonded to Si. We expect that the proportion of Si H bonds in the material
is correlated to a pyrolysis reaction parameter which is the flame temperature. Indeed, for
SiC151, SiCN12 and SiCN27, this temperature is about 1500–1600◦ C (Table 5.4.2) whereas
for SiC152a and SiN7, in which a higher reduction of the coordination number (20–30%) in
the first coordination shell is found, it is about 1100–1200◦ C.
The results of the fits show that both C and N atoms are present in the first coordination shell
of Si atoms in SiCN12 and SiCN27. For SiCN12, both SiC4 and SiN4 tetrahedra are present
in the compounds, since XRD measurements show the existence of β-SiC and α, β-Si3 N4
crystallites in the powder. For SiCN27, SiN4 tetrahedra are present in α, β-Si3 N4 crystallites,
but we cannot conclude about the existence of SiC4 or SiCx N4−x tetrahedra, since a two-shell
fit of the EXAFS data provides an average picture of the local arrangement of C and N atoms
in the first coordination shell of the absorbing Si atoms.
5.4.3 Short-range order determination in amorphous
SiCN-HMDS nanopowders: evolution as a function of
the C/N ratio and annealing treatment
This part reports a detailed structural analysis of nanosized SiCN powders produced from the
liquid precursor hexamethyldisilazane (HMDS). We focused our study on the intermediate
compositions, for which a delay in the crystallisation is observed. XAS was used to describe
the short- and medium-range order in the amorphous powders. The amorphous → crystal
transition which occurs beyond 1500◦ C was also studied by X-ray and neutron diffraction
(see Section 5.4.4 ND and XRD). The goal of this study is to give a model for the structural
evolution of these powders when the annealing temperature increases. The informations
obtained from absorption and diffraction measurements are related to the structure of the
powders at the atomic scale and are then particularly adapted to the study of amorphous com-
pounds. The XAS experiments at the Si K edge give a radial distribution function (RDF)
around the Si atoms in the material, and diffraction measurements give a total radial distrib-
ution function. The analysis of these RDF allows the determination of structural parameters,
such as bond lengths or coordination numbers, and of information related to the intermediate-
medium-range order, which can be modelised and tested through XAS and diffraction spectra
calculations. This detailed study of the amorphous phases was performed to obtain structural
information, which could explain the delay in the crystallisation and give information about
the mechanism that leads to the crystallisation of the nanopowders.
5.4.3.1 Mixed tetrahedra and C N bonds
Short-range order deduced from the analysis of the first

coordination shell of Si atoms
Figure 5.4.11 shows the extracted EXAFS signal as a function of the powder composition
for the as-formed samples. The FT curves obtained for the various C/N ratio samples are
-Si3N4
-SiC
k × (k) (Å–1)
HMDS45 as-formed
HMDS44 as-formed
HMDS43 as-formed
HMDS40 as-formed
3 6 9
k (Å–1)
Figure 5.4.11 Si K EXAFS raw spectra for β-SiC, α-Si3 N4 and Si/C/N with variable C/N.
The spectra have been vertically displayed for convenience. The corresponding
concentration of the samples are displayed (Table 2.5).
(a)
-SiC
2
-Si3N4
|FT| (au)
HMDS40 as-formed
2
HMDS42 as-formed
HMDS43 as-formed
|FT| (au)
HMDS44 as-formed
1 HMDS45 as-formed
0
0 2 4 6
R (Å)
(b) 2
HMDS40 as-formed
HMDS42 as-formed
HMDS43 as-formed
HMDS44 as-formed
Im(FT) (au)
HMDS45 as-formed
0 2 4 6
R (Å)
Figure 5.4.12 (a) FT modulus of the k 2 weighted EXAFS oscillations for the two references β-SiC,
α-Si3 N4 , and for the Si/C/N samples; (b) imaginary part of the FT for the Si/C/N
samples as a function of C/N.
reported in Figures 5.4.12(a) and (b), and one can take out some qualitative information
of their observation: absence of long-range order (for R values higher than 4 Å), short and
intermediate orders very slightly dependent on the C/N ratio, as evidenced clearly by both
the magnitude and the imaginary part of the FT, which are very similar up to 4 Å. In order to
determine the local order around Si atoms, a two-shell fit has been calculated on the basis of
Si C and Si N pairs. The structural parameters obtained as a function of the C/N ratio are
summarised in Table 5.4.3.
Table 5.4.3 First-shell structural parameters obtained with a two-shell
fit (Si C + Si N) for the different samples. !N/N =
10%, !R = 0.02 Å
HMDS40 1.4 1.88 2.1 1.73 3.5

HMDS43 0.9 1.9 3.2 1.73 4.1
HMDS44 0.9 1.87 3.2 1.72 4.1
HMDS45 0.7 1.88 3.3 1.73 4.0
We first used a fitting procedure where the two interatomic distances have been kept fixed
to their crystalline values, within 0.02 Å. As we used experimental electronic parameters,
the values of the adjustable disorder factors are just the difference between the unknown and
the model compound !σ 2 = σalloy 2 − σmodel
2 , where σmodel
2 is included in the experimental
amplitude. This difference, in all cases, is found to be negligible by the fitting procedure.
One has to evaluate the DW factor for Si C and Si N bonds by fitting the first coordination
shell in model compounds with the calculated backscattering amplitudes and the phase shifts
taken from McKale et al. (1988). We found a DW factor value less than 5·10−2 Å, consistent
with the value found in ZnSe (Diop and Grigenti 1995), and in c-Ge (Dalba et al. 1993).
Then, during the fitting procedure, the damping factors !σ 2 were kept equal to 0, which
means that we considered a DW factor for the unknown structure equal to those of the
reference phases. As for the values of the energy edge shift !E0 = E0 alloy − E0 model , we
checked that small variations of this parameter (±2 eV) leave the fit unaltered, therefore,
this parameter was not varied during the fits. Then in a second step, the only parameters
which were varied during the fit procedure were the interatomic distances and the partial
coordination numbers. The different interatomic distances appear to be constant over the
C/N range. The values obtained for the different pairs may be well compared with the model
values. Such constancy has already been observed in hydrogenated amorphous silicon carbide
alloys (Pascarelli et al. 1992). The total coordination number of Si is expected to be close to
4, as there is limited bonding of Si to H. Actually, hydrogen with its single electron shows
no measurable scattering, and its structural effect can only be evidenced when it is located
between the absorber and the backscatterer in well-defined sites. In disordered structure as
the one described here, the main effect of the presence of H in the samples would result in a
reduction of the effective coordination. The results concerning the total coordination number
are 4 ± 10%, an acceptable uncertainty for EXAFS measurements.
The proportion of the different pairs (partial coordination numbers) follows approxi-
mately the chemical composition, as it can be seen in Figure 5.4.13, which shows the evolution
of the ratio of the partial coordination numbers NC /NN as a function of C/N. One can observe
that this evolution is linear with a slope equal to 0.5.
As the chemical composition of the powders relies on the presence of oxygen in the
powders, fits including Si O pairs were also performed. Table 5.4.4 reports the results
obtained with a three-shell fit and the result of the adjustment for HMDS43 is given in
Figure 5.4.14. The introduction of Si O bonds improves definitely the quality factor of the
fit (from 1.3 × 10−2 to 5.5 × 10−3 ). The proportion of Si O pairs, that never exceeds 10%,
increases with the O atomic content of the alloy.
I
HMDS40
II
HMDS43
HMDS42
0.6
HMDS44
NC/NN
HMDS45
Si3N4
0
0 0.4 0.8 1.2
C/N
Figure 5.4.13 Variation of the ratio of the partial coordination numbers NC /NN with C/N: I is for
parameters given in Table 5.4.3 and II for those in Table 5.4.4.
Table 5.4.4 First-shell structural parameters obtained with a three-shell fit (Si C + Si N)

for the different samples. !N/N = 10%, !R = 0.02 Å
Sample Si C Si N Si O NSi C+Si N+Si O
NSi C RSi C (Å) NSi N RSi N (Å) NSi O RSi O (Å)
HMDS40 1.6 1.89 1.9 1.73 0.2 1.61 3.7

HMDS43 0.9 1.88 2.6 1.75 0.7 1.62 4.2
HMDS44 0.9 1.87 2.7 1.73 0.8 1.58 4.4
HMDS45 0.5 1.88 3.0 1.75 0.8 1.63 4.3
Experiment
0.4
Fit (C + N + O)
k × (k) (Å–1)
–0.4
2 4 6 8 10
k (Å–1)
Figure 5.4.14 Best fit of the filtered first peak (0.6–2 Å) of the FT for HMDS43 (as-formed).
The estimation of the uncertainties in the fitted parameters is a non-trivial problem, because
of the correlation between the different parameters, Rij and !E0 on one hand, and Nij
and σij on the other. One should also consider the role played by the anharmonicity of pair
potentials, which means the deviation from a gaussian behaviour. In another strongly covalent
system, amorphous Ge, the study of the local disorder using the cumulant expansion leads to
corrections, to interatomic distances and to coordination numbers (Dalba et al. 1993). These
corrections are fully within the error bars we have quoted here. So we did not consider any
anharmonic behaviour, which should be in any case very difficult to evidence in a two-shell
disordered model. Furthermore, a non-negligible uncertainty of the first-shell fit procedure
comes from the fact that C and N, acting as backscatterers, are neighbours in the periodic
classification table, which means that they cannot easily be distinguished.
Last, a two-shell model, with partial coordination numbers NC and NN , provides an average
picture of the local arrangement of the C and N atoms in the first coordination shell of the
absorbing Si atoms. It does not allow the discrimination of a locally demixed phase with
SiC4 and SiN4 tetrahedra arrangement (complete chemical ordering), or a random stacking
of mixed SiCx N4−x tetrahedra. This point will be clarified by looking at the near edge
structure in the next section.
The Si K XANES studies

In X-ray absorption, an electron absorbs an incident photon and is promoted to an empty state
in the conduction band. Within the dipolar approximation, only transitions corresponding to
!l = ±1 between the orbital quantum numbers of the initial and final states are allowed.
The experimental Si K edge spectrum therefore reflects the p local DOS on a Si atom. For
instance, a sharp and intense resonance is observed at the threshold of spectra of molecular
species. This resonance has been associated for molecular spectra to a Si 1s electron promoted
to σ ∗ orbitals with appreciable Si 3p character (Hitchcock et al. 1993) and its energy position
and intensity vary with the nature of the first Si neighbours. An alternative way to interpret the
experimental XANES spectra is to use the full multiple scattering formalism, where the effect
of the core hole is also taken into account. This has been applied with success to reproduce the
polarisation dependence of XANES of α-quartz, for which very large clusters are required
(Briois et al. 1993), and of β-SiC (Sainctavit 1993) using the CONTINUUM code developed
by Natoli et al. (1980). It has been shown that the structures B and C (Figure 5.4.5) in the SiC
XANES spectrum can be related to the size of the microcrystals through EXAFS information
and full multiple scattering calculations. As a passing note one can observe the very peculiar
shape of the β-SiC XANES. It has to be compared with the one of Si (CH3 )4 (Bodeur et al.
1990), where Si is also surrounded by 4 C, the XANES of which exhibit a prominent edge
resonance. The effect of the long-range order in β-SiC appears as a corner cut-off of the edge.
In all Si reference compounds, the structures, present between the resonance at the edge and
the broad resonance located about 20 eV above the threshold, are strongly dependent on the
structural medium-range order. The different calculations described above show definitely
this point. One can notice as an illustration that α- and β-Si3 N4 can be differentiated by
taking a glance at the XANES: the β form, where the unit cell is half as large as that of the
α phase, presents the most structured XANES spectrum. The second point to notice is the
chemical shift existing when going from pure Si to silicon oxide. The threshold position is
strongly dependent upon the nature of the atoms which built the tetrahedral environment of
Si, and is directly related to the electronegativity of these atoms, that is, to the more or less
large density of p conduction states on Si sites.
This allows us to give qualitative conclusions concerning the XANES spectra of the Si/C/N
compounds (Figure 5.4.15(a)). First of all the shape (which remains similar whatever the
C/N ratio) of the near edge domain is constituted of a well-defined threshold, with a broad
resonance (A) followed only by a broad structure (C) at about 15 eV above the edge. The
fact that all the XANES structure between A and C is washed out indicates a medium-range
disorder between the tetrahedra, and clearly confirms the amorphous state of the as-formed
sample. Second, looking at the energy position of the absorption threshold, we see that it
varies continuously but stays at an intermediate position between that of SiC and Si3 N4 v. the
C/N ratio. We think that this is a direct evidence for a mixed environment of a SiCx N4−x type.
Actually, a demixed environment would lead to a two-steps edge, as it can be observed for
samples heated above the crystallisation temperature. Figure 5.4.15(b) is a clear illustration
of the demixing process accompanying the beginning of the crystallisation: the XANES
(a)
HMDS40 as-formed
A HMDS42 as-formed
HMDS43 as-formed
HMDS44 as-formed
Absorption (au)
HMDS45 as-formed
-SIC
-SI3N4
C
0
1840 1850 1860 1870
E (eV)
(b)
HMDS44 1550°C/4 h
-SIC
Absorption (au)
-Si3N4
0
1840 1850 1860 1870
E (eV)
Figure 5.4.15 (a) Evolution of the Si K XANES spectra of Si/C/N powders for different C/N
ratio (b) Si K XANES spectrum for the two references β-SiC and α-Si3 N4 and
for the HMDS44 sample after heating above the crystallisation temperature. The
last one appears clearly as a combination of the two references ones.
1844
Si3N4 HMDS45
HMDS44
HMDS43
1843
E (eV)
HMDS40
HMDS42
1842
0 0.4 0.8 1.2

C/N
Figure 5.4.16 Variation of the edge position with the C/N ratio.
becomes very structured near the threshold, and looks more like a linear combination of both
SiC and Si3 N4 spectra: the two kinds of tetrahedral environment are now present in different
proportions, depending on the annealing conditions.
Therefore, concerning the as-formed samples, a local chemical ordering can be excluded
by just looking at the XANES spectra. Figure 5.4.16 shows the evolution of the edge position
when the C/N ratio increases, and C atoms are replaced by N atoms in the Si environment.
Such a mixed configuration for Si atoms was also evidenced previously for laser synthesised
Si/C/N nanoparticles, using gaseous Si precursor (Gheorghiu et al. 1992) or an aerosol
precursor with a low C/N value (Driss-Khodja et al. 1996). Such a mixed environment for Si
atoms has already been suggested from NMR studies by Suzuki et al. (1995), who concluded
to the presence of SiCN3 tetrahedra in Si/C/N systems at high N content.
EXAFS – Analysis of the intermediate order: modelisation of

the experimental data
Beyond the first peak of the pseudo-radial distribution function (FT), which corresponds to the
first coordination shell of the Si atoms, one can observe (see Figure 5.4.12) two small peaks in
the range 2–3.5 Å (uncorrected from phase-shift). These peaks are very little dependent on the
C/N ratio, and this means that the intermediate order is in average independent of the chemical
composition. Focusing on one sample (HMDS43 with a C/N equal to 0.7), an attempt has
first been made to fit these peaks with Si Si contributions, with a wide distance distribution,
as one can expect in an amorphous covalent network where the close environment is well
defined, but where there can be an enhancement of the bond angle distortions. Figure 5.4.17(a)
shows the very bad quality obtained for the fit with only Si Si second environment. Fitting
the experimental data by Si N pairs at a distance of 2.78 Å only, or by Si C pairs at
2.84 Å, strongly increases the fit quality (Figure 5.4.17(b)). The improvement obtained by
this solution evidences the fact that most of the silicon tetrahedra are not in majority linked
by their corners. Such a two-shell simulation assumes also the presence of C N bonds in the
amorphous network. From these preliminary results, a model is proposed (Figure 5.4.18),
where mixed tetrahedra are randomly linked through C N bonds.
(a)
Experiment
Fit (Si)
k × (k) (Å–1)
(b)
Experiment
Fit (C)
k × (k) (Å–1)
3 6 9
k (Å–1)
Figure 5.4.17 (a) Best fits of the filtered second peak (2–2.8 Å) of the FT (Figure 5.4.13) for
HMDS43 sample with one Si Si shell; (b) One-shell fit of the filtered second
peak corresponding to Si C at 2.84 Å as second neighbours for Si atoms. A fit
corresponding to Si N at 2.78 Å gives also a good agreement with the experiment.
as-formed
N
C Si1
Si3
Si2
Calculation
Figure 5.4.18 Proposed model for the amorphous atomic structure of Si/C/N with C/N = 0.7.
This model was built with a molecular mechanic software (CERIUS). An analysis of
various two, three and four bodies interactions allows an evaluation of the forces on each
particle. The energy expression deduced for N-body systems, such as our model, is calculated
by superposition of single terms (bond, angle, torsion, inversion). The exact nature of each
term depends on the particular loaded force field. Here, we used the DreidingII force field
(Mayo et al. 1990), which is recommended for structures with novel combination of elements
and those for which there is little or no experimental data. A computational module allows then
the minimisation of the energy expression of the model and leads to an optimum geometry.
This average model is composed of SiN3 C tetrahedra linked through C N bonds, in order
to form six-edges polyhedra. The only constraints imposed before the relaxation process are
the first neighbours distances for Si C and Si N bonds. They were fixed to those found by
the experimental analysis (1.89 Å for Si C and 1.74 Å for Si N).
The coordinates of the atoms in the model are then extracted and used as input to the FEFF
code (Rehr et al. 1992), in order to compare the corresponding calculated EXAFS signal,
which includes multiple scattering paths, to the experimental one. In that calculation, the
default values were used for the input parameters. The calculation is performed with Si1 ,
Si2 and Si3 playing the role of the central atom (see Figure 5.4.18). The number of paths
is limited to four, and the maximum distance (Rmax ) to 6 Å. The first shell gives the main
contribution. Beyond it, one finds a large distribution of Si N and Si C two-legs paths
between 2.6 and 2.85 Å, followed by three-legs paths corresponding to Si/C/N and Si/N/C,
the distances of which are found between 2.9 and 3.15 Å. The first Si Si distances are found
around 3.3 3.4 Å. It happens that the best fit is obtained when averaging the results on Si2
and Si3 as central atom. Figure 5.4.19 shows the good agreement obtained by this way. The
calculated result obtained with Si1 as central atom leads to an enhancement of the second
neighbours peaks. This amplitude difference, due to the fact that Si2 and Si3 do not have all
their second neighbours, may have two explanations. First, this could evidence a static and/or
dynamic disorder on the outer shells distance, due to distortions of the valence bond angles of
C and N first neighbours. As it is well known in EXAFS and has been discussed previously,
2
HMDS43 as-formed
Model
|FT| and Im(FT) (au)
–1
0 2 4 6
R (Å)
Figure 5.4.19 Comparison of the FT (modulus and imaginary part) for the experimental spec-
trum of the HMDS43 Si/C/N sample, with the FEFF calculation using the atomic
coordinates of the model proposed in Figure 5.4.18.
such a disorder appears as a reduction of the coordination number, then the environment
of Si2 and Si3 could represent a more realistic situation than Si1 . This amplitude reduction
can also be interpreted as an anharmonic effect originating in the size of the nanometric
particles. But nanometric Si/C/N powders concern particles of an average diameter of about
30 nm, with only about 10% of the atoms in surface. The only disorder taken into account
intrinsically in our simulation is that coming from the calculated positions of the atoms, with
no further parameter: this accounts for the structural disorder and its deviation to a gaussian
distance distribution.
Second, this lower coordination number might be real and could come from dangling
bonds of N and C, or to a bonding to H atoms. In terms of an EXAFS analysis, these two
structural situations are indistinguishable, and can be both present in the material. Finally,
such a limited model is not able to reproduce the XANES part of the spectrum, probably
due to the fact that the muffin-tin approximation in the calculation of the potential is not
appropriate.
5.4.3.2 Evolution of the local order during the pyrolysis process
1400◦ C
Our purpose is then to understand the structural evolution before the crystallisation, when the
sample is treated under N2 at 1400◦ C for 24 h, 1500◦ C for 4 h and up to 1600◦ C. The observed
changes are rendered on the FT as modifications of the second and third neighbours in the
intermediate-range order (Figure 5.4.20). The comparison of the FT of the as-formed powder
and the annealed ones underlines the slight evolution of the short-range order after annealing
at 1400◦ C (Figure 5.4.20), while more important change occurs in the intermediate-range
order. In order to determine the local order around Si, a two-shell fit of the first peak has
been performed on the basis of Si C and Si N pairs. We obtained the structural parameters
presented in Table 5.4.5. As for the as-formed samples, a two-shell model with partial NSi C
2
HMDS44 as-formed
HMDS44 1400°C/24 h
1
|FT| and Im (FT) (au)
–1
0 2 4 6
R (Å)
Figure 5.4.20 FT (modulus and imaginary part) of the k 2 weighted EXAFS oscillations for
HMDS44, as-formed, and annealed 24 h at 1400◦ C.
Table 5.4.5 First-shell structural parameters obtained with a two-shell fit (Si C +
Si N) for two compositions and for two annealing temperatures
(1400◦ C for 24 h and 1500◦ C for 4 h). !N/N = 10%, !R = 0.02 Å
HMDS42-1400 1.4 1.87 2.8 1.74 4.2

HMDS42-1500 2.3 1.88 1.7 1.75 4
HMDS44-1400 1.2 1.87 2.8 1.73 4
HMDS44-1500 1.7 1.87 2.3 1.73 4
1400°C
Si N
Calculation
Figure 5.4.21 Proposed model for the amorphous atomic structure of the sample annealed at
1400◦ C (24 h).
and NSi N provides an average picture of the local arrangement of the C and N atoms in the
first coordination shell of the absorbing Si atoms.
Beyond the first peak of FT (Figure 5.4.20), the structures relative to intermediate-range
order evolve with the annealing temperature. Unlike the results obtained for the as-formed
powders, and as early as 1400◦ C, one has to introduce Si Si bonds as second neighbours.
A new 3D structure based on EXAFS results (short range and intermediate order) was built and
then tested through multiple scattering calculations at the Si K edge of central Si atoms of the
structure. The model presented in Figure 5.4.21 is related to the 1400◦ C annealed temperature.
It is composed of rigid SiN3 C tetrahedra (Si N = 1.74 ± 0.02 Å and Si C = 1.89 ± 0.02 Å
linked by C N bonds with large distance distributions (1.46–1.55 Å) or partially linked by
their corner. The evolution compared to the as-formed model is the possibility to link the
SiN3 C tetrahedra by their corner. This model was in a second step tested on 3 Si central
atoms through multiple scattering calculation using the FEFF code. The average calculated
spectrum and its FT presented in Figures 5.4.22(a) and (b) are compared to the corresponding
experimental parts. The agreement between experiment and calculation is good. Particulary,
the evolution beyond the first peak is well reproduced. The evolution in the way in which
tetrahedra are linked is confirmed by the calculations: Si atoms as second neighbour of Si
(a)
1 HMDA44 1400°C/24 h
Model
k × (k) (au)
–1
2 4 6 8 10
k (Å–1)
(b)
2
HMDA44 1400°C/24 h
1 Model
–1
0 2 4 6
R (Å)
Figure 5.4.22 Comparison of (a) k × χ (k) and (b) FT (modulus and imaginary part) for the
experimental spectrum of the sample (HMDS44), annealed at 1400◦ C for 24 h
with the FEFF calculation, using the atomic coordinates of the model proposed in
Figure 5.4.21.
atoms appear at 1400◦ C. This result is consistent with the increase of the density which is
also observed in the powders. Concerning the static disorder, the Si atoms taken as absorbing
atoms in the FEFF calculations still have an incomplete second coordination shell, which
simulates the static disorder. The increase of the coordination number compared to the as-
formed model simulates the decrease of the static disorder when the annealing temperature
increases.
1500◦ C
The same approach on the XAS spectra, corresponding to the 1500◦ C annealed sample,
shows this time an evolution of the NC /NN ratio. Figure 5.4.23 presents the FT of HMDS44
annealed at 1400◦ C (24 h) and 1500◦ C (4 h). Strong changes occur in the first coordination
2
HMDS44 1400°C/24 h
HMDS44 1500°C/4 h
1
HMDS44 1550°C/4 h
A
–1
0 2 4 6
R (Å)
Figure 5.4.23 FT of the k 2 weighted EXAFS for HMDS44 annealed at 1400◦ C (24 h), 1500◦ C
(4 h) and 1550◦ C (4 h).
HMDS45 1500°C/4 h
HMDS43 1500°C/4 h
HMDS44 1500°C/4 h
3 HMDS45 1500°C/4 h
-SiC
-Si3N4
Absorption (au)
0
1840 1850 1860 1870
E (eV)
Figure 5.4.24 Evolution of the Si K XANES spectra at 1500◦ C with different C/N ratio.
shell around the Si atoms. The amplitude of the first peak in the FT decreases at 1500◦ C
(4 h). Table 5.4.5 gives the results obtained for HMDS42 and HMDS44 with a two-shell fit
(Si C and Si N) of the first peak. The evolution of the ratio NC /NN as a function of the C/N
ratio is still linear. The first coordination shell of the Si atoms is enriched in C. This result
is confirmed by the XANES study of the samples annealed at 1500◦ C (4 h). For HMDS42,
HMDS43 and HMDS44, the spectra still exhibit a unique threshold, the energetic position of
which is intermediate between those of SiC and Si3 N4 (Figure 5.4.24). A small shift towards
lower energies of the threshold position is observed (<0.5 eV) compared to the as-formed
samples. The broad resonance C is shifted towards the lower energies (∼1 eV). According to
the Natoli rule (Bianconi 1983), this shift is interpreted by an increase of the average distance
between the Si absorbing atoms and the atoms located in the first coordination shell, which is
consistent with the increase of the NC /NN ratio underlined by EXAFS analysis. From these
results, we expect that SiC2 N2 tetrahedra appears in the amorphous powders at 1500◦ C. In
a first approximation by fitting the second peak (1.9–3.2 Å) of the FT, one can conclude
to an increase of the number of Si Si second neighbours corresponding to a structural
reorganisation, which may appear as an early beginning of crystallisation. This increase of
the number of Si Si second neighbour pairs is confirmed by FEFF calculations performed
on a cluster, where SiC2 N2 tetrahedra are in a majority linked by their corners. The Si atoms
chosen as central atoms in the calculations have now a nearly complete second coordination
shell and the decrease of the structural disorder is going on. These results assume that strong
modifications of the short- and medium-range order in the powders occur at 1500◦ C in the
amorphous state.
Beyond 1500◦ C
The FT corresponding to the samples annealed at 1500◦ C (Figure 5.4.23) exhibits the well-
known focusing peak at about 5.8 Å, which corresponds to the crystallised SiC phase (ZnS
blende structure) of the 8th shell. The compound is crystallised in a mixture of β-SiC and
Si3 N4 the proportion of which can be estimated by fitting the first shell.
The observation of the XANES spectra reinforces the conclusions drawn from the fitting
procedure. Until 1500◦ C (for a 4 h annealing time), the shape of the near edge domain is
constituted of a well-defined threshold (Figure 5.4.24), with a broad resonance (A) followed
by a broad structure (C). The lack of structures between A and C is the sign of a disordered
structure. The unique threshold inserted between those of β-SiC and α-Si3 N4 is a proof of
the presence of mixed tetrahedra. Above this temperature, or with longer annealing time, the
XANES becomes more structured showing already the characteristic structures of β-SiC,
and a two steps threshold (Figure 5.4.15(b)). We can conclude to the presence of a mixture
of β-SiC and α or β-Si3 N4 . From the chemical composition and assuming a complete crys-
tallisation, one can estimate the proportions of the two different phases, about 35% of β-SiC,
and 65% of α- or β-Si3 N4 for HMDS44. In order to check this assumption, mixtures of two
crystallised powders (β-SiC and β-Si3 N4 ) for different proportions were tested. Figure 5.4.25
compares the XANES of a mixture constituted of 70% of Si3 N4 and 30% of SiC and the one
of the HMDS44 powder treated at 1600◦ C for 4 h. The agreement between the two spectra
confirms that the crystallisation is achieved. At this point one has to underline that the slight
differences observed on the two XANES of α- and β-Si3 N4 does not allow one to determine
definitely which phase is present in the final powder.
5.4.4 Local structure of pre-alloyed Si/C/N/Al/Y nanopowders

studied by XAS at the Al K edge using fluorescence
yield detection
5.4.4.1 Introduction
The aim of the present part is to determine the atomic environment of Al both in as-formed
SiCNAlY and annealed powders, in order to get information on a possible formation of
the (Y)SiAlON liquid phase during sintering, necessary for producing dense ceramics and
leading to an intergranular phase after cooling. We compare it with the structure found in
crystalline Al(O)N, with YSiAlO(N) amorphous phases, and with a sintered sample where
the intergranular phase is present.
3
Absorption (au)
-SiC (30 at.%) + -Si3N4 (70 at.%)

