Tesi

Synthesis and characterization of optical
nanocrystals and nanostructures. An approach

to transparent laser nanoceramics
Montserrat Galceran Mestres
Doctoral Thesis
Supervised by:
Dra. Maria Cinta Pujol
Prof. Dra. Magdalena Aguiló
Departament de Quı́mica Fı́sica i Inorgànica

Fı́sica i Cristal·lografia de Materials i Nanomaterials (FiCMA-FiCNA)
Tarragona
2010
Synthesis and characterization of optical
nanocrystals and nanostructures. An approach
to transparent laser nanoceramics

c Montserrat Galceran Mestres, 2010
Fı́sica i Cristal·lografia de Materials i Nanomaterials (FiCMA-FiCNA)

Departament de Quı́mica Fı́sica i Inorgànica
Universitat Rovira i Virgili
C/ Marcel·lı́ Domingo, s/n
E-43007, Tarragona (Spain)
Prof. Dra. Magdalena Aguiló Dı́az, catedràtica de Cristal·lografia i Minerologia, i
Dra. Maria Cinta Pujol Baiges, professora agregat contractada, del Departament de
Quı́mica Fı́sica i Inorgànica de la Universitat Rovira i Virgili,
CERTIFIQUEM:
Que aquest treball, titulat ”Synthesis and characterization of optical nanocrystals

and nanostructures. An approach to transparent laser nanoceramics”, que presenta
Montserrat Galceran Mestres per l’obtenció del tı́tol de Doctor, ha estat realitzat sota
la nostra direcció al Departament de Quı́mica Fı́sica i Inorgànica d’aquesta universi-
tat i que acompleix els requeriments per poder optar a Menció Europea.
Tarragona, 26 de novembre de 2009

Abstract
Synthesis and characterization of optical nano-
crystals and nanostructures. An approach to trans-
parent laser nanoceramics
H is thesis presents the results of the synthesis as well structural and spectroscopic
T characterization of several types of oxide nanocrystals for optical applications.
The nanocrystals are activated by rare-earth ions, which can generate the laser emis-
sion. In the recent years, research has been intensified to obtain new nanomaterials
because their optical properties could be different that their respective bulk material
counterpart.
KRE(WO4 )2 (RE = Eu3+ , Gd3+ , Er3+ and Yb3+ ), RE2 O3 (RE = Sc3+ , Ho3+ , Er3+ ,
Yb3+ and Lu3+ ) nanocrystals for solid state laser and KTiOPO4 nanocrystals for non-
linear optical material were synthesized by the modified Pechini method. The exper-
imental variables were optimized as a function of the desired material to synthesize.
The synthesis of nanocrystals is the starting point to obtain ceramic materials using
the high pressure low temperature method.
The structural characterization of nanocrystals was investigated by a number of
techniques, the most common being X-ray diffraction and electron diffraction. The
morphology, the average particle size and the particle size distributions were carried
out using electronic microscopy. The optical absorption and luminescence measure-
ments were performed at room and low temperature in order to determine the energy
levels of the electronic states.
This doctoral thesis is divided in six chapters. The first chapter, the introduction,
explains the current research position in the context of the field of nanomaterials,
solid-state laser and non-linear optical materials. Chapter two describes the method-
ologies and experimental techniques used to synthesize and characterize the nano-
materials structurally and optically. Chapters three to five include overall the experi-
mental results of this thesis. The chapters discussed accurately the methodology used
during the synthesis of the nanocrystals and nanostructures. In addition to a deep
discussion about of the structural and optical characterization. The last chapter de-
scribes the methodology used to prepare transparent laser ceramics as well as their
structural and optical characterizations.
Keywords: nanomaterials, potassium rare earth tungstates, sesquioxides, potas-
sium titanyl phosphate, solid state lasers materials, non-linear optics materials.
i
”Si buscas resultados distintos,
no hagas siempre lo mismo”
Albert Einstein
Preface
He Ph.D. investigation contained in this thesis has been carried out at the group
T of Fı́sica i Cristal·lografia de Materials i Nanomaterials (FiCMA-FiCNA) in the
Departament de Quı́mica Fı́sica i Inorgànica of the Universitat Rovira i Virgili in
Tarragona, and was supervised by the Prof. Dra. Magdalena Aguiló Dı́az and Dra.
Maria Cinta Pujol Baiges.
Within the development of this thesis, we have collaborated actively with the fol-
lowing groups: Department of Spectroscopy of Excited States leaded by Prof. Wiesław
Strek at the Institute of Low Temperature and Structure Research (Wroclaw, Poland);
Institute of Physics coordinated by Prof. Iwan Kityk at the Jan Długosz University
(Czestochowova, Poland), Departamento de Materiales Ferroeléctricos leaded by Dr.
Carlos Zaldo at the Instituto de Ciencia de Materiales (Madrid, Spain) and Servicio
Láser leaded by Dr. Luis Roso of the Universidad de Salamanca (Salamanca, Spain).
This project was possible thanks to financial support from Departament d’Univer-
sitats, Recerca i Societat de la Informació de la Generalitat de Catalunya under projects
2005SGR-00658, and from the Ministerio de Educación y Ciencia (MEC) of the Span-
ish Government under projects MAT2005-06354-C03-0 and CiT-020400-2005-14 and
also supported by EU-Commission under project DT-CRYS (STRP-NMP3-CT-2003-
505580). I would also like to thank for personal financial support from Universitat
Rovira i Virgili and Departament d’Universitat, Recerca i Societat de la Informació
de la Generalitat de Catalunya under URV grants and BE- DRG044276.

Tarragona, 2010
v
Acknowledgements
R om the beginning, my PhD studies have been like an adventure in which I have
F enjoyed the trip. A journey is easier when you travel with somebody. Many peo-
ple have cooperated, encouraged and assisted in the process of my thesis work and
helped me. This thesis is the result of four years of work whereby I have been accom-
panied and supported by many people. This is a pleasant opportunity to express my
gratitude to all of them.
First, I would like to thank my advisors, Prof. Dra. Magdalena Aguiló and Dra.
Maria Cinta Pujol, for giving me the opportunity to join the Fisica i Cristal·lografia
de Materials i Nanomaterials (FiCMA-FiCNA) group and for their support, guidance
and encouragement over the development of my PhD investigation. I would like to
thank especially Magdalena Aguiló for introducing me to the basics of crystallog-
raphy during my last undergraduate year, for giving me a deeper knowledge of it
during my PhD and for having her office door always open for me. I would like to
thank Maria Cinta not only for her enthusiasm towards her work, but also for her
dedication, help and good conversations that accompanied undrinkable coffees and
sometimes good music; but above all her friendship.
I would also like to convey my sincerest thanks and deepest gratitude to my
group leader Prof. Dr. Francesc Dı́az for giving me the opportunity to join the FiCMA-
FICNA group and for his day to day involvement in this work. Thank you very much
for giving me your enthusiasm and passion for science. I have enjoyed every scientific
discussion together with our friendly sports conversations.
I also want to thank the other members of the FiCMA-FiCNA group Dr. Jaume
Massons, Dra. Josefina Gavaldà, Dra. Ma Rosa Solé, Dr. Xavier Mateos and Dr. Joan
Josep Carvajal for their collaboration and scientific discussions during my stay in this
research group.
I would like to acknowledge specially the technicians Agustı́ Montero, Nicolette
Bakker and Laura Escorihuela for their invaluable contribution and support to this
thesis. I thank them for cutting and polishing almost impossible, delicate, very small
and strange samples with a good sense of humor.
To all my colleagues of the FiCMA-FiCNA group Western Bolaños, Venkatesan
Jambunathan, Martha Segura, Raj Kumar, William Barrera, Muhammad Qadri and
Oleksandr Bilousov; it has been a pleasure working. Having the opportunity to learn
about other cultures makes one to prosper. I would also like to thank Jaume Cugat for
our breakfasts, coffees and happy days with nonsense talks. I enjoyed every moment.
I would like to thank especially all the old members of the FiCMA-FiCNA group,
Arantxa Vilalta, Ana Aznar, Isabel Parreu, Alexandra Peña, Òscar Silvestre (you will
vii
always be in our heart) together with Maria Cinta Pujol. Thank you for this wonder-
ful time together, for these wonderful trips, for incredible dinners, for our surrealist
conversations through Skype and especially for your friendship. It is very hard to
put down in words the moments spent together. It is possible to work and meet nice
people who will endure the lifelong.
I would like to express my appreciation to all the research groups that have collab-
orated with me during the PhD investigations. I have had the great pleasure of work-
ing with Prof. Wieslaw Strek, who shared with me his knowledge of spectroscopy
and laser ceramics at the Department of Spectroscopy of Excited States at the Insti-
tute of Low Temperature and Structure Research in Wroclaw. I would like to thank
everybody I met there for making my stay more enjoyable, especially Przemyslaw
Jacek Deren, Dariusz Hreniak, Pawel Gluchowski, Katarzyna Halubek, Adam Wa-
tras, Rafal Jakub Wiglusz, Anna, Monika and Marek. I greatly appreciate the piezoop-
tic and photo-induced second harmonic generation measurements of the nanocom-
posites made by Professor Ivan Kityk at the Institute of Physics at the University of
Czestochowa. I would like to thank Dr. Carlos Zaldo for the spectroscopic discussions
and his help with the lifetime measurements at the Instituto de Ciencia de Materiales
of Madrid. Finally, thanks to Dr. Luis Roso of the Servicio Láser at the Universidad
de Salamanca for synthesizing nanocrystals from bulk single crystal using the fem-
tosecond laser ablation.
I would like to acknowledge John Bates, who has read this entire thesis except for
this part, for the effort of correctly the language in a record time.
Many heartfelt thanks to all my friends, that I have met at every stage of my
life (school, high school, university, basketball team). Especially, to my best friends
Susana, Marta and Jordi, thank you very much for our friendship, our meetings, our
trips and our Wii-competitions, you know that you have to train more. Thank you
to all my friends in la Palma d’Ebre, my town and the place where I go to relax.
Especially, I would like to thank Núria, Maite and Sònia (thanks for fighting to stay
alive). Thank you very much to my friends that I met while playing basketball: Yoli,
Carme, Cristina, Mònica, Laia, Anaı̈s. Thank you for enjoying our time together in the
court, in the changing room, during our trips and overall in our meetings outside of
the court. During this time I have met a lot of nice people and would like remember
them. I would not like to forget my currently team-mates, thanks for making the last
few months easier and especially to Ainhoa, thank you for the effort of correcting the
language of this part in the changing room just a few minutes. To ”my boys” during
the past years, many thanks for enjoying all the training sessions and matches and
for enduring my shouts. I have learnt a lot with you and from you.
I would like to remember all the people that I met during my months at the Uni-
versity of Tübingen (Germany). Thank you very much to Dr. Prof. Dr. h.c. Joachim
Strähle for guiding me in my first scientific experience, the first mentor of my sci-
entific career. Many thanks to Simon Schwarz, Carlos F. Barboza da Silva, Guintaras
Pivoriunas and Daniel Morrogh for our Freietags-Bier team, and nice and funny con-
versations at the laboratory.
Last but not the least, I would like to remember the affection and the education of
my parents Josep Galceran and Ma Àngels Mestres, my brother LLuı́s and his partner
Natalia and the love of my sister Ma Àngels. Thanks for their support and patience
everyday, and for the encouragement when I was living abroad, and specially many
thanks for being as you are. I would not like to forget all the support received from
my grandmothers Joaquima and Francisca as well as Assumpción, who is like my
grandmother, thanks for trying to understand my work. I could not have done this
without them.
Everyone else whom I have forgotten.

To my parents, and Lluı́s and Ma Àngels
with great love
List of publications
H is
doctoral thesis is partially based on the work contained in the following pa-
T pers, referred to by roman numerals in the text:
Paper I: M. Galceran, M. C. Pujol, M. Aguiló, F. Dı́az, ”Sol-gel modified Pechini

method for obtaining nanocrystalline KRE(WO4 )2 (RE = Gd and Yb)”, Journal
of Sol-Gel Science and Technology, 2007, 42(1), 79-88.
Paper II: M. Galceran, M. C. Pujol, C. Méndez, A. Garcı́a, P. Moreno, L. Roso, M.
Aguiló, F. Dı́az, ”Synthesis of monoclinic monoclinic KGd(WO4 )2 nanocrystals
by two preparations methods”, Journal of Nanoparticle Research, 2009, 11(3),
717-724.
Paper III: S. Tkaczyk, M. Galceran, S. Kret, M. C. Pujol, M. Aguiló, F. Dı́az, I. V. Kityk,
”UV- operated piezooptical effects in oxide nanocrystals incorporated into the
PMMA matrices”, Acta Materialia, 2008, 56(1-3), 5677-5684.
Paper IV: M. Galceran, M. C. Pujol, C. Zaldo, M. Aguiló and F. Dı́az, ”Size depen-
dence of structural and optical properties in monoclinic Er:KYb(WO4 )2 nano-
crystals”, Journal Physical Chemistry C, 2009, 113, 15497-15506.
Paper V: M. Galceran, M. C. Pujol, P. Gluchowski, W. Strek, J. J. Carvajal, X. Mateos,
M. Aguiló and F. Dı́az, ”Structural and optical characterization of Eu:KYb(WO4 )2
nanocrystals. A promising red phosphor” submitted to Journal of Solid State
Chemistry.
Paper VI: M. Galceran, M. C. Pujol, M. Aguiló, F. Dı́az, ”Synthesis and characteriza-
tion of nanocrystalline Yb:Lu2 O3 by modified Pechini Method”, Materials Sci-
ence and Engineering B-Solid State Materials for Advanced Technology, 2008,
146(1-3), 7-15.
Paper VII: M. Galceran, M. C. Pujol, J. J. Carvajal, X. Mateos, C. Zaldo, M. Aguiló
and F. Dı́az, ”Structural and spectroscopic characterization of Ybx :Sc2− x O3 na-
nocrystals”, submitted to Journal of Luminescence.
Paper VIII: M. Galceran, M. C. Pujol, P. Gluchowski, W. Strek, J. J. Carvajal, X. Ma-
teos M. Aguiló and F. Dı́az, ”A promising Lu2− x Hox O3 laser nanoceramics:
Synthesis and characterization” submitted to Journal Physical Chemistry C.
Paper IX: M. Galceran, M. C. Pujol, J. J. Carvajal, S. Tkaczyk, I. V. Kityk, F. Dı́az,
M. Aguiló, ”Synthesis and characterization of KTiOPO4 nanocrystals and their
PMMA nanocomposites”, Nanotechnology, 2008, 20(3), 035705-035715.
xiii
Contents
Abstract i
Preface v
Acknowledgements vii
List of Publications xiii
1 Introduction 5
1.1 Nanoscience and Nanotechnology . . . . . . . . . . . . . . . . . . . . . 7
1.1.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.1.2 A brief history of nanotechnology . . . . . . . . . . . . . . . . . 7
1.1.3 Characteristics of nanomaterials . . . . . . . . . . . . . . . . . . 9
1.1.3.1 Melting point and phase transition temperature . . . . 10
1.1.3.2 Mechanical properties . . . . . . . . . . . . . . . . . . . 11
1.1.3.3 Optical properties . . . . . . . . . . . . . . . . . . . . . 11
1.1.4 Nanotechnology applications . . . . . . . . . . . . . . . . . . . . 12
1.2 Overview of the laser history. Solid-state lasers . . . . . . . . . . . . . . 13
1.3 Solid active laser media materials . . . . . . . . . . . . . . . . . . . . . . 15
1.3.1 Host materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.3.1.1 Potassium rare earth tungstates (KRE(WO4 )2 ) . . . . . 16
1.3.1.2 Sesquioxides (RE2 O3 ) . . . . . . . . . . . . . . . . . . . 17
1.3.2 Transparent laser ceramics . . . . . . . . . . . . . . . . . . . . . . 19
1.3.2.1 Introduction to laser ceramics . . . . . . . . . . . . . . 19
1.3.2.2 State of the art . . . . . . . . . . . . . . . . . . . . . . . 20
1.3.2.3 Advantages of transparent laser ceramics . . . . . . . 22
1.3.3 Active ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3.3.1 Ytterbium . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3.3.2 Erbium . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.3.3.3 Holmium . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.3.3.4 Europium . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.4 Nonlinear optical materials: Potassium titanyl phosphate (KTiOPO4 ) . 24
1
CONTENTS M. Galceran Mestres
1.5 Fundamentals of template-based methods . . . . . . . . . . . . . . . . . 26