HMDS44 1600°C/4 h
0
1840 1850 1860 1870
E (eV)
Figure 5.4.25 Comparison of the XANES spectrum of the sample annealed at 1600◦ C with one
of the mixture of the two crystallised phases (30% of β-SiC and 70% of β-Si3 N4 ).
5.4.4.2 Experiment
Al K edge (1559 eV) XANES and EXAFS spectra were recorded at room temperature at
beamline SA32 of the 800 MeV positron storage ring SuperACO at LURE, by collecting the
total electron yield for the references compounds and the fluorescence yield for the dilute
samples. We used a mono-element Ge detector (Eurisys-Mesures), with an energy resolution
of 150 eV. The monochromator was a scanning two-crystals set-up with quartz (1010) crystals.
As a consequence, the EXAFS data were recorded only up to 1830 eV. For the XANES part
of the absorption spectra, a constant background has been subtracted in the pre-edge region,
and except for α-Al2 O3 , the spectra were normalised to the atomic absorption above the
threshold. All Al XANES spectra were calibrated with an Al metallic foil at the inflection
point (1559 eV). The extraction of the EXAFS oscillations was performed in a classical way:
modelisation of the atomic background by a fifth-order polynomial, and normalisation using
the Heitler approximation. FTs of the k 2 weighted oscillations were calculated over the same
energy range for all compounds and references. The chemical compositions of the studied
samples as well as those of the amorphous references are presented in Table 5.4.6.
5.4.4.3 Results
As we are dealing with amorphous compounds, where XANES multiple scattering
calculations in the ‘muffin-tin approximation’ are difficult to perform, our approach was to
measure aluminium oxides and nitrides, as well as amorphous YSiAlO(N), pure or embed-
ded in the sintered material. From direct comparison with that in model compounds, the
Al environment of unknown compounds can be ‘fingerprinted’ in terms of differences in
XANES (Ildefonse et al. 1994, 1998 and references therein). Experimental Al spectra of refer-
ences compounds are plotted in Figure 5.4.26(a). The differences observed between berlinite
(AlPO4 , with AlIV O) and corundum (α-Al2 O3 , with AlVI O) have been fully investigated
and simulated previously (Cabaret et al. 1996). In AlN, Al is coordinated to four N atoms. Its
XANES spectrum presents a large resonance located 3 eV below the characteristic white line
Table 5.4.6 Elemental analysis (at%) of the amorphous reference phases, and
of the pre-alloyed samples (AF = as-formed, AN = annealed at
1600◦ C)
Si C N O Al Y
HSAl17-AF 33.5 26 33.5 6.2 0.6 0.2

HSAl17-AN 44 24 29.9 1.6 0.4 0.1
YSiAlON 12.3 — 7.5 54.7 18.5 12.3
YSiAlO 6.8 — — 63.6 17.7 11.9
(a)
4 AIN
AION
AIPO4
AI2O3
Absorption (au)
–2
(b) YSiAlON-am
2 + YSiAlO-am
SC2X
Absorption (au)
0
1560 1580 1600
E (eV)
Figure 5.4.26 (a) Al K edge XANES spectra for references where Al is fourfold coordinated
(AlPO4 and AlN), sixfold coordinated (Al2 O3 ), and in a mixture of sites (AlON),
(b) Al K edge XANES spectra for amorphous references. (Reprinted from Flank
et al. (1999) with kind permission of International Union of Crystallography.)
of AlIV O in AlPO4 . The oxynitride phase AlON is usually described as a solid solution in
the Al2 O3 AlN structure, isostructural to γ -Al2 O3 , where it is expected that Al has a range
of local tetrahedral and octahedral environments, including mixed anion (i.e. N and O) coor-
dinations (Dupree et al. 1988). The XANES spectrum of this last system is characteristic of a
mixture of sites, but we have to point out that the threshold position is more than 3 eV below
the one found in corundum, in line with the presence of Al four-fold coordinated, and that
the spectrum presents some structures characteristic of an ordered structure also evidenced
by XRD.
In Figure 5.4.26(b), XANES spectra of the amorphous phases YSiAlO(N) are compared
with the Al spectrum of the sintered compound, where Al is supposed to be both in the
intergranular phase YSiAlON and in the β-SiAlON obtained after annealing treatment. The
sintered compound (SC2X) is composed of 20 wt% of a SiC laser synthetised nanopowder
and 62 wt% of a Si3 N4 conventional powder (UBE-SNE10, α phase) and 12 wt% of Y2 O3
and 6 wt% Al2 O3 . Except for a very small shift towards high energy values of the threshold of
the sample without N (YSiAlO), all the spectra are identical, reflecting a structural similarity
between these different phases. From previous observations (Ildefonse et al. 1998), the edges
shapes: a small white line located at 1566.6 eV followed by a wide resonance, lead us to the
assumption that the dominant site for Al atoms in these phases is fourfold with some amount
of penta and hexa coordinated aluminium. But it is difficult to conclude about the existence
of mixed environment. Actually the edge position in fourfold coordinated Al compounds
depends on the nature of the second neighbour of Al atoms (Ildefonse et al. 1998).
As well, qualitative conclusions can be drawn about the coordination number and the
nature of the neighbours of aluminium in pre-alloyed Al/Y/SiCN powders. The XANES of
the as-formed powder presents a double structure (Figure 5.4.27). The threshold position is
located at the same position than for the amorphous references phases, that is, between AlPO4
and AlN. We cannot then conclude to a single Al environment. After annealing at 1600◦ C,
the Al K edge is much more structured (Figure 5.4.27): a resonance A appears at the same
position than that of Al fourfold coordinated to O atoms indicating the presence of AlO4
A
HSAl17 as-formed
4 HSAl17 1600°C/N2/1 h
AIN
AIPO4
Absorption (au)
B
2
C
0
1560 1580 1600
E (eV)
Figure 5.4.27 Al K edge XANES spectra for pre-alloyed Al/Y/SiCN nanopowders: evolution
with annealing and comparison with references.
2
AlN
HMDS44 1600°C/N2/1 h
|FT| and Im(FT) (au)
–1
0 2 4 6
R (Å)
Figure 5.4.28 Comparison of the FT (k 2 weighted oscillations over 2–7 Å−1 EXAFS k range) for
AlN and HSAl17 annealed at 1600◦ C. (Reprinted from Flank et al. (1999) with
kind permission of International Union of Crystallography.)
sites, the edge position is shifted to lower energy, when compared to the as-formed spectrum
indicating the presence of AlN4 sites, and finally the resonances B and C also observed for
the AlN crystalline structure prove the formation of AlN crystallites.
An EXAFS analysis of these compounds has been undertaken at the Al K edge. The
pseudo-radial distribution function of the AlN phase presents four peaks. The first one comes
from the first shell of 4 N atoms at R = 1.88 Å. The three following peaks are a mixture
of the different contributions of the next shells. AlON’s FT exhibits three main peaks. The
amorphous phases give both significant peak at a smaller distance than the first peak of AlN,
but a similar amplitude. The FT of the sample HSAl-17 annealed at 1600◦ C (Figure 5.4.28)
confirms the hypothesis drawn from the observation of the XANES: Al atoms are mainly
present in a crystalline AlN type structure.
5.4.4.4 Discussion
The unknown compounds have also been investigated by NMR, which reveals that Al can be
found in three different sites in the as-formed compound: tetra, penta and octa coordinated to
O atoms, while after annealing, four sites are still present: Al octa, Al tetra with AlO4 , AlN3 O,
and AlN4 . Because of the limited k range which does not allow a sufficient distinction between
the AlN and the other phases, the EXAFS spectrum seems dominated by the contribution
of Al atoms in the ordered phase AlN. But the shape of the XANES induces to claim the
presence of other different disordered sites, consistent with NMR results.
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5.5 Neutron and X-ray diffraction applied
to the study of the medium-range order
in SiCN nanopowders
François Ténégal, Brigitte Bouchet-Fabre, Jean Dixmier
and Robert Bellissent
5.5.1 Diffraction applied to the study of disordered

compounds
The early stages of the crystallisation of SiCN powders involve precipitation phenomena
through atomic diffusion processes within the disordered network. The goal is to investigate
the induced changes of the local order leading to nuclei of the equilibrium phases. The Fourier
transform (FT) of the interference function S(q) yields the radial distribution function (RDF)
G(r) that gives the values and number of interatomic distances between pairs of atoms. But
since we measure the beam intensities and not the amplitudes we lose the phases of the waves
and no information can be derived from G(r) on the statistics of higher order functions of
3, 4, etc. atoms. This knowledge is needed to build a three-dimensional image of the local
order. For example, the G(r) results cannot tell if Si C and Si N pairs belong to mixed
SiCx N4−x tetrahedra or to demixed SiC4 and SiN4 ones. It is the reason why the inverse
calculation of S(q) has been performed for three-dimensional atomic models as suggested
by the G(r) results and have been compared with the experimental ones.
5.5.2 Early stages of the crystallisation of Si/C/N-HMDS

nanopowders studied by X-ray and neutron diffraction:
Nano-ordered Si/C/N structures
5.5.2.1 Contrast effect between neutron and X-ray diffraction

measurements
Neutron and X-ray diffraction measurements were performed on SiCN nanopowders to take
advantage of the drastic differences of the weighting factors on silicon (Si), nitrogen (N) and
carbon (C) affecting diffraction spectra to selectively observe Si and N subnetwork. Such
contrast effect was also used for the structural study of SiCN ceramics obtained by pyrolysis
of polysilycarbodiimide polymer (Dürr et al. 1999). The total structure factor obtained from
diffraction measurements can be written as (Warren 1969):

S(q, E) = Wij (q, E)Sij (q) (5.5.1)
i,j >i
where Sij (q) are the partial structure factors for the atomic pair i–j and Wij (q) are the
weighting factor which depend on the composition of the studied samples and on the
Neutron XRD
0.4 Si9Si
N9N
Wij (q)
Si9N
Si9N
0.2 N9C
Si9C
Si9C N9N
N9C
Si9Si Si9O
C9C
0 Si9O C9C
6.74 13.48 0 6.9 13.8
q (Å–1) q (Å–1)
Figure 5.5.1 Weighting factors Wij (q) for the six pairs of atoms in the HMDS44 (1400◦ C for 24 h)
samples, defining the profile of the X-ray and neutron high angle spectra. The values
are also given for the Si O pair. Note that Wij (q) varies with q in X-ray experi-
ments but remains constant for neutron experiments. The important fact is that the
subnetwork of Si is reinforced by X-ray while the N one is preferentially seen by
neutron.
energy of the incident radiation. A complete determination of the six partial structure
factors (Si Si, Si N, Si C, N N, N C, C C) requires six experiments. Unfortunately,
anomalous wide angle X-ray scattering measurements (AWAXS) are experimentally unreach-
able at Si, N and C photoabsorption edges and then the complete determination of partial
structure factors is impossible. The difference in the nature of the radiation used in X-ray and
neutron experiments is responsible for a strong contrast effect on N and Si amorphous sub-
network. Figure 5.5.1 compares the Faber–Ziman weighting factors (Waseda 1984) (Wij (q))
calculated for X-ray and neutron radiations for HMDS44 (annealed at 1400◦ C for 24 h). In
the range of composition of the HMDS powders, the contrast is very strong between the X-ray
spectra which reflects for 80% Si Si and Si N correlations, whereas the neutron spectra
reflects for 80% N N, N Si and N C correlations.
5.5.2.2 Experimental and data analysis
Neutron
The neutron experiments have been performed on the 7C2 spectrometer at Laboratoire Léon
Brillouin (LLB) at Saclay (CEA-France). The neutrons wavelength (λ = 0.7 Å) was selected
with a copper monochromator (Cu(111)). The diffracted intensity was measured with a 640
BF3 -cells detector which allows to perform measurements with a constant !θ path. The
larger measurable scattering angle 2θ is 128◦ . The corresponding scattering vector q is equal
to 16 Å−1 (q = 4π sin θ/λ). The experimental data are corrected for absorption effect. The
contribution of the container I c(q) was subtracted from the measured diffracted intensity
I (q). The Placzek correction was applied (Placzek 1952) to correct I (q) from inelastic
scattering process. The spectra were then normalised by the coherent scattering cross-section
Neutron and X-ray diffraction application 213
of the sample to obtain the structural factor S(q) (small contribution of the incoherent cross-
section):
I (q)
S(q) = (5.5.2)
αN σcoh
where I (q) is the total elastic scattered intensity, S(q) is the total structure factor, N is the
number of atoms, σ the coherent scattering cross-section (Neutron 1992) and α a constant.
X-ray
The wide angle X-ray diffraction experiments were performed at LURE-DCI (Orsay-France)
on the wiggler DW31B beamline equipped with a 2-circles goniometer using a scintillator.
A 2-crystal (Si (220)) monochromator with sagitally focalisation and a double setup of distant
slits define the energy resolution. A 20.2 keV incident energy has been chosen in order to
use a q window going from 1 to 16 Å−1 (the same as for neutron experiments). Due to low
absorption coefficient of the studied materials, the spectra have been recorded in the reflection
mode with a nearly grazing incidence (θ0 = 2.5◦ ). The Compton contribution to the total
signal has been removed using the analytic Hajdu’s formula (Hajdu 1971) adapted for light
elements. The reduction of the recorded data after correction for absorption and asymmetric
geometry has been made by integration assuming:
qmax qmax
2
I (q, E)q dq = N
2
f + Icomp (q) q 2 dq (5.5.3)
qmin qmin
where Icomp (q) is the modelised Compton contribution and N the number of diffracting
atoms, I (q, E) is the total experimental scattered intensity. The elastic scattered intensity for
one atom i(q, E) can be written as:
i(q, E) = |f 2 | + |f |2 [S(q, E) − 1] (5.5.4)

where |f |2 = i,j ci cj fi fj∗ and |f 2 | = i ci |fi |2 , S(q, E) is the total structure factor
and fi are the complex atomic scattering factors given by:
fi (q, E) = fi0 (q) + f (q, E) + if (q, E)fi (5.5.5)
are calculated for each element from tabulated values (Waasmaier and Kirfel 1995; Sazaki
1984). ci are the atomic fractions of each element in the powders.
5.5.2.3 Structural transition in the amorphous state
Evaluation of the hydrogen content

The strong incoherent (q dependent) and inelastic scattering of neutrons by hydrogen gives
a form factor to the H-rich powders neutron spectra. Figure 5.5.2 presents crude spectra of
the composition HMDS44 for the as-prepared sample and for annealed samples at 1000◦ C
(4 h), 1500◦ C (4 h) under N2 atmosphere.
The reduction of the form factor (decrease with q) with temperature is the consequence
of the hydrogen effusion during annealing treatment. At 1500◦ C, H has totally effused. The
residual decrease of the intensity at high q (1500◦ C) comes from the minor contribution
As-prepared
8000
4000
1000˚C-4 h
2000
I (q) (au)
1000
1500˚C-4 h
2000
1000
4 8 12 16
q (Å–1)
Figure 5.5.2 Evolution of the HMDS44 original spectra after the usual corrections with the anneal-
ing temperature. Note the incoherent scattering form factor of H which allows to
measure its content in the as-formed powder (21.5 at%) and in the 1000◦ C sample
(6 at%). At 1500◦ C, H has totally effused.
of inelastic scattering process concerning the other atoms (Si, N, C). For the sample which
present an important form factor, a quantitative evaluation of the atomic proportion of hydro-
gen in the powder can be performed (Dixmier et al. 1994). This can be achieved by making
the assumption that at high q values, the measured intensity corresponds to the coherent con-
tribution from Si, C, N atoms without the H contribution which has drastically decreased. The
theoretical asymptotic scattering cross-section σ is calculated for one average atom using the
tabulated scattering cross-section of the elements and the composition. The I (q = ∞) theo-
retical value is equal to αNσ , where N is the number of atoms (hydrogen excluded) and α is
a constant. The atomic form factor for one H atom is evaluated using the inelastic scattering
theory and the H content is then estimated by a trial and error method which consists in
subtracting from the spectrum a certain proportion of the background, in order to force the
curve to oscillate around the constant asymptotic value I (q = ∞). The subtracted intensity
corresponds to the contribution from H atoms: αNH σH , where NH is the number of H atoms
and σH the incoherent scattering cross-section for one H atom (σH = 80 barn for q = 0).
From this value and from the asymptotic value I (q = ∞), we calculated the H content. One
will find 21.5 at% for the as-prepared powder and 6 at% for the 1000◦ C annealed powder.
Structural evolution of Si/C/N nanopowders during the

pyrolysis process: 1400◦ C → 1500◦ C
SHORT-RANGE ORDER: EXISTENCE OF C N BONDS
The coupled X-ray and neutron diffraction experiments have been performed on the com-
position HMDS44 for two annealing temperatures (1400◦ C for 24 h and 1500◦ C for 4 h).
X-ray absorption spectroscopy (XAS) measurements underlined strong modification in the
short-range atomic structure around Si atoms between 1400◦ C and 1500◦ C. An increase of
the NSi C /NSi N ratio is observed. The neutron (Sn (q)) and X-ray (SX (q)) structure factors
for HMDS44 (1400◦ C for 24 h and 1500◦ C for 4 h) are reported in Figure 5.5.3.
As expected, X-ray and neutron spectra, which respectively reflect silicon and nitrogen sub-
network, are very different. The structure factors exhibit a set of broad diffuse halo characteris-
tics of covalent amorphous compounds. At low q values, on the neutron spectra, one can find a
first sharp diffraction peak (FSDP) related to the nitrogen medium-range atomic arrangement
in the powders. Dixmier (1992) showed that in a disordered network in which four coordinated
atoms (Si or C) are connected to three coordinated atoms (N), the structure factor S(q) exhibits
a main peak near 3 Å−1 generated by the first neighbour and two prepeaks at 2 and 1.5 Å−1
generated respectively by the mixture of four and three valencies. At 1400◦ C, we expect
that the extreme sharpness of the peak located near 3 Å−1 is a signature of the stacking of
disordered layers on coherent length of 2–3 nm. In contrast, the Si dominated X-ray spectrum
exhibits a diffuse first peak, but small sharp diffraction structures for q > 6 Å−1 . These small
peaks indicate the existence in the amorphous state of well-defined long-range correlations
in the Si amorphous subnetwork. At 1500◦ C, the shape of the structure factors change. The
(a)
Sn(q)
Sx(q)
1500°C-4 h
S (q)
(b)
1
1400°C-24 h
0 6 12
q (Å–1)
Figure 5.5.3 Neutron (Sn (q)) and X-ray (SX (q)) interference functions for HMDS44 annealed at
(a) 1500◦ C for 4 h and (b) 1400◦ C for 24 h . The two spectra (Sn (q) and SX (q)) reveal
the different evolutions of the Si and N subnetwork with the annealing temperature.
prepeak of neutron spectrum is split into two components and the morphology of the succes-
sive haloes changes. For X-ray spectrum, the first halo becomes sharper. This evolution is the
signature of the decrease of the chemical and topological disorder of the Si amorphous subnet-
work when the annealed temperature goes from 1400◦ C to 1500◦ C. Strong structural modifi-
cations occur in the short-range and medium-range order (MRO) of the amorphous compound
at 1500◦ C. These evolutions are consistent with those underlined by extended X-ray absorp-
tion fine structure (EXAFS) measurements concerning the evolution of the local order around
Si atoms with annealing temperature. The EXAFS results show that the Si subnetwork is very
disordered at 1400◦ C due to the mixture of the configurations for Si Si pairs (Si N(C) Si
and Si N(C) C(N) Si). The reduction of the number of Si N(C) C(N) Si bonds at
1500◦ C is responsible for the decrease of the topological and chemical disorder.
The contrast effect is clearly visible on the corresponding pair of correlation functions
G(r) presented in Figure 5.5.4. The first peak is not much affected (hetero-atomic bonds) but
the second one is definitively shifted (homo-atomic pairs such as N N or Si Si).
An attempt to simulate the first peak of the RDF (= 4πρ0 r 2 G(r)) was done. The procedure
starts with the modelisation of the distribution of j type atoms around an i type atom by
a Gaussian distribution fij (r). This distribution is related to the partial i–j pair correlation
function Gij (r) by:
fij (r) = 4πρ0 r 2 cj Gij (r)

3
where ρ0 is the atomic density (at/Å ), cj the atomic fraction of the element j and Gij (r)
the partial pair correlation function associated to the partial structure factor Sij (q). An FT of
the r-space contribution is then performed to obtain the q-space contribution Sij (q) and the
(a) Gn(r)
GX(r)
1500°C-4 h
G (r)
(b)
1400°C-24 h
0
0 2 4 6 8
r (Å)
Figure 5.5.4 Neutron (Gn (r)) and X-ray (GX (r)) pair correlations functions for HMDS44
annealed at (a) 1500◦ C for 4 h and (b) 1400◦ C for 24 h. The common integration limit
S(qmax) = 15 Å of the FT generate non-physical peaks before 1 Å at the same value
of r in the both experiments but not with the same amplitude. We expect that due
to the strong decrease of the X-ray scattering factors at high q, the neutron descrip-
tion of the short-range atomic structure is more accurate than the X-ray description
(particularly for the shortest correlations). The contrast effect is well marked for the
homo-atomic pairs N N and Si Si regrouped in the second peak near 3 Å.
20
(Si9N + Si9C)
15
RDF (at/Å)
10
0 1 2 3
r (Å)
Figure 5.5.5 Result of the simulation (neutron) of the first peak of the RDF with only two contribu-
tions (Si C and Si N) for HMDS44 annealed at 1400◦ C (24 h). The corresponding
structural parameters are given in Table 5.5.1.
Faber–Ziman weighting factor Wij (q) of the i–j pair is applied. Then, one goes back to the
real space by a new FT of the weighted contribution of the i–j pair (Wij (q)Sij (q)). If several
contributions have to be taken into account to simulate the first RDF’s peak, the components
are added. The obtained contribution is directly comparable to the experimental RDF since
the limits of integration used to calculate the FT are in both cases the same (1.5–15 Å−1 ).
Figure 5.5.5 presents the result of the simulation (neutron) using only two components (Si C
and Si N) for the 1400◦ C annealed sample.
Note that the values found for the centroid of Gaussian distributions are those found in
the crystalline compounds SiC and Si3 N4 for the Si C bond length (1.89 Å) and the Si N
bond length (1.74 Å). The results of the EXAFS analysis revealed that the Si N and Si C
bond lengths remain similar in the amorphous state compared to the crystalline state. These
two contributions (Si C + Si N) cannot fit the experimental shape of the first RDF’s peak
(Figure 5.5.5). A third shorter contribution must be added. Figure 5.5.6 shows the very good
fit (neutron) obtained when a C N (1.5 Å) contribution is added. Following this procedure,
two fits were realised for each spectrum taking as origin either Si or C and N atoms in the
modelisation of fij (r). Table 5.5.1 gives the structural parameters obtained for the samples
annealed at 1400◦ C (for 24 h) and 1500◦ C (for 4 h). One can observe that the proportion
of C N bonds decrease with annealing treatment. For the sample annealed at 1400◦ C, one
finds 3N + 1C around one Si atom, and 2.3Si + 0.7C around one N atom. At 1500◦ C, the
proportion of C atoms around one Si atom increases (2.2N + 1.8C) while the proportion
of C N bonds decreases. Let us recall that EXAFS results give 3N + 1C at 1400◦ C and
2N + 2C at 1500◦ C. The results obtained by coupling X-rays and neutron diffraction are in
very good agreement with those obtained by EXAFS. C N bonds are taken into account
in EXAFS local order models and are detected by X-ray photoelectron spectroscopy (XPS)
measurements. C C bonds detected by XPS are not introduced in the simulation since the
corresponding weighting factor WCC is lower than 5% (HMDS44). Their contribution to the
experimental spectra cannot be unambiguously proved. C C bonds from free carbon phase
were reported in the study by Dürr et al. (1999) for Si/C/N ceramics obtained by pyrolysis
20
(C9N + Si9N + Si9C)

15
RDF (at/Å)
10
0 1 2 3
r (Å)
Figure 5.5.6 Result of the simulation (neutron) of the first peak of the RDF with three contributions
(Si C, Si N and C N) for HMDS44 annealed at 1400◦ C (24 h). The corresponding
structural parameters are given in Table 5.5.1.
Table 5.5.1 First shells structural parameters obtained with a three-shell fit

of the first peak of the radial distributions functions (!R =
±0.02 Å, !N/N = ±10%, !σ = ±0.01 Å). For each compound,
two set of simulations (Si N + Si C + N C or N Si + C Si +
N C) were realised corresponding to two different choices for the
central atom taken for the modelisation of the distribution functions
R(Å) N σ (Å)
X-ray Neutron X-ray Neutron X-ray Neutron
1400◦ C (24 h)
Si N 1.76 1.74 2.8 2.8 0.07 0.07
(N Si) 2.4 2.3
Si C 1.89 1.89 1 0.9 0.07 0.05
(C Si) 3.2 3
N C 1.50 0.7 0.2
1500◦ C (4 h)
Si N 1.76 1.73 2.1 2.2 0.08 0.06
(N Si) 2.2 2.4
Si C 1.91 1.88 1.7 1.8 0.07 0.04
(C Si) 3.6 3.4
N C 1.51 0.4 0.18
of a polymer species (C/N = 1.3). In their study, the weighting factor ωcc was of the order
of 20% and the peak related to C C bonds was clearly observed in the neutron correlation
pair functions.
ANALYSIS OF THE MEDIUM-RANGE ORDER: THE TRANSITION 1400◦ C(α) → 1500◦ C(β)
The existence of a layered structure evidenced at 1400◦ C for N atoms must already occur in
the initial mineral residue at 1000◦ C. This should be induced by the possible sp2 bonding of
1550°C-4 h
4 0r (G (r)-1)
1500°C-4 h
1400°C-2 h
1000°C-4 h
A
3 4 5 6
r (Å)
Figure 5.5.7 Reduced neutron pair correlation function (4πρ0 r(Gn (r) − 1)) in the MRO domain
for HMDS44. The peak at 3.9 Å (A) is specific of the a stacking mode of α-Si3 N4 .
This correlation disappears at 1500◦ C and is replaced by a new one at 3.6 Å. The
stacking mode for the N atoms changes at 1500◦ C.
C atoms but also by the flat three coordinated N environment. Figure 5.5.7 presents the MRO
of Gn (r) (neutron) for HMDS44 for annealing treatments ranging from 1000◦ C to 1550◦ C.
At 1000◦ C, one can observe two small bumps at 3.4 and 3.9 Å which become sharper at
1400◦ C. The existence in the pair correlation function of a correlation at 3.9 Å is attributed
to the alpha stacking mode for the atoms in silicon nitride (α-Si3 N4 ). Calculations using the
Debye formula were performed on clusters of silicon nitride (Dixmier et al. 1994) which
evidenced a correlation between the peak at 3.9 Å and the α stacking mode in silicon nitride.
We performed a calculation of the atomic pair distribution in the two known crystalline
forms of silicon nitride (α and β). The result is that the correlation at 3.9 Å in α-Si3 N4 can be
associated with N N pairs at 3.82 Å between alternated layers. In the α form, the stacking
mode (along the crystallographic c axis) is ABCDABCD. . . and N N pairs at 3.82 Å exist
between N atoms of the layer A and N atoms of layer C, and N atoms of the layer B and N
atoms of the layer D. In the β form, the mode is ABABAB. . . This modification in the stacking
mode leads to the disappearance of the N N pairs at 3.82 Å and so to the annihilation of the
correlation at 3.9 Å in Gn (r). Then, the correlation at 3.9 Å in Gn (r) is the signature of the
α stacking mode for nitrogen atoms.
At 1500◦ C, the correlation at 3.9 Å disappears while a new one appears at 3.6 Å on the
experimental Gn (r). So, locally the increase of the NSi C /NSi N ratio at 1500◦ C is accom-
panied by a change in the sequential stacking mode of the layers. We expect that the α-mode
is replaced by the β-mode at 1500◦ C. In the amorphous state, nanometric (2–3 nm) SiCN
structures which are reminiscent of a crystalline topological order (α- and β-Si3 N4 ) exist. The
amorphous structure cannot definitely be considered as a mixture of an amorphous silicon
nitride phase and free C phase since mixed SiCx N4−x tetrahedra are detected by a X-ray near
edge structure (XANES) study at the SiK edge and by NMR measurements. Carbon atoms
induced structural and chemical disorder in α- and β-type SiNy phases. The term ‘chemical
disorder’ should be used with caution here. Indeed, the XANES and RMN studies show the
existence of mixed tetrahedra SiCx N4−x . For temperatures below 1400◦ C, the environment
of Si atoms are composed of 3N + 1C (around the same Si atom) or 4N. This allows us to
make the hypothesis of a relatively well chemically ordered SiCN structure in which C atoms
are homogeneously distributed. The chemical order is then different from those found in
crystallised SiC and Si3 N4 . At 1500◦ C, a broadening of the peak relative to Si environment
measured by RMN is observed. This broadening is attributed to an increase of chemical
disorder around the Si atoms: all the environments are detected for Si atoms. This increase of
the chemical disorder is acccompanied by an increase of the NSi C /NSi N ratio. In short,
before 1400◦ C we expect the existence of a nano-ordered α-SiCN structure composed of
SiCN3 and SiN4 tetrahedra and of C N bonds. At 1500◦ C, nano-ordered β-SiCN, in which
a beginning of demixion occurs, are formed. Gradients of C concentrations appear at the
atomic scale in the β-SiCN structure. Locally, an early formation of six member rings of SiC
occurs but the number of mixed tetrahedra remain dominant.
5.5.2.4 Nanocrystalline SiCN structural models
Building of the models and calculations

From the experimental results, the hypothesis of nano-ordered SiCN structures was
tested. This could be achieved by the modelisation of nanocrystalline structures involving
experimental data (XAS, RMN, XPS and diffraction). In order to simulate the α → β tran-
sition, we have decorated the structure of the two polytypes α-Si3 N4 and β-Si3 N4 with C
atoms substituting Si and N atoms in such a manner that mixed tetrahedra must be formed
as well as C N bonds. C atoms substituted to Si form CN4 tetrahedra and C atoms substi-
tuted to N atoms form CSi3 sites (Table 5.2.2). Then, a relaxation of the mechanical stress
is performed by using an algorithm which allows the potential energy minimisation of the
substituted structure. We used the CERIUS software to build the models and to perform
potential energy minimisation (see section modelisation). The bond distances in the models
were forced to those given by the experimental analysis (1.74 Å for Si N, 1.89 Å for Si C
and 1.5 Å for C N) during the relaxation process. This could be done by the addition in the
energetic expression of a term which is zero if the bond distances reach the constraint values.
We obtained new periodic (low symmetric) SiCN structures in which C atoms are bonded to
Si and N atoms. Figure 5.5.8 presents the α-substituted model which is related to 1400◦ C.
The theoretical scattered intensities of the models are calculated using the Debye formula
(Debye 1915):
sin(qrnm )
I (q) = fn (q)fm (q) (5.5.6)
n,m
qrnm
where I (q) is the total scattered intensity, rnm the distance between the atoms n and m, fn (q)
and fm (q) the scattering factor. The sum is taken over all the atomic pairs of the cluster.
The theoretical structure factors are deduced and compared with the experimental ones.
The calculations were performed using the INSIGHT program.
Table 5.5.2 Construction of the α- and β-substituted models and structural parameters
1400◦ C (24 h) 1500◦ C (4 h)
1 Construction of the cluster of crystalline Si3 N4

α-Si3 N4 β-Si3 N4
(P 31c; a = b = 7.753 Å, c = 5.618 Å; (P 63/m; a = b = 7.606 Å, c = 2.909 Å;
α = β = 90◦ , γ = 120◦ ) α = β = 90◦ , γ = 120◦ )
16 cells (2a × 2b × 4c) 32 cells (2a × 2b × 8c)
448 atoms (1.5 nm × 1.5 nm × 2 nm) 448 atoms (1.5 nm × 1.5 nm × 2 nm)
2 New description of the structures
Space group → P1 Space group → P1
gathering of 2 cells:
(1a × 1b × 2c) → (1a × 1b × 1c )
3 Periodic substitution of Si and N atoms by C atoms
(Experiment – HMDS44) (Experiment – HMDS44)
160Si → 36% Si 38.9% 176Si → 39% Si 41.0%
224N → 50% N 42.8% 176N → 39% N 41.2%
64C → 14% C 15.5% 96C → 22% C 15.9%
O 2.9% O 2.4%
SiCN3 in the majority SiC2 N2 , SiCN3
SiN4 , SiC3 N2 in the minority a few CN4 tetrahedra
CN4 tetrahedra
4 Relaxation of the geometric stresses
d Si C = 1.89 Å ± 0.02 Å d Si C = 1.89 Å ± 0.02 Å
d Si N = 1.74 Å ± 0.02 Å d Si N = 1.74 Å ± 0.02 Å
d N C = 1.5 Å ± 0.02 Å d N C = 1.5 Å ± 0.02 Å
N(C) Si N(C) from 100◦ to 120◦ N(C) Si N(C) from 90◦ to 125◦
Si N Si(C) from 105◦ to 135◦ Si N Si(C) from 105◦ to 135◦
Si(N) C Si(N) from 100◦ to 120◦ Si(N) C Si(N) from 100◦ to 130◦
Results of the calculations and discussion
NEUTRON
The neutron structure factor Sn (q) of the model relative to 1400◦ C (α-substituted) and for the
reference α-Si3 N4 are given in Figure 5.5.9. Figure 5.5.10 presents the calculated spectra for
the model relative to 1500◦ C (β-substituted) and for the corresponding cluster of β-Si3 N4 .
The hypothesis of nanocrystal of α-Si3 N4 can be dismissed. The structures of the exper-
imental spectrum (1400◦ C) are too different from those of the α-Si3 N4 cluster. The general
features of the experimental spectra are well reproduced by the models. In particular, the
evolution observed in the low q domain (q < 6 Å−1 ) characterised by the splitting in two
components of the FSDP at 1500◦ C is reproduced. For q > 6 Å−1 , the interference functions
exhibit small sharp diffraction peaks as expected since the models are small crystallites of
α- or β-SiCN. These structures which are not present in the experimental spectra simulate
a too strong topological order in the models which are derived from crystal structures. The
geometry obtained after relaxation is close to those of crystalline α- and β-Si3 N4 . The net-
works of connections between the atoms are the same as in the crystals since the C atoms
are only substituted to N and Si atoms and the mixing of the valence states is the same as in
silicon nitride. Nevertheless, the haloes which support the small sharp diffraction structures
-SiCN
N
C
Si
Figure 5.5.8 Nanocrystalline α-SiCN model for the intermediate compositions (HMDS43,
HMDS44). This structure is relative to 1400◦ C.
are reproduced as well as the width and position of the first sharp diffraction peak which
show that the size of the nano-structures to be considered in the calculations are those of the
models. To improve the experiment–theory agreement, we simulated the loss of the medium–
long-range order in the model (1400◦ C) by a Fourier Transform (FT) filtering of the high r
correlations in the RDF. This corresponds to the disappearance in the interference function of
high frequency contributions. We performed the FT on the theoretically calculated S(q), we
suppressed the high r contributions (r > 5 Å) and then we made a back FT calculation on the
filtered real space contribution (0 → 5 Å). Figure 5.5.9 presents the results for the α-model.
The process smooth high frequencies contributions and the agreement with the experiment
at high q values is better. Unfortunately, the FSDP is broadened by this process and the
agreement in the low q (q < 4 Å−1 ) domain is deteriorated. We expect that this procedure
will simulate a too drastic increase of the structural disorder beyond 5 Å. The smoothing
process simulates an abrupt decrease of the structural order beyond 5 Å around each of the
448 atoms of the model. From these results, we can conclude that the experimental spec-
trum is intermediate between those of non-smoothed model and smoothed model the sizes of
which (1 nm) are close to those of local order models obtained from EXAFS measurements.
It is interesting to note that for the β-model (1500◦ C), all the small diffraction peaks appear
on the experimental spectrum of the sample annealed at 1550◦ C.
-Si3N4
-SiCN model
Sn (q)
FF (model)
Experiment-1400°C
0 5 10 15
q (Å–1)
Figure 5.5.9 Calculated neutron interference functions (Sn (q)) for the α-model compared with
the experimental spectra (1400◦ C). The Fourier filtered (FF) calculated spectrum is
given as well as the crude one for the cluster of α-Si3 N4 .
-Si3N4
-SiCN model
Sn (q)
Experiment/1550°C-4h
Experiment/1500°C-4h
0 5 10 15
q (Å–1)
Figure 5.5.10 Calculated neutron interference functions (Sn (q)) for the β-model compared with
the experimental spectra (1500◦ C and 1550◦ C). The calculated spectrum for the
cluster of β-Si3 N4 is also given.
Figure 5.5.11 presents the calculated and experimental RDF. The evolution of the MRO is
reproduced by the calculations.
X-RAY
The structure factors SX (q) of the models compared to the experimental ones are presented in
Figure 5.5.12. The Fourier filtered theoretical spectra are also given (the correlations at r ≥
Experiment
1400°C-24 h
1500°C-4 h
RDFn
Models
1400°C-24 h
1500°C-4 h
RDFn
2 4 6
r (Å)
Figure 5.5.11 Calculated and experimental neutron RDF. The disappearance of the correlation at
3.9 Å is well reproduced by the modification of the stacking mode (α → β) when
going from 1400◦ C to 1500◦ C.
4 Å for the α-model and r ≥ 3.8 Å for the β-model are removed). As for the neutron calculated
spectra, the X-ray calculated spectra exhibit a lot of small sharp structures relative to long-
range interatomic correlations in the models, but contrary to neutron, experimental spectra
exhibit the signatures of long-range correlations in the high q domain (q > 5 Å−1 ). These
correlations are pretty well reproduced by the α-model (1400◦ C). The experimental spectra
are, on the whole q range, intermediate between the theoretical smoothed and theoretical
non-smoothed spectra. The differences concerning the low q domain are also reproduced by
the calculation: the X-ray spectra do not exhibit a FSDP.
The main result of these calculations is the existence of nano-ordered structures α- and
β-SiCN in these powders. The structure change when the annealing temperature increases
and the modifications of local order are accompanied by ‘phases transition’ which occur in
the amorphous state. This result underlines the importance of the existence of the β-SiCN
(β-Si3 N4 substituted and relaxed) phase in the nucleation of β-SiC crystallite. The nucleation
of β-SiC is beginning within the β-SiCN phase at 1500◦ C. For intermediate compositions
(HMDS43 and HMDS44), the C content does not allow the local formation of β-SiC nuclei
at 1500◦ C. More energy is needed to allow the diffusion of C atoms in the β-SiCN structure
to reach locally the SiC stoichiometry. At 1500◦ C, for the rich C powders (HMDS40 and
HMDS42), the β-SiCN structure is saturated by C atoms; locally one finds SiC4 tetrahedra
and nuclei of β-SiC that are formed. The excess C forms a free C phase. For the N-rich powder
(a)
-SiCN model
SX(q)
FF (model)
Experiment – 1400°C
0 5 10 15
q (Å–1)
(b)
-SiCN model
SX(q)
FF (model)
Experiment – 1500°C
0 5 10 15
q (Å–1)
Figure 5.5.12 (a) Calculated X-ray interference functions (SX (q)) for the α-model compared
with the experimental spectra (1400◦ C), (b) calculated X-ray interference functions
(SX (q)) for the β-model compared with the experimental spectra (1500◦ C). The
Fourier filtered (FF) spectrum is also given.
(HMDS45), there is not enough C in the structure to prevent the formation of nano-crystallites
of β-Si3 N4 .
References
Debye, P. (1915) Ann. Physik, 46, 809.
Dixmier, J. (1992) J. Phys. I France, 2, 1011.
Dixmier, J., Bellissent, R., Balhoul, D. and Goursat, P. (1994) J. Eur. Ceram. Soc., 13, 293.
Dürr, J., Schempp, S., Lamparter, P., Bill, J. and Aldinger, F. (1999) Precursor-derived Ceramics (eds
J. Bill, F. Wakai and F. Aldinger), Wiley-VCH, p. 224.
Hajdu, F. (1971) Acta Crystallogr., A27, 73.
Mayo, S. L., Olafson, B. D. and Goddard III, W. A. (1990) J. Phys. Chem., 94, 8897; (1992) Neutron
News, 3(3), 29–37.
Placzeck, G. (1952) Phys. Rev., 86(3), 377.
Sazaki, S. (1984) KEK report, anomalous scattering factors for synchrotron radiation users, cal-
culated using Cromer and Liberman’s method, National laboratory for high energy physics.
www-lib.KEK.jp/cgi-bin/img_index?198324022.
Waasmaier, D. and Kirfel, A. (1995) Acta Crystallogr., A51, 416.
Warren, B. E. (1969) X-ray Diffraction, Addison-Wesley Publishing Company.
Waseda, Y. (1984) Lecture notes in physics, novel application of anomalous X-ray scattering for
structural characterization of disordered materials, Springer Verlag, Berlin Heidelberg, New York,
Tokyo.
6 Conductivity and dielectric properties of
Si/C nanopowders
Abdelhadi Kassiba
6.1 Introduction
Nano-sized powders of silicon carbide (SiC) have recently attracted a great deal of interest
mainly oriented towards the improvement of mechanical and thermal properties of nanocom-
posite materials such as MgO SiC, Al2 O3 SiC (Niihara and Nakahira 1991) and oxide
matrices reinforced by SiC fibres (Karlin and Colomban 1998; Monthioux and Delverdier
1996). The nanometric SiC grains are obtained by pyrolysis of polycarbosilane polymers in
inert gas (Yajima 1980) or by laser pyrolysis of (SiH4 , C2 H2 ) gaseous mixture (Cauchetier
et al. 1988). Whatever the used process, the final network contains carbon (C) in excess
arranged as isolated clusters or associated with the SiC grains (Charpentier et al. 1999,
Monthioux, Chapter 4). Several reports have pointed out the correlation between the struc-
tural, mechanical and electrical properties of SiC fibres with the C in excess content (Karlin
and Colomban 1998; Mouchon and Colomban 1996; Monthioux and Delverdier 1996).
Particularly, the enhanced thermal stability of the ceramics and their improved mechan-
ical features as well as the electrical conductivity of SiC-based ceramics depend on C
excess, which prevails in materials annealed at temperatures below 1400◦ C. Electron para-
magnetic resonance (EPR) investigations (Kassiba, Chapter 5.2) on the SiC nanopowders,
reveal a high content of delocalised unpaired spins (1019 spin g−1 ) thermally activated by low
energies (∼10 meV) (Charpentier et al. 1999). Furthermore, a drastic damping of an EPR
λ/2-resonant cavity was found in these materials when annealed above 1400◦ C. Dielec-
tric losses by conducting paths modify the quality factor of the cavity and the microwave
absorption rate. All experimental investigations (Charpentier et al. 1999; Kassiba et al.
2000) have demonstrated that annealing alters irreversibly all the physical properties includ-
ing the grain morphology, size and composition as well as the crystalline structure and
interface features. The latter which are dominated by the C-rich phase at the outermost
particle surfaces and the disorder are expected to play an important role in the conduc-
tion process and dielectric behaviour. Moreover, we have demonstrated earlier (Kityk et al.
2000), that SiC nanocrystallites embedded within a polymer matrix show promising non-
linear optical phenomena. In that case, the interface SiC-polymer is of particular importance
on the induced second harmonic generation signal. This can open new areas through the
search of original electronic and non-linear optical properties in materials based on SiC
nanocrystallites.
The following report is dedicated to the analysis of the dielectric behaviour, electrical and
transport properties in SiC nanopowders with regard to the structure, grain sizes and inter-
face features. Different experimental approaches are conjugated for a better understanding
of the electrical properties. Among them, we have used dielectric relaxation spectroscopy
228 Abdelhadi Kassiba
(DRS), microwave method (MWC), 4-points method and Hall effect measurements. These
investigations are carried out as functions of annealing which modulate in large extent the
physical properties of the network. Measurements with variable temperatures (150, 570 K)
and frequencies (0.1 Hz, 10 GHz) are achieved for a quantitative understanding of the
electronic, relaxation and transport phenomena in these SiC nanopowders.
6.2 Material specifications

SiC nanopowders are synthesised by CO2 laser pyrolysis of gaseous mixture (SiH4 , C2 H2 )
(Cauchetier et al., 1988, Chapter 2). The rate of C in excess is monitored by the gas fluxes
while the residence time of the reactants in the laser beam monitors the particle diameters in
the as-formed powder. The composition, the SiC crystalline structures and the particle sizes
can be modulated to a large extent by annealing under argon up to 1800◦ C (Charpentier et al.
1999). The mean particle diameter varies from ∼30 nm (annealing temperature 1200◦ C) to
the micrometer range (annealing at 1800◦ C).
Transmission electron microscopy (TEM) investigations (Monthioux, Chapter 4) have
shown that the grains are constituted by SiC polytypes partially covered by thin layers of C in
one batch SiC177 (C in excess 10%) or by an oxide in SiC212 (C in excess 4%).
Structural investigations import on the involved SiC polytypes which are essentially 6H
and 3C polytypes with annealing-dependent ratios. Amorphous SiC is also present in a minor
concentration (≤10%) as well as sp2 C for annealing below 1500◦ C in SiC212 and remains in
SiC177 annealed up to 1800◦ C. Whatever the C in excess rate (SiC163: 1.11, SiC173: 1.10
and SiC212: 1.04), the batches exhibit similar electrical behaviour at the same annealing
stages. So, the following report is limited to the SiC212 batch with the powders referred
below as SiC212/1200◦ C and SiC212/1800◦ C, following their annealing temperatures at
1200◦ C and 1800◦ C.
6.3 Experimental results and interpretation
6.3.1 Dielectric losses and electrical conductivity in the

microwave range (MWC)
These measurements are of a particular interest since neither ohmic contacts nor a particular
sample shape processing is required. A simple diagnostic of the conducting states in the
10 GHz domain can be obtained easily. This requires an EPR spectrometer with a λ/2-resonant
cavity in order to evaluate the dielectric losses in the SiC nanopowders. The mechanism is
based on a damping of the resonant cavity and lowering its quality factor by conducting
materials. The resonant cavity design is devoted to enhance these effects by using a small
amount of the SiC powder (∼10 mg) located in the cavity region where the microwave electric
field is maximum. In all the investigated SiC batches, Ta = 1500◦ C corresponds to the critical
temperature where the dielectric losses are manifested and alters significantly the microwave
response of the materials. Figure 6.1 shows the behaviour of the reflected microwave power
by the SiC nanopowders annealed between 1200◦ C and 1800◦ C. Narrow dips correspond to a
minimum of the reflected power realised in the samples annealed below 1500◦ C. Conversely,
flat and broad dips correspond to the materials annealed between 1500◦ C and 1650◦ C. This
behaviour is consecutive to the occurrence of macroscopic conduction induced by annealing
at T ≥ Ta .
Conductivity and dielectric properties of Si/C nanopowders 229
1800°C
Reflected microwave power (a.u.)
1550°C
1200°C
–2 × 10–3 0.0 2 × 10–3
/( – 0)
Figure 6.1 Reflected microwave power by SiC212 powder located in the region of an X-band
(ω0 = 9.5 GHz) EPR resonant cavity where the microwave electric field is maxi-
mum. The dip shapes represented from bottom to top are due to the samples SiC212
annealed at 1200◦ C, 1300◦ C, 1400◦ C, 1500◦ C, 1550◦ C, 1600◦ C, 1650◦ C, 1700◦ C
and 1800◦ C. The maximum of dielectric losses (flat dip) is realised in the
SiC212/1550◦ C sample.
Microwave electrical conductivity (S m–1)
SiC212 1800°C
0.8
1650°C
1500°C
0.6
0.4
0.2
100 150 200 250 300 350 400 450 500

T (K)
Figure 6.2 Electrical conductivity in the microwave range v. the sample temperature in SiC212
nanopowders annealed at 1500◦ C (), 1650◦ C (•) and 1800◦ C (); the lines are
a guide for the eye.
Quantitative measurements of the electric conductivity by using the process developed by

J. G. Theobald in Besançon University (Frand et al. 1995; Kassiba et al. 1999) are shown in
Figure 6.2. The conductivity increases with the sample temperature and follows qualitatively
an activated law:
σmW (T ) = σ0 e−(Eg /kT )
with [σ0 (S m−1 ), Eg (meV)] ≈ [1.1, 20], [0.7, 6], [0.9, 9] respectively for annealing
at 1500◦ C, 1650◦ C and 1800◦ C.
4.0
SiC212 1650°C
3.5
ln( (T ))
3.0
2.5
2.0
0.002 0.004 0.006 0.008 0.010 0.012 0.014 0.016 0.018
1/T (K–1)
Figure 6.3 Electrical conductivity measurements in SiC212 by the conventional 4-points method.
The evolution with the temperature shows a thermal activation of the conductivity with
energies, 3 meV below 185 K and 30 meV above.
Then, it seems that a substantial electrical conductivity is induced by annealing above

1400◦ C with a thermal activation of the charge carrier motions by low energies 6–20 meV.
These values are in agreement with those required to delocalise some paramagnetic species
(Kassiba, Chapter 5.2).
6.3.2 Electrical conductivity by the 4-points method

The samples are prepared as pressed pellets (diameter 12 mm and 0.5 mm thick). On each
pellet, four gold contact points are deposited by CVD technique. Annealing under hydro-
gen at 300◦ C during 5 min improves the contact resistors which change from 1000 to 40 J
and remain ohmic on all the explored temperature range. Figure 6.3 shows the dc conduc-
tivity v. the sample temperature in the SiC212/1650◦ C sample. Above 185 K, a thermally
activated conductivity is found, that is, σdc (T ) = σ0 exp(−Eg /kT ) with Eg ∼ 30 meV
and a pre-factor σ ≈ 60 S m−1 . The activation energy is in agreement with those obtained
from the above microwave characterisations (MWC). However, a discrepancy is found in
the absolute conductivity values. The main origins are plausibly due to the shape of the
investigated materials, the different porosity degree and the inhomogeneous conducting
paths.
Furthermore, transport measurements by the Hall effect are carried out in order to determine
the nature and concentration of the charge carriers as well as their mobility. n-type conduction,
charge carriers concentration N ∼ 1019 cm−3 and a mobility µ ∼ 1 cm2 V−1 s−1 are the main
parameters of the electronic transport in these SiC nanomaterials.
6.3.3 Dielectric relaxation spectroscopy (DRS)
Theoretical background and phenomenology

DRS determines the relative complex permittivity ε∗ (ω, T ) = ε (ω, T ) − iε (ω, T ) v. the
alternative applied voltage frequency (ω/2π) and the sample temperature T . The overall
complex conductivity is deduced from the relation: σ ∗ (ω, T ) = iωε0 ε ∗ (ω, T ),
where ε0 is
the vacuum permittivity.
As far as the forthcoming experimental facts are concerned, the real conductivity part can
be set in the form of contributions from the steady-state (σdc ) conductivity and a frequency-
dependent part as follows:
σ (ω) = σdc + ωε0 ε (ω)
However, phenomenological representations are usually employed to account for the fre-
quency behaviour of ε∗ (ω) in heterogeneous media (Hunt 1998). Among them, the Havriliak
Nagami (HN) response (Havriliak and Nagami 1966), which reads:
σdc !ε
ε∗ (ω) = + ε∞ +
iε0 ω (1 + (iωτ )α )β
!ε represents the difference between the low frequency limit, that is, the relaxed permittivity
(εs ) and the high frequency limit ε∞ with respect to the explored frequency range. The
phenomenological parameters α, β monitor the asymptotic behaviour of ε ∗ (ω). Indeed, when
ωτ % 1; ε ∼ ω−αβ and for ωτ & 1; ε ∼ ωα , τ , represents also a phenomenological relax-
ation time (Hunt 1998) even if it can be associated to the experimental dielectric loss peak
position.
Experimental details
Novocontrol Broadband Dielectric Spectrometer is well adapted for a class of materials with
a conductivity lying between 1 S cm−1 to that of high insulating materials. Measurements of
the dielectric function are possible over a wide frequency range (0.1 Hz–1 GHz) by using two
experimental configurations. From 0.1 Hz up to 10 MHz, a solartron Si1260 combined with
a broadband dielectric converter (BDC) determines the overall sample impedance. In the high
frequency limit (1 MHz–1 GHz) an HP4291 radio frequency impedance analyser is used with
a precision coaxial line (Kremer and Arndt 1997). For both configurations, the sample cell
consists of two round golden plates electrodes filled with the material (pressed pellet with
diameter 12 mm and 0.5 mm thick) to form a capacitor. In the high frequency range, the sample
capacitor is used as a termination of a golden coaxial line. The corresponding impedance is
deduced from the complex reflection factor at the end of the line. The measurements were
performed as a function of temperature between 198 and 573 K. A gas stream of nitrogen (N)
is used and the measured temperature close to the sample is controlled within the accuracy
of ±0.1 K.
Dielectric behaviour
Due to the critical annealing temperature Ta = 1500◦ C, which alters significantly all the
physical properties of the SiC nanopowders, we have examined in detail the conduc-
tion and dielectric behaviour of two representative samples, namely SiC212/1400◦ C and
SiC212/1700◦ C.
In the former, the absence of pertinent details on the dielectric functions, above 10 MHz,
allows us to limit the measurements to the frequency range 0.1 Hz, 10 MHz. Figure 6.4(a)
and (b) shows in a log–log scale, the frequency and thermal evolution of the dielectric function
[ε (ω), ε (ω)]. The continuous curves are plotted from HN response with the parameters
(α1400 = 1; β1400 = 0.5). α and β are independent of the sample temperature (Ts ) as well
as ε∞ = 8. Following the frequency range, two variation regimes of ε (ω) are evidenced.
In the low frequency side, the linear variation occurs from the steady-state dc conductivity.
The second regime, in the high frequency side, is marked by a dielectric loss peak centred at
a frequency νmax = 1/τmax , which varies from ∼10 Hz to ∼1 MHz with increasing Ts . The
real dielectric function ε (ω) is also marked by a relaxation process with the frequency νmax
and by a low frequency dispersion (LFD). The latter behaviour depends on the experimental
conditions and testifies the existence of contributions from the contacts between the sample
and the electrodes. So, in the adjustment of ε (ω) by the (HN) equation, we have ignored the
(LFD) contribution. The relaxed parameter εs1400 ≈ 140 is one order of magnitude larger than
the value in bulk crystalline SiC. This can be due to an interfacial polarisation favoured by
the high specific surface of the SiC212/1400◦ C sample and by the inhomogeneous particle
surface composition through the predominance of C in excess.
(a)
100
573 K
⬘
513 K
468 K
423 K
378 K
333 K
288 K
10 243 K
198 K
HN fit
10–1 100 101 102 103 104 105 106
Frequency (Hz)
(b) 108
573 K
107 513 K
468 K
106 423 K
378 K
105 333 K
288 K
104 243 K
198 K
⬙
HN fit
103
102
101
100
10–1
10–1 100 101 102 103 104 105 106
Frequency (Hz)
Figure 6.4 Log–log representation of the (a) real and (b) imaginary dielectric function v. the
frequency in the sample annealed at 1400◦ C. The continuous lines are fits from HN
equation. Similarly (c) and (d) represent the dielectric function in the SiC212/1700◦ C
sample.
(c) 50
40
30
⬘
20
193 K
273 K
373 K
453 K
533 K
HN fit
10
106 107 108 109
Frequency (Hz)
(d)
103
193 K
273 K
373 K
453 K
533 K
102 HN fit
⬙
101
100
106 107 108 109
Frequency (Hz)
Figure 6.4 (Continued).
Similar investigations were performed on the SiC212/1700◦ C sample (Figure 6.4(c)