1.5.1 Porous silicon templates . . . . . . . . . . . . . . . . . . . . . . . 26
1.5.2 Porous alumina templates . . . . . . . . . . . . . . . . . . . . . . 28
1.6 Aims of this doctoral thesis . . . . . . . . . . . . . . . . . . . . . . . . . 29
2 Experimental Techniques 31
2.1 Synthesis of nanocrystals: the modified Pechini method . . . . . . . . . 33
2.2 Synthesis of nanocrystals: the femtosecond laser ablation method . . . 36
2.3 Ceramic sintering method: High pressure low temperature (HPLT) . . 37
2.4 X-Ray diffraction method: X-ray powder diffraction technique (XRD) . 38
2.5 Thermal analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.5.1 Differential thermal analysis (DTA) . . . . . . . . . . . . . . . . 41
2.5.2 Thermogravimetric analysis (TG) . . . . . . . . . . . . . . . . . . 42
2.6 Electron microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.6.1 Scanning electron microscopy (SEM) . . . . . . . . . . . . . . . . 42
2.6.2 Environmental scanning electron microscopy (ESEM) . . . . . . 43
2.6.3 Transmission electron microscopy (TEM) . . . . . . . . . . . . . 44
2.6.3.1 Electron diffraction . . . . . . . . . . . . . . . . . . . . 45
2.7 Electron probe microanalysis (EPMA) . . . . . . . . . . . . . . . . . . . 46
2.8 Spectroscopy techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.8.1 Fourier transform infrared . . . . . . . . . . . . . . . . . . . . . . 48
2.8.2 Raman spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.8.3 Optical absorption and transmission . . . . . . . . . . . . . . . . 49
2.8.4 Luminescence measurements . . . . . . . . . . . . . . . . . . . . 50
2.9 Photoinduced second harmonic generation (PISHG) . . . . . . . . . . . 52
2.10 Piezooptic measurements . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3 Synthesis and Characterization of Oxide Nanocrystals 55

3.1 Sol-Gel: the modified Pechini method . . . . . . . . . . . . . . . . . . . 57
3.2 Potassium rare earth tungstates, KRE(WO4 )2 . . . . . . . . . . . . . . . 59
3.2.1 Determination of the crystallization temperature: phase transi-
tions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.2 Dopant concentration analysis . . . . . . . . . . . . . . . . . . . 60
3.2.3 Structural characterization of KRE(WO4 )2 : variation of lattice
parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.2.4 Particle size and dispersion . . . . . . . . . . . . . . . . . . . . . 62
3.2.5 Raman scattering of KRE(WO4 )2 . . . . . . . . . . . . . . . . . . 65
3.3 Sesquioxides, RE2 O3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.3.1 Determination of the crystallization temperature . . . . . . . . . 66
3.3.2 Structural characterization of RE2 O3 : variation of lattice param-
eters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.3.4 Raman scattering of RE2 O3 . . . . . . . . . . . . . . . . . . . . . 72
3.4 Potassium Titanyl Phosphate, KTiOPO4 . . . . . . . . . . . . . . . . . . 73
3.4.1 Determination of the crystallization temperature: phase transi-
tions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2
3.4.2 Structural characterization . . . . . . . . . . . . . . . . . . . . . 74

3.5 Femtosecond laser ablation . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.5.1 Synthesis of KGd(WO4 )2 nanocrystals . . . . . . . . . . . . . . . 77
3.5.2 Structural characterization of KGd(WO4 )2 . . . . . . . . . . . . 77
4 Synthesis and Characterization of Nanostructures 79

4.1 PMMA, poly(methyl methacrylate), nanocomposites of oxide nano-
crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.1.1 Synthesis of PMMA nanocomposites of oxide nanocrystals . . . 81
4.1.2 Structural characterization of nanocomposites . . . . . . . . . . 82
4.1.3 Distribution of oxides nanocrystals into polymer matrix . . . . 82
4.2 PMMA microcolumns with embedded (Er,Yb):Lu2 O3 nanocrystals . . 84
4.2.1 Synthesis of PMMA microcolumns with embedded (Er,Yb):Lu2 O3
nanocrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.2.2 Structural characterization of (Er,Yb):Lu2 O3 nanocrystals em-
bedded in PMMA microcolumns . . . . . . . . . . . . . . . . . . 85
4.2.3 Visualization of PMMA microcolumns by electron microscope 86
4.3 (Er,Yb):Lu2 O3 nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.3.1 Synthesis of (Er,Yb):Lu2 O3 nanowires . . . . . . . . . . . . . . . 87
4.3.2 Structural characterization of (Er,Yb):Lu2 O3 nanowires . . . . . 87
4.3.3 Visualization of (Er,Yb):Lu2 O3 nanowires by electron microscope
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
5 Spectroscopic and Optical Characterizations 91

5.1 Spectroscopic properties of Yb3+ and Er3+ in KRE(WO4 )2 nanocrystals 93
5.1.1 Optical absorption . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.1.2 Optical emission . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5.1.3 Lifetime measurements . . . . . . . . . . . . . . . . . . . . . . . 96
5.2 Spectroscopic properties of Yb3+ and Eu3+ in KRE(WO4 )2 nanocrystals 97
5.3 Spectroscopic properties of Yb3+ in RE2 O3 nanocrystals . . . . . . . . . 100
5.3.3 Influence of the Yb3+ doping concentration in Sc2 O3 nanocrys-
tals on the lifetime measurements . . . . . . . . . . . . . . . . . 102
5.4 Spectroscopic properties of Ho3+ in Lu2 O3 nanocrystals . . . . . . . . . 103
5.5 Piezo-optical measurements of oxide film nanocomposites . . . . . . . 106
5.6 Photoinduced second harmonic generation of KTiOPO4 nanocomposites107
3
6 Fabrication and characterization of Ho:Lu2 O3 nanoceramics 109

6.1 Fabrication of Ho:Lu2 O3 laser nanoceramics . . . . . . . . . . . . . . . 111
6.2 Structural characterization of Ho:Lu2 O3 nanoceramics . . . . . . . . . 112
6.3 Raman scattering of Ho:Lu2 O3 nanoceramics . . . . . . . . . . . . . . . 113
6.4 Morphology and particle size of Ho:Lu2 O3 nanoceramics . . . . . . . . 114
6.5 Physical characterization of the Ho:Lu2 O3 nanoceramics . . . . . . . . 115
6.6 Spectroscopic Properties of Ho3+ in Lu2 O3 nanoceramics . . . . . . . . 115
Conclusions 119
References
List of Errata 137
Paper I 139
Paper II 151
Paper III 161
Paper IV 171
Paper V 183
Paper VI 201
Paper VII 213
Paper VIII 231
Paper IX 255
4
Chapter 1
Introduction
1.1 Nanoscience and Nanotechnology
1.1.1 Overview
1.1.2 A brief history of nanotechnology
1.1.3 Characteristics of nanomaterials
1.1.3.1 Meting point and phase transition temperature
1.1.3.2 Mechanical properties
1.1.3.3 Optical properties
1.1.3.4 Magnetic properties
1.1.4 Nanotechnology applications
1.2 Overview of the laser history. Solid-state lasers
1.3 Solid active laser media materials
1.3.1 Host materials
1.3.1.1 Potassium rare earth tungstates (KRE(WO4 )2 )
1.3.1.2 Sesquioxides (RE2 O3 )
1.3.2 Transparent laser ceramics
1.3.2.1 Introduction to laser ceramics
1.3.2.2 State of the art
1.3.2.3 Advantages of transparent laser ceramics
1.3.3 Active ions
1.3.3.1 Ytterbium
1.3.3.2 Erbium
1.3.3.3 Holmium
1.3.3.4 Europium
1.4 Nonlinear optical materials: Potassium titanyl phosphate (KTiOPO4 )
1.5 Fundamentals of template-based methods
1.5.1 Porous silicon templates
1.5.2 Porous alumina templates
1.6 Photonic crystals
1.7 Aims of this doctoral thesis
H is chapter can be divided into three different blocks. The first big block is an
T overview of nanotechnology, which deals with its history, the characterization
and applications of nanomaterials. The second block deals with the solid state laser
materials used in this doctoral thesis and the transparent laser ceramics. And finally,
the last block describes photonic crystals as a result of nanomaterials obtained from
template-based methods.
5
CHAPTER 1. INTRODUCTION M. Galceran Mestres
1.1 Nanoscience and Nanotechnology

1.1.1 Overview
In recent years, nanoscience and nanotechnology have become one of the most im-
portant fields in physics, chemistry, engineering, biology, etc. The many diverse de-
finitions of nanotechnology reflect the fact that the nanotechnology covers a broad
research field spectrum and requires interdisciplinary and multidisciplinary efforts.
The nanoworld is extremely broad and it is practically impossible to find any field in
the sciences that is not in the some way or another connected with nanostructures.
Nanoscience involves studying relationships between the physical properties and
phenomena of materials in the range from 0.1 to 100 nm 1 . Nanotechnology, on the
other hand, focuses on the design, fabrication and applications of nanomaterials, and
also, includes a fundamental understanding of physical properties and phenomena
of nanomaterials. The term nanomaterials covers a various types of nanostructures
from zero dimension to three dimension nanostructures. They are summarized in
table 1.1 [1].
TABLE 1.1. Typical nanomaterials.

Size (approximate) Materials
(a) 1D Nanocrystals and clus- Metals, semiconductors, magne-

1-10 nm diameter
ters (quantum dots) tic materials
Other nanoparticles 1-100 nm diameter Ceramic oxides
Metals, semiconductors, oxides,
(b) Nanowires 1-100 nm diameter
sulfides, nitrides
Carbon, layered metal chalcoge-
Nanotubes 1-100 nm diameter
nides, oxides
from several nm2 to Metals, semiconductors, magne-
(c) 2D Arrays (of nanoparticles)
µm2 tics materials
Surfaces and thin films 1-100 nm thick Different materials
(d) 3D Structures (superlatti- from several nm in Metals, semiconductors, magne-
ces) all three dimensions tics materials
Nanocrystals-polymer nano-
Nanoparticles in polymers 1-100 nm
composites
To put nanoscale in context, we could be say that a nanometer is to a meter what

a marble is to the earth. For example, the diameter of a human hair is around 75.000
nm which is considered to be a giant in this field and the smallest that the eyes can
see is around 10.000 nm (figure 1.1).
1.1.2 A brief history of nanotechnology

Although, nanotechnology is a relative new word, structures and devices of nanome-
ter dimensions are by no means new. They have existed on Earth for a long time [2].
1 Nanos means a dwarf in Greek, a nanometer (nm) equals 10−9 m
7
The idea of nanotechnology was first introduced by the physicist Richard Feynman
in 1959, when he presented his talk ”There’s Plenty of Room at the Bottom” at an
American Physical Society meeting at the California Institute of Technology. He sug-
gested the possibility that objects could be manipulated with atomic precision [3, 4].
For this reason, Feynman is regarded as the father of the nanotechnology. However,
the term nanotechnology was not used until 1974, when in the paper ”On the Basic
Concept of Nano-Technology” N. Taniguchi stated that ”Nano-technology mainly con-
sists of the processing of, separation, consolidation, and deformation of materials by one atom
or one molecule” [5].
F IGURE 1.1. Approach of the macroscale to nanoscale.
Later, in 1977, E. Drexler promoted the concept of the Molecular Nanotechnology

(MNT) at Massachusetts Institute of Technology (MIT). His vision about nanotechno-
logy is often called ”molecular nanotechnology” or ”molecular manufacturing”. He
published his books ”Engines of Creation: The Coming Era of Nanotechnology” (1986) [6].
In 1982, a major advance in the nanoworld was the invention of the Scanning Tun-
neling Microscope (STM) by G. Binning and H. Rohrer [7]; later, in 1986, was in-
vented the atomic force microscope (AFM) was invented by G. Binning and his col-
leagues [8]. These two microscopes were used to observe three-dimensional images
of the surface structure and electronic information with atomic resolution. Another
nanotechnology breakthrough was in 1985, when H. Kroto et al. were discovered the
C60 known as Buckministerfullerene [9]. In 1986, R. Smalley founded the first orga-
nization called Foresight Institute. One year later, T. Fulton and G. Dolan pioneered
8
a new technique called a single-electron tunneling (SET), which could control the
movement of individual electrons at the nanoscale [10]. Later, Dr. Louis Brus and his
team discovered the nanocrystalline semiconductor materials called quantum dots
and observed solutions of striking colors made from these materials. This contributed
to the understanding of the quantum confinement effect which explains the correla-
tions between size and color for these nanomaterials [11]. In 1989, the scientists D.
Eigler and E. Schweizer used STM to move a 35 individual atoms of the gas xenon
cooled to an extremely low temperature to write the word ”IBM” on a nickel sur-
face [12]. The first nanotechnology journal called ”Nanotechnology” was founded
in 1990. In 1991, S. Iijima discovered that the carbon nanotubes consisted of several
tubes one inside the other which enhance the physical properties of the whole [13]
and in 1992, E. Drexler published ”Nanosystems: Molecular Machinery, Manufactu-
ring and Computation” [14]. Today, in the young field of nanotechnology, scientists
and engineers can control of individual atoms and molecules, manipulating them
with extraordinary precision.
1.1.3 Characteristics of nanomaterials

Materials at the nanometer scale exhibit different physical, chemical, optical, elec-
trical and biological properties from material on the large scale, whereas, the mi-
crostructured materials have properties that are similar to the corresponding bulk
material. For example, a golden grain of 5 nm has a grey color, more catalytic effi-
ciency and lower melting point. Due to the laws of quantum physics, electrical and
magnetic properties of materials are to some extent size-dependent, meaning that for
very small crystals these properties may be different from those encountered in the
bulk. Some characteristics of these materials that are not present in the bulk materials
are [15]:
1. A large fraction of surface atoms

2. A large surface energy
3. Spatial confinement, which brings quantum effects
4. Fewer imperfections
It is clear that the surface plays an important role in the properties of a mate-
rial, since the surface area to volume ratio increases as the particle radius decreases.
The surface atoms are chemically more active than the bulk atoms because they usu-
ally have fewer adjacent coordinated atoms and unsaturated sites or more dangling
bonds.
The huge fraction of surface atoms decreases the melting point and the phase
transition temperature. The reduction in the particle size leads to reduction of imper-
fections in nanomaterials and enhances the mechanical properties of nanomaterials.
Size confinement has a deep effect on the optical and electronic properties of nano-
materials. The electrical conductivity decreases because surface scattering increases.
We are particularly interested in so-called large-sized nanocrystallites (LSNC) (lar-
ger than 10 nm but smaller than 80-100 nm) [16]. These nanocrystals have properties
9
that are caused by their low dimensions (so called quantum-confined quantization)
but at the same time, they present typical properties typical of bulk-like crystals, such
as long-range k-dispersion.
F IGURE 1.2. Principal sketch explaining the structure of large-sized nanocrystals. The regions
are explained in the text.
A representative scheme of LSNC is shown in figure 1.2. Region I corresponds to

crystalline bulk-like region which has long-range ordering and the translation sym-
metry of a perfect crystal. The Region II is crucial for LSNC, because the surrounding
disordered matrix background disturbs the perfect crystalline structure. One of the
main parameters here is the thickness of the reconstructed surfaces and their homo-
geneity. Finally, Region III presents a disordered background because it incorporates
regions I and II. Usually, there are two kinds of the surrounding region. One its an
amorphous-like background consisting of the same material, and the other presents
a surrounding polymer- or glass-like disordered matrix. The ratio between the re-
constructed sheet (interphase between the nanocrystals and the matrix) and the total
volume is crucial for the manifestation of the confined effects. If this ratio is below
0.05, the nano-confinement effects may be neglected due to behaviour of bulk-like
long-range ordered contribution. At the same time, when this ration exceeds 0.08,
we have traditional nanocrystals and all the intermediate values correspond to the
LNSC.
More detailed effects in physical properties of nanomaterials respect to the bulk
material counterpart will be discussed thoroughly below.
1.1.3.1 Melting point and phase transition temperature

Nanomaterials have a lower melting point and phase transition temperature than
their bulk material. This could be attributed to the large fraction of surface atoms of
the total number of atoms. The lower melting temperature and phase transition are
attributed to fact that the energy surface increases as the the particle size decreases.
For example, for CdS nanocrystals, Goldstein et al. observed a decrease in the melting
point of over 50 % attributed to the large surface energy which is lower in the liquid
phase than in the solid phase [17].
Other phase transitions such as the Curie temperature (the temperature above
which it loses its characteristic ferromagnetic ability) have a similar dependence on
the particle size. Ferroelectric properties in polycrystalline materials may disappear
when the particle is smaller than a particular size, taking into account that the phase
transition temperatures decrease when particle size decreases. In the case of PbTiO3
10
nanoparticles, the Curie temperature appears at lower temperatures and decreases as

particle size decreases [18].
1.1.3.2 Mechanical properties
Generally, the mechanical properties of nanomaterials such as hardness, elastic mo-

dulus, toughness, scratch resistance, fatigue strength, etc. are different from those of
bulk materials; they increase when the particle size decreases.
The first studies about mechanical properties were carried out on whiskers by
Herring and Galt in 1952 [19]. They found that the increase in mechanical strength
was appreciable, when the diameter of a whisker was less than 10 µm. Two different
mechanisms have been proposed to explain this enhancement in mechanical strength
in nanowires and nanorods. The first one is related to their high internal perfection:
their small diameter implies that the probability of finding any imperfections such as
dislocations, micro-twins, impurity precipitates, etc. is lower [20]. The other mecha-
nism is the perfection surface: nanowires with a diameter of 10 µm or less had no de-
tectable defects on the surface; on the other hand, when the diameter was higher than
10 µm irregular growth steps were observed [21]. This dependence between strength
and the particle size was found in a whiskers, metals and semiconductors [22, 23].
1.1.3.3 Optical properties
Nanomaterials have attracted a great deal of interest because of their novel optical
properties, which differ considerabily from bulk crystals because of the quantum
size effect. Because nanomaterials are smaller, the electrons are confined to a small
space and lose their degree of freedom, which quantizes their allowed energy states
(the energy level separation between adjacent levels increases with decreasing di-
mensions). These changes in the density of the electronic energy levels produce a
strong variations in the electrical and optical properties [24].
The spectroscopic properties of lanthanide doped-nanocrystals (emission lifetime,
luminescence quantum efficiency, concentration quenching, etc.) can be different from
those of their bulk counterpart due to their particle size. This may be attributed to a
greater fraction of active ions near the surface, the disorder on the surface of the nano-
crystals and, in some cases, the reduction of the surface site symmetry for the doping
ion [25, 26].
In the field of optical materials, the fact that a well-known optical material can
exhibit new properties in the nanodimensions is a new challenge. Physical properties
such as spectroscopic or non-linear optical parameters are affected by the dimen-
sion of the material [27]. This change in the physical properties has created interest
in the synthesizing and characterizing nanocrystals in well-known optical materials
such as laser or non-linear optical materials. The LSNC have the potential to cre-
ate materials with enhanced nonlinear optical response susceptibilities, because the
smaller the nanocrystallite, the larger the contribution originating from interface elec-
trostatic potential gradients. These gradients determine dipole moments on the sur-
face and are important for inducing nonlinear optical effects at the interface due to
high gradients between the ordered and disordered structural phases. Additionally,
11
the nonlinear optical properties of nanomaterials are of significant interest for opti-
cal switching, pulse power shaping in optical parametric oscillators (OPOs), optical
parametric generators (OPGs) and other nonlinear optical applications [28]. More-
over, some nonlinear optical nanocrystals have been embedded into polymer matri-
ces with vanishing values of second harmonic generation by the guest-host polymer
technique [29, 30] and the nanocomposites obtained have shown enhanced nonlin-
earity, primarily resulting from the effects of surface trapped states in nanoscale ma-
terials [31]. For example, the photoinduced second harmonic generation has already
been extensively studied and interesting results have been obtained in some nonli-
near nanocomposites such as Ca4 GdO(BO3 )3 [32], and PbS [33].
Another optical property studied in nanocomposites is the piezo-optical effect,
which can also be enhanced by the formation of nanocomposites. The piezo-optical
effect presents a superposition of the bulk-like contribution of the ”softer part”, be-
cause the sheets originate from the nanocrystal surface itself and from the remaining
materials. Owing to the existence of phases with intermediate stiffness of nanometer
sizes, elasto-optical effects can be enhanced quite considerably. These materials can
be used for mechanically induced light intensity operation and mechanically oper-
ated light transmission as well as in tensosensors and photoelastic fibers. Also, the
acousto-optical parameters related to the piezooptical properties are important for
different acousto-optical applications. The use of nanocomposites for these applica-
tions has many advantages over the use of the bulk crystals: the piezo-optical coeffi-
cients are fixed in several crystals and cannot be varied in the desired direction.
1.1.4 Nanotechnology applications

At present, the nanomaterials are used in a wide range of fields. In chemistry, they
are used in a number of new reactions as a catalyst or a sensor systems, and to fabri-
cate new compounds of previously unknown properties. For example, nanomaterials
are more effective for catalysis applications because their extremely small size yields
large surface area to volume ratio so catalytic activity is higher.
Small inorganic particles can be lead to novel or improved applications as a con-
sumer goods such as cosmetics, foods, sport, textiles, cutting tools, etc. One field of
application is in sunscreens. The use of small particles to protect against the sun’s UV
radiation implies two mechanisms: intrinsic absorption due to the electronic proper-
ties of the compound and light scattering and reflection in which size and shape play
an important role.
Currently, nanoscale structuring of optical devices, quantum dot lasers and pho-
tonic crystal materials is leading to additional advances in information and commu-
nications technology. Nanotechnology makes it provide to decrease the bit size of the
stored information, thus leading to high-density, high-speed, solid-state electronic
memories and magnetic and optical discs. In the communications technology, elec-
trical devices are being replaced by optical and optoelectronic devices due to their
bandwidth and capacity. For example, the photonic crystals and quantum dots are
two potential devices for communications.
Words such as nanomedicine, biological nanotechnology or bionanotechnology
are used to describe this emerging field. The nanomaterials are the same size as most
12
biological molecules and structures. This has led to the development of diagnostic
devices, analytical tools, drug delivery systems, physical therapy applications, etc.
Nanotechnology creates radical new approaches to material property enhance-
ment and synthesis and will lead to new technologies, applications and industries.
1.2 Overview of the laser history. Solid-state lasers

In 1917, Albert Einstein described the theory of stimulated emission phenomena,
which is well-known as the basic principle of the laser effect [34]. Stimulated radi-
ation was first demonstrated in the microwave range in 1954 by Nobel Prize winner
C. Townes and co-workers. At this point, the term MASER (Microwave Amplification
by Stimulated Emission of Radiation) was created [35]; and in 1958, the same author
reported the possibility of maser action in the infrared and visible spectrum, which
G. Gould was later to refer to as LASER [36].
In 1960, Theodore Maiman obtained the first solid-state laser (SSL), a pulsed syn-
thetic ruby crystal Cr3+ :Al2 O3 [37]. In the same year, A. Javan made the first gas
laser (He-Ne). In 1962, R. N. Hall demonstrated the first semiconductor laser diode
made of GaAs, which emitted at 850 nm, and N. Holonyak demonstrated the first
laser diode with visible emission which could be used only in pulsed operation and
cooled to liquid nitrogen temperatures (77 K). From 1963 to 1966, in chronological or-
der, the infrared CO2 laser, the ion laser in mercury vapor, the argon ion laser and the
blue He-Cd metal vapor laser were invented. In the following years, the first vacuum
ultraviolet laser (H2 ), XeF2 and the first quantum-well laser (GaAs semiconductor)
were reported.
LASER is the acronym of Light Amplification by Stimulated Emission of Radiation.
Laser light is a monochromatic (consisting of a single wavelength), coherent (the wa-
ves of light are in phase) and directional (the beam of light has very low divergence).
A laser consists of an active medium placed in an optical cavity consisting the sim-
plest of two parallel mirrors facing each other. In laser materials, the light emitted is
amplified by physical phenomena, and the laser beam can escape through one of the
partially transparent mirrors.
There are three possible interactions between matter and light which cause the
transition from one state of energy to another: absorption, spontaneous emission and
stimulated emission (figure 1.3). However, stimulated emission is the key to obtain-
ing the laser effect, whereby the photon emission is triggered by other photons. When
a photon (hν=E2 -E1 ) interacts with the matter in the excited state, there is a deexcita-
tion decay to the ground state and a new photon is also emitted with the same phase,
frequency, polarization and direction of travel as the original.
Previously, the population is inverted, and excited state becomes more populated
than the lower energy states. This transition to the excited level is due to the external
pumping by flashlamps or laser diodes. The population inversion depends highly on
the energy-level scheme of the active ion.
Figure 1.4 shows two possible energy-level schemes of the active medium: the
three-level and the four-level lasers. The first laser demonstrated by Maiman (Cr3+ :Al2 O3 )
was a three-level laser. For this energy-level scheme, the laser transition is caused by
13
F IGURE 1.3. Scheme of the interaction between the light and energety levels in the material: (a)
absorbtion, (b) spontaneous emission and (c) stimulated emission.
F IGURE 1.4. Energy level diagram of (a) three-level laser and (b) four-level laser.
a radiative transition from the E1 state to the E0 state. However, for the four-level
laser, the laser transition is caused by a radiative transition from the metastable state
(E2 ) to the excited state (E1 ), which has a higher energy than the fundamental state.
In this case, the population inversion is easier than in the case of the three-level laser
because the lower laser level does not coincide with the ground level, which has a
significant population at room temperature. A solid-state laser consist of three prin-
cipals elements:
1. Solid active media consist of a crystals, glasses or ceramics as a host materials

and doped with the active ions such as rare-earth or transition-metal ions
2. A pump source to excite the gain medium
3. A laser cavity or laser resonator, in which the laser radiation can circulate and
pass a gain medium which compensates the cavity losses
As mentioned above, the first solid-state laser was discovered by Maiman in 1960
(Cr3+ :Al2 O3 ). In the same year, Sorokin and Stevenson obtained the first SSL, which
used the first lanthanide ion as the active ion (Sm2+ :CaF2 ) [38]. The following year,
Johnson and Nassau developed the first SSL with a trivalent lanthanide ion as an
active ion (Nd3+ :CaWO4 ) [39]. Then, the laser action was developed from triva-
lent lanthanides (Ce3+ , Pr3+ , Nd3+ , Eu3+ , Gd3+ , Er3+ , Ho3+ , Tm3+ , Yb3+ ), divalent
lanthanides (Sm2+ , Dy2+ and Tm2+ ), transition metals (Ti3+ , V2+ , Cr3+ , Ni2+ and
Co2+ ) and actinide ion U3+ . The most commercial SSL, yttrium aluminum garnet,
Y3 Al5 O12 (YAG) as a host material doped with trivalent neodymium as a laser-active
ion (Nd3+ :YAG), was demonstrated by Geusic et al. in 1964 [40].
14
1.3 Solid active laser media materials

Solid active media are made up of the host material and the active ion. The host ma-
terial should be thermally and mechanically stable, and it should have a good trans-
parency in the wavelength regions of pump and laser radiation. Crystalline solids
with a periodic or regular structure provide a regular environment for laser materials;
therefore, the glass is easy fabricated but a disordered structure. Table 1.2 shows the
principal characteristics of the most representative laser crystalline host [41–48].
TABLE 1.2. Characteristics of the most used laser crystalline oxide host.
Y3 Al5 O12 REVO4 YAlO3 KRE(WO4 )2 RE2 O3
Dopants RE, TM RE, TM RE, TM RE, TM RE, TM
Melting point (K) ≈ 2200 ≈ 2090 ≈2120 ≈ 1320 ≈ 2700
Crystal system cubic tetragonal orthorhombic monoclinic cubic
Space group Ia3d I 41 /amd Pnma C 2/c Ia3
Site symmetries of D2 , C3i , S4 D2d Cs C2 C2 , C3i
RE3+
Coordination num- 8,6,4 8 12 8 6
bers of RE3+
Transparency range 0.2-6 0.3-5.2 0.2-6.8 0.34-5.5 0.2-8
[µm]
Thermal conductivity 11.5 3.9-5.1 11 2.5-3.5 12-16
non-doped [W/mK]
Mohs-hardness 8.2-8.5 5 8.5-9 4.5-5 ≈7
RE = rare earth, TM = transition metals, depending on the literature
The most commonly laser active ions used are the rare earths, the metal transition
ions and actinide ions. They totally or partially replace some of the the constitutive
ions of the solid host.
The lanthanide series comprises the 15 elements with atomic numbers 57 through
71, from lanthanum to lutetium. The trivial name rare earths is used to describe all the
lanthanides -except for promethium- together with scandium and yttrium. The elec-
tronic configuration of these active ions is [Xe]6s2 4fn except La, Gd and Lu, which
have [Xe]6s2 5d1 4fn (where n=1 to 14). The trivalent rare earth ion is the most stable
oxidation state because it tends to lose three electrons, usually 5d1 and 6s2 . These
ions are good active ions in solid-state lasers because they exhibit a wealth of sharp
fluorescence transitions in the almost visible and near-infrared region of the electro-
magnetic spectrum. The basic property of lanthanide ions is their behavior with the
radial component of the wave function of 4f electrons. The optical spectra of the rare
earth ions are caused by electronic transitions among levels of the partially filled 4f
shell, which are shielded by the 5s and 5p shells. For this reason, radiation transi-
tion lines are narrow and the energy level differs only slightly as a function of the
host. The effect of the crystal field is normally treated as a perturbation on the free-
ion levels, where the perturbations are smaller than the spin-orbit and electrostatics
15
interactions among the 4f electrons. The primary change in the energy levels is a split-
ting of each of the free-ion levels (manifolds, 2s+1 L J ) in many closely spaced levels,
which is caused by the stark effect of the crystal field.
The narrow radiation transitions lines are caused by the electric-dipole transitions,
which are the result of the interaction between the lanthanide ion and the electric field
vector across electric dipole of the light.
1.3.1 Host materials

1.3.1.1 Potassium rare earth tungstates (KRE(WO4 )2 )
KRE(WO4 )2 (KREW, RE = rare earths) are interesting solid-state lasers due to their
high emission and absorption cross section [41]. Potassium double tungstates present
a polymorphism with the temperature and as can be seen in figure 1.5, five different
phases can be distinguished as a function of the rare-earth ion radius and the tempe-
rature. Only three of them were obtained at high temperature with a trigonal and or-
thorhombic structure. On the other hand, for laser applications, the interesting phase
is the low temperature phase, which is the monoclinic phase.
F IGURE 1.5. Polymorphic forms and transition temperatures of potassium double tungstates
[49].
In this family of compounds, the monoclinic phase with the C 2/c space group has
been the most studied for the laser operation. This monoclinic low-temperature can
be grown as a single crystal from high temperature solutions. This thesis discusses
about the KGdW and mainly the KYbW material, since it is used as a host material.
Figure 1.6 shows the ytterbium polyhedra in projection parallel to [010], and Yb3+ is
eight-coordinated by O atoms to form a square antiprism. The coordination figure of
the tungstate anion is a distorted octahedron, WO6 . On the other hand, the K+ cations
is 12-coordinated by O atoms to form a distorted icosahedron. These polyhedra form
a bidimensional layer consisting of chains that share edges in the [101] and [110]
directions. These chains fill the holes in the framework of ytterbium and tungstate
polyhedra. A more detailed description of the structural analysis can be found in
Pujol et al. [50, 51].
An important characteristic of these materials is their high anisotropy and the
high value of the third-order nonlinear coefficient (χ3 ), which makes them highly
efficient materials for Stimulated Raman Scattering (SRS) applications [52–54]. Fur-
thermore, KREW maintains their high crystalline quality and properties when they
16
F IGURE 1.6. Ytterbium environment and chain formed by ytterbium polyhedra in projection
parallel to [010] [50].
are highly doped with active laser rare earth ions [55–58]. Table 1.3 shows some ex-
amples of the SSL with KREW as a host crystal and RE as an active ion.
TABLE 1.3. Some examples of the monoclinic solid state tungstates.