and (d)). However, higher frequencies (up to 1 GHz) are needed in order to characterise
the dielectric loss peak as in the SiC212/1400◦ C sample. The phenomenological parameters
are (α1700 = 0.5; β1700 = 1) and ε∞ = 11, independent of Ts . The relaxation process is
marked by a characteristic frequency (νmax ) in the order of 100 MHz and increases towards
high frequencies with increasing Ts . The relaxed dielectric constant, εs1700 = 40, is quite
lower than in the SiC212/1400◦ C sample. This is connected with the grain surfaces being
striped from the C in excess (Charpentier et al. 1999) and with a coalescence of SiC particles,
that is, mean diameter 1600 nm for annealing at 1700◦ C, limiting the interface polarisation
effects which prevail in the SiC212/1400◦ C sample.
(a) 1 × 10–4
1 × 10–5
Real conductivity ⬘ (S cm–1)
1 × 10–6
1 × 10–7
1 × 10–8 573 K
513 K
1 × 10 –9 468 K
423 K
378 K
1 × 10–10 333 K
288 K
243 K
10–11 198 K
HN fit
10–12
10–1 100 101 102 103 104 105 106
Frequency (Hz)
(b) 1
Real conductivity ⬘ (S cm–1)
0.1
193 K
233 K
373 K
453 K
533 K
HN fit
0.01
106 107 108 109
Frequency (Hz)
Figure 6.5 Log–log representation of the conductivity v. the frequency obtained by DRS
spectroscopy: (a) SiC212/1400◦ C and (b) SiC212/1700◦ C.
Electrical conductivity
In SiC212/1400◦ C and SiC212/1700◦ C samples, the frequency dependence of the conduc-
tivity are depicted in Figures 6.5(a) and (b) where the continuous lines are drawn from the
(HN) equation. We may note that the behaviour at low frequencies is dominated by σdc
up to crossover values about 1 kHz and 10 MHz respectively in the SiC212/1400◦ C and
SiC212/1700◦ C samples. These values are temperature dependent and follow qualitatively
the behaviour of the dielectric loss peak positions. In the high frequency side, no universal
behaviour such as σac (ω) ∝ ωp with 0 < p < 1 was identified (Jonscher 1977; Funke
1993). This excludes any speculation on the real nature of the conduction process in these
heterogeneous media.
The thermal behaviour of the dc conductivity are summarised in Figures 6.6(a) and (b).
In the SiC212/1400◦ C sample, an activation law σdc (Ts ) = σ0 exp(−Eg /kTs ) with Eg =
500 meV and a pre-factor σ0 = 7 S m−1 are realised above T1 = 330 K. Similarly, in the
1 2 3 4 5 6
1×10–5
SiC1400 10–3
1×10–6 SiC1700
(S cm–1) (SiC1400)
1×10–7
dc
(S cm–1) (SiC1700)
1×10–8
1×10–9
dc
1×10–10
10–11
10–12 10–4
1 2 3 4 5 6
1000/Ts (K–1)
Figure 6.6 Dc conductivity v. 1000/T obtained from DRS spectroscopy measurements. Activated
conductivity following Arrhenius law is realised in a limited temperature range.
SiC212/1700◦ C sample, by limiting the temperature range to 250 ≤ Ts ≤ 430 K, σ (Ts ) is also
accounted by an activated process with an Eg1700 = 35 meV and a pre-factor σ0 = 0.3 S m−1 .
Below 250 K, the thermal variation of the conductivity is characterised by a continuous
decrease of the activation energy without any defined variation law such as that relevant in
a variable range hopping process (Mott and Davis 1979) or that used in SiC fibres (Chauvet
et al. 1992).
Above 430 K, as shown in Figure 6.6(b), the conductivity exhibits a rounded shape behav-
iour (negative temperature coefficient). This process is reversible but it is no longer connected
with a metallic character of the SiC212/1700◦ C sample (Kassiba et al. 2000). The observed
behaviour has to be analysed with respect to the conductivity supports in the material, that
is, charge carriers diffusion in the crystallite bulk, tunnelling through the interface barriers as
well as the material porosity. All these parameters have to be optimised for relevant insights
on the particular behaviour around 430 K observed in all the SiC nanomaterials annealed
above 1400◦ C.
It is worth noticing the agreement between the absolute conductivity values and the acti-
vation energies obtained by DRS and MWC methods even if different sample processing
(pellet, powder) are used.
With regard to the relaxation process, the parameter νmax varies with the sample temper-
ature as the inverse of the dc conductivity (Figures 6.7(a) and (b)). From the experimental
value of νmax and limiting the temperature range to that where an Arrhenius law is realised,
we have established the following relations:
−11 5890/T ε0 ε∞
τ 1400
max = 3.10 e (s) ≈
σdc
1400
(Ts )
and
−10 450/T ε0 ε∞
τ 1700
max = 2.10 e (s) ≈
σdc (Ts )
1700
(a) 1e – 5
1e – 6
1e – 7
dc (s cm )
–1
1e – 8
1e – 9
1e – 10
1e – 11
1e – 6 1e – 5 1e – 4 1e – 3 1e – 2 1e – 1 1e + 0
max (s)
(b)
1e – 3
dc (s cm )
–1
1e – 4
4e – 10 1e – 9 2e – 9
max (s)
Figure 6.7 Representation of the static conductivity v. the relaxation time of the HN response in
the samples (a) SiC212/1400◦ C and (b) SiC212/1700◦ C.
This proportionality is quite general and encountered both in electronic (Hunt 1993; Pelster
et al. 1994) and in ion conducting systems (Macedo et al. 1972; Moynihan 1994) as well.
No physical supports have been clearly assigned to this conductivity-relaxation dependence
as relevant in transport phenomena dominated by surface or bulk effects.
On the other hand, EPR investigations (Charpentier et al. 1999) have evidenced charged
vacancies, in the SiC crystallites, submitted to a thermal delocalisation by energies 13 meV.
Qualitatively, this value can be looked as the binding energy of individual charges to their
local sites and constitute a low contribution to the overall activation energy associated with
the macroscopic conductivity. The main part comes from the energy barriers at the grain
boundaries. The exact mechanism cannot be drawn rigorously but it is worth noting that
the large difference in the activation energies 500 meV and 35 meV respectively in the
SiC212/1400◦ C and SiC212/1700◦ C samples agrees with that between the specific surfaces
(SiC212/1400◦ C : 35 m2 g−1 and SiC212/1700◦ C : 1.2 m2 g−1 ). This analysis is supported
by the magnitude of the static dielectric constant being enhanced in materials with high
specific surfaces due to the interface polarisation effects. Then, surface effects at the grain
boundaries monitor the electrical behaviour of these powders and the conductivity-relaxation
dependence can be attributed to such effects.
6.4 Conclusion
We have used complementary techniques in order to quantify the electrical, dielectric and
transport properties in SiC nanopowders. A thermally activated conductivity is pointed out
in the materials annealed at T ≥ Ta = 1500◦ C. At this stage, a removal of the C in excess is
operated as well as a coalescence of the SiC particle. These modifications favour the develop-
ment of conduction channels through the increase of the mean free path of the charge carriers
and the lowering of the barrier thickness between the grains. The interface effects seems
crucial and explain the conductivity and dielectric behaviour in these media. The interpre-
tation correlates the dielectric properties with the structural and morphological changes by
annealing. It is worth noting also the possibility to modulate the electrical behaviour of SiC
nanopowders as well as their effective dielectric constant by suitable thermal treatments.
References
Cauchetier, M., Croix, O. and Luce, M. (1988) Adv. Ceram. Mater., 3(6), 147.
Charpentier, S., Kassiba, A., Bulou, A., Monthioux, M. and Cauchetier, M. (1999) Europ. Phys. J: AP,
8, 111.
Charpentier, S, Kassiba, A., Emery, J. and Cauchetier, M. (1999) J. Phys. Cond. Matter, 11, 4887.
Chauvet, O., Stoto, T. and Zuppiroli, L. (1992) Phys. Rev. B, 46(13), 8139.
Frand, G., Bohnke, O., Lacorre, P., Fourquet, J. L., Carré, A., Eid, B., Theobald, J. G. and Gire, A.
(1995) J. Solid State Chem., 120, 157.
Funke, K. (1993) Prog. in Solid State Chem., 22(2), 111.
Havriliak, S. and Nagami, S. (1966) J. Polym. Symp., 14, 89.
Jonscher, A. K. (1977) Nature, 267, 673.
Karlin, S. and Colomban, Ph. (1998) Composites, 29B, 41.
Kassiba, A, Tabellout, M., Charpentier, S., Herlin, N. and Emery, J. R. (2000) Solid State Comm., 115,
389.
Kityk, I. V., Makowska, M., Kassiba, A. and Plucinski, K. J. (2000) Opt. Mater., 13, 449.
Kremer, F. and Arndt, M. (1997) Dielectric Spectroscopy of Polymeric Materials, Ch. 2 (eds J. P. Runt
and J. J. Fitzgerald), American Ceramic Society.
Macedo, P. B., Moynihan, C. T. and Bose, R. (1972) Phys. Chem. Glasses, 13(6), 171.
Monthioux, M. and Delverdier, O. (1996) J. Eur. Ceram. Soc., 16, 721.
Mouchon, E. and Colomban, Ph. (1996) J. Mater. Sci., 31, 323.
Mott, N. F. and Davis, E. A. (1979) Electronic Process in Non-Crystalline Materials, 2 edn. Clarendon
Press, Oxford.
Moynihan, C. T. (1994) J. Non-Cryst. Solids, 1395, 172.
Niihara, K. and Nakahira, A. (1991) Ann. Chim. Fr., 16, 479.
Pelster, R., Nimtz, G. and Wessling, B. (1994) 49(18), 12718.
Yajima, S. (1980) Philos. Trans. R. Soc. London Ser., A 294, 419.
7 Processing and tailoring of Si/C/N-based
nanocomposites
Paul Goursat, Djamila Bahloul-Hourlier,
Benoît Doucey and Martine Mayne
7.1 Introduction
Silicon nitride exists in two structural forms with a hexagonal unit cell α-Si3 N4 = (space
group P31c ) (Lang 1977) and β-Si3 N4 (space group P63/m ) (Grün 1979). The covalent nature
of Si N bonds provides very good mechanical properties, such as high strength and high
toughness up to elevated temperatures. The sintering of a powdered sample corresponds
to the formation of necks between grains due to the presence of evaporation–condensation
and/or diffusion mechanisms with an atomic or molecular redistribution. In the case of Si3 N4
the self-diffusion for silicon (Si) or nitrogen (N) is very low in the tridimensional network
of SiN covalent bonds, which explains the difficulties encountered to densify this material.
Moreover, decomposition occurs at high temperature which blocks the increase in mobility
of the species with rising temperature. These difficulties are usually partially solved in other
systems by using nanosized powders, but in the case of Si3 N4 , it is necessary to add a driving
force – mechanical and/or gas pressure, sintering aids, etc. – which explains the different
types of processes and materials: reaction bonded silicon nitride (RBSN); hot-pressed silicon
nitride (HPSN); hot isostatically pressed silicon nitride (HIPSN); gas pressured silicon nitride
(GPSN).
The additives used for the sintering of silicon nitride (MgO, Al2 O3 , Y2 O3 , etc.) react with
silica always present at the surface of the grains and lead to the formation of an oxyni-
trided eutectic phase with the general formula MSiM ON, where M and M are metallic
cations. These vitreous phases, which have been studied in quaternary or quinary sys-
tems (Figure 7.1), play a very important role during sintering and on the properties at
high temperature of the sintered material (Hampshire et al. 1978). Experiments on these
glasses and, in particular, the vitreous domain show that the N content changes with
the metallic cations and the temperature range (Lewis 1993). Among the main charac-
teristics of these materials it has been shown (Hampshire et al. 1994) that the viscosity
increases with N content which explains that crystallisation is slower than for the cor-
responding oxide glasses and that after sintering, the thermodynamic equilibrium is not
reached.
7.2 Sintering of silicon nitride with additives

A lot of papers are devoted to the sintering of silicon nitride for modelling, the determination
of mechanisms or the development of microstructures (Ziegler et al. 1987). During the heat
treatment of the powdered sample (α-Si3 N4 +additives : Al2 O3 , Y2 O3 , etc.), the oxynitrided
eutectic flows in the porosity and induces capillary forces, dissolution of fine particles and
Processing and tailoring 239
4YN
2Y2O3
4AIN Si3N4
3/2 Si2N2O
50
eq%N
10
2AI2O3 3SiO2
Figure 7.1 YSiAlON system.
∆I
I0 +
III
II
Time
Figure 7.2 Shrinkage and α → β phase transformation v. time.
a rearrangement process. The shrinkage is usually described by three different overlapping

mechanisms (Figure 7.2).
7.2.1 Particle rearrangement

The liquid phase wets the α-Si3 N4 grains and it localises mainly at the contact points. Under
the forces of capillary action, a rapid densification is obtained by grain sliding. In the case
of HP or HIP, the densification rate is sharply increased, the applied mechanical pressure
being much more higher. The densification rate changes with the particle size, the viscosity
and the volume fraction of the liquid. Different modelling emphasise the influence of these
parameters.
7.2.2 Dissolution–Diffusion–Reprecipitation
The applied pressure induces a preferential dissolution at the contact points of α-Si3 N4
crystals in the liquid phase with concentration gradients. A kinetic regime is established
with an intergranular migration of the dissolved species and a reprecipitation of β-Si3 N4
crystals or the β -SiAlON solid solution when alumina is used as a sintering additive. The
240 Paul Goursat et al.
flow of mobile species explains the redistribution of matter and a macroscopic shrinkage.
The comparison of the rate (dτ /dt) of the α → β transformation and the rate of densification
(dρ/dt) shows that the ratio
dτ/dt
=1
dρ/dt
corresponds to a diffusion regime. In the case of hot-pressing (Bowen et al. 1978), the rate
of densification is given by the following equation which is derived from the Coble model
established for the creep of materials:
dρ 4.75 × P D b JW
= (7.1)
dt G3 × KT
where P is the applied mechanical pressure; Db the diffusion coefficient in grain boundaries;
J the volume of the mobile species; W the thickness of grain boundaries; G the diameter of
the crystals; K is the Boltzmann constant.
7.2.3 Grain growth

When soluble particles with different particle sizes (radius r1 , r2 ) are in the presence of
a liquid, the difference in solubility provides the driving force for grain growth which cor-
responds to the Ostwald ripening phenomena. The grain growth rate (Greenwood 1956) has
been formulated as:
dr1 −2γ JD 1 1
= C∞ − (7.2)
dt KT d r1 r2
C∞ is the equilibrium concentration for a planar surface, γ the surface energy, J the molecular
volume of the mobile species, T the absolute temperature, K the Boltzmann constant, D the
diffusion coefficient in the liquid phase, d the mean distance between particles 1 and 2. The
grain growth kinetics by liquid phase sintering usually follows the equation:
r̄ n − r̄on = kt (7.3)
where r̄ is the mean particle radius, n = 3 the growth exponent, k the growth rate constant
and t is time.
As a matter of fact, for the sintering of silicon nitride, a lot of parameters are to be considered
and the equations are more complex. The presence of acicular crystals of β-Si3 N4 in the
starting powder hinders the rearrangement mechanism which overlaps the diffusion stage. It
is better to use α-Si3 N4 with an equiaxed morphology from the kinetics point of view.
The content and the size of β-Si3 N4 grains in the starting powder also play an important
role during the 2nd and 3rd densification stage. β-Si3 N4 crystals can act as the nuclei during
the reprecipitation process if their size is higher than the size of nuclei issued from the
homogeneous precipitation. According to Kang and Han (1995), the growth of β grains
along the c axis is due to the different roughness of the liquid–solid interface at an atomic
scale of (100) and (001) planes. If the number of β-Si3 N4 crystals is low, the free grain
growth of large crystals induces a microstructure with a bimodal particle size distribution. It
is possible to control and adjust the microstructure of sintered materials with a given size or
aspect ratio of β grains by adding β nuclei (Lee et al. 1994) or with a specific post sintering
heat treatment (Rossignol 1994).
The viscosity of the liquid phase also influencing the sintering rate is also very important.
For the same content of liquid phase, impurities such as oxides of Ca, Mg, Na, Fe, etc. which
lower the viscosity, facilitate the rearrangement and the diffusion processes. In return, other
elements such as carbon (C) have a deleterious effect.
7.3 Sintering of silicon carbide

Silicon carbide is usually densified by solid-state sintering with aluminium, boron and C as
sintering additives (Greskowich et al. 1977). Recently it was shown that silicon carbide can
be densified at 1800–1900◦ C with a liquid phase containing Y2 O3 and Al2 O3 (Kleebe 1992).
The β → α-SiC transformation is observed with a growth of elongated α-SiC grains. It is
also possible for SiC to design microstructures for specific properties.
7.4 Si3 N4 /SiC nanocomposites

In recent years, much interest has been focused on nanophase materials, which, due to their
small grain size, can offer improved properties compared to traditional materials (Siegel
1994). A further advantage of these materials is their ability to be hot-formed because of
their fine microstructures (Waikai 1990).
The main objective of this work is to elaborate Si3 N4 /SiC nanocomposites in order to fabri-
cate ceramic parts by hot-forming. The approach consists in introducing SiC (N) nanometric
powders as a second phase into a Si3 N4 matrix in order to influence the α-Si3 N4 to β-Si3 N4
phase transformation and the microstructural development of Si3 N4 /SiC nanocomposites.
Usually nanocomposites are ordered in two groups (Niihara 1991):
• micro–nano materials: a matrix with microscale crystals and an intragranular or an

intergranular nanoscale second phase;
• nano–nano materials: a matrix and a second phase with nanoscale crystals.
These materials are fabricated according to three different routes. The sintering of mixtures
of commercial silicon nitride with additives and a nanopowder of SiC. In the second route
the nanoparticles are synthesised in situ during sintering by a reaction between silica and C
deposited on silicon nitride crystals (Ishizaki and Yanai 1995). The last one corresponds to
the sintering of a mixture of nanopowders: Si3 N4 , SiC and additives or Si/C/N and additives
(Niihara et al. 1990). Till now, the number of papers devoted to the study of the sintering
kinetics is very limited, in particular to determine the influence of nanoparticles on the
different stages during the sintering of silicon nitride.
7.4.1 Dispersion and slip casting of Si/C/N nanopowders with Si3 N4

in organic liquids
It is well known that the method by which dispersions are prepared is a critical issue in
forming high quality green bodies and reliable ceramic parts. The present study concerns the
fabrication process of such materials which must be optimised because of the different sizes of
powders, and the hard agglomerates in Si/C/N nanopowders. The aim is to obtain a homoge-
neous distribution of the nanometric second phase in order to prevent the presence of defects
(essentially nanopowder agglomerates) decreasing drastically the mechanical properties.
Si3 N4 used as the matrix is the commercially available α phase Si3 N4 powder (UBE-
SNE 10). Si/C/N nanopowders used as second phase are synthesised by laser pyrolysis. Y2 O3
(Lonza) and Al2 O3 (Rhône Poulenc) are used as sintering aids. It has been observed by X-ray
photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and
X-ray near edge structure (XANES) that Si/C/N nanopowders obtained by laser pyrolysis are
composed of mixed tetrahedra SiCx N4−x with a small amount of Si O bonds (Gheorghiu
et al. 1992; Ténégal et al. 1996). The surface of such powders, analysed by IR spectroscopy,
contains Si OH and Si H bonds (Cauchetier et al. 1991).
Preparation of the green bodies

Two successive stages are necessary to prepare green bodies: the mixing of the different
powders and the forming process. In order to avoid the reagglomeration phenomenon induced
by dry mixing, the mixing process in liquid medium is well adapted. Moreover, the use of
organic liquids is preferable to prevent hydrolysis of silicon nitride based powders. Four
different organic liquids are tested: ethanol, acetone, acetophenone and hexane. Each powder
(Si3 N4 , Si/C/N) is mixed in each liquid (concentration = 50 g/l), and the evaluation of the
most suitable liquid is realised by sedimentation tests.
A mechanical device and a dispersing agent are chosen in order to, respectively, break
down agglomerates and stabilise the suspensions. Two mechanical devices are selected: the
‘turbula’ (system Schutz) allowing powder mixing by helicoidal movement, and the ultrasonic
probe (Vibra Cell 72412, Bioblock Scientific) involving the breaking of hard agglomerates.
Two dispersing agents (ICI Chemicals) having different nature are tested: the basic PS2
surfactant soluble in alcohol and the acid PS4 surfactant soluble in ketones. Each powder
(Si3 N4 or Si/C/N) is mixed using ‘turbula’ or ‘turbula’ + tultrasonic probe in ethanol +
PS2 or acetophenone + PS4 . The evaluation of the most suitable mechanical device and
dispersing agent is achieved by sedimentation tests. Viscosity measurements coupled with
sedimentation tests allow one to determine the optimum concentration of the well-adapted
dispersing agent.
After the homogenisation and the dispersion of suspensions, the liquid must be removed in
order to obtain green bodies. The forming process selected is slip casting in a plaster mould
because it allows to preserve the dispersed state of the suspension.
Organic liquid medium

Whatever the powder (Si3 N4 or Si/C/N) and the organic liquid (ethanol, acetone, acetophe-
none, hexane), flocculation occurs in the suspensions. Sedimentation tests consisted of
evaluating the relative height of sedimentation (hrelative = hsediment /htotal ). In the case of
flocculated suspensions, a low relative height indicates a compact stacking of powders due
to a beneficial effect of the liquid on particle dispersion.
The evolution of relative height of sedimentation in each liquid is presented for the two
silicon nitride based powders (Figure 7.3). For the two powders, an increase of the relative
height is observed as follows: ethanol, acetone, acetophenone, hexane. Such an evolution
corresponds to the classification of the more adapted liquid to the less adapted.
The suitability of each liquid for powders can be explained by acid–base interactions
between the surface sites of the particles and liquid molecules. The surface of Si3 N4 or
Si/C/N powders is essentially composed of acid Si OH bonds and some basic Si2 NH and
N H bonds.
1.0
Si3N4
Relative sedimentation height
0.8 SiCN
0.6
0.4
0.2
0.0
Hexane Acetophenone Acetone Ethanol
Liquid
Figure 7.3 Evolution of the relative sedimentation height for each powder in each liquid.
The interactions liquid/powder result mainly from the attraction of basic liquid by acid
Si OH groups. Thus, the more basic liquid (acetophenone) should be the best medium for the
dispersion of powders. Meanwhile, the adsorption of large molecules, such as acetophenone,
on all Si OH sites is difficult because of the rigidity of Si NH Si bonds and also of the
repulsion between the lone electron pair of N and the π orbitals of benzene group. That’s
why the linear ethanol molecule, even though it is less basic than acetophenone, is easily
adsorbed on Si3 N4 and Si/C/N powders.
Mechanical device for mixing and dispersion, and dispersing agent

Whatever the liquid, flocculation occurs in the suspensions. So the use of a well-adapted
mechanical device to disperse powders and of a dispersant to stabilise the suspensions is
necessary.
Sedimentation tests reveal that basic PS2 surfactant in ethanol does not have an effec-
tive action on powders, because for various dispersant contents, the suspensions remain
flocculated. This is probably due to the low number of acid Si OH sites available for the
adsorption of basic PS2 molecules. Effectively, these sites should be occupated by the basic
ethanol molecules.
The suspensions dispersed with PS4 (5% for Si3 N4 , 10% for Si/C/N, wt% of the dry matter
content) are deflocculated, indicating the beneficial effect of this surfactant. The evolution
of the sediment height with time for Si3 N4 and Si/C/N suspensions mixed with ‘turbula’ or
‘turbula’ + ultrasonic probe (Figure 7.4) indicates the positive effect of ultrasonic probe,
suggesting that this device is necessary to break down agglomerates. The suitability of PS4
dispersant is linked to a good compatibility between acid surfactant molecules and basic
surface sites of particles, non-occupated by the acetophenone molecules.
Forming process
For slip casting in plaster mould, suspensions should have high dry matter content
(≥50 vol%) in order to eliminate all the liquid by capillarity. The studied slurry is composed
6
Relative sedimentation height (mm)
0
1 2 3 4 5 6 7 8
Time (days)
Figure 7.4 Evolution of sedimentation height with time. T: Turbula, US: Ultrasonic Probe;
Si3 N4 , Si/C/N(T), × Si3 N4 (T + US), ' Si/C/N(T + US).
of a mixture containing of 71 wt% of Si3 N4 , 20 wt% of Si/C/N, 6 wt% of Y2 O3 , 3 wt% of

Al2 O3 and acetophenone. The dry matter content is 60 wt%. The dispersant content adapted
to this slurry is determined by both sedimentation tests and viscosity measurements. For
a 2.5 wt% of PS4 , sedimentation tests indicate a sediment height near to zero during three
days. This result gives evidence that the suspension is stabilised by 2.5 wt% of PS4 surfactant.
Viscosity measurements as a function of dispersant content (Figure 7.5) reveal a minimum
of viscosity around 2.5 wt% of PS4 which is in agreement with sedimentation tests.
Slip casting of this slurry takes place over one or two days, and the density of the green
bodies obtained is high (≈57% of the theoretical density) linked to a compact stacking of
powder particles resulting from the well-dispersed suspension.
This study has shown that compact green bodies can be produced in an organic liquid from
a mixture of two silicon nitride based powders with different granulometries. Although the
acetophenone is not the most convenient medium for the mixing process of these powders,
the acetophenone/PS4 surfactant seems to be a good chemical couple to disperse suspensions.
Thus, stable and well-dispersed slurries containing nanometric powders are obtained using
an ultrasonic probe to break down hard agglomerates of nanopowders.
Slip casting of such slurries leads to well-compacted green bodies associated with the
homogeneous and dispersed state of the suspensions.
7.4.2 Sintering of micro–nanocomposites

Powders (Si3 N4 , (UBE SN E10), Si/C/N) and additives (Y2 O3 = 6 wt%, Al2 O3 = 3 wt%)
are deagglomerated in liquid media. After drying, the green bodies are hot-pressed (35 MPa)
in the presence of N (1 atm) (Table 7.1).
The theoretical density of the composites is calculated from the density of each constituent
(Si3 N4 , SiC, glass-phase) and by using the rule of mixtures.
60
55
Viscosity (mPa s)
50
45
40
35
2 4 6 8 10
Dispersant content (wt %)
Figure 7.5 Viscosity as a function of dispersant content.
Table 7.1 References of micro–nanocomposites

Compounds (wt%) Theoretical SiC Grades
content (wt%)
Si3 N4 SiCN29 SiCN35 SiC173
91 — — — 0 Si3 N4
71 20 — — 1.7 Si3 N4 /SiCN29 (20)
79.9 — 11.1 — 5 Si3 N4 /SiCN35 (11.1)
68.8 — 22.2 — 10 Si3 N4 /SiCN35 (22.2)
46.6 — 44.4 — 20 Si3 N4 /SiCN35 (44.4)
71 — — 20 20 Si3 N4 /SiC (20)
51 — — 40 40 Si3 N4 /SiC (40)
Sintering kinetics with a linear increase of temperature

The shrinkage curves for the different compositions with the same content of nanopowders
of SiC show a sigmoidal shape (Figure 7.6(a)). The degree of densification at 1700◦ C is close
to 98%. On this figure is also represented the curve concerning the shrinkage of Si3 N4 . In
order to evidence the different behaviours, the derived curves giving the rate of densification
are shown in Figure 7.6(b). For monoliths and nanocomposites containing a SiCN second
phase, the beginning of the shrinkage corresponds to the formation of the oxynitrided eutectic
in the YSiAlON system at about 1350◦ C. The content, the composition and the properties,
particularly the viscosity of the liquid phase change strongly with temperature. Up to 1470◦ C
with a high viscosity, the rate of densification corresponding to a rearrangement process and
a dissolution of small particles is low. The shift to high temperatures for the Si3 N4 /SiC
(a)
100
90
Relative density (%)
80
70
60
50
1200 1300 1400 1500 1600 1700

Temperature (°C)
(b)
0.35
0.3
Rate of densification (˚C–1)
0.25
0.2
0.15
0.1
0.05
1200 1300 1400 1500 1600 1700

Temperature (°C)
Figure 7.6 Isobar densification curves. (a) Relative density, (b) rate of densification. ' Si3 N4 ,
Si3 N4 /SiCN29(20), × Si3 N4 /SiCN35(22, 2), Si3 N4 /SiC(20).
mixtures is explained by the SiC nanopowders. In this case, free C can react during the
heat treatment with oxygen at the surface of Si3 N4 grains and/or the additives. This reaction
delays the formation of the liquid phase and modifies its quantity or composition and therefore
the viscosity (Hampshire et al. 1978). Furthermore, SiC particles and agglomerates being
insoluble in the liquid phase, the dissolution stage is suppressed. At 1470◦ C, the sharp increase
in the rate of densification is explained by the dissolution of Si3 N4 and SiCN particles which
initiates the α → β phase transformation. These results show that at the beginning, the
rate of densification for the monolith is higher than for Si3 N4 /SiCN composites and it is the
opposite situation above 1550◦ C. The contributions of the rearrangement and dissolution
processes to the overall densification change with the size of the crystals and the thickness
of the intergranular vitreous phase (see equations 7.1 and 7.2). For nanopowders, at the same
liquid phase content the large specific surface area and the presence of agglomerates induce
a decrease of the thickness of grain boundaries and the flow of the species which explains the
lower rate of densification at the beginning of sintering for Si3 N4 /SiCN composites compared
to Si3 N4 monoliths. At higher temperatures (T > 1550◦ C), the increase for composites is
explained by a faster dissolution of SiCN nanoparticles (see equation 7.2).
One notices that the temperature corresponding to the end of densification depends on
the SiC content in the final material. The rate of densification during the dissolution–
reprecipitation stage is governed by the thickness of grain boundaries (see equation 7.1).
The thickness diminishes when the content of intergranular SiC particles increases. The flow
of mobile species is impeded which explains the shift to higher temperatures. The same phe-
nomenon is observed for Si3 N4 /SiC composites. Moreover, the starting SiC powder contains
an excess of free C which reacts with oxygen from silica or amorphous silicon oxynitride
located at the surface of silicon nitride grains or from additives and modifies the viscosity
and the liquid phase content. These experiments show clearly that the source of SiC nanopar-
ticles plays an important role on the dissolution–reprecipitation process and consequently
on the rate of densification. The SiCN nanoparticles are more soluble in the oxynitrided liq-
uid phase than SiC nanoparticles that are practically inert in this temperature range (Kleebe
1992).
Densification kinetics during isothermal treatments