Host crystal Active ion Emission wavelengths References
KY(WO4 )2 Pr3+ 1.02µm Kaminskii et al. (1997) [59]
KGd(WO4 )2 Nd3+ 1.07µm Kushawaha et al. (1994) [60]
KLu(WO4 )2 Ho3+ 2.08µm, 2.99µm Kaminskii et al. (1980) [55]

Avsievich et al. (1986) [61]
KLu(WO4 )2 Er3+ 0.85µm, 1.07µm, 2.08µm Kaminskii et al. (1979) [62]
Yb:KY(WO4 )2 Er3+ 1.5µm Kuleshov et al. (1997) [63]
KGd(WO4 )2 Tm3+ 1.79µm, 2.04µm F
Petrov et al. (2004) [64]
KLu(WO4 )2 Tm3+ 1.94µm F
Mateos et al. (2006) [65]
KY(WO4 )2 Yb3+ 1.02µm Lagatsky et al. (1999) [66]
KGd(WO4 )2 Yb3+ 1.04µm Lagatsky et al. (1999) [66]
KYb(WO4 )2 Yb3+ 1µm F
Klopp et al. (2002) [67]
KLu(WO4 )2 Yb3+ 1µm F Mateos et al. (2004) [68]
F FiCMA-URV
1.3.1.2 Sesquioxides (RE2 O3 )
Rare earth sesquioxides (RE2 O3 ) present a polymorphism with the temperature. Fi-
gure 1.7 shows how these materials vary as a function of temperature. The phases,
A (trigonal with space group P3m1), B (monoclinic with space group C2/m) and
17
C (cubic with space group Ia3) are obtained at temperatures below to 2273 K. Over
this temperature, two phases are obtained, H-phase is hexagonal with space group
P63 /mmc and X-phase is a cubic system with Im3m as a space group [69].
F IGURE 1.7. Polymorphic forms and transition temperatures of sesquioxides [69].
The phase studied here is the space group Ia3 because it is one of the most rep-
resentative classes of host crystal for lasing lanthanides and transition-metal ions
[42, 70]. It is also called bixbyite and is a body-centered cubic structure. The unit cell
contains 48 oxygen ions and 32 rare earth ions. The oxygen atoms occupy a general
site (C1 ) and the 32 rare earth atoms occupy two different sites, 24 in a noncentro-
symmetric site (C2 ) oriented parallel to the [100] directions and 8 in a centro-symmetric
site (C3i ) oriented to [111]. There is no preferential occupation of RE at these two sites:
that is, dopant ions are incorporated into the crystal in the both symmetry sites (figure
1.8) [71].
Rare earth sesquioxide materials are known to be excellent laser host materials
[72–74]. They exhibit higher conductivity and larger ground state splitting than YAG,
when are doped rare earths [75]. They also have good physical properties such as
phase stability, a high melting point and low thermal expansion (table 1.2) [76].
An excellent sesquioxide for ytterbium (0.87 Å) ion substitution is Lu2 O3 because
lutetium (0.86 Å) has a similar ionic radii and mass. On the other hand, scandium
(0.75 Å) has a smaller ionic radii than ytterbium, which leads to an increase in the
18
F IGURE 1.8. Unit cell of cubic RE2 O3 oriented to the [111] directions where the metals ions are
shown with each distorted octahedron C2 and C3i symmetry sites.
lattice when the scandium ions are substituted for ytterbium ions. In this thesis, the
sesquioxides used as a host material were Lu2 O3 and Sc2 O3 . Both materials have C-
phase structure at room temperature and the solid liquid polymorphic transitions
occur over 2273 K [69] and are the most important sesquioxide matrices for laser
applications.
1.3.2 Transparent laser ceramics
1.3.2.1 Introduction to laser ceramics
Traditionally, the gain media in SSL were crystals or glasses. However, since 1990, the
polycrystalline gain media with very small domains, called ceramics, emerged and
gave low scattering losses. The sintering is started using nanopowders or nanoparti-
cles with vacuum and temperature. The result is a ceramic with a well-controlled size
distribution, very small crystals and very low porosity, which means that scattering
losses. The processing of high performance ceramics can be presented in three steps
(figure 1.9):
1. Powder synthesis: The materials obtained must have a desirable particle size
distribution and high chemical purity to make the best use of the potential
properties of ceramics.
19
2. Green-body formation: A ceramic green body is a molded shape made from

a multitude of particles. The shape is modulated by applying external forces
to provide a porous and fragile ceramic green body.
3. Sintering: The sintering process removes the porosity from the ceramic green
body to give a dense and compact ceramics. It reduces the surface area by
increasing the temperature or pressure.
F IGURE 1.9. Schematic diagram of transparent ceramic processing.
1.3.2.2 State of the art

Polycrystalline ceramics have been used for optical applications since 1962, when
Coble made the first transparent Al2 O3 [77]. Since then, several oxide and nitride
transparent ceramics have been developed for optical applications.
The first ceramic laser made from ceramic polycrystalline cubic material Dy:CaF2
dates back to 1966 [78,79]. The second ceramic laser was developed ten years later by
Greskovich (Nd:Y2 O3 –ThO2 ) [80]. In 1995, Ikessue et al. reported the first polycrys-
talline ceramic laser made of Nd:YAG [81, 82]. They demonstrated that the optical
quality of is equal to or superior than that of conventional laser bulk single crystals.
They also showed that laser oscillation was more efficient than bulk single crystal.
Since 1998, it has been possible to manufacture highly transparent ceramics for solid-
state lasers by vacuum sintering and nanotechnology [83, 84]. Some transparent ce-
ramic lasers that have been developed are Nd:Y2 O3 [85] and later Nd:Lu2 O3 [76],
Nd:YAG [86], Nd:YGdO3 [87], Yb:Sc2 O3 [88] and Yb:Lu2 O3 [89]. At the same time,
another research group, Institute of Low Temperature and Structure Research, Pol-
ish Academy of Sciences in Wroclaw (Poland) manufactured highly transparent YAG
and RE:YAG nanoceramic lasers using a high pressure and low temperature method
(HPLT). Some of these were YAG [90, 91], Nd:YAG [92], Ce:YAG [93].
Table 1.4 summarizes these transparent laser ceramics fabricated by different meth-
ods and in different experimental conditions.
20
TABLE 1.4. Development progress of transparent laser ceramics.
Material Ceramic fabrication technique Conditions Reference
MgO doped, 2123-2173 K for 12 h, H2 at-
Al2 O3 Cold press method Coble et al. (1962) [77]
mosphere
Dy:CaF2 Hot press method Vacuum hot pressing Hatch et al. (1996) [78, 79]
ThO2 and Nd2 O3 doped, 2443 K for 58-125
Nd:Y2 O3 –ThO2 Hot press method Greskovich et al. (1973) [80]
CHAPTER 1. INTRODUCTION
h, H2 atmosphere
Nd:YAG Hot press method 1423-1723 K for 7 h, 6000-7000 psi vacuum Gazza et al. (1973) [94]
SiO2 or MgO doped, 2123 K for 4 h, 10−5
Nd:YAG Cold press method de With et al. (1973) [95]
Torr
2
Nd:YAG Urea method P=2000Kg/cm , 1973 K for 3 h in vacuum Sekita et al. (1990) [96]
Solid state reaction method and Cold
Nd:YAG P=140 MPa, 2023 K in vacuum Ikessue et al. (1995) [81]
press method
21
Vacuum sintering method and nano-
Nd:Y2 O3 1973 K for 5 h Lu and Murai et al. (2001) [85]
technology
Nd:Lu2 O3 1973 K for 5 h Lu and Takaichi et al. (2002) [76]
technology
Nd:YAG 2023 K for 5-20 h Lu and Ueda et al. (2002) [86]
technology
Nd:YGdO3 Patent Lu and Takaichi et al. (2003) [87]
technology
Yb:Sc2 O3 Patent Lu and Bisson et al. (2003) [88]
technology
Yb:Lu2 O3 Patent Takaichi et al. (2005) [89]
technology
YAG HPLT 723 K for 1 min, 2-8 GPa Fedyket al. (2007) [91]
Nd:YAG HPLT 773 K, 5 GPa Strek et al. (2007) [92]
Ce:YAG HPLT 723 K for 1 min, 8 GPa Pazik et al. (2008) [93]
M. Galceran Mestres
1.3.2.3 Advantages of transparent laser ceramics
Laser ceramic materials have a several advantages over bulk single crystals. For ex-
amble:
1. They are easier to fabricate.

2. They cost less.
3. They are easier to fabricate on a large scale.
4. They have a higher concentration of active ions.
5. They have a better mechanical properties.
6. They have a better thermal properties.
But above all they can be used to manufacture a laser materials with high melting
points. For example, it is difficult to grow RE2 O3 bulk single crystals using conven-
tional crystal growth methods because of their high melting point (around 2700 K).
The spectroscopic properties of nanocrystals are known to be different from those
of their bulk counterparts (for example, luminescence efficiency is greater) [97, 98].
For this reason, here we propose to synthesize cubic sesquioxides and monoclinic
tungstates materials to manufacture nanoceramics for laser applications.
1.3.3 Active ions

1.3.3.1 Ytterbium
The electronic configurations of ytterbium is [Xe] 6s2 4f14 and when ytterbium is em-
bedded in a solid, it assumes the trivalent state (Yb3+ ) with [Xe] 4f13 as an electronic
configuration. The most commonly laser active ion used as a dopant is Nd3+ ([Xe]
4f3 ); however, the ytterbium-doped media now compete with neodymium in the 1
µm region because they have the following advantages over neodymium [99–101]:
1. A very simple energy level that consists of only two manifolds: 2 F7/2 as a
ground state and 2 F5/2 as an excited state.
2. Quantum defect, which leads to greater laser power efficiency of laser and
lower thermal effects.
3. A higher emission bandwidth, which provides broad wavelength tuning ranges
and generates ultrashort pulses in mode-locked lasers.
4. A longer upper-state lifetime to maximize the electronic storage by pumping.
On the other hand, Yb3+ exhibits a quasi three level behavior, which tends to lead
to a lower threshold. Its principal properties (lower threshold, reabsorption losses
and temperature related defects) are common to both between three- and four-level
lasers, whereas, neodymium is a four-level laser [102]. As if, the advantages of ytter-
bium outweigh the disadvantages, it is said that ytterbium is the most promising ion
in non-Nd laser.
22
1.3.3.2 Erbium
The electronic configuration of erbium is [Xe]6s2 4f12 , but it assumes the trivalent
(Er3+ ) state with [Xe]4f11 as an electronic configuration when it is embedded in a
solid. The trivalent erbium ion has a rich energy level structure, which has sev-
eral different sharp lines spectra depending on the host material. The erbium ion
presents a rich electronic structure with numerous energy levels, five of which are
metaestables (2 H9/2 , 4 S3/2 , 4 F9/2 , 4 I11/2 and 4 I13/2 ) and its optical spectroscopy has
been extensively studied by Dieke (Er:LaCl3 ) [103], Carnall (Er:LaF3 ) [104] and Pol-
lack (Er:CaF2 ) [105].
Erbium-doped crystals can be used as to obtain lasers radiation in the near-infrared
region after diode pumping. Erbium ions are pumped at around 980 nm (the absorp-
tion band between 0.9 and 1.1 µm correspond to 4 I11/2 energy level), then the first ex-
cited is populated and then is emitted to the ground state (4 I13/2 →4 I15/2 transition at
1.5 µm), which is interesting because it belongs to eye-safe spectral region [106, 107].
This wavelength can be used for optical communications devices because it corre-
sponds to one telecommunication window. The problem is that its low absorption
cross section in this spectral range limits pump efficiency. To increase the efficiency,
a sensitizer ion is required. In this case, trivalent ytterbium acts as a good sensitizer
ion for trivalent erbium because ytterbium ions have a high absorption cross section
in this spectral range and a high-energy overlap between the 4 I11/2 (Er3+ ) and 2 F5/2
(Yb3+ ) excited energy levels of erbium and ytterbium, respectively.
Another important erbium is in the range spectra around 2.8 µm, 4 I11/2 →4 I13/2
transition, and is attractive for medical applications [108–110] because water absorp-
tion is strong in this range.
The green laser emission in trivalent erbium (4 S3/2 →4 I15/2 transition) is interes-
ting for color displays, high-density optical storage, biomedical diagnostics, sensors
and undersea optical communications. The population of the 4 S3/2 is achieved by
up-conversion, which was first studied by Auzel [111].
1.3.3.3 Holmium
The electronic configuration of holmium and the trivalent cation are [Xe]6s2 4f11 and
[Xe]4f10 , respectively. The Ho3+ ion has four metaestable levels (5 S2 , 5 F5 , 5 I6 , 5 I8 )
and fourteen different laser channels from 0.55 µm to 3.9 µm reported in different
hosts. Dieke and Pandley reported a detailed optical characteristics of the Ho3+ ion
in Ho:LaCl3 [112] and later were Caspers et al. studied Ho:LaF3 [113]
The emission near 2µm, 5 I7 →5 I8 transition is interesting because of it belongs to
the eye-safe spectral region, their absorption properties in water and medical ap-
plications involving coagulative cutting and tissue welding. On the other hand, the
emission 5 S2 + 5 F4 →5 I8 around 0.5 µm is interesting due to the present requirement
for short wavelength emitting solid-state lasers. Using the holmium cation as an
active laser ion, green or blue upconversion emission can be obtained in different
hosts [114–118] upon red or infrared pumping. In the field of the sensitising lasers,
the holmium cation can be sensitised by many different ions: Cr3+ , Fe3+ , Tm3+ , Er3+ ,
Dy3+ , Er3+ /Tm3+ and Er3+ /Tm3+ /Yb3+ [119–122]
23
1.3.3.4 Europium
The electronic configuration of europium is [Xe]6s2 4f7 and the trivalent europium is
[Xe]4f6 . The Eu3+ has a simply energy level structure, where the ground state and the
main emitting state are not degenerated. The emission lines occurs from the lowest
excited state level (5 D0 ) to the ground level (7 F J where J = 0 - 6). There are transition
associated to the higher levels 7 F5 and 7 F6 , but they are difficult to detect due to their
low intensity [123].
Trivalent europium is a promising strongest visible red emitter (5 D0 →7 F2 ), this
fact makes this ion interesting as a doping ion for applications in a fluorescent lamps,
color lightning and optoelectronic devices [124]. On the other hand, when Eu3+ is
co-doped with Yb3+ , the material can present an interesting features in the laser
wavelengths of 1 µm (2 F5/2 →2 F7/2 ) and besides, an offer a new alternative mate-
rial as a red emitter. The co-doping Eu-Yb, usually shows different energy trans-
fer schemes such as down-conversion cross-relaxation of Eu3+ (5 D0 →7 F6 ) and Yb3+
(2 F7/2 →2 F5/2 ) and up-conversion cooperative process between pairs of Yb3+ to effi-
ciently transfer to the red europium emission. Europium has only one laser channel
action reported at 612 nm that correspond to 5 D0 →7 F2 transition and a cooling is
required [125].
1.4 Nonlinear optical materials: Potassium titanyl phos-

phate (KTiOPO4 )
Nonlinear optical materials present the nonlinear behavior of light: that is the polar-
ization (P ) responds nonlinearly to the electric field (E ) of the light. This effect is only
observed when the intensity of the incident radiation is high [126]. Since 1960, when
Maiman demonstrated the first SSL, interest in using lasers as an important part of
everyday life has increased. Nonlinear interacctions were first observed in 1961 by
Franken, who generated the 347 nm second harmonic of 694 nm ruby laser in a piece
of crystal quartz [127].
The new generation of SSL that combine infrared laser emission combined with
nonlinear optical materials has increased the number of wavelengths available. Non-
linear optics produce wavelengths that are both longer and shorter than the origi-
nal. Particular interest is focused on developing powerful and compact sources (red,
green, blue and UV light) for such applications as medicine, high density optical data
storage, laser printing, stereo lithography, etc. [128]. The most important type of non-
linear effect is probably the second harmonic generation (SHG), where a part of the
light passing through the nonlinear medium is converted to light of on-half the orig-
inal wavelength. For example, the green light at 532 nm is generated from the 1064
nm beam of infrared light from a Nd:YAG laser.
Other important nonlinear processes are sum frequency generation (SFG), which
generates light with a frequency that is the sum of two other frequencies, difference
frequency generation (DFG), which generates light with a frequency that is the dif-
ference between two other frequencies, optical parametric amplification (OPA), in
which a long wavelength signal field amplifies the presence of a higher-frequency
24
pump wave and optical parametric oscillation (OPO), which is a coherent optical
light sources based on parametric amplification within an optical resonator.
The first self-frequency doubling lasers were two ferroelectrics niobates Tm:LiNbO3
[129] and Nd:MgO:LiNbO3 [130]. The crystal for an optically non-linear crystal must:
1. Be noncentrosymmetric
2. Be resistant to optical damage
3. Have high mechanical hardness
4. Exhibit a good thermal and chemical stability
5. Have appropriate phase-matching properties
Potassium titanyl phosphate, KTiOPO4 (KTP) was described as a non-linear opti-