The densification curves (Figure 7.7(a)) for the various grades exhibit the same shape with
a monotonous decrease of the rate of densification with time (Figure 7.7(b)). The differences
are mainly due to the composition and the content of the second nanometric phase. These
results are consistent with the previous experiments.
At 1530◦ C, the oxynitrided eutectic is formed which explains the high rate of densification
for the rearrangement stage. The rate increases with the content of SiCN nanoparticles. The
dissolution of these particles starts at the beginning of the rearrangement when the pressure
is applied. The overall rate is faster than for Si3 N4 alone. On the contrary, for Si3 N4 /SiC
composites the shrinkage is low due to the inertness of SiC nanoparticles towards the eutectic.
Moreover, SiC precipitates hinder the diffusion of species in grain boundaries which limits
the densification whatever the starting nanopowder used. The densification for composites is
uncompleted after 2 h at 1530◦ C under a pressure of 35 MPa.
Composites microstructure
It is known that it is possible to modify or adjust the microstructure of ceramic materials
by introducing an inert second phase but little work is published on the Si3 N4 /SiC micro–
nanosystem. Due to the fact that a lot of parameters influence the microstructure of silicon
nitride, it is necessary to study carefully all the phenomena. First, the α → β phase transfor-
mation for Si3 N4 and the crystallisation of β-Si3 N4 from SiCN nanopowders are analysed,
then the behaviour of mixtures is studied in order to determine the interactions and to localise
SiC nanoprecipitates.
(a) 100
90
80
70
60
50
40
0 20 40 60 80 100 120
Temperature (°C)
(b) 0.03
0.025
Rate of densification (˚C–1)
0.02
0.015
0.01
0.005
0
0 2 4 6 8 10
Time (min)
Figure 7.7 Isothermal densification curves. (a) Relative density, (b) rate of densification. ' Si3 N4 ,
Si3 N4 /SiCN29(20), × Si3 N4 /SiCN35(22, 2), Si3 N4 /SiC(20).
SEM OBSERVATIONS
After sintering, the samples are polished and plasma etched (CF4 /O2 ). Then, they are analysed
in a plane perpendicular to the hot-pressing direction.
Si3 N4 /SiCN29–Si3 N4 /SiCN35 COMPOSITES
A fine microstructure composed of equiaxed grains, with a mean diameter close to 0.2 µm
is observed when samples are heat treated at 1550◦ C. Then the aspect ratio increases with
(a) (b)
3 µm 3 µm
Figure 7.8 Si3 N4 /SiCN29(20) micro–nanocomposite sintered (a) 1550◦ C, (b) 1650◦ C.
3 µm
Figure 7.9 Si3 N4 /SiC35(22.2) micro–nanocomposite sintered at 1650◦ C.
the sintering temperature (Figure 7.8). The comparison of Si3 N4 /SiCN29 and Si3 N4 /SiCN35
microstructures (Figure 7.9) indicates that the growth of β-Si3 N4 crystals is hindered by
higher SiC contents, but the agglomerates of nanograins are present. For these two grades the
grain size is smaller than in the case of monolithic Si3 N4 densified with the same experimental
conditions and with the same additives (Figure 7.10).
Si3 N4 /SiC173 COMPOSITES
For these composites the influence of SiC nanograins on the development of the microstructure
and the growth of β-Si3 N4 crystals is detected, but with these nanopowders large agglomerates
3 µm
Figure 7.10 Monolithic Si3 N4 sintered at 1650◦ C.
1 µm
Figure 7.11 Si3 N4 /SiC micro–nanocomposite sintered at 1650◦ C.
are revealed by a chemical attack (Figure 7.11). The presence of agglomerates is mainly due
to the insolubility of SiC in the eutectic phase in the temperature range used for sintering.
PHASE TRANSFORMATIONS
The different powders have been heat treated according to the following conditions:
T: treated at 1530◦ C, 2 h, under N2 , 1 atm; TP: T + 35 MPa pressure; TPA: TP +
additives(Y2 O3 6 wt%, Al2 O3 wt%).
The α-, β-Si3 N4 contents were determined by XRD experiments. The results are
summarised in Table 7.2.
The values for the α/β ratios after T and TP heat treatments are nearly equivalent and with-
out additives no phase transformation is observed. On the contrary, when Y2 O3 and Al2 O3
Table 7.2 Influence of heat-treatment conditions on the densification and
the rate of α → β transformation. T: treated at 1530◦ C/
2 h/N2 ; TP: treated at 1530◦ C/2 h/N2 /35 MPa; TPA: treated at
1530◦ C/2 h/N2 /35 MPa/(+6%Y2 O3 + 4%Al2 O3 )
Starting α/β (wt%) α/β ratio after Relative

heat treatment (wt%) density (%)
TPA
T TP TPA T TP TPA
Si3 N4 UBE 100/0 100/0 70/30 0 0 30 /

SiCN29 49/51 49/51 0/100 0 0 100 90
SiCN35 79/21 78/22 20/80 — — 74 63
1.8
1.6
1.4
Ratio (β/)
1.2
0.8
0.6
0.4
1560 1580 1600 1620 1640
Temperature (°C)
Figure 7.12 β-Si3 N4 content v. temperature. ' Si3 N4 , Si3 N4 /SiCN29(20), × Si3 N4 /SiCN35(22, 2),
Si3 N4 /SiC(20).
are added, crystals or SiCN particles are dissolved in the YSiAlONC eutectic and β-Si3 N4
reprecipitates. The rate of the α-β transformation is higher for SiCN nanopowders than for
Si3 N4 . Moreover, the densification decreases when SiC content is raised.
In the case of powder mixtures (Si3 N4 , SiCN, additives), samples are hot-pressed under
N at different temperatures during 2 h. The ratios α + β are compared with previous results
corresponding to the individual constituents (Figure 7.12 and Table 7.3).
The α → β transformation being thermally activated, the β-Si3 N4 content increases with
the sintering temperature for all the materials. When the same heat treatment conditions are
used, the curves on Figure 7.13 show an increase of the α → β transformation rate with SiC
content. For sintering temperatures lower than 1600◦ C and whatever the SiCN nanopowder
content the nanocomposites contain more β-Si3 N4 than the monoliths. Above 1600◦ C, the
β-Si3 N4 content is always higher in nanocomposites than for monoliths but the gap is less
pronounced.
Table 7.3 α-Si3 N4 content after sintering
Materials Sintering Experimental Theoretical
temperatures (◦ C) results (%) ratio α/α + β
α/α + β
Monolith Si3 N4 1550 70

1600 30
1650 15
Si3 N4 /SiCN29(20) 1550 43 57
1600 27 24
1650 12 11
Si3 N4 /SiCN35(11.1) 1550 52 67
1600 22 28
1650 10 14
Si3 N4 /SiCN35(22.2) 1550 42 64
1600 24 26
1650 7 13
Si3 N4 /SiCN35(44.4) 1550 70 55
1600 15 21
1650 0 11
Si3 N4 /SiC(20) 1550 68 70
1600 15 30
1650 0 15
Si3 N4 /SiC(40) 1550 87 70
1600 53 30
1650 0 15
1.7
1.65
Ratio (β/)
1.6
1.55
1.5
1.45
0 5 10 15 20 25
SiC content (wt%)
Figure 7.13 β-Si3 N4 /τ v. SiC content (T = 1650◦ C).
These changes can be explained by the more important contribution to the phase trans-
formation by nanopowders at low temperatures compared to that of microscale Si3 N4 .
A very interesting result is obtained in the case of samples containing SiC nanopow-
ders which are practically insoluble in the eutectic. An increase of the rate of the
α → β-Si3 N4 transformation is clearly obtained and the transformation is completed at
1650◦ C.
Conclusion
The overall experiments show that the morphology, the composition and the content of the
second phase play an important role on the α → β-Si3 N4 transformation. The transformation
rate changes with the SiC content in the SiCN starting powder. This effect is more pronounced
with SiC nanopowders. Similar observations are mentioned in the literature, nevertheless,
they are fragmentary and much debated. Sasaki et al. (1992) suggest that SiC nanoparticles act
on the precipitation process as heterogeneous nuclei. However, this explanation is questioned
by Pan et al. (1996) who show that for Si3 N4 /SiC nanocomposites SiC nanoprecipitates are
not nuclei but only included by β-Si3 N4 during the grain growth. The present work which
concerns mixtures with SiCN or SiC shows that the nanopowders influence the germination
and reprecipitation stage. Si3 N4 nuclei are formed at the surface of SiC nanoparticles which
lower the energetic barrier. It corresponds to a heterogeneous nucleation induced by SiC
nanoparticles. Moreover, it has been shown (Kleebe 1992) that SiC is weakly soluble at very
high temperature in the presence of YSiAlONC liquid phase. This very limited solubility is
in favour of the reprecipitation of β-Si3 N4 or β-SiAlON on SiC particles. The influence of
SiC is more effective when its content increases from 10% to 40%, but the number of nuclei
is too high for the transformation, and the main part is localised at grain boundaries.
7.4.3 Sintering of nanocomposites

The study of the rheology of these nanopowders in different organic liquids and the nature
of dispersing agents is in progress. Different grades of nanopowders, synthetised by laser
pyrolysis are mixed with oxides (Y2 O3 , ∅ ∼ = 1 µm, 99.9%, Rhône-Poulenc; Al2 O3 , ∅ ∼ =
50 nm, 99.9%, Marketech International) in ethanol. The starting compositions and their
references are given in Table 7.4.
The powders are mixed and deagglomerated by milling in a polyethylene jar with Si3 N4
balls. The mixtures are dried at 200◦ C and hot-pressed (35 MPa) in a atmosphere at various
Table 7.4 References and starting compositions

Grade Starting composition (wt%) Theoretical composition (wt%)
Nanopowder Y2 O3 Al 2 O3 SiCNO phase Y2 O3 Al 2 O3
HSAl09 HSAl09 100 — — 97 — 3

HMDS35 + 3A HMDS35 97 — 3 97 — 3
SiCN35 + 6Y3A SiCN35 91 6 3 91 6 3
SiCN29 + 6Y3A SiCN29 91 6 3 91 6 3
HMDS35 + 6Y3A HMDS35 91 6 3 91 6 3
HSAl07 + 6Y HSAl07 94 6 — 90.2 6 3.8
HSAl15 + 6Y HSAl15 94 6 — 90.5 6 3.5
HSAl09 + 6Y HSAl09 94 6 — 91.2 6 2.8
SiCN35 + 9Y4.5A SiCN35 86.5 9 4.5 86.5 9 4.5
SiCN29 + 9Y4.5A SiCN29 86.5 9 4.5 86.5 9 4.5
HSAl09 + 6Y3A HSAl09 91 6 3 88.3 6 5.7
temperatures. After sintering, the different phases are determined by X-ray diffraction and
the chemical composition is obtained by elemental analysis. The rate of densification is
calculated by using the rule of mixtures and the theoretical density of the crystalline phases.
Up to now, the number of papers devoted to sintering of silicon carbonitrided powders is
very limited compared to papers on the synthesis of nanopowders. In particular, the route of
sintering aids addition, in situ or by mixing powders may influence the development of the
microstructure.
The thermal stability studies of different grades of nanopowders have shown the influence of
the precursors used and the chemical composition. In order to fabricate dense nanocomposites,
it is necessary to study sintering kinetics of various nanopowders and to establish relationships
between the characteristics of the powders and the sintering behaviour.
Influence of the synthesis process
NANOPOWDERS FROM LIQUID PRECURSORS
The mixtures are densified with a linear increase of temperature or during isothermal
treatments. The shrinkage curves on Figure 7.14 show that powders with a high N con-
tent (C/N = 0.2) exhibit a better ability for sintering than carbon-rich powders (C/N = 2.5).
The presence of additives containing aluminium (HSAl09, HMDS35 + 3A) enhances the
densification rate due to a possible oxynitride liquid phase. In the case of a high N content
combined with the addition of Al introduced during the synthesis (HSAl09) a positive effect
is observed compared to the grade HMDS35+3A where Al is added by a mechanical mixing.
The rate of densification is higher for the HSAl09 powder than for HMDS35 + 3A at the
same temperature. However, the shrinkage is blocked at around 70% as it is shown by the
60
55
50
45
40
35
30
1300 1400 1500 1600 1700

Temperature (°C)
Figure 7.14 Isobar densification curves. Relative density • HMDS35 + 3A, HMDS66,
HSAl07, × HSAl09.
100
90
80
70
60
50
40
30
0 20 40 60 80 100 120
Time (min)
Figure 7.15 Isobar densification curves. Relative density. • HMDS35 + 6Y3A, ' HSAl09 + 6Y,
× HSAl09.
Table 7.5 Chemical composition of the mixtures HMDS35 + 6%Y2 O3 +

3%Al2 O3 and HSAl09 + 6%Y2 O3
Grade Chemical composition (wt%)

Si C N O Al Y
91% HMDS35 46.0 5.4 35.0 4.6 — —

6% Y2 O3 — — — 1.3 — 4.7
3% Al2 O3 — — — 1.4 1.6 —
HMDS35 + 6Y3A 46 5.4 35.0 7.3 1.6 4.7
94% HSAl09 46.6 6.4 33.8 5.7 1.5 —
6% Y2 O3 — — — 1.3 — 4.7
HSAl09 + 6Y 46.6 6.4 33.8 7.0 1.5 4.7
isothermal experiment carried out at 1650◦ C on the HSAl09 powder (Figure 7.15). A sharp
increase of the shrinkage is observed at the beginning of the isotherm, then the rate of den-
sification decreases progressively. This behaviour could be related to the decomposition of
the nanopowder (see thermal stability) which hinders the sintering.
In order to restrict this decomposition, 6 wt% of Y2 O3 is incorporated in the starting
mixture (HMDS35 + 6Y3A, HSAl09 + 6Y) to have the same additive content (Table 7.5).
Isobar curves reported in Figure 7.16(a) show clearly that an increase of the additive content
favour the wetting of the surface by the liquid phase which stabilises the nanoparticles. This
phenomenon explains that the beginning of the shrinkage starts at a lower temperature and
the relative density is higher for all the grades. One notices that whatever the additive contents
(HSAl, HSAl + 6Y), the rate of densification (Figure 7.16(b)) depends on the percentage of
(a) 100
90
80
70
60
50
40
30
1400 1450 1500 1550 1600 1650 1700 1750
Temperature (°C)
(b) 0.5
0.4
Rate of densification (°C-1)
0.3
0.2
0.1
0.0
1400 1450 1500 1550 1600 1650 1700 1750

Temperature (°C)
Figure 7.16 Isobar densification curves. (a) Relative density. (b) rate of densification. HSAl07+
6Y, ♦ HSAl09 + 6Y, HSAl15 + 6Y, • HMDS35 + 6Y3A.
C in the starting nanopowders. When the C/N ratio increases, the rate of densification and
the final density are lowered.
Shrinkage curves with a sigmoidal shape are obtained only in the case of N rich powders.
The comparison of the different powders confirms the beneficial approach of prealloyed pow-
ders when Al is introduced in situ during the synthesis (Figure 7.16). The phase contents
(α-Si3 N4 , β-Si3 N4 , Si2 N2 O) of the nanocomposites are reported in Table 7.6. The incorpo-
ration of additives promotes the α- to β-Si3 N4 transformation but also the precipitation of
silicon oxynitride.
Table 7.6 Crystallised phases
Grade Si2 N2 O Si3 N4 β/(α + β) (%)
HSAl09 + +++ 30
HSAl09 + 6Y ++ ++ 80
HSAl09 + 6Y3A +++ + 100
100
90
80
70
60
50
40
30
1300 1400 1500 1600 1700
Temperature (°C)
Figure 7.17 Isobar densification curves. Relative density. SiCN35 + 6Y3A, SiCN35 +
6Y3A, SiCN29 + 9Y4, 5A, SiCN29 + 6Y3A.
NANOPOWDERS FROM GASEOUS PRECURSORS
Different grades of SiCN powders mixed with the same additives are hot-pressed with a lin-
ear increase of temperature. The kinetic curves are reproduced in Figure 7.17. A better
compaction at room temperature of these powders is observed, compared with the previous
grades; moreover, the relative density changes with the gas used during the synthesis of
the powder. This difference could be related to the nature and the quantity of the adsorbed
species on the surface of the particles as it has been demonstrated by TGA–MS (see thermal
stability). These species influence the behaviour of the nanoparticles during the mixing in
ethanol.
Carbon is detrimental to the sintering processes whatever the additives percentage. When
C/N ratio increases, densification is delayed. The same relative density (80%) is reached at
1650◦ C for SiCN29 + 6Y3A and at 1740◦ C for SiCN35 + 6Y3A. XRD patterns evidence
the presence of β-Si3 N4 and an amount of β-SiC which increases with the C/N atomic ratio
in the starting powders.
Comparative study of micro–nano and nano–nanocomposites

In order to compare the sintering behaviour and to determine the experimental conditions
to obtain fully dense composites, different micro or nanopowders were used. The mixtures
(SCN29 + 6Y3A, HMDS35 + 6Y3A, HSAl09 + 6Y, Si3 N4 /SiCN35 + 6Y3A) with the same
additive content were heat treated. The C/N ratio equal to 0.2 represents a compromise to
obtain a composite with a final composition of Si3 N4 /8 wt% SiC which exhibits a ductile
behaviour at high temperature. SiC particles stabilise the microstructure during a transitory
stage for hot forming. Then this ratio allows an acicular grain growth of β-Si3 N4 crystals
during a post forming treatment to obtain a good toughness.
The shrinkage curves evidence the difficulties to have a high compactness with nanopow-
ders (Figure 7.18(a)). Nevertheless, the rate of densification (Figure 7.18(b)) increases rapidly
and fully dense composites are obtained at lower temperatures than for the micro–nano mix-
ture. Isothermal curves confirm the ability for sintering of these fine powders. On the contrary,
(a) 100
90
80
70
60
50
40
1300 1400 1500 1600 1700

Temperature (°C)
(b) 0.5
0.4
Rate of densification (°C–1)
0.3
0.2
0.1
0.0
1400 1450 1500 1550 1600 1650 1700 1750

Temperature (°C)
Figure 7.18 Isobar densification curves. (a) Relative density, (b) rate of densification.
• HMDS35 + 6Y3A, ♦ HSAl09 + 6Y, SiCN29 + 6Y3A, Si3 N4 /Si/C/N +
6Y3A.
micro–nanocomposites reach 90% of the theoretical density after 2 h at 1550◦ C under 35 MPa
(Figure 7.19).
The α → β-Si3 N4 transformation ratio was determined by XRD for the starting powders
and for the sintered composites. Si3 N4 content in the SiCN powders was calculated using the
rule of mixtures and by taking into account the chemical analysis results (Table 7.7). This
ratio is equal to 14% for micro–nanocomposites and 100% for the nano–nanocomposites
(Isotherm 1550◦ C, 2 h, N2 ). For the two mixtures, the beginning of the shrinkage is detected
at 1460◦ C which illustrates the beneficial effect of the size of the powders. For the nano–
nanocomposites with a densification higher than 96% after 90 mn 1550◦ C, the shape of the
curves changes with the starting powder. The SiCN29 + 6Y3A grade, nanopowders issued
from gaseous precursors, exhibits a higher rate of densification than the powders issued from
liquid precursors (HMDS35 and HSAl09).
100
90
80
70
60
50
40
30
0 20 40 60 80 100 120
Time (min)
Figure 7.19 Isobar densification curves (1650◦ C). Relative density • HMDS35 +
6Y3A, ♦ HSAl09 + 6Y, SiCN29 + 6Y3A, Si3 N4 /Si/C/N + 6Y3A.
Table 7.7 α → β-Si3 N4 transformation rate

α/α + β (wt%) Transformation rate
Si3 N4 –α → β(%)
Powders
Si3 N4 UBE 100
SiCN29 (87% Si3 N4 ) 47
SiCN35∗ (45% Si3 N4 ) 78
SiCN29 + 6Y 3A nano/nano
Mixture 37 100
Sintered material 0
Si3 N4 /SiCN35 + 6Y 3A micro/nano
Mixture 98 14
Sintered material 84
(a) (b)
1 µm 80 nm
Figure 7.20 SiCN29 nanocomposite sintered at 1600◦ C. (a) SEM, (b) TEM.
Microstructure
Si3 N4 /SiC NANOCOMPOSITES
Observations of SiCN nano–nanocomposites show a uniform microstructure with equiaxed

grains. The mean diameter of the grains is about 150 nm and the maximum length of β-Si3 N4
crystals is lower than 450 nm (Figure 7.20).
TEM micrographs confirm these observations. Small particles (∅ < 3 nm) with stacking
faults correspond to SiC nanoprecipitates which are randomly dispersed within β-Si3 N4
grains or at grain boundaries. The grain size for micro–nanocomposites (Figure 7.21) is
approximately twice greater than for nano–nanocomposites. The microstructure refinement
and the distribution of SiC precipitates is explained by the size of the starting powders. The
dissolution is faster in the case of nanopowders and the supersaturation of the liquid phase
is reached rapidly, which induces a more homogeneous nucleation process. Moreover SiC
nanoprecipitates formed can act as nuclei. In consequence, the number of precipitate seeds
increases and crystal growth is limited.
Si3 N4 /Si2 N2 O NANOCOMPOSITES
In the case of composites issued from HMDS or HSAl powders, the grain size is wider.
Equiaxed grains with 200 nm in diameter are observed but also acicular crystals which
are distributed all around agglomerates of small grains. The development of this bimodal
distribution of grains could be explained from results obtained by Emoto et al. (1998), on
the sintering of (Si3 N4 -Mg2 Al4 Si5 O18 ) powders. The precipitation of Si2 N2 O nuclei in the
first stage is due to the high oxygen content in the liquid phase. The growth of these crystals
is favoured by a rapid migration of the species linked to the low viscosity of the eutectic.
This process is followed by compositional changes around Si2 N2 O crystals which induce in
a second stage the precipitation of β-Si3 N4 . As a result, fine Si3 N4 crystals with equiaxed
morphology are confined by acicular Si2 N2 O grains.
1 µm
Figure 7.21 Si3 N4 /SiCN29 micro–nanocomposite sintered at 1600◦ C.
Discussion
According to previous works (Bellosi 1995) on the sintering of nanopowders, the compaction
at room temperature is lower than 40%. This value which characterises fine powders is
explained by hard agglomerates with particles bonded by Van der Waals forces but also by
the nature of chemical species on the surface of the particles. When a bimodal distribution is
used as in the case of the micro–nano system, the compactness is favoured. This difference
explains that at the beginning of the shrinkage the rate is higher for nano–nanocomposites. The
rearrangement process and the solubility of the nano particles which are inversely proportional
to the size are faster. As a result of these phenomena, the α → β-Si3 N4 transformation is
completed only for the nano–nanocomposites hot-pressed for 2 h at 1550◦ C.
These results emphasise the influence of the process to introduce additives for the sintering
of silicon nitride materials. Kinetic curves for prealloyed powders with the same additive
content are faster which shows that the distribution of aluminium at an atomic scale facilitates
the rearrangement process by a simultaneous wetting of the particles. On the contrary, with
the classical route by mixing powders the oxynitride eutectic is localised in a limited number
of grain boundaries which necessitates its migration and the impregnation of the porosity.
It has been demonstrated that the sintering of silicon nitride is closely linked to the volume
of liquid phase. A minimum quantity is necessary to impede its decomposition. The same
behaviour is observed with nanopowders. The too low content of aluminium introduced
in situ during the synthesis does not allow it to reach the theoretical density. Two processes
are competing when temperature increases. The densification starts due to the rearrangement
and dissolution–diffusion–reprecipitation mechanisms but also the degradation of SiCNO
grains with a release of volatile species. Above 1650◦ C, the decomposition exceeds the rate
of the shrinkage.
For the behaviour at high temperature of these powders, an important parameter is the C
content. The two different grades obtained by pyrolysis of liquid or gaseous precursors contain
a high C content. The presence of C delays the shrinkage but the role of C differs according
to its nature, free C or bounded to Si. In the case of HMDS and HSAl powders, it is mainly
free C which impedes the densification. As observed by Doug et al. (1997) and explained
in the study of thermal stability, at high temperature an in-situ carboreduction reaction takes
place in the powder and carbon monoxide is formed. The release of CO modifies the oxygen
content of the liquid phase and induces an increase in its viscosity. In consequence, these
changes are followed by a higher temperature for the beginning of the shrinkage and by
a lower densification rate.
Concerning C bounded to Si its influence on the sintering behaviour of powders issued
from gaseous precursors is less important than free C. SiC nanoprecipitates are progressively
formed but they are practically inert towards the liquid phase in this range of tempera-
ture. The densification of silicon carbide with Al2 O3 and Y2 O3 additives is only efficient
above 1750◦ C. This is the reason why SiC nanoparticles formed by the dissolution of
SiCNO phase impede the intergranular diffusion of the species and the oversell rate of
densification.
These studies show also the great reactivity of nanopowders which changes with the nature
of the precursors. When powders issued from liquid precursors are hot-pressed, Si2 N2 O is
formed during sintering. This oxynitride precipitates in the YSiAlON system only when the
eutectic is saturated by oxygen. This element comes from additives but also from reactions
with the environment during the mixing process of the powder in a liquid media. Recently,
Wada et al. (1999) have demonstrated that the oxygen content of carbonitrided nanopowders
increases when a slurry is prepared with ethanol. In the case of the HMDS nanopowders, the
amorphous state and the different surface groups could explain the specific reactions with
ethanol. The experiments on the thermal stability have evidenced the presence of NH and
NH2 groups bounded on the surface of the particles. It is known that these groups are easily
hydrolysed or can react with ethanol which induces the formation of Si O Si bonds. The
quantity of oxygen fixed at the surface varies with the surface groups which depend on the
pyrolysis conditions and the nature of the precursors.
7.5 Conclusion
These kinetics studies in the sintering of Si3 N4 /SiC composites from various powders evi-
dence the role of the SiC content on the starting and the development of the microstructure.
When Si/C/N nanopowders are added to a Si3 N4 micropowder, they generate an increase in
the densification rate due to the faster solubility of nanograins in the liquid phase. The densi-
fication kinetics are also closely linked to the grain structure and the chemical composition.
To fabricate fully densified composites, it is necessary to use crystallised powders which are
stable and more able to be sintered. The shrinkage curves show that better results are obtained
with powders issued from gaseous precursors than from liquids.
For the different grades of powders the rate of densification decreases with a higher C/N
atomic ratio. The incorporation of SiC nanoparticles hinders the shrinkage due to their inert-
ness towards the eutectic. Moreover, free C present at the surface of the grains or as particles in
the powders reacts with oxygen from additives which delays the formation of the liquid phase.
On the contrary, SiC nanoparticles quicken the α/β-Si3 N4 transformation and form nuclei
for β-Si3 N4 grains which induces a heterogeneous nucleation and a fine microstructure.
The route to incorporate additives is also an important factor. The distribution of aluminium
at an atomic scale favours the migration of the liquid, the wetting of the surface of the grains
and the rearrangement process. These experiments validate the interest of prealloyed powders
and their ability to fabricate Si3 N4 /SiC nanocomposites.
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8 Mechanical properties
Jean-Louis Besson
The composites used to assess the mechanical properties are mainly those fabricated using
Si/C/N nanoparticles synthesised from gaseous precursors as the source of SiC (grade
SiCN35). They are referred to as SiC micro–nanocomposite when the Si/C/N powder is
added to Si3 N4 powder and Si/C/N nanocomposite when the Si/C/N powder is the only
source of both Si3 N4 and SiC.
In the assessment of the compressive creep behaviour, composites elaborated with nanopar-
ticles coming from the decomposition of hexamethyldisilazane (grade HMDS35) or that of
a liquid mixture of hexamethyldisilazane and aluminium isopropoxyde (grade HSAl09) are
also briefly considered under the respective references: HMDS and HSAl nanocomposites.
8.1 Room temperature properties
8.1.1 Introduction
Niihara and coworkers (Niihara 1991) have observed a remarkable improvement in strength
and toughness by incorporating nanosized particles of SiC in various ceramics matrix
(Al2 O3 , MgO, Si3 N4 ). In every case, most of the finest SiC particles (typically less than
200 nm) were predominantly dispersed within the matrix grains and some larger particles
at the grain boundaries. From HRTEM investigations, it was concluded that no impurity
phases were present at the interfaces between the SiC particles and the matrix grains so that
the particles were directly bonded to the matrix. Moreover, the fracture mode was changed
from a mixed intergranular–intragranular mode to a completely transgranular mode. Though
different toughening and grain-refinement mechanisms were proposed for the different sys-
tems, the basic idea was that the intragranular nanosized particles play a major role in the
increase in toughness and strength up to high temperatures, and this for two main reasons:
first, the development, generated by the large thermal expansion mismatch, of high tensile
hoop stresses around the particles within the matrix grains, leading to crack deflection; sec-
ond, the direct bonding of the SiC particles with the matrix even in the presence of grain
boundary phases coming from sintering aids or impurities.
In the case of a Si3 N4 matrix (Niihara 1991), the fracture strength increases from 850 MPa
to a peak value of 1550 MPa and the fracture toughness from 4.5 to 7.5 MPa m1/2 . The peak
values were both obtained for 25 wt% SiC. Similar trends were observed by Niihara’s group
(Sawaguchi et al. 1991; Sasaki et al. 1992; Hirano and Niihara 1995) for Si3 N4 /SiC nanocom-
posites processed by various routes, though the peak position differed and the improvements
were less pronounced. The degradation of the properties at high SiC content was claimed not
Mechanical properties 265
to be caused by the dispersed nanoparticles but related to flaws coming from aggregation of
SiC particles (Sasaki et al. 1992).
In Al2 O3 /SiC nanocomposites, neither Zhao et al. (1993) nor Borsa et al. (1997) or
Xu et al. (1997) found an influence of the intragranular SiC nanoparticles on the intrinsic
material toughness. In the case of Si3 N4 matrix composites, Pezzoti and Sakai (1994), using
a material densified without any sintering agent, also excluded any strengthening effect due
to the presence of intergranular SiC particles. Their results are consistent with earlier work by
Greskowich and Palm (1980) who found that in Si3 N4 /SiC composites where the sintering
aids (BeSiN2 and SiO2 ) dissolve in the β-Si3 N4 lattice, the toughness was independent of
the SiC volume fraction up to 23 vol%.
Contrary to Niihara and co-workers, most of the other researchers (Rendtel et al. 1995;
Sajgalik et al. 1996; Sato et al. 1995; Liu et al. 1997; Hermann et al. 1998) have reported
at best no improvement of either toughness or strength and more generally a degradation.
As it seems to be now established that the intragranular location of SiC nanoparticles does
not enhance the ‘intrinsic’ fracture properties of these so-called ‘nanocomposites’, changes
in fracture toughness and fracture strength are to be related to the efficiency with which
the ‘classical’ energy dissipating mechanisms (such as crack deflection, crack bridging
or closing forces) are acting in the material under study, taking into account its actual
microstructure.
8.1.2 Fracture strength

Fracture strength, σr , was evaluated by 3-point bending test using rectangular bars (4 × 3 ×
25 mm3 ). The bars were bevelled parallel to their length in order to eliminate edge flaws.
The tensile surfaces of the specimens were perpendicular to the hot-pressing direction and
polished to a 3-µm diamond finish. The span length was 20 mm and the cross-head speed
0.2 mm/min.
3F x
σr = (8.1.1)
wh2
where F is the ultimate load, w the width, h the height and x the distance between the section
of rupture and the nearest fulcrum point.
Changes in fracture strength with the sintering temperature are shown in Figure 8.1.
For a sintering temperature of 1550◦ C, the strength increases with the SiC content in spite
of the lower densification. The strength of the monolith increases sharply after sintering at
1600◦ C and remains stable for higher temperatures. The same trend is observed for the 5 wt%
SiC micro–nanocomposite whereas in the case of the 10 wt% SiC micro–nanocomposite, the
strength increases slowly up to a sintering temperature of 1650◦ C. As the densification
of the monolith is complete after hot-pressing at 1550◦ C, the change in strength between
1550◦ C and 1600◦ C cannot be related to a change in porosity, and, as it remains constant
for higher sintering temperatures, it cannot be associated with the acicular growth of the
β-Si3 N4 grains. The remaining explanation is based on the existence of residual stresses.
X-ray diffraction (XRD) studies have shown that after sintering at 1550◦ C, the α-and β-Si3 N4
grains are under compression, which implies that the intergranular glass phase experiences
local tensile stresses (Rossignol 1995). These internal stresses decrease as the α- to β-Si3 N4
transformation goes on and stabilises when the α content becomes lower than about 50%.
In the case of the 5 wt% SiC micro–nanocomposite, the α content after sintering at 1550◦ C
is ∼55% instead of 70% for the monolith and the strength is higher, in spite of a lower
266 Jean-Louis Besson
1000
800
Flexural strength (MPa)
600
400
200
0
1550 1600 1650 1700
Sintering temperature (°C)
Figure 8.1 Fracture strength v. sintering temperature: monolith; 5% SiC micro–nano-

composite; • 10% SiC micro–nanocomposite; Si/C/N nanocomposite as-sintered;
annealed 5 h at 1600◦ C.
density, due to the lower residual tensile stress in the glass phase. The increase in strength
when the sintering temperature is raised to 1600◦ C can be attributed partly to an increase
in densification (from 97.5 to 99% TD) and partly to the progress in the α- to β-Si3 N4
transformation. As the α content in the 10 wt% SiC micro–nanocomposite is already lower
than 50% after sintering at 1550◦ C, the increase in strength is solely due to the increase
in densification from 83 to 99%. In the case of the Si/C/N nanocomposite, the strength is
rather low (470 ± 30 MPa) for the as-sintered material (1600◦ C, 1 h), but it increases to
570 ± 30 MPa after a 5 h heat treatment at the sintering temperature and becomes similar to
that of the 10 wt% SiC micro–nanocomposite.
8.1.3 Toughness
Fracture toughness, K1C was estimated by microhardness indentation method in a Vickers
test using Evans and Charles’ formula (Evans and Charles 1976).
P
K1C = 7.4 × 10−8 (8.1.2)
c3/2
where P is the indentation load (N) and c the half median crack length (m) and K1C is
expressed in MPa m1/2 .
The toughness of the monolith increases twofold in the sintering temperature range
whereas the increase in toughness of the micro–nanocomposites remains moderate
5
Toughness (MPa m1/2)
0
1550 1600 1650 1700
Sintering temperature (˚C)
Figure 8.2 Toughness v. sintering temperature: monolith; 5% SiC micro–nanocomposite;

• 10% SiC micro–nanocomposite; Si/C/N nanocomposite as-sintered.
(Figure 8.2). The toughness of the as-sintered Si/C/N nanocomposite is similar to that of
the micro–nanocomposite though a higher fraction of the SiC precipitates is found inside
the Si3 N4 grains. When similar microstructures are considered (full density and equiaxed
Si3 N4 grains, i.e. sintering temperatures of 1550◦ C, 1600◦ C and 1650◦ C for the monolith,
the 5 wt% SiC and the 10 wt% SiC micro–nanocomposites, respectively) the toughness is
similar (Figure 8.3). However, if the comparison is made for the minimum sintering temper-
ature leading to full density whatever the material (1600◦ C), the toughness of the monolith
is much higher than those of the micro–nanocomposites that enlightens the dominating role
of the aspect ratio of the Si3 N4 grains. The toughness of the monolith is enhanced by the
development of elongated β-Si3 N4 (the aspect ratio rises from 3.5 to 6) as usually observed
for self-reinforced silicon nitride. In contrast, the presence of a large amount of intergranu-
lar SiC nanoprecipitates, though accelerating the α- to β-Si3 N4 transformation, inhibits the
acicular growth of the β-Si3 N4 grains that remain quite equiaxed in shape and this saturation
in aspect ratio prevents an increase in fracture toughness.
In the case of the Si/C/N nanocomposite, post-sintering heat treatments at temperatures
superior to 1650◦ C, lead to a more and more acicular shape for the β-Si3 N4 grains and
the toughness increases from 3.6 ± 0.3 to 5.4 ± 0.4 MPa m1/2 (Table 8.1). An additional
increase in toughness is obtained after a further heat treatment at 1400◦ C leading to a partial
crystallisation of the amorphous intergranular phase.
So, it is confirmed that the main factor is the aspect ratio of the β-Si3 N4 grains and that
the intragranular SiC particles play a minor role, if any.
5
Toughness (MPa m1/2)
0
0 5 10 15 20
SiC (wt%)
Figure 8.3 Fracture toughness at room temperature: ——after sintering at 1600◦ C;

- - -- - - for similar microstructures.
Table 8.1 Room temperature toughness of the SiC

nanocomposite after various post-sintering
heat treatments
Heat treatment Toughness (MPa m1/2 )

Temperature (◦ C) Time (h)
As-sintered 3.6 ± 0.3

1600 5 3.5 ± 0.1
1650 5 3.8 ± 0.5
1700 5 4.6 ± 0.4
1750 5 5.4 ± 0.4
1750 + 1400 5+3 6.9 ± 0.7
8.2 High-temperature properties
8.2.1 Introduction
High-temperature properties of silicon nitride based ceramics, though influenced by the size
and morphology of the Si3 N4 grains, are primarily controlled by the nature and chemistry
of the intergranular phase. After sintering, the intergranular phase is amorphous but can be
converted more or less completely into crystalline phases by a post-sintering heat treatment.
However, there always remain thin intergranular films. The most profound influence on the
properties comes from the viscosity of these grain boundary films. For instance, MgO additive
leads to a low viscosity intergranular phase whereas Y2 O3 converts easily to N-melilite
(Y2 Si3 N4 O3 ). The viscosity of the residual glass phase must be high enough to prevent
cavitation and grain separation, but low enough to accommodate grain boundary sliding
through diffusion of matter. The rheology of the intergranular phase can also be modified
by a small amount of impurity such as fluorine, which has a detrimental effect on the high-
temperature strength (Tanaka et al. 1994; Rendtel et al. 1995).
Then, in order to assess the actual role of SiC nanoparticles on the high-temperature behav-
iour, it is necessary to compare the behaviour of the composites with that of their monolithic
counterpart densified with the same additives. Moreover, the choice of the densification
aids will be different depending on the high-temperature properties which are desired, high
strength and high creep resistance or high ductility and even superplastic behaviour: in the
former case, yttria alone will be used whereas it will be a mixture of yttria and alumina in
the latter case.
So, Niihara and co-workers (1990) have obtained an improvement in the flexural strength
by incorporating 32 wt% SiC nanoparticles in a silicon nitride densified with 8 wt% yttria.
The 4-point bending strength was still 840 MPa at 1500◦ C whereas that of the corresponding
monolith had decreased to 500 MPa at 1400◦ C. This improvement was attributed to the fact
that the SiC nanosized particles in the grain boundaries were directly bonded to the Si3 N4
adjacent grains, without any impurity phase. The same grade of composite was also tested
in tensile creep and it was noted that, contrary to the monolith that suffered severe cavitation
induced by grain boundary sliding, cavity formation was rarely observed in the composite
(Hirano et al. 1996). From the study of the bending creep of silicon nitride doped by nanosized
SiC particles from different origins and sintered with Y2 O3 aid only, Rendtel et al. (1995,
1998) also concluded that the addition of SiC nanoparticles is a very effective means of
improving creep resistance of silicon nitride ceramics.
On the contrary, if it is a high ductility that is desired, Si3 N4 /SiC nanocomposites densified
with Y2 O3 or MgO are not suitable as they fracture in a brittle manner with less than 2%
elongation whereas the grades sintered with Y2 O3 plus Al2 O3 exhibit a high ductility which
can reach more than 100% elongation (Rouxel et al. 1992).
8.2.2 Tensile ductility

For the present materials, the high-temperature tensile behaviour was studied in the
1595–1640◦ C temperature range under nitrogen atmosphere. Dog-bone shape specimens
with 10 mm long and 3 mm diameter cylindrical gauges were used. The gauges were pol-
ished finally with 0.3 µm diamond paste. Since large elongations were involved, true strain,
εt and true stress, σt , were calculated on the basis of a constant volume throughout the
deformation:
εt = ln(1 + ε) (8.2.1)
σt = σ (1 + ε) (8.2.2)
where ε is the nominal strain (or elongation), !l/l0 , with l0 the initial gauge length and σ the
nominal stress.
The experiments were conducted at constant strain rate by monitoring the cross-head speed,
ε̇, from the measurement of the elongation, ε:
1
ε̇t = ε̇ (8.2.3)
1+ε
Table 8.2 Theoretical SiC content, sintering temperature (Ts ), mean grain size, aspect ratio of β-Si3 N4
grains and α/β-Si3 N4 ratio
Material SiC (wt%) Ts (◦ C) Mean grain size (nm) Aspect ratio

β-Si3 N4
Si3 N4 SiC α/β-Si3 N4
Monolith 1550 250–300 70/30

1600 350a 30/70 3–5
1700 400a 0/100 5–7
Micro–nanocomposite 10 1600 400 30–40 30/70 Low
20 1650 100–400a 30–40 0/100 3–4
Si/C/N nanocomposite 8 1600 150–450 <30 0/100 Low
Note
a Grain diameter.
Deformation 0 (%)
10 20 30 40 50 60 70
40 300
35
250
Hardening rate (d /d (MPa)

30
True stress (MPa)
200
25
20 150
15
100
10
1 50
5 2 3 4
0 0
0.0 0.1 0.2 0.3 0.4 0.5
True strain
Figure 8.4 Tensile curve —— and hardening rate - - - - - of the 70/30 monolith tested at 1595◦ C
under a strain rate of 5 × 10−5 s−1 .
As underlined above, in order to separate the effect of the SiC nanoparticles, the behaviour
of the composites must be compared with that of their monolithic counterparts. To achieve
this goal, and as the primarily role of the α/β-Si3 N4 ratio has been enlightened (Rouxel et al.
1997), monolithic silicon nitride ceramics were fabricated under sintering conditions leading
to the same α/β-Si3 N4 ratios. However, due to the presence of the SiC nanoprecipitates, the
β-Si3 N4 grains in the composites exhibited significantly lower aspect ratios than those in the
corresponding monoliths. Finally, a monolith sintered at 1550◦ C to retain the highest possible
α/β ratio, and for which the ductility had been studied previously (Rossignol et al. 1995;
Rouxel et al. 1997) was also fabricated to serve as a reference. The hot-pressing conditions
are recalled in Table 8.2 together with structural features.
Figure 8.4 shows the tensile curve and the change in hardening rate of the 70/30 monolith
tested at 1595◦ C under a strain rate of 5 × 10−5 s−1 .
Four regions can be identified on the tensile curve. The first region corresponds to the
elastic response and a transient stage. The second and the third regions are associated with
regimes of permanent and uniform deformation and the fourth regime to a stage of cavitation
damage. The hardening rate in region 2 was smaller than in region 3. It was concluded that
deformation in region 2 was essentially controlled by the α-phase whereas it was controlled by
the acicular β-grains in region 3. The transition between the two regions occurs for a volume
fraction of α-phase of about 30%. The low hardening rate in region 2 was attributed to the
equiaxed shape of the α-Si3 N4 grains and to the transient liquid phase which accompanies the
α- to β-phase transformation. In region 3, the strong hardening, with a quasi-linear hardening
rate, was related to the increase of the cross-linking degree in the acicular β-grain network
and, to a lesser extent, to grain growth, that makes more difficult grain boundary sliding
which is the major mechanism of superplasticity (Langdon 1994).
The tensile curves for the composites and their corresponding monoliths are shown in
Figure 8.5. The constant strain rate was 5 × 10−5 s−1 and the temperature 1615◦ C. The
10 wt% SiC composite was also tested at 1595◦ C and 1640◦ C. The experimental data are
collected in Table 8.3.
The deformed specimens had uniform elongation all along their gauge sections and the
rupture always happened within the gauge. The surfaces were smooth and free of cracks but
were covered with a thin whitish layer, which could be due to volatilisation of SiO gas from
the YSiAlON liquid phase and/or to a slight active oxidation by oxygen atoms present in
small quantity in the nitrogen gas. The resulting weight loss increased with the test duration
but was at worst 0.6%.
60
50
True stress (MPa)
40
30
20
10
4 1 2 3 M 0/100 M 30/70
0
0.0 0.1 0.2 0.3 0.4 0.5
True strain
Figure 8.5 Tensile curves under a strain rate of 5 × 10−5 s−1 : M 30/70 and M 0/100 monoliths
and ④ 20% SiC micro–nanocomposite at 1615◦ C; 10% SiC micro–nanocomposite ①
1595◦ C, ② 1615◦ C, ③ 1640◦ C.
Table 8.3 Experimental data from the tensile curves
Material Temperature ε̇t (s−1 ) εrupture εt σmax dσt /dεt

(◦ C) (%) (MPa) (MPa)
70/30 monolith 1615 5 × 10−5 66.5 0.510 35 55/83

30/70 monolith 1615 5 × 10−5 61.2 0.480 55 110/123
0/100 monolith 1615 5 × 10−5 24.6 0.220 37 130
10 wt% SiC composite 1595 5 × 10−5 5.4 0.053 35
10 wt% SiC composite 1615 5 × 10−5 10.0 0.095 38 133
10 wt% SiC composite 1640 5 × 10−5 17.4 0.160 29 80
20 wt% SiC composite 1615 5 × 10−5 3.3 0.033 30
10 wt% SiC composite 1595 10−5 37.7 0.320 23 46
The only grade which shows up the four regions identified in the reference is the 30/70
monolith. In this case, the deformation at rupture is high (ε ∼ 60%) and a slight decrease in
stress occurs before fracture. However, region 2 is barely marked due to an initial α-Si3 N4
volume content close to that for which the transition between regions 2 and 3 occurs. The
fracture surface was rough on the whole section suggesting that rupture is brought about
by cavitation damage. Neither region 2 nor region 4 are observed for the 0/100 monolith
which had a starting microstructure consisting entirely of acicular β-Si3 N4 grains and for
which rupture was governed by slow crack growth. The presence of an increasing fraction of
β-Si3 N4 grains with higher and higher aspect ratios explains the increase in hardening rate
in region 3 from 80 to 130 MPa and the decrease in elongation at rupture from 66.5 to 24.6%.
The tensile behaviour of the 10 wt% SiC composite contrasts strongly with that of its
monolithic counterpart. The deformation at rupture is very low and the fracture surface shows
a well-demarcated rough region, associated to slow crack growth, and a smooth region of
fast and essentially brittle fracture regime. This underscores the primary role of the SiC
nanoparticles and of their distribution. Three arguments can be invoked to explain the role
of the SiC particles (Mayne et al. 1988). First, since a large amount of glass phase is being
trapped in the SiC grain pockets, the intergranular films are thinner than in the monolith.
Second, sliding of the β-Si3 N4 grains is hampered by the SiC particles located along the grain
boundaries. Finally, the largest Si3 N4 grains support the stress and the SiC particles gathered
together in the pockets are essentially unstressed and do not participate in the deformation.
This is accentuated by an increase in the SiC content. On the contrary, an increase in the test
temperature, lowering the viscosity of the intergranular glass phase and possibly increasing
its amount, facilitates grain boundary sliding, reduces the hardening rate and increases the
deformation at rupture. In all cases, failure occurs at the maximum stress after a deformation
of less than 25%.
In Figure 8.6, the tensile curves at 1595◦ C of the 10 wt% SiC composites tested under
different strain rates (5 × 10−5 and 10−5 s−1 ) are compared. The behaviour of the specimen
tested at the lower strain rate is strongly different from that of the specimen tested at the higher
strain rate. The elongation at rupture is seven times greater, the maximum stress one-third
lower and the rupture happens after a significant lowering of the stress. A pseudo-stationary
hardening stage is well developed, with a low hardening rate (dσ /dε ∼ 46 MPa). The fracture
surface is rough on the whole section and cavitation damage shows up on polished sections.
The volume fraction of cavities, derived from density and Young’s modulus measurements,
was about 1.5%. This change in behaviour with strain rate contrasts with the behaviour
40
30
True stress (MPa)
20
10
1
2
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
True strain
Figure 8.6 Tensile curves of the 10% SiC micro–nanocomposite at 1595◦ C: ① 5 × 10−5 s−1 ; ②
10−5 s−1 . (Reprinted from Mayne, M., Rouxel, T., Bahloul-Hourlier, D. and Besson,
J.-L. (1998) J. Eur. Ceram. Soc., 18, Si3 N4 /SiCN nanocomposites: tensile ductility
and rupture behaviour, 1985–1994 with permission from Elsevier Science.)
of the monolithic ceramic where the hardening was strain-enhanced and essentially time-
independent (Rouxel et al. 1997). Again, an explanation involving SiC nanoprecipitates has
to be put forward.
With regard to the temperature, it is speculated that the α- to β-phase transformation
goes on during the tests and that grain growth occurs with more and more acicular grains
as the transformation proceeds. Moreover, the acicular grains must tend to align towards
the tensile axis. Indeed, this trend had been observed in the case of the monoliths though
grain growth remained limited. The presence of a deformation texture was also corroborated
by X-ray diffraction results which suggested the alignment of the c-axis of the elongated
β-Si3 N4 towards the tensile axis. In the case of the 10 wt% SiC composite tested under
a strain rate of 5 × 10−5 s−1 , the change in microstructure remained very limited due to the
short duration of the test. Differences between the deformed and undeformed microstructures
become substantial in the case of the composite tested under the strain rate of 10−5 s−1 for
which the α- to β-Si3 N4 phase transformation is complete and the majority of the grains
elongated and aligned towards the tensile axis. However, the length of the acicular grains
(1.2–1.9 µm) remains significantly lower than in the monolith tested during a similar duration
(∼2.5 µm), that confirms the role of the SiC nanoparticles in the limitation of grain growth.
From these differences in the final microstructure ensuing from the lower strain rate, it is
suggested that:
• When the strain rate is high, the Si3 N4 grains interlock and the diffusion is too slow to
release the stresses that appear at the buttressing points, that results in a poor ductility
and a rupture essentially brittle.
• On the contrary, under a sufficiently low strain rate, enough time is provided to release
the local stresses at the interlocking points and the acicular β-grains align towards the
tensile axis. The stress is then transferred to the SiC nanoprecipitates and sliding becomes
active between the rounded SiC particles inside the pockets.
The fact that in the latter case, the hardening rate is comparable to that in region 2 of the
70/30 monolith, where deformation is controlled by sliding of equiaxed grains, supports this
hypothesis.
In conclusion, under the higher strain rate, deformation is controlled by grain boundary
sliding of the microsized Si3 N4 grains whereas the SiC nanoprecipitates contribute to the
deformation under the lower strain rate.
8.2.3 Creep behaviour

The creep behaviour was investigated during compressive tests performed in air between
1200◦ C and 1450◦ C with nominal stresses ranging from 40 to 180 MPa. The specimens were
parallelepipedic bars (3 × 3 × 8 mm3 ).
In the previous studies, as recalled above, different grades of Si3 N4 /SiC nanocomposites
were developed according to whether an enhanced creep resistance or a high ductility were
aimed at: grades for high creep resistance were densified with Y2 O3 as the only sintering
additive whereas a mixture of Y2 O3 and Al2 O3 was used for grades with high ductility. The
present study focuses on grades sintered with yttria and alumina as additives. As in the case
of tensile ductility, the creep behaviour was compared and discussed with reference to that
of the monolith sintered at 1550◦ C.
After testing in air at 1350◦ C, the monolithic specimens were covered with a 100 µm thick
oxide scale, white in colour, and showed underneath a zone (400 µm in depth) depleted in
yttrium. In contrast, the composite samples were black and the zone depleted in yttrium only
about 100 µm thick. This underlines a better oxidation resistance of the composites.
The compressive creep tests being conducted under constant load instead of constant stress,
as soon as deformation becomes noticeable, true strain, true stress and true strain rate were
calculated using equations (8.2.1), (8.2.2) and (8.2.3) which stand for the frictionless case
(Debschütz et al. 1993). Though, in compression, εt , σt and ε̇t are negative, their absolute
values were considered in drawing the curves.
Typical creep curves obtained at 1350◦ C under a nominal stress of 180 MPa are shown
in Figure 8.7 for the monolith and the composites. For the SiC micro–nanocomposites, the
creep resistance is higher than that of the monolith and increases with the SiC content. On the
contrary, the Si/C/N nanocomposite has a lower creep resistance. In the as-sintered state, it
fails in 33 h after a brief tertiary stage whereas it sustains the 50 h test duration after annealing
for 5 h at the sintering temperature (1600◦ C). The HMDS and HSAl materials have a very
low creep resistance and fail in 2 and 5 h, respectively.
Change of true strain rate v. time is displayed in Figure 8.8 for the monolith, the 10% SiC
micro–nanocomposite and the Si/C/N nanocomposite tested at 1350◦ C under 90 MPa. For the
micro–nanocomposite, the strain rate decreases rapidly during the first 15 h (primary creep)
and then tends slowly towards a nearly constant value. After 35 h, the residual decrease is
essentially due to the slow decrease in the true stress, (secondary creep). The primary stage is
shorter for the Si/C/N nanocomposite and a steady-state creep is reached in about 5 h. In the
case of the monolith, after the sharp initial decrease, the creep rate goes through a maximum
around the tenth hour and, next, diminishes slowly (pseudo-stationary creep). In this latter
45
40
8
35
30 6
True strain (%)
5
25
20
7
15 1
10
2
5 3
4
0
0 10 20 30 40 50
Time (h)
Figure 8.7 Creep curves at 1350◦ C under 180 MPa: (1) monolith; (2) 5% SiC micro–
nanocomposite; (3) 10% SiC micro–nanocomposite; (4) 20% SiC micro–
nanocomposite; (5) Si/C/N nanocomposite, as-sintered; (6) Si/C/N nanocomposite,
heat treated 5 h at 1600◦ C; (7) HMDS; (8) HSAl.
1×10–5
True strain rate (s–1)
10–6
10–7
10–8
0 10 20 30 40 50
Time (h)
Figure 8.8 True strain rate v. time at 1350◦ C and 180 MPa: Monolith; • 10 wt% SiC micro–
nanocomposite; Si/C/N nanocomposite. Open symbols: data corrected for constant
stress.
case, the decrease remains too pronounced to be solely attributed to the decrease in the true
stress.
No signs of cavitation were evidenced in the materials by transmission electron microscopy
(TEM) investigation that is consistent with the absence of a tertiary regime on the creep
curves. The most distinctive deformation-induced features were strain whorls located in grain
boundaries with thin glassy film, and, in the case of the monolith, an increased number of
acicular grains. In both cases, once the oxidised scale had been removed, no other crystalline
phases were detected by XRD in addition to β-SiC and the Si3 N4 polymorphs.
The α/β-Si3 N4 ratio in the composite samples remained unchanged during creep tests up
to 1350◦ C, diminished slightly at 1400◦ C and the α-phase was no longer detected after creep
at 1450◦ C. For the monolith, the α/β ratio decreased slowly up to 1300◦ C and then rapidly
for higher temperatures.
The data were analysed using the Dorn–Boltzmann relation:
ε̇ = Ad −p σ n exp(−Ea /RT ) (8.2.4)
where A is a constant, d the mean grain size, p the grain size exponent, σ the stress, n the
stress exponent, Ea the apparent activation energy, R the gas constant and T the absolute
temperature.
Actual stresses, calculated according to equation (8.2.2), were used to determine the stress
exponents. From the best fit straight lines in the ln ε̇/ ln σ diagram, values of n = 0.78, 1.05
and 0.94 were obtained for the monolith, the 10 wt% SiC micro–nanocomposite and the
Si/C/N nanocomposite, respectively (Figure 8.9).
The apparent activation energies were derived in the ln ε̇/T −1 diagram (Figure 8.10)
with strain rates normalised for a stress of 180 MPa using the stress exponents previously
determined. Values of 514, 590 and 580 kJ/mol were found for the monolith, the 10 wt%
SiC micro–nanocomposite and the Si/C/N nanocomposite, respectively. Activation energies
n = 0.94
10–6
True strain rate (s–1)
n = 0.78
n = 1.05
10–7
10–8
40 50 60 70 80 90 100 200
Stress (MPa)
Figure 8.9 True strain rate v. stress at 1350◦ C: Monolith; • 10 wt% SiC micro–nanocomposite;
Si/C/N nanocomposite; data corrected for constant stress.
Temperature (°C)
1450 1400 1350 1300 1250 1150
–10
580 kJ/mole
1×10–5
–12 514 kJ/mole
590 kJ/mole
10–6
ln strain rate (s–1)
–14
10–7
–16
–18 10–8
–20
0.56 0.58 0.60 0.62 0.64 0.66 0.68 0.70
1000/T (K)
Figure 8.10 True strain rate v. reciprocal absolute temperature: Monolith; • 10% SiC micro–
nanocomposite; Si/C/N nanocomposite.
reported in the literature for silicon nitride densified with yttria and alumina range from 400
to 800 kJ/mol. For Si3 N4 /SiC nanocomposites, the only values are those reported by Rendtel
et al. (1995). They range from 975 to 1085 kJ/mol with the exception of a value as high as
1435 kJ/mol.
It is well established that the creep of Si3 N4 ceramics containing an intergranular phase
is strongly influenced by it (Lange et al. 1980a). The primary stage is dominated by the
viscoelastic response of the glass itself (Lange et al. 1980b; Arons and Tien 1980) and
diffusional creep in the stationary stage, characterised by a stress exponent ∼1, is enhanced by
the viscous grain boundary phase that provides paths of high diffusive conductance (Stocker
and Ashby 1973). The redistribution and the exudation to the surface of a noticeable fraction
of the glass phase (Clarke 1985; Besson et al. 1986) results in an improved packing of
the grains. The contribution due to the viscoelastic response of the glass phase vanishes in
about 20 h. Then, grain boundary sliding becomes restricted by grain-to-grain contacts at
asperities along grain boundaries. These contacts induce localised elastic deformations that
are evidenced by the ‘strain whorls’ observed in crept samples cooled under load (Lange
et al. 1980b). Differential chemical potentials that arise due to stress gradients provide the
driving force for a solution – migration – precipitation process to relax the localised stresses.
The increase in the number of grain-to-grain contacts leads to a pseudo-stationary stage with
a slowly decreasing creep rate until the hardening effect is balanced by the recovery effect
due to diffusion.
A detailed discussion of the creep behaviour of the materials tested in the present study
has already been published (Besson et al. 1998; Doucey 1999). The conclusions are that this
scenario applies to the composites. In the case of the monolith, the maximum in the creep rate,
which is not observed in the composites where the α to β transformation does not proceed
during the test, is very likely to be associated to this transformation. The transformation is
accompanied by an increase in the quantity of liquid phase and the precipitation of small-
sized β-Si3 N4 grains that favours an increase in the creep rate. Later, the strain hardening due
to the acicular growth of the β-Si3 N4 grains has the upper hand and the creep rate decreases.
Eventually, grain-to-grain contacts form and the behaviour is then similar to the one observed
in low α-Si3 N4 containing silicon nitride ceramics.
Since the stress exponents and the apparent activation energies of the monolith and of
the composites are basically the same, the difference in creep resistance must derive from
differences in the microstructure.
Several features can be put forward to explain, the better resistance of the SiC micro–
nanocomposite:
• the intergranular phase in the composite is more refractory than in the monolith as
evidenced by the change in Young’s moduli with temperature (Figure 8.11);
• the SiC grains present in the intergranular films obstruct the easy paths of diffusion;
• due to their larger size, the Si3 N4 grains form a rigid network that bears the stresses
so that the SiC grains gathered together in pockets are virtually stress-free and do not
contribute to the deformation;
• because of the trapping of a large amount of glass phase in these stress-free SiC grain
pockets, the intergranular films in the composite are thinner than in the monolith.
On the contrary, due to its very fine and quasi-equiaxed microstructure, the Si/C/N
nanocomposite exhibits a high ductility, even higher than that of the monolithic counterpart.
105
100
95
90
E/E0 (%)
85
80
75
70
0 200 400 600 800 1000 1200 1400
Temperature (°C)
Figure 8.11 Change in Young’s modulus v. temperature: monolith; • 10 wt% SiC micro–
nanocomposite. (Reprinted from Besson, J. L., Mayne M., Bahloul-Houlier D. and
Goursat P. (1998) J. Euro. Ceram. Soc., 18, Si3 N4 /SiCN nanocomposites: influence
of SiC nanoprecipitates on the creep behaviour, 1893–1904, with permission from
Elsevier Science.)
As it has been demonstrated (Rossignol et al. 1995; Rouxel et al. 1997) that the monolithic
silicon nitride can be tailored to exhibit a very high ductility, it is anticipated that this mate-
rial, that presents a creep rate four times higher than that of the monolith, should behave
superplastically at a lower temperature and a higher strain rate.
8.2.4 Influence of heat treatments