cal material in 1976 by Zumsteg et al. [131]. It is the most commonly used ferroelec-
tric material for electrooptics and nonlinear optics applications [132]; principally, for
a frequency doubling neodymium-doped lasers at 1 µm radiation [133–135].
KTP exhibits a exceptional properties for several non-liner optical applications
[136, 137], sum and difference frequency mixing [138–140] and optical parametric
oscillation [141–146]. It is optically transparent from 0.35 to 4.5 µm [147]. KTP is a
unique combination of properties: it has high nonlinear coefficients, a high optical
damage threshold, a good phase-machability and excellent thermal stability [148].
Therefore, this material is well suited for laser system applications requiring high
power, high efficiency and durability. It is also frequently used as an optical paramet-
ric oscillator for near IR generation up to 4 µm.
The general formula described by these materials is ABOXO4 , where A = K, Rb,
Na, Cs, Tl, NH4 , B = Ti, Sn, Sb, Zr, Ge, Al, Cr, Fe, V, Nb, Ta, and X = P, As or Si [132].
The crystal structure of KTP was determined by Tordjman et al. [149] and subse-
quently refined by Thomas et al. [150]. These materials crystallize in the orthorhom-
bic system and belong to the non-centrosymmetric Pna21 space group [151,152]. This
means that the crystallographic axes a, b and c are parallel to the optical axes x, y
and z, with c being the polar axis.
The KTP structure was described as a network of helicoidal chains of distorted
TiO6 octahedra along the [001] direction with alternating long and short Ti-O bonds,
which are linked at two corners and the chairs are separated by PO4 tetrahedra with
periodic bond chains in the a direction and also along the ac diagonal. The alter-
nate between short and long lengths in Ti-O bonds give to a net c-directed polariza-
tion and contribute to the larger values of nonlinear optical and electrooptical coeffi-
cients [131, 153]. However, other recent studies by Xue and Zhang presented the PO4
and the K-O groups as the origin of the nonolinearity [154]. Figure 1.10a shows the
primitive cell of the KTP in a projection parallel to the [010] direction, where the two
non-equivalent positions for each atom can be observed. The K + cations are located
at the channels along the [001] direction formed by the TiO6 octahedral and the PO4
tetrahedra, and can occupy two non-equivalent sites: either eight-fold coordinated
K(1) or nine-fold coordinated K(2) (figure 1.10b). These cations can travel along chan-
nels by diffusion along the c-direction causing the ionic conductivity with higher
order magnitude order than the other directions [155].
25
F IGURE 1.10. The crystal structure of KTP as viewed (a) parallel to the [010] direction and (b)
parallel to the [001] direction [150].
Table 1.5 summarizes several properties of KTP and the most important isomorphs.
All theses facts have been compiled form various references [156–178]. At present, it
would be attractive to dope KTP and its isostructurals with rare earths ions to pro-
duce a self frequency doubling [179–181].
1.5 Fundamentals of template-based methods

In recent years, materials have increasingly been synthesized within the pores of a
porous templates. These templates have a uniform porous diameters and a particu-
lar material is obtained for each pore. Therefore, it is possible to fabricate a variety
of interesting and different materials. For example, nanotubes and nanofibrils com-
posed of conductive polymers [182–184], metals [185,186], carbon [187], semiconduc-
tors [188] and other materials. These nanostructures made from a porus template can
remain inside the pores of the template or they can be freed from it.
The templates used in this thesis are porous silicon and alumina and they were
fabricated by the Nanoelectronic and Photonic Systems research group (NePHoS) at
the Departament d’Enginyeria Electrònica, Elèctrica i Autonomatica of the Universi-
tat Rovira i Virgili (Tarragona) in collaboration with the research center Enginyeria
de Materials i Micro/Nano Sistemes (EMaS).
1.5.1 Porous silicon templates

Porous silicon was discovered in 1956 by Uhlir [189]. It was found to be a very promi-
sing nanostructured material that was intensively investigated because of its excel-
lent mechanical and thermal properties, its obvious compatibility with silicon-based
microelectronics and its low cost [190].
Porous silicon was obtained by electrochemical etching in hydrofluoric (HF) so-
lutions by the NePHoS research group [191, 192]. Figure 1.11 shows the porous sili-
con template used to obtain the micro- and nanostructure. The diameter and height
26
TABLE 1.5. Several properties of KTP and its important isostructurals.

Properties KTP KTA RTP RTA
Stoichiometric formula KTiOPO4 KTiOAsO4 RbTiOPO4 RbTiOAsO4
Crystallographic properties
Space group Pna21 Pna21 Pna21 Pna21
Point group mm2 mm2 mm2 mm2
Lattice parameters [Å]
a 12.819 13.130 12.974 13.264
b 6.399 6.581 6.494 6.682
c 10.584 10.781 10.564 10.7697
Density [g/cm3 ] 2.99 3.48 3.60 4.05
Electrical properties (295 K)
Dielectric constant, ε 33 55 (100 kHz) 26 (200 kHz) 18 (100 kHz) 19 (200 kHz)
Conductivity, σ33 [S/cm] 9.9· 10−6 10−6 2.5· 10−6 3.2· 10−8
Curie temperature (K) 1165-1233 1076-1153 1058-1102 1038-1083
Linear optical properties
Refractive indices (1064
nm), > (706.5 nm)
nx 1.740 1.782 > 1.799 1.803
ny 1.748 1.790 > 1.799 1.809
nz 1.830 1.868 > 1.799 1.881
Transparency range (µm) 0.35-4.5 0.35-5.3 0.35-4.5 0.35-5.3
Laser damage threshold,
31 1.2 0.9 0.4
highest value reported
(GW/cm2 , 1064 nm) 1 pulse, 8.5 ns 103 pulses, 8 ns — —
NLO coefficients (pm/V) at
1064 nm
d31 2.54 2.8 3.3 2.24
d32 4.35 4.2 4.1 7.73
d33 16.9 16.2 17.1 19.62
d24 3.64 3.2 — —
d15 1.91 2.3 — —
Electrooptic properties
electrooptic coefficients
(pm/V), (632.8 nm)
r13 9.5 15 9.7 13.5
r23 15.7 21 10.8 17.5
r33 36.3 40 22.5 40.5
r24 9.3 — 14.9 —
r15 7.3 — 7.6 —
of pores were 1 µm and 90 µm, respectively, and the thickness of the template was
around 350 µm. Some applications that can be highlighted are:
27
F IGURE 1.11. ESEM images of disorder porous silicon template with a porous diameter of 1
µm and a porous depth of 90 µm (a) top view and (b) cross section.
1. Waveguides. The first porous silicon optical waveguide was reported in 1960
by Loni et al. [193]. Various research groups have studied silicon waveguides
and their properties [194, 195].
2. Sensors. Porous silicon multilayers are used to sense different substances. For
example, hydrocarbon sensors [196] or biosensors [197].
In this thesis, the disorder porous silicon template were used to fabricate poly(methyl
methacrylate) (PMMA) microcolumns where luminescence nanoparticles in within
were embedded.
1.5.2 Porous alumina templates

Porous alumina membranes are formed by the anodization of Al in appropriate acidic
or basic electrolytic solutions and the dimensions of the pores depend on the anodiz-
ing conditions [198]. The depth of the holes (thickness of the oxide films) has a good
linear relationship with the period of the anodization. These membranes have re-
cently a attracted considerable interest as a starting material for the fabrication of
several kinds of nanodevices. The geometrical structure of anodic porous alumina
is schematically represented as a honeycomb structure consisting of a close-packed
array of columnar alumina units called cells, each containing a central straight hole.
Figure 1.12 shows the alumina template fabricated by the NePHoS research group
used to synthesize nanowires. The porous (porous diameter are 200 nm) in these
membranes are arranged in a regular hexagonal lattice [199].
28
F IGURE 1.12. ESEM images of alumina template with a porous diameter and depth of 200 nm
and 80 µm respectively.
1.6 Aims of this doctoral thesis

During the last years, there has been a growing interest in researching in the field of
nanotechnology because it is a new scientific field or a new scientific domain, which
deals with materials in the nanometer range. This new field includes design, fabri-
cation and application of nanomaterials, and the fundamental understanding of the
relationships between material properties and material dimensions. Therefore, the
design and development of new promising materials does not stop.
It is now 45 years since Maiman demonstrated the first laser. Since then, research
in the field has emerged and thousands of scientists have sought to build the most
efficient. The literature shows extensive investigations of a vast amount of laser com-
ponents. Choosing among those components, controlling the needed materials spec-
ifications and engineering the right systems became an art.
Laser ceramics are very attractive to solid-state laser because they have several
advantages such as easier fabrication, lower cost, high concentration of active ions
and good mechanical and thermal properties. Laser ceramics emerged in the 1990s,
producing lower scattering losses from nanopowders or nanoparticles with vacuum
and temperature. since then, research in this field has increased spectacularly. The
result is a ceramic with a well-controlled size distribution, very small crystals and
very low porosity, leading to insignificant scattering losses respect to the bulk single
crystal. But, above all, it is possible to manufacture laser materials with a high melting
point. In the case of Y3 Al5 O12 nanoceramic, better mechanical and thermic properties
compared to the bulk single crystal have been observed.
The rare earths (RE) are one of the most used active ions for optical applications.
Their most common and stable oxidation state is 3+ and they exhibit a wealth of sharp
fluorescence transitions in the almost visible and near-infrared region of the electro-
magnetic spectrum. The rare earths have found wide technological applications as in
communications, lasers, solar concentrators and infrared upconverters. In this thesis,
europium, holmium, erbium and ytterbium as active ions have been studied.
29
The main objective of this thesis was to enlarge the knowledge of new nanomate-
rials. One aim was to establish and optimize the synthesis of optical nanocrystals as
starting point to obtain laser ceramics. Chapter 3 describes the synthesis of the opti-
cal nanocrystals, potassium rare earth tungstates (KRE(WO4 )2 ), sesquioxides (RE2 O3 )
and potassium titanyl phosphate (KTiOPO4 ), using the modified Pechini method.
Secondly intensive structural characterization has been carried out with these nano-
materials as host materials. The synthesis and characterization of new nanostructures
obtained from the previous nanocrystals will be discussed in chapter 4. For optical ap-
plications, it is essential to fully characterize the active ions. For this reason, chapter 5
gives extensive studies of the optical and the spectroscopic results of the optical nano-
crystals in order to determine the energy level schemes of the rare earth ions and how
they affect the particle size in these measurements. The last chapter, chapter 6, focuses
on the synthesis of Ho:Lu2 O3 nanoceramics using the high pressure low temperature
method and extensively structural, spectroscopical and optical characterizations in
order to evaluate this material as a promising transparent laser nanoceramics.
30
Chapter 2
Experimental Techniques
2.1 Synthesis of nanocrystals: the modified Pechini method
2.2 Synthesis of nanocrystals: the femtosecond laser ablation method
2.3 Ceramic sintering method: high pressure low temperature (HPLT)
2.4 X-Ray diffraction method: X-ray powder diffraction technique (XRD)
2.5 Thermal analysis
2.5.1 Differential thermal analysis (DTA)
2.5.2 Thermogravimetric analysis (TG)
2.6 Electron microscopy
2.6.1 Scanning electron microscopy (SEM)
2.6.2 Environmental scanning electron microscopy (ESEM)
2.6.3 Transmission electron microscopy (TEM)
2.6.3.1 Electron diffraction
2.7 Electron probe microanalysis (EPMA)
2.8 Spectroscopic techniques
2.8.1 Fourier transform infrared (FT-IR)
2.8.2 Raman spectroscopy
2.8.3 Optical absorption and transmission
2.8.4 Luminescence measurements
2.9 Photoinduced second harmonic generation (PISHG)
2.10 Piezooptic measurements
H ischapter discusses the fundamentals and basics principles of the characteri-

T zation techniques that are most widely used for characterizing nanomaterials.
The characterization and manipulation of nanostructures requires not only extreme
sensitivity and accuracy, but also high resolution.
The experimental equipments were available by the laboratories of the research
group Fı́sica i Cristal·lografia de Materials i Nanomaterials (FiCMA-FiCNA) and at
the Serveis de Recursos Cientı́fics i Tècnics of the Universitat Rovira i Virgili of Tar-
ragona (Spain), the Serveis Cientı́fico-Tècnics of the Universitat Autonoma of Barce-
lona (Spain) , the Institute of Low Temperature and Structure Research of the Pol-
ish Academy of Sciences in Wroclaw (Poland), the Instituto de Ciencia de Materi-
ales (ICMM) of the Consejo Superior de Investigaciones Cientı́ficas (CSIC) of Madrid
(Spain), the Servicio Láser of the Universidad de Salamanca (Spain) and the Institute
of Physics at the University of Czestochowa (Poland).
31
CHAPTER 2. EXPERIMENTAL TECHNIQUES M. Galceran Mestres
2.1 Synthesis of nanocrystals: the modified Pechini method

Sol-gel methods are synthetic routes for preparing inorganic powders at low tempe-
rature. The literature shows that, a sol is a fluid colloidal dispersion of solid particles
in a liquid phase where the particles are sufficiently small to remain suspended by
Brownian motion. A gel is a colloidal suspension of a liquid in a solid, an intercon-
nected polymeric network formed by assembly of the sol [200].
F IGURE 2.1. Overview of the sol-gel technologies.
Figure 2.1 shows an overview of the sol-gel technologies. Usually, the starting
materials are inorganic metals or metal organic compounds such as metals complexes
that are subjected to a series of hydrolysis and polymerization reactions to form a sol.
By processing the sol, several ceramic materials can be obtained (e.g. ceramic fibres
or dense ceramics). Thin films are prepared on a piece of substrate by dip-coating
or spin coating. To obtain the aerogel, which is a highly porous and extremely low
density material, the liquid is removed under a supercritical condition. Ultra-fine and
uniform ceramic powders are formed by precipitation, spray pyrolysis, or emulsion
techniques.
A simple description of the sol-gel synthesis route is that a sol is prepared by dis-
solving metal ion complexes in a suitable organic solvent, and then by hydrolysing,
the sol forms as a colloidal metal oxide/hydroxide precipitate. After heating, the sol
is transformed into a gel in which the metal oxide or hydroxide particles form a poly-
33
meric network enclosing the solvent. Then, the gel is heated at higher temperatures
and the organic compounds are evaporated or decomposed, allowing the inorganic
solid to crystallize, (figure 2.2).
F IGURE 2.2. The basic steps of the sol-gel method.
These processes have several advantages for obtaining powders and are alter-
native methods for manufacturing ceramic materials for a variety of applications.
Because of, they present several advantages such as high purity due to the precur-
sors are commercially available, low cost, its versatility and simplicity, stoichiometry
control, low processing temperature and high homogeneity degree due to the fact
that the reagents are mixed at the molecular level [201]. The Pechini method, devel-
oped by M. Pechini, is a variant of this methodology [202, 203]. It is an alternative
to the conventional sol-gel method, which is based on the ability of certain weak
acids to form metallic complexes by a complexation reaction using α-polycarboxylic
acid, generally citric acid. The metal cations are chelated by the carboxyl groups and
remain homogeneously distributed in the polymeric network. Then, these chelates
react with a polyalcohol such as ethylene glycol (EG) that is added to the solution.
When the solution is heated, the polymeric resin is formed by a sterification reac-
tion (eq. 2.1), leading to a dehydration reaction of α-polycarboxylic acid and ethylene
glycol.
(2.1)
The dimeric product of the ester contains one alcoholic hydroxyl group (HO-)
and one carboxyl acid group (-COOH). This reaction occurs in sequence to obtain a
polymeric network (eq. 2.2).
(2.2)
The principle of the Pechini method is to obtain a random polymeric resin pre-
cursor in which the cations are uniformly distributed, as is schematically shown in
figure 2.3. Heating of the polymeric resin at 573 K causes the polymer to break down.
Later, during the pyrolysis,the cations are segregated because of low cation mobility
in the branched polymer.
34
In the modified Pechini method, ethylene diamine tetraacetic acid (EDTA) was
used to replace citric acid due to its strong chelating power. EDTA has four carboxylic
acid groups (citric acid has three) and can react with EG to form a more branched
polyester thus giving a more homogeneous sol [204]. P. A. Lessing has discussed
the polymeric chain, which can be formed between EDTA-EG, EDTA-EDTA and EG-
EG [205].
F IGURE 2.3. The concept of the polymeric precursor method.
The last stage in the synthesis of the nanocrystals is the total calcination of the
precursor powder. The calcination temperature and time must be controlled. The cal-
cination procedure was performed in a vertical furnace using a Kanthal AF resis-
tance heating wire (1 mm Ø wire) made in the laboratories of FiCMA-FiCNA (figure
2.4). The temperature was controlled by the Eurotherm 902-904 controller/program,
which was connected to a thyristor to control the power furnace.
Each different material is calcined at a particular temperature according to the

DTA-TG analysis and X-ray powder diffraction patterns. In this study, the modified
Pechini method is used to obtain such materials such as KYbW, Er:KYbW, RE:Lu2 O3
(RE = Yb and Ho), Yb:Sc2 O3 as a host materials for solid-state lasers and KTP for
non-linear optical material in the nanometer range.
35
F IGURE 2.4. Scheme of the vertical furnace used in the calcination procedure.
2.2 Synthesis of nanocrystals: the femtosecond laser ab-

lation method
Laser ablation is a novel method to obtain nanoparticles disperses in liquid. The ir-
radiation of solid targets in liquid environments with laser pulses has also proved
to be a promising technique for producing colloidal solutions of nanoparticles with
good control of mean and dispersion size [206–212]. To induce laser ablation, a high
amount of light energy has to be deposited in a small volume of the substrate ma-
terial. Because of energy transport in the substrate, especially heat diffusion, this is
only possible if the energy is deposited in a short time. The duration of laser pulses
can vary over a very wide range, from milliseconds to femtoseconds. This makes la-
ser ablation very valuable for both research and industrial applications. In this study,
we have used femtosecond pulses to obtain nanoparticles from bulk single crystals
grown in our laboratories by top seeded solution growth.
Recently, infrared femtosecond laser pulses were used to produce silver, gold [213,
214] and advanced ceramic nanoparticles [215]. Irradiation with short, intense laser
pulses can remove material from a surface layer consisting of atoms, ions and small
nanoclusters by means of non-thermal mechanisms at least for moderate fluences
[216]. For short pulse durations, it is advisable to speak of fluence instead of intensity.
Here, fluence is defined as the intensity integrated over the whole pulse duration (i.e.
energy per pulse per area).
Femtosecond laser ablation was carried out with a commercial Ti:Sapphire oscilla-
tor (Tsunami, Spectra Physics) and a regenerative amplifier system (Spitfire, Spectra
Physics) based on chirped pulse amplification (CPA). The system delivers linearly
polarized 120 fs pulses at 795 nm with a repetition rate of 1 kHz. The pulse energy
can reach a maximum of 1.1 mJ, is controlled by neutral filters and measured with a
powermeter. The transverse mode is Gaussian and the beam width is 8.5 mm (1/e2
criterion). This equipment is available at the Servicio Láser of the Universidad de
Salamanca.
36
2.3 Ceramic sintering method: High pressure low tem-

perature (HPLT)
Ceramic materials are prepared from nanopowders, which can be obtained by several
methodologies such as sol-gel, Pechini, combustion, co-precipitation and solvother-
mal. The total process has lower cost and temperature than the bulk single crystal
growth. However, the most important condition is to obtain nanocrystals at the low-
est possible crystallization temperature since the crystal size is increased with tempe-
rature of synthesis [217].
During the last years a great deal of research has been made such on ceramic ma-
terials because of the promise of new and interesting properties. Dense ceramics with
particle nanosize may display new structural, magnetic, electric or electronic proper-
ties and have comparable optical and thermomechanical properties with great poten-
tial and can substitute the bulk single crystal in many applications [86, 89, 218]. These
new properties are linked to the high density of grain boundaries interfaces that re-
sult from their nanoscale structure. Sintering process usually causes grain growth to
micrometer range, however, there are tree main approaches to prevent grain growth
associated with densification to provide final microstructure in the nanometer range:
(1) application of hot-pressing or sintering forging techniques, (2) addition of dopants
to modify diffusion process and (3) sintering powders in metaestable crystallographic
phase that during the sintering acts as a seeds for the final phase. But there are also
non-conventional sintering methods like high pressure low temperature that can pro-
duce dense ceramics without grain growth [219, 220].
The nanoceramics were sintered by the high pressure low temperature method at
the Department of Spectroscopy of Excited States in the Institute of Low Tempera-
ture and Structure Research of the Polish Academy of Sciences in Wroclaw (Poland)
together with the collaboration of the Institute of High Pressure Physics of the Pol-
ish Academy of Sciences in Warsaw (Poland). The most important advantage of the
HPLT technique is the lower sintering temperature. One of the first systems for the
sintering of the nanoceramics at high pressure has been demonstrated by Urbanovich
et al. [221].
The high pressure low temperature technique combines a high pressure with low
temperature in order to decrease the diffusion process, so that increase the nucleation
process of the most phase stable. The fabrication process consists in several steps:
Step 1 Synthesis of the nanocrystals: The synthesis of nanocrystals was carried
out by the modified Pechini method.
Step 2 Preparation of the green body: The green body is obtained from the nano-
crystals and by cold pressing in cylindrical cell under low pressure (around 5
MPa) and vacuum. The green body has a diameter and thickness of 5 and 2
mm, respectively.
Step 3 Sintering: The sintering process occurs by the high pressure low tempera-
ture method in a high pressure cell of toroid-type. Figure 2.5 shows the rep-
resentative scheme of the high pressure cell. The cell is formed by a graphite
tube as a resistance heater and the press medium (ceramic made of CaCO3 )
37
F IGURE 2.5. Representative scheme of the high pressure cell.
situated between two anvils that plays the role of the pressure container. The
green body is placed in the centre of the cell and sounded by hexagonal boron
nitride (BN) and acetone to avoid the graphite impurities in the sample. Due
to the configuration of the pressure cell, the forces provided by the anvils
created a quasiisostatic pressure (figure 2.6.
F IGURE 2.6. Scheme of the forces applied in the sample.
On the other hand, the equipment can work in the temperature range of 723 - 1473
K and pressure range of 2 - 8 GPa.
2.4 X-Ray diffraction method: X-ray powder diffraction

technique (XRD)
−
→
X-rays are electromagnetic radiation characterized by the wave vector K , which
gives the direction and sense of the propagation. Moreover, this electromagnetic radi-
ation is of the same nature as the light but it has a much shorter wavelength (0.5-2.5
Å). X-rays were discovered in 1895 by C. Röentgen and seventeen years later, Von
Laue and his co-workers discovered X-ray diffraction through the crystalline lattice.
When X-rays interact with crystalline material, the light will come on some few di-
rections and all other observed shadow, this is the diffraction phenomenon.
38
Within the diffraction phenomenon, there are different processes such as elastic
diffraction (0 order), diffuse diffraction (elastic diffraction with higher orders), ab-
sorption and fluorescence. This section focuses on elastic diffraction of 0 order, which
is the most used experimentally. This can be described as the process in which the in-
cident diffracted rays have the same energy and therefore the emitted photons change
their direction of propagation in the crystal cross only. Information about the crys-
talline structure will be given by diffracted rays (geometric law) and their intensities
(law intensities).
Basically, the geometric law can be expressed by two equations. The first one de-
scribes the photon energy conservation in the elastic diffraction of 0 order indicating
that the module of the diffracted wave vector and the incident wave vector is the
same (equation 2.3).
1
ki = kd = (2.3)
λ
where ki and kd are the wave vector of incident radiation and diffracted radiation,
respectively. The second equation is a consequence of the crystal being a periodic
medium (equation2.4)
−
→ −→
k f = k i+−
→
r ∗hkl (2.4)
where − →
r ∗hkl is the reciprocal lattice characterized by a set of vectors perpendicular
to the reticular planes (hkl) of the direct lattice, which is giving by:
−
→
r ∗hkl = ha∗ + kb∗ + lc∗ (2.5)
The set of diffracted vectors described by this first equation gives a sphere called
Edwald’s sphere, the radius of which is the modulus of the incident and diffracted
radiation.
To carry out second equation, the only points in the Ewald’s sphere that repre-
sent the diffracted wave vectors will coincide with a point in the reciprocal lattice
(defining the origin of the reciprocal lattice as the end of the incident wave vector).
This method of determining the directions of the diffracted beams is called the Ewald
construction
From equation 2.4, Bragg’s law can be derive [222]. W. L. Bragg was the first to use
the diffraction of X-rays by crystals to explore matter in 1913. Bragg’s Law (figure 2.7)
makes it possible to calculate the positions of the atoms within a crystal from the way
an X-ray beam is diffracted by the crystal lattice. If 2θ, the angle between the incident
and diffracted vector, and the modulus of the wave vector of the incident beam is the
inverse of its wavelength and the equation 2.4 is squared, then we can write:
1 2 1 1
2
− 2 cos 2θ + 2 = 2 (2.6)
λ λ λ dhkl
From equation 2.6, it achieves the expression for the Bragg’s law by the following
equation (eq. 2.7):
λ = 2dhkl sin θ (2.7)

39
where λ is the wavelength of the incident x-ray beam, dhkl is the spacing between
the planes in the atomic lattice and θ is the angle between the incident ray and the
scattering planes [223].
F IGURE 2.7. Schematic description of the diffraction of lattice planes according to W. L. Bragg
[222].
Bragg’s Law is expressed by squaring vectorial equation 2.6, so this equation

losses information about diffraction geometric. The Bragg’s law is a monodirectional
law.
As mentioned above, the intensity of the diffracted rays provides information
about atomic positions and this is expressed by the following equation:
I (hkl ) = k | Fhkl |2 (2.8)

where Fhkl is called the structure factor. If we consider that the atom is not in a
fixed position that is, there is presents a thermal agitation around its position (−→r j)
with a probability of vibration amplitude (u) that is equal to P(u) ; then the structure
factor can be expressed as:
N −
→ −
→ −
→
Fhkl = ∑ f j exp(2πi h −
→
r j ) exp(− h Uj h ) (2.9)
j =1
where f j is the atomic diffusion factor of atom j and − →r j is the position vector
−
→ − →
of atom j. The exponential exp(- h U j h ) is called the temperature factor and U is a
matrix of thermal agitation coefficients. The structure factor is the Fourier transform
of the electron density of a crystal, so the atomic position for all the atoms of a crystal
can be found by measuring all its diffraction intensities. The structure of a crystal is
determined by this process [224].
X-ray powder diffraction is a non-destructive technique that is widely used to
characterize crystalline materials (e.g. phase identification, quantitative analysis and
determination of the crystal structure). The files of the Joint Committee for Powder
Diffraction Standards (JCPDS) are used to identify which phases are present in the
sample analyzed [225].
The crystal size (L ) was measured using Scherrer’s equation (eq. 2.10) for peak
broadening [226].
Kλ
L= (2.10)
β cos θ B
40
where λ is the wavelength used, θ B is the Bragg angle for the measured hkl peak,
K is a constant equal to 0.9 for L taken as the volume-averaged crystallite dimension
perpendicular to the hkl diffraction plane and β is the full width at half maximum
(FWHM) measured in radians on the 2θ scale (eq. 2.11) [227]:
q
β= β2s − β2r (2.11)
where βs and βr are the FWHM for the speaks in the sample and for the standard
reference, respectively. The standard used to correct the instrumental broadening was
LaB6 . The validity of the Scherrer’s formula has also been widely discussed in the lit-
erature. As it is valid only for small particles <500 nm and the nanoparticles obtained
is below this value; the particles size calculated are truthful. We used the results to
estimate the particle size.
For the measurements were using a two different diffractometers from at the
Servei de Recursos Cientifics i Tecnics of the Universitat Rovira i Virgili. The first
was a Siemens D-5000 diffractometer, with Bragg-Brentano parafocusing geometry,
and θ-θ configuration. It contained an X-ray standard Cu-tube, so the radiation used
was Kα1 (λ1 = 1.540560 Å) and the detector was a double collimated scintillation
counter. The other was a Bruker-AXS D8-Discover diffractometer with parallel inci-
dent beam (Göbel mirror) and vertical - goniometer, a 0.02◦ receiving slit and scin-
tillation counter as a detector. Cuk radiation was obtained from a copper X-ray tube
operated at 40 kV and 40 mA. This last diffractometer was also used for measuring
Micro X-ray (µXRD), where An X-ray collimator system allows to analyze areas of
500 µm and as a detector was used the GADDS detector 30x30 cm with a 1024x1024
pixel CCD sensor. The measurements were carried out in step-scanning mode and the
diffraction angle (2θ) ranged from 10 to 70◦ . The X-ray powder diffraction patterns
were recorded at step size = 0.05◦ , step time = 3 s to identify the crystalline phases and
at step size = 0.02◦ , step time = 16 s to refine the unit cells. Lattice parameters were
calculated using the FULLPROF program based on the Rietveld method [228–230].
2.5 Thermal analysis

Thermal analysis comprises a group of techniques in which the physical property of a
substance is measured as a function of temperature, while the substance is subjected
to a controlled temperature programme. Output is in the form of a thermal analysis
curve and such features of this curve as peaks, discontinuities, changes in slope, etc.
These changes are related to thermal events in the samples such as a phase transitions,
chemical reactions, oxidation, decomposition, etc.
2.5.1 Differential thermal analysis (DTA)

Differential thermal analysis studies the thermal behavior of a sample as a function
of time or temperature under a controlled atmosphere. The temperature difference
is measured between a sample and a thermally inert reference by heating or cooling
under identical conditions. The plot obtained from differential thermal analysis as a
41
function of temperature or time provides information on exothermic and endother-

mic reactions taking place in the sample. The temperature changes are shown as
exothermic peaks (positive ∆T) or endothermic peaks (negative ∆T) on DTA curves.
The area under the DTA peak is associated with enthalpy change during the sub-
stance transformation [231].
2.5.2 Thermogravimetric analysis (TG)

Thermogravimetric analysis is a simple analytical technique used to determine the
thermal stability of the sample. It measures changes in the weight of the material as a
function of temperature. Normally, it is carried out in air or an inert atmosphere such
as helium, argon or oxygen. The amount of water and the presence of volatile species
such as carbonate and organic components can be determined with this technique.
Sometimes two of these techniques can be used simultaneously on the same sam-
ple. In this thesis, the combination of DTA-TG analysis was used to simultaneously
measure thermal behaviour and mass changes using an SDT 2960 analysis from TA
instruments at the FiCMA-FiCNA group. The measurements differentiate between
endothermic or exothermic transitions with associated weight loss (e.g. degradation)
or with no weight loss (e.g. melting point or crystallization).
2.6 Electron microscopy

Electronic microscopy is an extremely important technique for examining particle
size, size distribution and the degree of sample homogeneity. In an electron micro-
scope, the high energy electrons are generated from a filament by using a large ac-
celerating voltage; electrons interact much more strongly with matter than photons.
According to the Broglie equation, the voltage is higher at shorter wavelengths, so
it is necessary to accelerate the electrons in a vacuum. Beams of these fast-moving
electrons are focused on an object and are absorbed or scattered by the object so as to
form an image on an electron-sensitive photographic plate.
The electron microscopy techniques that have been used in this study are the
scanning electronic microscopy (SEM), environmental scanning electron microscopy
(ESEM), transmission electron microscopy (TEM) and the high transmission electron
microscopy (HRTEM). Generally, the TEM resolution is better than the SEM resolu-
tion. However the SEM images depend on surface processes rather than transmission.
Therefore, SEM can produce images that are a good representation of the 3D struc-
ture of the sample. The theory underlying these techniques is developed below. Also
discussed is the basic theory about electron diffraction, which was performed from
TEM.
2.6.1 Scanning electron microscopy (SEM)

The scanning electron microscope (SEM) is an electron microscope capable of pro-
ducing high resolution images of a sample surface and microstructure. It is probably
the most widely used technique in several research fields today. The electron beam
42
usually consists of a tungsten or LaB6 filament. However, field emission gun (FEG) is
becoming increasingly necessary for imaging nanostructures at high resolution. The
accelerating voltage is usually between 1 and 30 kV, and the lower voltages increase
the brightness. This technique can provide magnifications between 20 and 300000.
The surface of the sample is scanned with an
electron beam with a fine focal spot size by con-
denser lenses. This spot size determines the res-
olution of the image, which is obtained by scan-
ning (figure 2.8). Several types of signals are pro-
duced when the focussed electron beam impinges
on the specimen surface, and they can be used to
form an SEM image. Some of the quanta are sec-
ondary electrons, backscattered electrons, X-rays,
cathodoluminescence generated by the impinging
electrons. The signals obtained are used to mea-
sured a variety of sample characteristics; for exam-
ple, topography, the sample’s atomic number, com-
position, the distribution of elements, etc.
F IGURE 2.8. Schematic diagram of
The only requirement for using this technique
the SEM. is that the samples need to be conductive. Non-
conductive samples are coated with a line layer of
a conductive metal such as carbon or gold. The SEM images are produced by de-
tecting secondary electrons which are emitted from the surface due to excitation by
the primary electron beam. The scanning electronic microscope JEOL JSM 6400 was
used to observe the resulting samples, which were coated with gold using Bal-Tec
SCD004. All equipment is available at the Servei de Recursos Cientı́fics i Tècnics of
the Universitat Rovira i Virgili.
2.6.2 Environmental scanning electron microscopy (ESEM)