A 5 h post-sintering heat treatment at 1600◦ C on the monolith develops an acicular β-Si3 N4
structure with a high aspect ratio whereas the same treatment performed on the 10 wt%
SiC micro–nanocomposite has little effect, that enlightens the role of the intergranular SiC
nanoprecipitates in hindering grain growth. As a consequence, the creep resistance of the
monolith was improved and became similar to that of the composite which was not affected
(Figure 8.12).
A heat treatment for a longer time and/or at a higher temperature is required for the
SiC nanoprecipitates to be incorporated in the Si3 N4 matrix (Sajgalik et al. 1996; Pan
et al. 1996) and permit the development of an acicular structure enhancing the creep
resistance. It is the case for the Si/C/N nanocomposite for which the creep resistance
increases, as the toughness does, after heat treatments at temperatures superior to 1600◦ C.
As for the toughness, the higher the temperature, the higher the creep resistance. As for
the toughness too, an additional treatment at 1400◦ C further enhances the creep resis-
tance which becomes similar to that of the heat-treated monolith or that of the SiC
micro–nanocomposite.
30
25
20
True strain (%)
15
10
0
0 10 20 30 40 50
Time (h)
Figure 8.12 Creep curves at 1350◦ C under 180 MPa: monolith; • 10 wt% SiC micro–
nanocomposite; Si/C/N nanocomposite; full symbols: as-sintered; open symbols:
monolith and 10 wt% SiC micro–nanocomposite after heat treatment at 1600◦ C for
5 h. Si/C/N nanocomposite after heat treatment at 1600◦ C for 5 h and at 1400◦ C
for 3 h.
8.3 Conclusion
The role of SiC nanoparticles on the strength and the toughness of Si3 N4 /SiC composites
is not yet clear. The increases obtained by Niihara’s group were not observed by other
researchers.
Concerning the ductility, the grades densified with yttria as the only densification aid have
a better creep resistance than the ones sintered with both yttria and alumina whether they
contain SiC nanoparticles or not.
However, the amount, and above all, the distribution of the SiC particles strongly affect
the high-temperature behaviour. The main effect is the pinning of the grain boundaries by
the intergranular precipitates that hinders the acicular growth of the β-Si3 N4 grains during
sintering. This can result, for well-tailored conditions (in particular, a low sintering temper-
ature), in a very fine, equiaxed microstructure with a high ductility suitable for hot-forming.
Afterwards, post-forming heat treatments, at higher temperatures, may be carried out during
which the SiC particles become included into the silicon nitride grains (Pan et al. 1996). Then,
the grain growth of the β-Si3 N4 grains is no longer inhibited and an acicular microstructure
develops leading to an improved creep resistance.
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9 Theoretical investigations of
Si/C/N-based alloys
Fabio Finocchi
9.1 Introduction
Numerical simulations are a powerful tool for the study of the physical and chemical prop-
erties of various systems, as shown by the increasing number of scientific publications in
which this technique is used.∗ The flexibility of the model representing the physical system
makes it possible to perform several numerical experiments, as well as to assess the influence
of the various parameters on the final results. On one hand, the information obtained can
complement the experimental data and help the experimentalist to draw microscopic models
which will be able to explain the observed behaviour. On the other hand, numerical exper-
iments can be used as benchmarks for approximated analytical theories on model systems.
Last but not least, the tremendous advances in computing power make numerical simulation
an easily accessible technique and open the way to the simulation of bigger systems with a
higher degree of complexity and closer to real materials. This fact, in conjunction with the
progresses that have been achieved in the construction of reliable theoretical models, has
largely contributed to the computer-aided design of novel materials.
However, the contribution of numerical simulations to the investigation of the mechanical,
structural and electronic properties of the Si C N based system is presently rather thin.
Three main factors have so far limited the applications: (i) the gap between the relevant
experimental time scales and the simulation time; (ii) the size of the system which mimics
the real sample; and (iii) the structural and chemical complexity of the alloys.
Regarding (i), the microscopic structure of the SiCN nanopowders is sensitive to prepara-
tion conditions. They are generally obtained through laser synthesis from organic precursors
(Cauchetier et al., Chapter 2). The relative abundance of the constituents, and other ther-
modynamic parameters (such as the temperature), has been used to design nanopowders
with specific characteristics. The time scales involved in such processes are by many orders
of magnitude bigger than those that are presently affordable in simulations, which usually
range from some picoseconds to a few tens of nanoseconds. Therefore, in order to bypass
∗ In molecular dynamics simulations, the individual trajectories of particles (atoms, molecules) are followed over a
period of time, making full allowance for their mutual interactions. The thermodynamic properties are computed
as time averages over the trajectories. In the Monte Carlo method, a sequence of random moves in the configuration
space of the system of particles is made, according to a statistical weight. It is chosen in such a way that the
probability of each configuration be asymptotically equal to its statistical weight in some ensemble (canonical,
macro-canonical, etc.). Some aspects are common to both molecular dynamics and Monte Carlo simulations: the
choice of the inter-particle potential energy, the treatment of finite-size effects, and the selection of the starting
configuration. For more details, the reader can look to the book by Allen and Tildesley (1987), while an account
of recent developments can be found in vol. 106 of the Faraday Discussions, in the book edited by Meyer and
Pontikis (1991), and in the review by Baskes (1999).
Theoretical studies of Si/C/N-based alloys 283
the stage of the simulation of the full history of the real material, a good hint on its structure
at the atomic scale is often crucial. When amorphous materials are considered, such a hint
is not generally trivial. A practical alternative is to generate the metastable phase through a
rapid quench from the melt. The quench rate appears as the most relevant parameter which
influences the disordered structure obtained at low temperature. It is impossible to cite all
the literature devoted to the subject. However, in some cases, the use of a quench rate that
is many orders of magnitude larger than its experimental counterpart, had not prevented the
results of the simulation to be comparable to the experimental data (Servalli and Colombo
1993; Wang et al. 1993; Vollmayr et al. 1996; Rosato et al. 1999).
Regarding (ii), the simulation of bulk phases often makes use of periodic boundary condi-
tions, which eliminate surface effects (Figure 9.1). In such a case, the limiting parameter is
the number of atoms contained in the unit cell. The simulation of heterogeneous nanophases,
or nanoassembled materials, may need of the order of a million atoms per unit cell, which is
rarely affordable. Ab initio simulations (Car and Parrinello 1985, 1988; Oguchi and Sasaki
1991), in which the interatomic forces are derived from the knowledge of the electronic
structure, are presently unable to treat more than some hundreds of atoms. One way out is
to make the problem simpler, by choosing a model interatomic potential that is devised to
fit the most important physical properties of the system under study. Since a model potential
may be hardly transferable to many different physical context, one has to pay attention to its
reliability in the actual conditions of the simulation. A meaningful example is provided by the
simulation of the various phases of amorphous hydrogenated carbon, which is characterised
D C B
1 4
L
E A 2
5
3
F G H
L
Figure 9.1 Sketch of a two-dimensional periodic system. The particles are free to cross any one of
the box edge. Note that the knowledge of the positions and velocities of the particles
inside one cell is sufficient to know the dynamic of all the other particles, by making
use of the periodic boundary conditions. They are said to be the periodic images of the
particles inside the simulation box.
284 Fabio Finocchi
by qualitative variations of the C C and H C bonding that deeply affects the macroscopic
properties of the sample (Robertson 1991).
The two previous issues are especially delicate points when the system is formed by
distinct atomic species, each having a specific chemical behaviour. First, as the number
of distinct atomic species increases, the number of bonding configurations as well as the
number of fitting parameters in the interatomic potential grows up rapidly. Second, each
bond is characterised by specific physical properties, such as the charge transfer, the bond
angle, etc., which can depend on the nth neighbour configuration (n = 2, 3, . . .) in a non-
trivial way. It is thus more difficult to assess the transferability and the reliability of the model
interatomic potential energy as the complexity of the system grows. Third, the landscape of the
corresponding thermodynamic potentials is generally rather complex, because of the presence
of many local minima, eventually separated by huge barriers. The dynamic simulation of
phase separation, or of frustrated systems, are examples in which the complexity of the
problem results from the competition between atoms with different chemical behaviours.
As a consequence, the simulation of disordered alloys is particularly challenging. Presently,
the use of ab initio based molecular dynamics simulations does not permit the treatment of
more than some hundreds of atoms, and to follow their dynamics for more than few tens of
picoseconds. On the other hand, the fitting of an effective model interatomic potential and
its validation, through transferability tests, may require a formidable effort.
All the previous considerations apply to the case of systems very close to thermodynamic
equilibrium. When one is interested in kinetics, specific techniques, able to cope with rare
events, such as the overcoming of a free energy barrier, should be used. They are in gen-
eral quite complex and more time consuming than the usual methods for simulations of
(meta-)stable systems. For a critical discussion of these methods, the interested reader can
look to the review written by Ciccotti in the book edited by Meyer and Pontikis (1991).
9.2 Simulations of Si/C and Si/N disordered alloys

Both amorphous silicon carbide (α-Si1−x Cx ) and silicon nitride (a-SiNy ) are materials which
have attracted much attention. From a technological point of view, they are useful as hard
coatings, resistant to corrosion and chemically inert. α-SiC has also been used as p-type
window layer in amorphous-silicon based solar cells.
At odds with their crystalline counterparts, they can exist in many different stoichiometries.
It is therefore relevant to understand the influence of the stoichiometry on the mechanical
and electronic properties of these amorphous alloys. For tiny C (N) concentrations, the pro-
posed microscopic models consider the C (N) atoms as impurities hosted in the α-Si network
(Wooten and Weaire 1987; for a critical discussion see also Mousseau and Lewis 1997).
Such a picture is consistent with most of the measured structural properties. On the other
hand, for compositions close to those of the crystals (C/Si = 1; N/Si = 4/3), the amorphous
networks have been built from the corresponding ordered structures through the deformation
of bond angles and the lack of long-range order. Indeed, the Si C (Si N) bond lengths are
remarkably similar in both amorphous and crystalline phases. Apart from above mentioned
values of C/Si (N/Si) concentrations, it is a priori not evident in any known reference system,
it is useful to understand the topology and the connectivity of the network of the amorphous
alloy that could exist. Thus, much room is left to numerical simulations, to propose structural
models that may be able to account for the experimental data collected for the α-Si1−x Cx
and a-SiNy alloys.
9.2.1 Chemical order
Before starting to discuss the results obtained from the numerical simulation, however, it
is important to define the concept of chemical order. Since the SiC and Si3 N4 crystals (the
actual phase is not important for the sake of the following discussion, provided that it is close
enough in energy to the most stable phase at normal conditions) are stable, the formation
of heteronuclear Si C (Si N) bonds is always energetically favoured on the formation of
Si Si and C C (N N) bonds within two separated pure phases. Therefore, an amorphous
alloy is said to be totally chemically ordered when the number of heteronuclear bonds are as
large as possible.
In disordered materials, the coordination number of the species A with the species B is
usually defined as the integral of the A B pair distribution function up to the first mini-
mum (see Figure 9.3). Such a definition is adopted in the following discussions. However,
one should pay attention to the presence of dilated A B bonds, as well as to slow struc-
tural relaxation, which reflect in a non-zero value of the first minimum. Strictly speaking,
only a characterisation of bonds in terms of the electronic distribution (Bader 1991) is
non-ambiguous.
Although the concept of chemical order is very clear and intuitive, the choice of the order
parameter is not unique and may hinder some important physical aspects of the question
(Cargill and Spaepen 1981). For this purpose, let us define the following quantities, for
a binary A B alloy. NA , (NB ): number of atoms of the A (B) species. ZA (ZB ): average
coordination number of the A (B) species. NAA , NAB , NBB : number of A A, A B, B B
bonds, respectively. Obviously, these quantities are not independent. They are linked by the
following equations:
ZA NA = 2NAA + NAB ZB NB = NAB + 2NBB
Let us express, in the case of A1−x Bx , the degree of chemical order in terms of the above-
defined quantities. In the case of full disorder, given an A-type atom, the a priori probability
to form an AA bond is equal to that of forming an AB bond. Therefore:
NAA = ZA NA /(ZA NA + ZB NB )
2 2
NBA = ZB NB ZA NA /(ZA NA + ZB NB )
At odds, in the case of perfect chemical order, a type A atom always forms an AB bond
whenever type B atoms are available. Therefore:
NAA = 0 NBA = ZA NA for x < x0
and
NAA = ZA NA − ZB NB NBA = ZB NB for x > x0
where x0 is the critical concentration, equal to x0 = ZB /(ZA + ZB )

In the case of a-Si1−x Cx , a currently used order parameter is τ = NCC /NSiC . One can see
that for a fully disordered system τ = (ZC /ZSi )x/(1 − x), which is in general smaller than
x/(1 − x), since Si has a larger average coordination number than C. For a perfectly ordered
systems, τ = 0 (x < x0 ); (ZC /ZSi )x/(1 − x) − 1(x > x0 ). Apart from the fact that τ is ill
defined for very high C concentration (x → 1), one can see that τ does not purely depend
on the C concentration x, but also on the ratio of the average coordination numbers of C
286 Fabio Finocchi
3.0
Full disorder, ZC = 3.5, ZSi = 4.2

Full disorder, ZC = 4, ZSi = 4
Complete order, ZC = 3.5, ZSi = 4.2
Complete order, ZC = 4, ZSi = 4
2.0

1.0
0.0
0.0 0.2 0.4 0.6 0.8
X
Figure 9.2 Order parameter τ = NCC /NCSi computed for two virtual Si1−x Cx systems, having
all the C and Si coordination numbers equal to ZC = 3.5 and ZSi = 4.2, or ZC =
4.0 and ZSi = 4.0, respectively. Both cases are representative of real amorphous
samples. The cases of full disorder and perfect chemical order are plotted. Note that
the curve corresponding to the disordered alloy for ZC < ZSi may be close to that of
the completely ordered Si1−x Cx system with both C and Si atoms fourfold coordinated.
and Si. This is not a purely academic question, since an appreciable amount of graphitic-like
bonding implies ZC < ZSi . Even when other order parameters, which are free from the
singularities at x = 0 or x = 1, are adopted, such as ζ = NCC /(NCC + 2NSiC + NSiSi ), the
degree of order is invariably a function of both C concentration and C average coordination
number, compared to that of Si. Also the critical value of the C concentration (x0 ), at which
some homonuclear bonds appear even in the case of perfect chemical order, is a function of
the average C and Si coordination numbers (Figure 9.2).
The previous discussion is noteworthy, since many experimental data were discussed on
the basis of a simplified model for the chemical order, in which ZC = ZSi = 4, even if sp2
C bonding was actually detected in the amorphous sample. Moreover, in the case of strong
departure from the chemical order, the crystalline, tetrahedral phase of SiC cannot be used as
a starting model for the microscopic structure of amorphous Si C alloys. Therefore, in the
following, we prefer to discuss the observed trends for the chemical order, keeping in mind
that the precise values of the order parameter cannot be always considered as a definitive
measure of the degree of chemical order in the absence of an independent estimate of both C
and Si average coordination numbers.
9.2.2 Amorphous silicon carbide

Kelires (1991) carried out a Monte Carlo simulation of amorphous SiC, by adopting an
effective interatomic potential energy introduced by Tersoff (1989). The model potential
for SiC is derived from a two- and three-body interaction originally designed for elemental
semiconductors, and then modified in order to take into account the chemical specificity of
C and Si through environment-dependent parameters.
Kelires found a moderate trend towards chemical order (τ = 0.5 at C/Si = 1). A non-
negligible fraction of C atoms are threefold coordinated. In the following first-principles
molecular dynamics simulation, in which the interatomic forces are derived on quantum
mechanical grounds, Finocchi et al. (1992, 1993) obtained α-SiC at stoichiometric composi-
tion and density close to that of the β crystalline phase, through a quench from the melt. The
final sample, at room temperature, has a complex structure which can be classified neither as
chemically ordered nor as completely random. Although the Si Si, Si C and C C equilib-
rium bond lengths (characterised by the first peaks in the pair correlation functions) are very
close to those in the corresponding crystals, they are statistically distributed over a different
range of distance, depending on the specific bonding. For instance, the width of first peaks of
the C C, Si C and Si Si pair correlation functions increase in the order, showing a greater
disorder on the Si sub-lattice than on that of carbon (C). The resulting total radial distribution
function, being a sum of the various contributions, may be difficult to be interpreted. As
a consequence, only the access to the partial correlation functions by means of complemen-
tary and species-sensitive techniques, allows one to disentangle the specific contributions.
Although the simulated system may strongly differ from the real amorphous samples, we
think that such an ambiguity is characteristic of semi-conducting alloys with (i) a large degree
of disorder and (ii) competition between different type of bonding (e.g. sp2 /sp3 for C).
In a following paper, Tersoff (1994) focused on the influence of the enthalpy of formation
of Si C bonds from Si Si and C C bonds (!HSi C ), on the degree of chemical order.
In the crystal, !HSi C is equal to −16 kJ/mol/bond, according to the experimental data at
normal conditions. Tersoff performed Monte Carlo simulations of amorphous Si1−x Cx , using
different interatomic potentials, which correspond to distinct !HSi C . In that way, he studied
the order parameter τ as a function of !HSi C . He found that both !HSi C and atomic size
difference between Si and C drive the system towards the chemical order. However, the steric
factor is much more effective at driving ordering in the crystal than in the amorphous alloy,
since in the latter the microscopic stress resulting from the formation of homonuclear bonds
can be more efficiently released than in the long-range ordered phase. All these arguments
are valid at not too high temperatures, when the entropy contribution, which usually favours
disorder, can be neglected.
Further ab initio molecular dynamics simulations (Finocchi and Galli 1994) show that
the inclusion of hydrogen in the α-SiC network, at small concentrations, favours tetrahedral
bonded carbons. Since a trend of sp2 -like carbons to segregate has been observed in the
ab initio simulations – as a result of the strong C C bonding – the authors concluded that
the inclusion of H promotes chemical order, towards values of the order parameter (τ = 0.5)
consistent with most experimental data (Figure 9.3).
A recent molecular dynamics simulation (Mura et al. 1998) studied the influence of the
quenching rate and the C/Si ratio on the final chemical order. The use of a modified version
of the Tersoff effective potentials (instead of the more accurate, but time-consuming first-
principle-based interatomic potential energy) allows the authors to carry out much longer
simulations. Apart from quantitative differences from the results of the ab initio simulations,
they also found that the Si sub-lattice can be easily distorted, a fact which attenuates the
preference for a chemical order, which is far from being complete in the network.
Some of the previous results can be discussed on the basis of simple arguments based
upon the thermodynamic data, which, in the case of silicon carbide, drive the metastable
288 Fabio Finocchi
2.0
Si9Si
0.0
6.0
4.0
C9C
2.0
0.0
8.0
6.0
C9Si
4.0
2.0
0.0
0.0 1.0 2.0 3.0 4.0
R (A)
Figure 9.3 Pair distribution functions for α-SiC : H, as computed by Finocchi and Galli (1994).
They are defined as gij (r) = V /(Ni Nj )nij (r)/(4π r 2 !r) where nij denotes the time-
averaged number of atomic species j in a shell between r − !r/2 and r + !r/2
centred on a type i atom. V is the volume of the simulation box and Ni the number of
atoms of type i inside V . From the gij , the total pair distribution function is obtained

as: G(r) = ij Ni Nj gij (r)/( i Ni )2 . For the equations connecting gij (r) with the
X-ray, neutron diffracted intensities (Finocchi and Galli 1994; Waseda 1980).
amorphous phases towards the chemical order. However, three factors conspire to maximise
disorder:
i the entropy contribution, which is especially important at high temperatures;

ii the presence of a remarkable disorder on the Si sub-lattice; indeed, the absolute value
of the energy of formation of two stretched Si C bonds from a C C and a stretched
Si Si bond, may be reduced in this case;
iii the presence of sp2 -like carbon, which reinforces C C bonding, lowers the average
C coordination number, and distorts the tetrahedral network. Although the energetic
terms should prevail for small C concentrations, and drive the α-SiC towards chemical
order, the C-rich systems might exhibit a complex behaviour, which depends on the
macroscopic thermodynamic parameters (density, temperature, H contents, etc.) as well
as on the preparation conditions and on the history of the sample.
9.2.3 Amorphous silicon nitride

The enthalpy of formation of crystalline silicon nitride from Si and molecular nitrogen is equal
to −828 kJ/mole (O’Hara et al. 1997). The degree of chemical order expected for amorphous
Si3 N4 and SiC on the basis of purely energetic arguments can thus be compared by considering
the enthalpy of formation of one heteronuclear Si N(Si C) bond, obtained by normalising
the enthalpy of formation of the crystalline compounds from the respective elemental phases,
by the number of heteronuclear bonds. This amounts to −0.70 eV per Si N bond, and to
−0.16 eV per Si C bond. The absolute values of the two enthalpies correspond to very
different temperatures, of about 8000 and 2000 K, respectively. This crude estimation shows
that, according to thermodynamics, a-Si3 N4 should be almost perfectly chemically ordered.
Moreover, the segregation of a Si-rich phase might be accompanied by the formation of highly
diffusing N dimers, resulting in a continuous N loss. In agreement with this framework, all
the simulations so far performed on a-Si3 N4 indicate a high degree of chemical order, with
small amounts of homonuclear bonds.
Umesaki et al. (1992) carried out molecular dynamic runs on amorphous Si3 N4 , using
a simple Busing-type potential, which consists of a point charge Coulomb interaction, plus
a short-range repulsive term. The parameters were fitted to reproduce the α and β crystalline
phase of silicon nitride. The density was fixed at 2.6 g/cm3 , and 420 or 1260 particles were
used in the simulation. The structure of the simulated samples was characterised in terms of the
partial pair distribution functions. The computed Si N mean bond length is equal to 1.74 Å,
and the Si N first coordination number is slightly lower than 4 (3.95). The second neighbour
distances (the corresponding coordination numbers are given in brackets) are 2.65 Å (8.3) and
3.05 Å (7.1), for N N and Si Si, respectively. All these numbers are in very good agreement
with the X-ray and neutron diffraction experiments. The authors conclude that the short-range
order of amorphous Si3 N4 is very similar to that of the crystals. However, the presence of
some dangling bonds, and the distortions of the dihedral angles between the SiN4 tetrahedra
result in the loss of the medium-range order with respect to the crystal.
Recently, de Brito Mota et al. (1998, 1999) simulated a-SiNx systems (for 0 ≤ x ≤ 1.5)
through Monte Carlo runs in the constant-temperature constant-pressure (NPT) ensemble.
They used interatomic potentials of the Tersoff type, which were fitted to crystalline silicon
nitride, as well as to molecules containing Si, N and H. The inclusion of N in the a-Si network
favours denser metastable phases, since the equilibrium density grows from 2.31 g/cm3 at
x = 0 to about 3.5 g/cm3 at x = 1.5. This trend compares well with the available experimental
results (Guraya et al. 1990). It is a consequence of the formation of Si N bonds, at the expense
of the longer Si Si bonds, as N is incorporated in the amorphous sample. Correlated with such
a behaviour, the angular disorder around Si sites grows as a function of the N concentration x.
a-SiNx can be considered as well chemically ordered, although a non-negligible number of
Si Si bonds are detected (τ = 0.15 for x = 1.33, which corresponds to the stoichiometric
composition), in accord with the interpretation of the X-ray photoemission spectra for SiNx
powders (Sénémaud et al. 1993). The inclusion of hydrogen reduces the number of dangling
bonds, releases the microscopic stress and improves the conductivity properties. However, no
major structural changes are recorded in the Si Si and the Si N pair distribution functions,
between the hydrogenated and the unhydrogenated simulated systems. They are shown in
Figure 9.4, for SiN1.33 .
Given the relative success of the empirical potentials in describing a-Si3 N4 , Vashista
and collaborators (Vashista et al. 1995; Kalia et al. 1997) performed large-scale molecular
dynamics simulations on disordered silicon nitride phases, adopting a slightly more com-
plicated interatomic potential which, in addition to the Coulomb charge–charge interaction,
and to the short-range repulsion, contains a charge–dipole interaction. In a first simulation
(Vashista et al. 1995), they prepared the amorphous samples (consisting of 1344 atoms)
by quench from the melt, at different macroscopic densities. As the density decreases, the
290 Fabio Finocchi
x = 1.5
x = 1.33
x = 1.0
x = 1.5
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
R (Å)
Figure 9.4 Total pair correlation functions for amorphous SiNx . Copyright (1998) by the American
Physical Society for x = 0.5, 1.0, 1.33 and 1.5. The experimental results for a-SiN1.33
(Guraya et al. 1990) are shown in the inset for comparison. (Reprinted with permission
from de Brito Mota, F., Justo, J. F. and Fazzio, A. (1998) Phys. Rev., B58, 8323–8328.)
network connectivity is reduced and floppy modes appear in the vibrational spectra. The
consequences for the mechanical and thermal properties of a-Si3 N4 are discussed. In a fol-
lowing study, they assembled pre-formed Si3 N4 clusters to form a nanophase Si3 N4 system,
containing about a million atoms. The system was characterised as composed by (1) interfa-
cial regions with a large fraction of undercoordinated Si, which separate (2) bulk-like domains
from (3) the pores (three-phase model). The dependence of the computed elastic moduli on
porosity and grain size, as well as the behaviour of the material under crack propagation, can
be understood on the basis of the three-phase structural model. In particular, the nanophase
system is able to sustain an order-of-magnitude larger external strain than crystalline Si3 N4 .
9.3 Simulations of ternary Si/C/N systems