Environmental scanning electron mi-
croscopy (ESEM) was developed about
15 years ago. An ESEM is very similar to
standard SEM and retains all of the per-
formance advantages of a conventional
SEM. However, it removes the high vac-
uum constraint on the sample environ-
ment; thus permitting the microscopist
to vary the sample environment through
a range of pressures, temperatures and
gas compositions. Wet, oily, dirty and non-
conductive samples can be examined sam-
ple in their natural state without prepa- F IGURE 2.9. Schematic representation of a
ESEM.
ration. One advantage of using ESEM is
that you can work in the wet mode, without having to coat non-conductive samples
with conductor media such as gold and their original characteristics can be observed
43
for further manipulation. ESEM offers high resolution secondary electron imaging in
gaseous environment.
Figure 2.9 shows the scheme of the ESEM. An ESEM contains gas at low pres-
sure in the sample chamber, where the primary electrons travel across the gas phase
and interact with the surface of the sample, which releases secondary electrons that
interact with the phase gas to produce additional secondary electrons. The primary
electrons interact with the gas molecules to produce ions and additional electrons.
Thus, the phase gas functions as an amplifier of the electron signal from the sample.
ESEM also has a chamber in which experiments can be performed up to around 1600
K and can be obtained of all stages of the heating/cooling process, because environ-
mental secondary electrons are insensitive to heat.
FEI QUANTA 600 environmental scanning electron microscope from the Serveis
de Recursos Cientı́fics i Tècnics of the Universitat Rovira i Virgili was used to obtain
images and analyze the nanomaterials.
2.6.3 Transmission electron microscopy (TEM)
The transmission electron microscope (TEM) is an optical analogue to the conven-
tional light microscope but it has a high voltage of up 100 KeV or higher (up to 1
MeV using an electron beam like light). The high voltage increases the imaging res-
olution, because the electron wavelength decreases. TEM uses electrons as the light
source and their much lower wavelength means that the resolution is better than
that of the optical analogue microscope. At the same time, the electron microscopes
require a vacuum system to remove interfering air molecules that might impede the
flow of electron down to column.
The key requirement for using TEM
is that the sample must be very thin.
Because of the wide range of signals
generated by the incident electron beam,
a TEM allows a sample to be fully
characterized at high resolution. The
greatest advantages that TEM offers
are the high magnification from 50
to 106 and its ability to provide both
image and diffraction information about
samples. The electron beam emitted
by a cathode is focused on a spec-
imen using a several condenser lenses
causing an enlarged version to appear
on a fluorescent screen. This electron
beam carries information about the
specimen (figure 2.10). F IGURE 2.10. Schematic diagram of TEM.
To prepare the sample, the nanopow-
ders were dispersed in ethanol solution (MercK, pro analysis 99.8) and a drop was de-
posited on a copper grid covered by holey carbon film (HD200 Cooper Fomvar/Carbon).
This study used several microscopies, JEOL JEM-1011 with a MegaView III Soft Imag-
ing System and a current accelerating voltage of 100 kV from the Serveis de Recursos
44
Cientı́fics i Tècnics of the Universitat Rovira i Virgili and JEOL JEM 2100 and TEM 300
kV Philips CM30 with Digital Micrograph software are from the Servei de Recursos
Cientı́fico-Tècnics of the Universitat de Barcelona.
Another imaging mode of TEM called high resolution transmission electron mi-
croscopy (HRTEM) allows the crystallographic structure and lattice imperfections in
several kinds of materials to be imaged on the atomic scale. Depending on the imag-
ing conditions, it is possible to show one or more sets of lattice planes of certain zone
axis orientation.
The HRTEM used (JEOL JEM 2010F) is a 200 kV field emission transmission elec-
tron microscope with a Schottky field emission electron source. It is equipped with
Electron Energy Loss Spectroscopy (EELS), a Gatan imaging filter (GIF) and a Z-
STEM unit with a high-angle annular detector, which is available at the Servei de Re-
cursos Cientı́fico-Tècnics of the Universitat de Barcelona. The samples are prepared
using the same methodology as TEM, and the same holey carbon film can be used for
the both microscopes.
Transmission electron microscopy was used to make the electron diffraction mea-
surements under the beam of the TEM or HRTEM , which is most frequently used to
study the crystal structure of materials. The section below discusses the basics of the
electron diffraction measurements.
2.6.3.1 Electron diffraction
One of the great advantages of the transmission electron microscope is that by ad-
justing the electron lenses, both electron microscope images and diffraction patterns
can be observed for the same region. By inserting a selected area aperture and using
the parallel incident beam illumination, you obtain a diffraction pattern from a spe-
cific area. This is the observed on a fluorescent screen, and recorded on photographic
film or by a CCD camera. The area of the specimen that contributes to the diffraction
pattern can be defined by the positioning the selected area diffraction (SAED), and
the smaller areas can be selected using a focused probe rather than aperture. This is
called convergent electron beam diffraction (CBED).
For crystalline materials, electron diffraction will only occur at specific angles,
which are characteristic of the crystal structure present. For crystalline materials, the
periodic atomic arrangement of atoms scatters the electrons through well-defined
angles given by Bragg’s law (eq. 2.7). Since λ is small, the Bragg angles are generally
small (sinθ ≈θ), so λ=2dθ. Hence diffraction occurs only when the planes of atoms are
closely parallel to the incident beam, as shown in figure 2.11a. The electron diffraction
pattern will be obtained only when the incident electron beam enters the crystalline
lattice at the appropriate Bragg angle. In the case of polycrystalline materials, the elec-
tron diffraction produces a pattern of concentric rings from many spots very close to-
gether, which exhibit virtually all the possible d spacings, because the crystallites are
randomly oriented. Amorphous material does not consist of atoms arranged in or-
dered lattices; they are completely disordered. For these materials, the electron beam
that enters the specimen is diffracted in multiple directions and will consist of fuzzy
rings of light on the fluorescent screen. The diameters of these rings of light are re-
lated to the average nearest neighbor distances in the material. Figure 2.11b-d shows
45
F IGURE 2.11. Schematic diagram of (a) the geometry of electron diffraction in the TEM and
the diffraction patterns for the (b) amorphous, (c) polycrystalline and (d) single-
crystalline sample regions.
the schematic geometric diagram of electron diffraction and the electron diffraction
patterns for amorphous, polycrystalline or single crystalline material.
2.7 Electron probe microanalysis (EPMA)

Electron probe microanalysis (EPMA) is an elemental analysis technique for deter-
mining the concentration of the any atom into the material. This analysis was carried
out in Cameca SX 50 microprobe analyzer operating in the wavelength dispersive
mode at the Servei de Recursos Cientı́fico-Tècnics of the Universitat de Barcelona.
The sample is bombarded
with a beam of accelerated elec-
trons and these energetic elec-
trons produce characteristic X-
rays. The electron beam is gen-
erated at an intensity of 30 nA
or 100 nA (depending on the
concentration of the element
to be determined) and an ac-
celerating voltage of 20 kV. The
characteristic X-rays are de-
tected at particular wavelengths
associated at one element and
their intensities are measured
to determine concentrations
using a wavelength-dispersive F IGURE 2.12. Scheme of EPMA equipmet
spectrometer (WDS) (figure 2.12).
The most commonly used spectrometer crystals are lithium fluoride 200 (LIF),
pentaerythritol 002 (PET), thallium acide phtalate 1011 (TAP) and W/Si multilayered
46
pseudo crystal (PC0, PC1, PC2 and PC3). The wavelength range covered by these
crystals is between 1 and 24 Å. This means that K-lines for elements with an atomic
number between 9 and 35, L-lines for elements with Z less than 83 and all M lines can
be recorded.
The chemical composition of the samples is calculated by comparing the X-ray
intensity of the sample with the standard samples, which contains known concentra-
tions. Details of the measurement conditions are summarized in table 2.1. The inten-
sity ratio of an element’s X-ray line is not directly proportional to its concentration.
They are affected by absorption, fluorescence and atomic number. The correction was
done with PAP (Pouchou and Pichoir) [232].
TABLE 2.1. Measurements conditions used in EPMA analysis
Element Line Spectrometer crystal Standard
K Kα PET KLuW
W Mα TAP KLuW
Ti Kα PET RTP
P Kα PET RTP
Lu Lα LIF KLuW
Sc Kα PET Sc
O Kα PC1 KLuW or KTP
Ho Lβ LIF REE2
Er Lα LIF REE1
Tm Lα LIF REE2
Yb Lα LIF REE3
To determine the experimental error (ε) of the measurement for all elements ana-
lyzed equation 2.12 was used.
v
I ps Ibs
u
u Ip I
u t p + tbb t s + ts
p b
ε=t + x100 (2.12)
( I p − Ib )2 ( I ps − Ibs )2
where I p and Ib are the intensities of the peaks and the background of the sam-
ple in counts per second (c/s), respectively; t p and tb are the integration times of the
peak and the background of the sample in seconds (s) and super index label s means
the intensities (sample and background) and the integration times (sample and back-
ground) for the standards.
The detection limit (DL ) for each element can be calculated using the follow equa-
tion (eq. 2.13)
√ 21
Cs

I
DL = 3 2 b (2.13)
( I ps − Ibs ) tb
47
where Cs is the concentration of the minority element in the standard expression

of weight (%).
The samples are prepared using the same procedure. The piece of sintering pel-
let formed by the nanocrystals is put in a cylindrical container and included in a
polyester resin (styrene and phthalic anhydride) with its corresponding catalyst (methyl
ethyl ketone peroxide). Then the mixture is completely solidified after around 12
hours. The solid cylindrical sample obtained is planed with a SiC disk and distilled
water is used as a coolant. Then the surface that contains the pellet is polished to op-
tical quality with diamond powder of 3 and 1 µm with lubricant MGS. The samples
were prepared in the FiCMA-FiCNA laboratories using a Struers DAP-7 polisher. Be-
fore the analysis the samples must be coated with a fine layer conductor metal (gold
or carbon) because of the low electric conduction of the samples.
Additionally, the electron microprobe can function like a scanning electron micro-
scope (SEM) and obtain highly magnified images of the samples.
2.8 Spectroscopy techniques

Optical spectroscopy has been widely used to characterize nanomaterials, and these
techniques can be divided into two groups: vibrational spectroscopy (infrared spec-
troscopy and Raman spectroscopy) and absorption and emission spectroscopy. The
vibrational frequencies provides the information about chemical bonds in the sam-
ples. The second group determines the electronic structures of samples by exciting
electrons from the ground state to the excited state (absorption) and relaxing them
from the excited to the ground state (emission).
2.8.1 Fourier transform infrared

Fourier transform infrared (FT-IR) is the most useful technique for identifying chemi-
cals that are either organic or inorganic. Infrared spectroscopy may be used to identify
the type of bond between two or more atoms and consequently identify functional
groups. This techniques is also widely used to characterize the attachment of organic
ligands to organic/inorganic nanoparticles and surfaces. Because IR spectroscopy is
quantitative, the number of a type of bond may be determined.
To prepared the sample, a small amount of the nanopowder is added to potas-
sium bromide (KBr, which has no infrared absorption in this region), after which this
mixture is grounded into as a fine powder as possible. Subsequently, it is placed in
a small die and mechanically put under pressure for several minutes. The success of
this technique depends on the powder being ground as fine as possible to minimize
infrared light scattering off the surface of the particles. It is also important that the
sample be dry before preparation.
The analysis of the characteristics vibration bands associated rotational-vibrational
structure of the nanocrystals was carried out in the range 7800-350 cm−1 (the average
measurement was 32 scans and a resolution equal to 4 cm−1 ) using Fourier Trans-
form Infrared Spectroscopy (FT/IR-680 Plus Fourier Transform Infrared Spectrome-
48
ter) available at the Serveis de Recursos Cientı́fics i Tècnics of the Universitat Rovira
i Virgili.
2.8.2 Raman spectroscopy

Raman scattering give us information about the vibrational energy levels of mole-
cules and, therefore, information about the material structure that makes it possi-
ble to identify solid, liquid or gaseous substances. This technique is non-contact and
non-destructive, and requires minimal sample preparation. Raman scattering and in-
frared absorption provide complementary information and together both techniques
characterizes the vibrational, rotational and other low-frequency modes of molecules
such as lattice vibrations of the crystals.
There are two types of scatter: Rayleigh scatter and Raman scatter. The most in-
tense form of scatter is Rayleigh scatter, which is known as an elastic process because
of the absence of an energy change. The excited molecules relax back to the ground
state by emitting a photon of the same frequency as that of the incident light. Raman
scattering is caused by inelastic scattering between photon and solid, so the ener-
gies of incident and scattered photons are different; there are shifted down or up for
Stokes or anti-Stokes lines, respectively. This shift in the energy is attributed to the vi-
brational energy spacing at the ground level. For Stokes lines, the emitted photon has
less energy than the incident photon and the molecule stays at a higher vibrational
level after emitting a photon. On the other hand, anti-stokes lines occur when the
emitted photon has more energy than the incident photon; in this case, the molecule
returns to a lower vibrational level. However, the anti-Stokes line is much less in-
tense than the Stokes line because only molecules that are in the first vibrational level
of the excited state would lead to anti-Stokes lines. The most intense Stokes lines are
measured in Raman scattering.
The experimental setup used consisted of a Jobin-Ybon T64000 spectrometer with
excitation in the visible by a cw argon laser (Coherent INNOVA 300, λ = 514 nm).
Behind triple the monochromator (1800 g/mm), the light was detected by a two-
dimensional CCD matrix cooled with liquid N2 . A pre-monochromator eliminated
the plasma discharge lines of the argon laser. An Olympus BH2 microscope with
high resolution was used to locate the laser spot in the sample. The laser power
incident on the sample was about 2 mW. Backward scattering was chosen to in-
crease the signal-to-noise ratio. This equipment is available at the Serveis de Recursos
Cientı́fico-Tècnics of the Universitat de Barcelona.
Micro-Raman measurements were carried out using Micro-Raman system Ren-
ishaw inVia equipped with a Microscope and a CCD camera as detector. The excita-
tion source was a diode laser that emits at 830 nm with a power level of 500 mW. The
equipment is available at the Institute of Low Temperature and Structure Research of
the Polish Science Academy in Wroclaw.
2.8.3 Optical absorption and transmission

Absorption is the fraction of incident electromagnetic radiation absorbed by elec-
trons, ions or molecules in the material over spectral ranges of light such as ultraviolet
49
(UV), visible and infrared (IR). The Beer-Lambert law (eq. 2.14) is an empirical rela-
tionship that relates the absorption of light to the properties of the material through
which the light is traveling:
I = I0 e−αd (2.14)
where I is the intensity of the emerging radiation, I0 is the incident light intensity,
α is the absorption coefficient and d is the thickness of the sample. Experimentally,
we measure the optical density (OD) using a double ray spectrophotometer.