As previously discussed in the Introduction (Section 9.1), the simulation of disordered
ternary systems is a formidable task, which has limited so far the application of atomic-
scale simulation techniques to the study of amorphous or poly-crystalline Si C N systems.
In the following, we mainly review the recent theoretical advances in the field of crystalline
Si C N systems, and in the study of disordered (amorphous or nanopowders) alloys.
9.3.1 Theoretical studies of C defects in Si3 N4 and N defects in SiC
In this section, we give a brief account of the theoretical work that has been carried out to
study the structural and electronic characteristics of the inclusion of either C or N in the
crystalline network of the crystal formed by the two other species. In particular, we account
for the most relevant modification of the structure and the electronic properties resulting
from the inclusion of the substitutional impurity at very low concentrations, as a first step
towards the understanding of the formation of ternary Si C N compounds. They are not
necessarily the most stable point defects in these compounds. For example, in SiC, the SiC
anti-site defects is more stable than both NSi and NC (Bernholc et al. 1989). The reader who
is interested to the more general issue of point defects in semiconductors can look to the
available reviews (see, for instance, Lannoo 1992).
Fukumoto (1997) studied the inclusion of N in 3C SiC within the density functional theory
(DFT) in the local density approximation (LDA) for the exchange and correlation effects (for
a review on the method, see Jones and Gunnarsson 1989). Super-cells containing 64 atoms in
total were used, and the relaxation of the atomic positions were performed through damped
dynamics. However, in those calculations, the volume of the super-cell is not varied as a
function of the position of the impurity, so that a spurious, residual pressure might somehow
affect the energetic, since finite N concentrations are considered. Fukumoto considered only
substitutional impurities, that is, NSi and NC . NC gives rise to a shallow donor state, with
electron density widely spread over the entire crystal, and a maximum close to off-bond
sites around Si. NSi , on the other hand, forms a deep level, characterised by a very localised
electron distribution around the substitutional N. He also studied the formation energy of the
defects, as a function of the Si chemical potential, and found that NC is always favoured over
NSi by about 7 eV, in the whole physical range of Si chemical potentials compatible with the
existence of stoichiometric silicon carbide.
Amadon and Finocchi (1999) recently studied, within the same theoretical framework
(DFT in the LDA) CSi β-Si3 N4 , at different C concentrations (1 or 2 carbons in a supercell
containing 84 atoms). Both the atomic and the external degrees of freedom (i.e. the lattice
parameters) are consistently relaxed for all the structures considered. For the lowest CSi
concentrations, the C N bonds are stretched with respect to those computed in β-C3 N4 .
When doubling the CSi concentration, scattered configurations of CSi are favoured over
geometries with second neighbours CSi . The resulting microscopic stress is long ranged
and lowers the cohesive energy of the host crystal. As a consequence, the formation of CSi
defects in β-Si3 N4 from diamond and silicon nitride crystals, and molecular nitrogen is
thermodynamically unfavoured, showing that the progressive substitution of Si with C in
silicon nitride is not a practical way towards the synthesis of ternary alloys.
9.3.2 Crystalline Si/C/N compounds

Si C N ordered systems have only recently been obtained. They have been initially
prepared in nanocrystalline phases by Riedel et al. (1997) through the reaction of silicon tetra-
chloride with trimethylsyl-carbo-diimide (CH3 )3 Si N C N Si (CH3 )3 , followed by
calcination. The resulting amorphous Si C N powder crystallises at 400◦ C to give SiC2 N4 .
The latter, when heated up to 900◦ C, decomposes in crystalline Si2 CN4 , C2 N2 and N2 . These
phases were studied by in situ X-ray diffraction. Si2 CN4 shows a layered structure, formed
by distorted SiN4 tetrahedra as in Si3 N4 , which are linked through carbodiimide groups. It
has an orthorhombic unit cell (lattice parameters: a = 5.44 Å, b = 13.58 Å and c = 4.81 Å),
292 Fabio Finocchi
[010]
[100]
[001]
Figure 9.5 Structure of Aaba2 Si2 CN4 . N atoms are dark grey, Si light grey and C white. The
three directions, parallel to the lattice vectors, are drawn. Note that in the [100] and in
the [001] directions, the structure is replicated, in order to get a better feeling of the
connectivity of the crystal.
with space group Aaba2 (Figure 9.5). However, the internal parameters defining the precise
atomic positions were only roughly determined. The structure of SiC2 N4 was obtained too,
but with less accuracy.
The stability of these structures has been theoretically investigated by Kroll et al. (1999)
through density functional calculations. They exploited the functional analogy between the
carbodiimide and the O groups to build up various structural model compatible with the
X-ray diffraction data. The cubic high-temperature β phase of SiC2 N4 consists of a Si atom
at the centre of a tetrahedron formed by the four NCN groups. However the authors, thinking
that the cubic phase may only reflect an average geometry, searched for other less symmetric
structures. Two tetragonal structures resulted to have a higher cohesive energy than the
cubic phase. The most stable one can be described as two interpenetrating Si N C N Si
networks. It has a c/a ratio equal to 2 and a space group P4322 . Such a structure is only
*4 KJ/mol more stable than the ideal cubic one, an energy difference which is close to
the intrinsic precision of the theoretical method employed. However, the P4322 structure
was proposed as a good candidate for the low-temperature α phase of SiC2 N4 , not only for
energetic reasons. Indeed, the energy plotted as a function of the bonding angle of N shows
a shallow minimum around 160◦ for the tetragonal structures, at odds with its 180◦ value in the
cubic structure. The tetragonal structure has thus more flexibility, with two consequences: its
computed bulk modulus (about 8 GPa) is much smaller than that of the cubic phase (108 GPa);
at higher temperatures, the tetragonal structure might appear as cubic on average, due to the
easy deformation of the bonding and dihedral angles.
As far as the crystalline Si2 CN4 system is concerned, two theoretical studies appeared
almost simultaneously: that by Kroll et al. (1999), and another one by Amadon and Finocchi
(1999). Both of them found that the orthorhombic structure with space group Aaba2 proposed
by Riedel et al. (1997) is a mechanically stable phase. The computed lattice parameters agree
within less than 2% with those extracted from the X-ray diffraction data: a = 5.51 Å,
b = 13.75 Å, c = 4.83 Å (Amadon and Finocchi 1999); a = 5.45 Å, b = 13.81 Å,
c = 4.82 Å (Kroll et al. 1999); a = 5.44 Å, b = 13.58 Å, c = 4.81 Å (Riedel et al.
1997). Apart from a small discrepancy about the b/a ratio, both calculations found a larger
equilibrium volume (by 2–3%) than the experiment. This is in contrast with the outcome
of most density functional calculations adopting the LDA, which usually gives a trend to
over-binding and to slightly underestimated lattice parameters – by 1–2% in elemental and
compound semiconductors (Jones and Gunnarsson 1989). Due to the presence of very soft
modes, essentially linked to the easy deformations of the Si N C angles, a non-monotone
behaviour of the phonon frequencies v. the volume cannot be excluded, which might give
a non-trivial value of the thermal expansion coefficient. However, for the moment, we are
still at the level of speculations. An important consequence of the coexistence of more rigid
Si N layers linked with deformable N C N sticks, into a highly non-isotropic structure,
is the relevance of the relaxation of the internal degrees of freedom (i.e. the atomic positions
inside the unit cell) for the calculation of the mechanical properties of these phases. From
the computed elastic constants, Amadon and Finocchi calculated a bulk modulus equal to
110 GPa.
Experimentally, Si2 CN4 decomposes at high temperatures in silicon carbide, silicon
nitride, plus molecular nitrogen (reaction 1). Both calculations give a positive reaction
enthalpy at 0 K, ranging from 215 to 285 kJ/mole. However, another possible reaction is
possible, giving solid C, silicon nitride and molecular N as products (reaction 2). The path
from the products in reaction 1 to those in reaction 2 implies a negative enthalpy, both experi-
mentally and theoretically, of the order of about −280 kJ/mole. This raises the question of the
stability of Si2 CN4 with respect to reaction 2. While Amadon and Finocchi found a reaction
enthalpy in the range −20 to +10 kJ/mol, the latter was estimated at −39 kJ/mole by Kroll
et al., who concluded for the thermodynamic instability of Si2 CN4 . However, Amadon and
Finocchi were less conclusive on this point, since (i) the reaction enthalpies are likely to be
too low by few tens of kJ/mole in the case of reaction 2, as a result of the use of the LDA, and
(ii) the presence of high barriers and entropy contributions should favour the decomposition
of Si2 CN4 in silicon carbide, silicon nitride, plus molecular N, as in reaction 1.
Crystalline Si C N thin films were recently grown by microwave plasma-enhanced
chemical vapour deposition on the (100) surface of Si (Chen et al. 1996), and then stud-
ied by X-ray absorption spectroscopy (Chang et al. 1998). The X-ray diffraction data were
interpreted on the basis on a crystalline structure analogous to that of the α phase of Si3 N4 ,
from which it differs for the values of the lattice parameters (those of α-Si3 N4 are given in
brackets): a = b = 6.908 Å (7.753 Å; c = 5.262 Å (5.618 Å). The XANES spectra of the
thin Si C N films, taken at the C, N and Si K edge, showed marked similarities with those
of the β phase of SiC, the α phase of Si3 N4 , and the combination of the two latter phases,
respectively. Moreover, from the EXAFS oscillations at the Si K edge, Chang et al. derived
an average Si N coordination equal to 3 (with a Si N bond length equal to 1.73 Å) and
Si C mean coordination number equal to 1 (Si C bond length: 1.88 Å). These facts suggest
that the local bonding environments of C and N in the ternary thin films are rather similar
294 Fabio Finocchi
to those in the binary crystals formed with Si (β-SiC and α-Si3 N4 ). Si, at variance, shows a
dominant Si N bonding, but the number of Si C bonds is not negligible. All the experimen-
tal results were complemented by theoretical calculations in the muffin-tin approximation
for the scattering potentials provided by the ions. From these results, the authors suggested
a structural model based on mixed C Si N3 tetrahedral units in which C N bonds should
represent a very small fraction of the total number of bonds.
These observations raise a few interesting issues. First, the thin films are said to be crys-
talline, but their composition was not precisely estimated. As a rough indication, under the
hypothesis that C and N atoms are fourfold and threefold coordinated to Si, respectively, and
that Si atoms form mixed C Si N3 tetrahedra, one obtains a C/Si ratio equal to 1/4, and
a N/Si ratio equal to 1. Thus, the progressive inclusion of C atoms in an hypothetical α-Si3 N4
network, should be made by substitution of N with C, with a much smaller proportion of Ni
replaced by Si atoms, which depends on the precise concentration of the three components.
As a consequence of the difference of Si N and Si C bond lengths, a microscopic stress
at the atomic scale would result, which may strongly influence the ground state properties
of the crystals, such as its stability, mechanical behaviour and electronic structure, as in the
case of CSi Si3 N4 and NC SiC, which have been discussed in Section 9.2. This observation
is also coherent with recent experimental results reported for amorphous CSix Ny thin films
(x ∼ 0.2, y ∼ 0.3) which were grown on (100) oriented Si substrates, by laser deposition
(Thangen et al. 1999). The films are hard and plastic, and show an internal compressive stress
of the order of a few GPa.
A reversed approach has been undertaken by some theorists, who searched for super
hard Si C N structures (for a review, see Badzian and Badzian 1997), obtained by pro-
gressive replacement of Si by C in β-Si3 N4 . On the basis of an empirical model, Cohen
(1985) suggested that the structures characterised by tetrahedral units with short (and strong)
covalent bonds are good candidates for materials with a high bulk modulus. Among them,
the hypothetical solid β-C3 N4 , iso-structural to the β phase of Si3 N4 , should have a very
large bulk modulus, comparable to that of diamond. Afterwards, some calculations (Liu and
Cohen 1989; Liu and Wentzcovitch 1994) studied, on first-principle grounds, the stability
and the mechanical properties of C3 N4 solids. In particular, through a variable-shape ab ini-
tio molecular dynamics simulations, Liu and Wentzcovitch (1994) confirmed the very low
compressibility of the β phase (space group P63 /m). Such a crystal would have a short C N
bond length (1.45 Å) and a bulk modulus equal to 437 GPa, just smaller than that of diamond.
However, the authors found a more stable rhombohedral structure (space group R3m), about
0.15 eV/unit formula lower in energy than the β-C3 N4 phase. The rhombohedral phase is
more similar to graphite than to diamond, with a C N bond length equal to 1.36 Å on aver-
age, and a quite low bulk modulus (51 GPa). Both phases are thermodynamically unstable
vis-à-vis of the decomposition in diamond plus molecular N (the enthalpy of reaction rang-
ing from −75 to −62 kJ/mol). However, as in the case of diamond, they found both phases
mechanically stable, and did not exclude that they might be synthesised.
These seminal studies motivated the search for hypothetical Si C N tetrahedrally bound
compounds, obtained through the replacement of Si with C in Si3 N4 . Among them, Wang
et al. (1998) proposed two model structures of β-Si2 CN4 and β-SiC2 N4 on the basis of
density functional calculations in the full potential linear augmented plane wave method. They
calculated the equilibrium structural parameters and the bulk modulus of the hypothetical
structures, under symmetry restrictions. However, these calculations did not provide any
information on the thermodynamic and mechanical stability of these compounds. Then,
Lowther (1999) compared the β and the cubic phases of hypothetical SiC2 N4 with C3 N4 . He
found that the electron distribution along the C N bonds in SiC2 N4 is rather similar to its
counterpart in β-C3 N4 , which suggests a remarkable stability of the strong C N bonding
in various chemical environments. Moreover, he found the cubic (P4n2) phase more stable
than the β phase by a very tiny energy. Once again, the comparison of the cohesive energies
of these ternary phases with respect to elemental or binary crystals was not done.
9.3.3 Si/C/N nanopowders and amorphous alloys

It is noteworthy that a fit to the X-ray or neutron diffraction spectra performed on Si C N
nanopowders at different temperatures gives results similar to the binary crystals, regarding
the Si N and Si C bond lengths (see Chapter 5). In analogy with the results by Chang et al.
on the Si C N crystalline thin films, Ténégal et al. (1996) found that the local bonding
structure of amorphous silicon carbonitride powders, as probed by EXAFS, may be described
in term of mixed C Si N3 tetrahedrons, but, at the same time, evidence for C N bonds
connecting the tetrahedrons was also found. The same samples were further analysed by
X-ray and neutron diffraction. The experimental spectra were interpreted (Ténégal et al.
1998) on the basis of a medium-range order based on different stacking of the Si/C/N layers,
reminiscent of either the α or β phase of crystalline silicon nitride. Also in that case, the Si3 N4
crystalline phases were used as input to build up structural models through: (i) replacement
of Si or N atoms by carbons and (ii) a local optimisation of the structure by using empirical
force fields.
One can note that all the models derived through the selective replacement of C atoms in
a silicon nitride crystalline network have the virtue of fitting the experimental data remarkably,
thereby providing an atomic scale picture of the configurations of ternary Si C N systems.
However, they are not complemented by any thermodynamic data, or by the calculation of the
electronic properties for the corresponding atomic arrangement. As a consequence, they are
neither able to explain the Si N, C N and Si C bonding properties within the disordered
network, nor understand the thermodynamic evolution of the Si C N systems. Moreover,
they have not been showed to be coherent with the measured electronic structure of the
ternary amorphous or crystalline Si C N systems. The comparison between photoemission
experiments (Driss-Khodja et al. 1996) and the electronic structure computed for the proposed
structural models would be thus significant to assess their validity.
To our knowledge, Matsunaga et al. (1999) were the first to simulate truly amorphous
Si3 Cz N4−z ceramics. They employed a Tersoff potential to describe the C C, Si S, Si N
and Si C interactions. Both C N and N N interatomic potentials are purely repulsive. The
justification of such a simplified model was given on the basis of the high mobility of N2
dimers – which do not contribute to the bonding in the condensed phase – as far as the N N
interaction is concerned. The C N attractive interaction was not taken into account since a
decomposition of C N bonds is observed during pyrolysis above 1273 K (Seher et al. 1994).
The molecular dynamics simulations were performed in the canonical (NVT) ensemble, by
generating the amorphous configurations through a rapid quench from a liquid-like structure
at ∼4000 K. The statistic was taken on the sample equilibrated at T ∼ 1270 K for about
50 ps. Several C concentrations z were simulated. The results were characterised in term of
partial pair distribution functions. For Si3 C1.5 N2.5 , both N and C atoms are undercoordinated
(ZN ∼ 2.4; ZC ∼ 3.1), at odds with Si (ZSi ∼ 4.2), which are bonded to 2 C atoms, 1.4 N
atoms and 0.8 Si atoms, on average. As more C is added, more and more Si C bonds are
created at the expense of Si N bonds.
296 Fabio Finocchi
The overall picture of the structure of the amorphous sample cannot in any case be
characterised as purely consisting of mixed C Si N3 and C2 Si N2 tetrahedra, since both
the presence of Si Si bonds, and the low coordination number of N and C reveal a bigger com-
plexity. However, the computed total pair distribution function for Si3 C1.5 N2.5 (Figure 9.6),
summed on the different bonding configurations, fairly compares to that measured by X-ray
diffraction (Uhlig et al. 1996) for Si3 C1.8 N2.7 .
(a)
(SiC0.50N0.83)
1
G (r )
0
(b)
(SiC0.60N0.90)
0
0.10 0.20 0.30 0.40 0.50 0.60
r (nm)
Figure 9.6 (a) Computed total distribution function for amorphous Si3 C1.5 N2.5 , by Matsunaga
et al. (1999). (Reproduced from kind permission of Ceramic Society of Japan.) (b) The
comparison with the experimental one (Uhlig et al. 1996) is also shown. The first peak
marked in the figure corresponds to both Si N and Si C bonds. The second one is
due to Si Si bonds, while the third peak comes from C C, N N and N C second
neighbours.
Such a simulation raises the interesting issues of the presence of (minority) Si Si and
C N bonding, as well as of C and N dangling bonds, eventually saturated by hydrogen,
which can be studied further. Also, the role of the formation of micro-voids may help the
release of the internal stress and the measured mechanical properties.
In conclusion, the available theoretical models give a still incomplete picture of Si C N
systems. Apart from the theoretical and experimental investigations on carbodiimide-based
Si C N crystals, some structural models are available, which fit the experimental data,
without explaining why the proposed structures are (meta)stable. Some other theoretical
investigations provide precise information on the energetic and the mechanical stability of
hypothetical compounds, which have not yet been experimentally obtained. In very few cases
the authors showed the way to a practical synthesis of these hypothetical compounds. A joint
theoretical and experimental effort should be done in order to bridge the gap between the
measured properties of these ternary systems and their explanation in terms of a unifying
model.
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Index
ab initio molecular dynamic simulations C/N ratio 38, 177, 192

(amorphous silicon carbide) 287 composite 264
acicular grain growth 258 composites microstructure 247
activation energy 235, 237 conduction band (CB) 154
additives 238 conductivity 227, 230, 231, 232, 235, 236
aerosol 8 core level binding energy (BE) 154
agglomerates 246 core levels 155
27
Al MAS–NMR 117 creep resistance 269
27
Al MAS–NMR of Si/C/N/Al/Y 132, 133, cross measurement interest 4, 5
135, 136 cross-polarisation (CP) 112
27
Al MAS–NMR of reference samples 134 Curie law 141, 146, 150
27
Al NMR gibbsite 117
27
Al NMR saponite 117 dangling bonds (DBs) 147
27
Al NMR spin flip angle 115 decomposition 26, 42
Al and Y additives 22 defect concentration 139, 141
Al2 O3 242 demixion 220
aluminium 27 Al NMR spectroscopy 115 densification kinetics 247
aluminium isopropoxyde 264 dielectric function 230, 232
amorphous ceramics by thermolysis of polymer dielectric loss 227, 228, 230, 232–4
precursors 2 dielectric properties 227
analytical method informations 4 dispersing agent 242
annealed SiC 58, 59, 60 dissolution–diffusion–reprecipitation 239
annealing treatment 192 ductility 269
Arrhenius law 235
atomic chemical composition Cx Siy Nz 127 EELS electron energy loss spectroscopy 79, 81
atomic NMR and chemical compositions effect of NH3 94
Cx Siy Nz 130 electrical conductivity 234
electrical properties 227
13
C MAS–NMR of Si/C/N/Al/Y 130, 132 electron paramagnetic resonance (EPR) 139–41,
carboreduction 50 143–4, 146, 148
carbothermal nitridation 51 electronic transport 230
charge carriers 230 EPR spectrometer 228
chemical and structural changes 38 evolution of structure 33
chemical composition 12 evolved species 42
chemical order 285 exhausted molecules 45
chemical shift anisotropy (CSA) 112 extended X-ray absorption fine structure
C–N bond 167, 168, 192, 217 (EXAFS) 163, 182, 187
300 Index
extended X-ray absorption fine structure microwave method 228
(EXAFS) modelisation 198 microwave power 229
milling 253
first sharp diffraction peak (FSDP) 215 mixed tetrahedra 166, 192
flame 9 mixing process 242
flame temperature 9 mobility 230
fluorescence yield (FY) 153 model interatomic potential energy 284
forming process 243 modelisation of nanocrystalline structures 220
fracture strength 265 molecular mechanic 200
free carbon 128, 135 morphological change 39
free carbon effect 131, 134 multiple scattering 185, 200
23
gaseous precursor 8, 54, 264 Na MAS–NMR 116
grain growth 240 nano–nano composites 2, 241
g-tensor 151 nanoparticles 264
nanopowders 6
Hall effect 228, 230 nano-sized powders 227
hardening rate 271 neutron diffraction 211
haxamethyldisilazane 8, 264 nitridation 27
heterogeneous nucleation 253 nitriding process 151, 152
high power decoupling (HPD) 112 numerical simulation limitations (gap, size,
high temperature properties (silicon nitride based alloys) 282
ceramics) 268
HMDS materials 274 octamer silicic trimethyl ester (Q8 M8 ) 112, 114
hot-pressed 244, 251, 253 order parameter 285, 286
HSAl materials 274 organometallic precursors 20
hyperfine diagonal tensor 140 oxynitride phase 46
hyperfine interactions 150 oxynitrided eutectic phase 238
hyperfine lines 141 147
hyperfine tensor 145 paramagnetic centres 139, 140, 143,
hyperfine triplet 151 145–7, 150
paramagnetic defects 144, 145, 146, 151, 152
inclusion of H promotes chemical order paramagnetic defects in Si/C/N
(amorphous silicon carbide) 287 nanopowders 139, 140
influence of hot pressing on 29 Si and 27 Al paramagnetic species 148, 151
MAS–NMR spectra 137 particle rearrangement 239
infrared laser pyrolysis 6, 19 Pauli 147
in-situ carboreduction reaction 262 permittivity 230
interfacial barriers 235 α → β phase transformation 239, 246
interfacial polarisation 232, 233, 237 α → β phase transformation rate 251
phase transformations 250
laser synthesis 6 α polytypes silicon carbides 118, 120
laser-driven reaction 9 post-sintering heat treatment 279
liquid precursor 8, 72 powder-making processes 3
low size dispersion 23 prealloyed powders 256, 261
preceramic nanopowders 41
magnetic field 144
mass change 27 quality factor 228
mechanical properties 264 quench rate 283
micro–nano composites 2, 241
microstructure 260 rate of densification 256
microwave 141 reactivity 41
Index 301
reactivity of nanopowders 262 Si–K edge 187
relaxation 228, 231–3, 235, 236 Si–K edge XANES 196
residence time 9 Silicon carbide 241
residual functionalities 53 silicon nitride (α and β) 124
resonance 139, 144, 147 silicon nitride 238
resonant cavity 228 simulation of amorphous Si3 Cz N4−z 295
room temperature properties of ceramics 264 simulation of amorphous silicon carbide 286
simulation of amorphous silicon nitride 288
second phase 253 simulation of crystalline Si/C/N 291
sedimentation tests 242 simulation of ternary Si/C/N 290, 291, 295
SEM observations 248 SiN3 C tetrahedra 200
Shrinkage curves 245, 254 sintered composites 95
29 sintering 238
Si chemical shift for crystallised
SiCx N4−x 121 sintering aids 238
29 slip casting 242
Si chemical shift for silicon carbides 118
29 soft X-ray spectroscopy (SXS) 153–5, 160, 163
Si chemical shift for silicon nitrides 120
29 specific surface area 18
Si MAS–NMR duty cycle influence on
Si/C/N/Al/Y spectrum 129 spin hamiltonian 140, 144
29 spin susceptibility 143, 145
Si MAS–NMR of Si/C/N/Al/Y 132, 136
29 spin-orbit coupling 140
Si MAS–NMR silicon carbide spectra 117
Si/C powders 156 strength 264, 269
α-SiCN 220, 222 superplastic behaviour 269
β-SiCN 220, 224 susceptibility 141, 150
Si/C/N nanopowders 41
Si/C/N powders 154, 164, 179 TEM operating conditions 108
Si/C/N/Al/Y nanopowders 172, 205 TEM operating procedure 106
Si/C/N/Al/Y/O 31, 38, 39 TEM sample preparation (powders) 105
Si/C/N/Al-based powders 83, 94 TEM sample preparation (sintered
Si/C-based precursors 54 materials) 106
Si/N powder 164 tensile ductility 269
α-Si3 N4 157, 186, 219 TG/MS analysis 42
α → β Si3 N4 transformation 259 TGA/MS study 42
β-Si3 N4 186 theoretical structure factors 220
Si3 N4 95 thermal behaviour 40
Si3 N4 /Si/C/N composites 100, 101, 104 thermal conversion 44
Si3 N4 /SiC composites 96 thermal stability 41
β-SiAlON 134 thermal treatment 25–7
SiAlON 105 total electron yield (TEY) 153
Si-base powders 8 toughness 264, 266
β-SiC 186 transamination/condensation reactions 43, 44
β-SiC silicon carbide 118, 120 transport properties 227
SiC 6, 246
SiC nanopowders 139 unpaired electron 141, 144, 145, 151
SiC phase 57 unpaired spin 139, 143, 150
SiC precipitates 260
SiC/Si3 N4 phase differentiation 94 vacancies 141, 145
SiC-based powders 64, 72 valence band 159
SiCN 6 valence bond (VB) 153
SiCx N4−x 158
SiCx N4−x tetrahedra 196, 219 X-band 141, 142, 144, 146, 148, 229
SiCx Ny Oz phase 46 X-EDS X-photon energy dispersive
SiH4 8 spectroscopy 56, 88, 109
302 Index
X-ray absorption near edge structure X-ray emission spectroscopy (XES) 153, 154
(XANES) 153, 154, 185 X-ray photoemission spectroscopy (XPS)
X-ray absorption spectroscopy 161, 162, 153, 154
176, 179
X-ray diffraction 22, 211 Y2 O3 242

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Nanostructured Silicon-based

Powders and Composites

“fm” — 2002/9/6 — page i — #1

“fm” — 2002/9/6 — page iii — #3

ISBN 0-203-27679-5 (Adobe eReader Format)

Cover: A laser irradiation cell observed through a KCl window

“fm” — 2002/9/6 — page iv — #4

“fm” — 2002/9/6 — page v — #5

1 Objectives and state-of-the-art of nanocomposites 1

2 Laser synthesis of nanosized powders 6

2.1 Generalities on the synthesis of nanosized powders by laser

3 Thermal behaviour of as-formed silicon-based

“fm” — 2002/9/6 — page vii — #7

3.2 Thermal reactivity of silicon-based nanopowders 41

4 Structure of some nanopowders and micro/nano composites by

4.1 As-prepared and heat-treated nanopowders 54

5 From short- to long-range order 110

5.1 Chemical order studied by solid-state nuclear magnetic

5.1.1 Nuclear magnetic methods 111

“fm” — 2002/9/6 — page viii — #8

5.2.1 Introduction 139

5.3 Electronic structure studied by X-ray photoemission (XPS) and soft-X-ray

5.3.1 Principles 153

5.4 Local order in Si/C/N nanopowders studied by X-ray absorption

5.4.1 X-ray absorption principles and data analysis 182

5.5.1 Diffraction applied to the study of disordered compounds 211

“fm” — 2002/9/6 — page ix — #9

6 Conductivity and dielectric properties of Si/C

6.1 Introduction 227

7 Processing and tailoring of Si/C/N-based nanocomposites 238

7.1 Introduction 238

8 Mechanical properties 264

8.1 Room temperature properties 264

9 Theoretical investigations of Si/C/N-based alloys 282

9.1 Introduction 282

“fm” — 2002/9/6 — page x — #10

Xavier Armand Commissariat à l’Energie Atomique, Service des photons, atomes et

“fm” — 2002/9/6 — page xi — #11

“fm” — 2002/9/6 — page xii — #12

The preparation of inorganic materials by thermolysis of preceramic compounds has become

“fm” — 2002/9/6 — page xiii — #13

“fm” — 2002/9/6 — page xiv — #14

“fm” — 2002/9/6 — page xv — #15

We thank the Chemistry Department of the Centre National de la Recherche Scientifique

“fm” — 2002/9/6 — page xvi — #16

Monomer unit Liquid or gaseous

Solid state thermolysis Laser pyrolysis

Micro–nano composite Nano–nano composite

Sajgalik et al. (1996) proposed a classiﬁcation into two main systems:

• micro–nano composites in which the matrix is constituted by micrometric crystals

1.2 Nanostructured ceramic elaboration

1.2.1 Amorphous ceramics obtained by solid state thermolysis of

1.2.2 The powder-making processes

• Solid phase: Evaporation–condensation, laser ablation, ball milling (or mechanical

• Nanophase Technologies Corp. has developed a gas condensation process to produce

1.3 Nanostructured Si3 N4 /SiC materials

• Micrometric silicon nitride, previously recovered with carbon, so as to produce the

SiO2 + 3C → SiC + 2CO ↑

1.4 Analytical methods

• Chemical analysis (CA)

Table 1.1 Available information depending on the method used

2.1 Generalities on the synthesis of nanosized powders by

2.1.1 The laser pyrolysis process