I
OD = − log (2.15)
I0
The absorption was measured using a Varian Cary 500 Scan spectrophotometer
available at FiCMA-FiCNA’s laboratories, which was a double beam spectropho-
tometer. The experimental spectra rang is from 0.175 to 3.3 µm and can measure opti-
cal densities from 0 to 10. This spectrophotometer has two monochromators that can
separate 1200 lines/mm in the UV-visible region and 300 lines/mm in the IR region.
The optical sources used were a deuterium lamp and a quartz halogen lamp in the
UV and visible-IR zones, respectively. The detectors were a photomultiplier (PMT) in
the UV-visible region and a lead sulfide in the IR regime.
The optical absorption was measured at low temperature (6 K) by Oxford Instru-
ments cryostats (SU 12 model) with a Leybold helium closed circuit and a tempera-
ture controller that stabilizes the temperature to a precision of ± 3 K and ± 5 K in the
6-100 and 100-300 K ranges, respectively.
This spectrophotometer was also used to determine the transparency window of
the nanocrystals from 0.175 to 3.3 µm. To determine their transmission in the IR re-
gion (from 3 to 10 µm) a FTIR Midac Prospect spectrophotometer was used at the
Serveis de Recursos Cientı́fics i Tècnics of the Universitat Rovira i Virgili.
2.8.4 Luminescence measurements

Optical emission, or luminescence, is the result of a radiative transition of an elec-
tron from an excited or higher energy level to a lower energy level. The luminescence
spectra are determined by fixing the excitation wavelength and changing the detec-
tion wavelength. It is also interesting to determine the energy of the various levels
and the temporal evolution of the luminescence after excitation. An important pa-
rameter is the lifetime (τ) which is the time between the start of emission and the
time when its intensity decreases exponentially (1/e) from its initial value. This pa-
rameter characterizes not only the depopulation of an electronic level but also the
thermal excitation mechanism.
The nanomaterials were excited by a Ti:Sapphire or Nd:YAG laser a particular
wavelength as a function of the active ion. For detection, the emission was collected
at the 90◦ geometry to minimize the influence of the laser pump and was dispersed by
a JOBIN YVON-SPEX HR 460 double monochromator with a focal length of 460 mm
and a spectral resolution of 0.05 nm. The detectors used waere a cooled Hamamatsu
R55092-72 NIR photomultiplier for the infrared range and Hamamatsu PMTR928
50
F IGURE 2.13. Scheme of the system used in the optical emission measurements.
for the visible range. The detectors were connected to the lock-in amplifier process
(Perkin Elmer DSP-7265). Figure 2.13 shows the experimental set-up used to measure
luminescence. On the other hand, to work at low temperature (10K) a cryostat Oxford
(CCC1104) with helium-gas flow was used as described above for low temperature
absorption measurements.
Fluorescence lifetimes were excited with a Quanta-Ray MOPO-HF optical para-
metric oscillator. This system provides laser pulses shorter than 10 ns from 440 to 680
nm and from 730 to 1750 nm. The pulse energies were ≈ 25 mJ for λ = 930 nm and
12 mW for λ = 1490 nm. The fluorescence was dispersed by a single grating SPEX
spectrometer (f = 34 cm) and measured by a Hamamatsu InP/InGaAs cooled photo-
multiplier, model H9170-75, sensitive in the 950-1700 nm range. The electrical signals
were recorded in a Tektronix oscilloscope, model TDS-520. (figure 2.14). This equip-
ment was available at the Instituto de Ciencia de Materiales of the Consejo Superior
de Investigaciones Cientı́ficas in Madrid.
F IGURE 2.14. Scheme of the equipment used in the lifetime measurements.
51
The model developed by Inokuti and Hirayama was for non exponential decay
times due to the high concentration due to the energy transfer phenomena [233]. The
time dependence of the light intensity decay follows the equation below (eq. 2.16).
3
−t

3 N t s
I (t) = I (0) exp −Γ 1− (2.16)
τ0 s c0 τ0
where τ0 is the intrinsic lifetime of the donor in the absence of the donors, Γ ( x ) is
the gamma function evaluated in x, the parameter s is equal to 6, 8 or 10 if the transfer
mechanism is dipole-dipole, dipole-quadrupole or quadrupole-quadrupole and c0 is
the critical concentration related to the distance Rc at which the donor-trap energy
transfer rate equals the spontaneous decay rate (eq. 2.17).
3
c0 = (2.17)
4πR3c
2.9 Photoinduced second harmonic generation (PISHG)

To measure the photoinduced nonlinear optical effect a pulsed Nd:YAG laser was
used at the fundamental wavelength 1064 nm and an UV pulsed laser (nitrogen laser
at a wavelength of 337 nm) was used as a source of the photoinduced light. The UV
power density was increased to several GW/cm2 . The measurements were recorded
in the temperature range from 77 K to 530 K using an optical cryostat. Figure 2.15
shows the experimental setup used for these measures. The light from a photoinduc-
ing nitrogen laser (at 337 nm) was temporarily synchronized with the light from the
probing fundamental laser beam (at 1064 nm).
F IGURE 2.15. Setup for the photoinduced second harmonic generation measurements.
52
To control the signal input to the samples inside the cryostat, beamsplitters (B1
and B2) were used and a system of two polarizes (P1 and P2) was used to polarize
the light. The three sample surface were controlled by a spectroellipsometer, E1. To
control the photoinduced and output beam power densities a Fast-respond photo-
multipliers (PM) was used. A boxcar operates as per the signal times.
These measurements were carried out at the Institute of Physics of the University
of Czestochowa (Poland).
2.10 Piezooptic measurements

The piezooptical (elastooptic) effect, discovered many years ago, is known as a phe-
nomenon that consists of the occurrence of birefringence under applied mechanical
stress. The physical behaviour is described by equation 2.16:
∆nij = ∏ ·σkl (2.18)

ijkl
where ∆nij corresponds to changes in birefringence under applied mechanical

stress, ∏ijkl is a fourth rank tensor described by the piezooptical coefficients and σkl
is the second order tensor of mechanical uniaxial stress.
This effect is used for mechanically induced operation by light intensity, mecha-
nically operated light transmission, tensosensors, photoelastic fibres, etc. and can be
observed in crystalline and amorphous materials. The piezooptical properties of ma-
terials can be used to evaluate of acoustic-optic parameters for use in this applica-
tions [234].
F IGURE 2.16. Schematic experimental setup for piezooptical measurements.
The experimental setup can be seen in figure 2.16. For the piezooptic measure-
ments a He-Ne laser (λ = 633 nm) with a dc-50 Hz electric fields between 1 to 10
kV/cm was applied at the samr time as a UV laser (λ = 337 nm) with a pulse of 10
ns and a power 1 MW. A quartz single crystal, the piezooptical coefficients of which
53
were known, was used for reference purposes. The elastooptic coefficient was deter-
mined from the birefringence using the Senarmont method (eq. 2.19) described by
Williams et al. [27]
∆φ
∆n = λ · (2.19)
d
where ∆φ is the angle of the analyzer necessary to rich the minimum of the trans-
parent light. This method consists of measuring the birefringence under applied uni-
axial mechanical stress. The precision of this process is about 10−5 which enables
piezooptics coefficients to be obtained with a precision of up 3·10−5 m2 /N. Indepen-
dently, they were also determined by the two-fold interferometric method [235].
The piezooptical effects were measured at the Institute of Physics of the Univer-
sity of Czestochowa (Poland).
54
Chapter 3
Synthesis and Characterization of
Oxide Nanocrystals
3.1 Sol-Gel: The modified Pechini method
3.2 Potassium rare earth tungstates, KRE(WO4 )2
3.2.1 Determination of the crystallization temperature: phase transitions
3.2.2 Dopant concentration analysis
3.2.3 Structural characterization of KRE(WO4 )2 : variation of lattice parameters
3.2.4 Particle size and dispersion
3.2.5 Raman scattering of KRE(WO4 )2
3.3 Sesquioxides, RE2 O3
3.3.1 Determination of the crystallization temperature
3.3.2 Structural characterization of RE2 O3 : variation of lattice parameters
3.3.4 Raman scattering of RE2 O3
3.4 Potassium titanyl phosphate, KTiOPO4
3.4.1 Determination of the crystallization temperature: phase transitions
3.4.2 Structural characterization
3.5. Femtosecond laser ablation
3.5.1 Synthesis of KGd(WO4 )2 nanocrystals
present, numerous techniques and methodologies are available for obtaining

A T
nanomaterials from top-down and bottom-up approaches. This chapter dis-
cusses two different methodologies that can be used to obtain several nanocrystals
for a variety of optical applications. The modified Pechini method was used to syn-
thesize nanocrystals of potassium-rare earth tungstates (KRE(WO4 )2 ), sesquioxides
(RE2 O3 ) and potassium titanyl phosphate (KTiOPO4 ). And femtosecond laser abla-
tion was used to obtain potassium gadolinium double tungstate (KGd(WO4 )2 ) nano-
crystals. In the case of KGd(WO4 )2 , the results obtained in both methodologies have
been compared. In general, the characteristic particle is less than a hundred nanome-
ters in size and mostly less than fifty nanometers.
55
CHAPTER 3. SYNTHESIS AND CHARACTERIZATION OF OXIDE NANOCRYSTALS M. Galceran Mestres
3.1 Sol-Gel: the modified Pechini method

The modified Pechini method was used to synthesize potassium-rare earth tungstates
(KRE(WO4 )2 , KREW), sesquioxides (RE2 O3 ) and potassium titanyl phosphate (KTiOPO4 ,
KTP) nanocrystals. The experimental method is represented in a schematic diagram
in figure 3.1. The raw materials used in the syntheses are summarized in table 3.1.
Stoichiometric amounts of the component n (n = 1, 2, 3 and 4) were first converted to
their nitrate forms by dissolution in concentrated HNO3 . Later, the excess solution
was removed to obtain nitrate precipitates by slow heating.
F IGURE 3.1. Schematic diagram for nanocrystal preparation using the modified Pechini
method.
In the next step, an aqueous solution of ethylenediaminetetraacetic acid (EDTA)

used as a chelating agent was added to the nitrate precipitates in a specific molar
ratio (C M ) to prepare metal-EDTA complexes. The molar ratio C M was defined as:
[ EDTA]
CM = (3.1)
[ METAL]
which describes the degree of the chelation process of the metal in the organic
product. Afterwards, ethylene glycol (EG, sterification agent) was added in a molar
ratio (CE ), which describes the degree of sterification between the chelating agent and
the ethylene glycol:
[ EDTA]
CE = (3.2)
[ EG ]
The resulting solution was heated to obtain the precursor resin, which is a rigid
polyester net that reduces any segregation of metals. The following stage is the two-
step calcination procedure using a furnace.
57
TABLE 3.1. Summary of reagents used in each nanocrystal synthesis

Component n
Nanocrystals Reference
1 2 3 4
KGdW — Gd2 O3 K2 CO3 (NH4 )10 W12 O41 ·7H2 O Paper I, II
KYbW — Yb2 O3 K2 CO3 (NH4 )10 W12 O41 ·7H2 O Paper I
Er:KYbW Er2 O3 Yb2 O3 K2 CO3 (NH4 )10 W12 O41 ·7H2 O Paper III, IV
Eu:KYbW Eu2 O3 Yb2 O3 K2 CO3 (NH4 )10 W12 O41 ·7H2 O Paper III, V
Yb:Lu2 O3 Yb2 O3 Lu2 O3 — — Paper VI
Yb:Sc2 O3 Yb2 O3 Sc2 O3 — — Paper VII
Ho:Lu2 O3 Ho2 O3 Lu2 O3 — — Paper VIII
Er2 O3
(Er,Yb):Lu2 O3 Lu2 O3 — — —
Yb2 O3
KTP — Ti2 O K2 CO3 (NH4 )H2 PO4 Paper IX
1. Calcination at 573 K for 3 hours, during which the precursor resin decom-
poses to provide the precursor powder.
2. The calcination procedure depends on the nanocrystals. Each material was
calcined at a certain temperature and for a particular length of time in accor-
dance with the previous studies.
The experimental variables that must be controlled are molar ratio (C M ), molar
ratio (CE ), calcination temperature (Tc ) and calcination time (tc ). The molar ratios C M
and CE were optimized for the synthesis of KGdW and KYbW nanocrystals (see table
1 in Paper I ). The other experimental variables (Tc and tc ) are part of the calcination
procedure and directly depend on the nanocrystals. A more detailed discussion of
this process can be found in a previous study of ours (Paper I). Table 3.2 summarizes
the experimental parameters used for the synthesis of each material.
TABLE 3.2. Experimental parameters optimized in the synthesis of nanocrystals by modified

Pechini method
Molar Molar Calcination Calcination
Nanocrystals Reference
ratio (C M ) ratio (CE ) Temperature (K) Time (h)
KGdW 3 2 973 K 6 Paper I, II
KYbW 1 2 973 K 5 Paper I
Er:KYbW 1 2 973 K 5 Paper III, IV
Eu:KYbW 1 2 973 K 5 Paper III, V
Yb:Lu2 O3 1 2 1073 K 2 Paper VI
Yb:Sc2 O3 1 2 1073 K 2 Paper VII
Ho:Lu2 O3 1 2 1073 K 2 Paper VIII
(Er,Yb):Lu2 O3 1 2 1073 K 2 —
KTP 1 2 1073 K 2 Paper IX
58
3.2 Potassium rare earth tungstates, KRE(WO4 )2

3.2.1 Determination of the crystallization temperature: phase tran-
sitions
The modified Pechini method used to obtain KREW nanocrystals was controlled by
thermal analysis (figure 2, Paper I ), infrared spectroscopy (figure 3, Paper I ) and X-
ray powder diffraction patterns (figure 4, Paper I ). In Paper I, the aspects related to
KREW nanocrystals were compared with KREW bulk single crystals.
The first experiments were made on KGdW nanocrystals, and the preliminary
optimum calcination temperature range was determinated. Figure 4a, Paper I, shows
that the first crystalline peak that correspond to the KGdW monoclinic phase appears
up to 723 K and the optimum range must be between 723-1073 K. Later, the optimum
calcination temperature was determinated more sharply, using smaller temperature
intervals in the previous preliminary optimum temperature range and using KYbW
compound (figure 4b, Paper I ). It can be observed that an increase in the calcination
temperature, increases the degree of crystallinity and the particle size. For this rea-
son, an optimum calcination temperature of 973 K agree provides a monoclinic phase
and good crystallinity. At the same time, a thermal analysis was made to study how
the precursor powder evolved with the temperature (figure 3.2). The strong exother-
mic peak at 797 K is attributed to the decomposition/combustion of the polyester
together with the crystallization process. As the crystallization process involves no
weight loss in the TG curve and one exothermic peak in the DTA curve, there is an
overlapping process in this temperature range.
F IGURE 3.2. DTA-TG analysis of (blue) precursor powder in the synthesis of KREW nanocrys-
tals and (orange) powder from KREW bulk single crystal.
On the other hand, the polymorphic transformation and the melting point of na-
nocrystals were also compared with the KREW bulk single crystal. For the bulk single
crystal, the endothermic peaks at 1322 K and 1327 K are attributed to the transforma-
tion phase and the crystal’s melting point, respectively [49, 236]. In the case of KREW
nanocrystals, both the processes overlap at only one peak around 1310 K. The melting
point shift between the KREW nanocrystals and the bulk single crystal was related
59
to particle size because the smaller size of the nanocrystals affected the material’s
thermodynamic properties [237].
3.2.2 Dopant concentration analysis

The results of EPMA make it possible to calculate the chemical composition for each
doping in Paper I, II, III, IV, and V The results are summarized in table 3.3.
TABLE 3.3. Results for KREW nanocrystals

Nanocrystals % Active Ion Dopant concentration Reference
KGdW — — Paper I, II
KYbW — — Paper I
Er:KYbW 50 KEr0.494 Yb0.506 (WO4 )2 Paper III, IV
Eu:KYbW 50 KEu0.504 Yb0.496 (WO4 )2 Paper III, V
Dopant concentration in the nanocrystals measured by EPMA.
3.2.3 Structural characterization of KRE(WO4 )2 : variation of lattice

parameters
The synthesized nanocrystals were structurally characterized by X-ray powder diffrac-
tion. Figure 3.3 shows the X-ray powder diffraction patterns of the KREW nanocrys-
tals associated with the low temperature phase (monoclinic system with space group
C 2/c), which is the most interesting phase for laser applications.
F IGURE 3.3. X-Ray powder diffraction patterns of monoclinic KREW nanocrystals.
To calculate the lattice parameters of the KREW nanocrystals, they were refined
with the Fullprof software and single crystal X-ray data diffraction was used as the
60
starting model. Table 3.4 shows the refined lattice parameters of the KREW nano-
crystals and they were compared with the lattice parameters of bulk single crys-
tals [50, 51, 238, 239]. The variation among the refined lattice parameters of different
KREW nanocrystals is attributed to the fact that the ionic radii of rare earth ions de-
crease in the period of the periodic table, leading to decrease in lattice parameters
1.
TABLE 3.4. Unit cell parameters of KREW nanocrystals synthesized by the modified Pechini
method
Nanocrystals a (Å) b (Å) c (Å) β (◦ ) V (Å3 ) Reference
KGdW 10.6851(6) 10.43276(6) 7.5986(4) 130.770(3) 641.493(6) Paper I, II

KYbW 10.6026(6) 10.2597(6) 7.5036(4) 130.753(3) 618.33(6) Paper I
Er:KYbW 10.6103(5) 10.2886(5) 7.5204(3) 130.75(2) 621.9(5) Paper III, IV
Eu:KYbW 10.667(2) 10.437(2) 7.585(1) 130.866(8) 638.6(52) Paper III, V
F IGURE 3.4. (a) HRTEM image of KYbW nanocrystals, (b) FFT pattern that indicates the crys-
tal orientation and the (hkl ) planes and (c) Laplacian filtered image of the inset
selected area.
KREW nanocrystals were studied by high resolution transmission microscopy

and lattice plane fringes were observed, which indicates the high degree of crys-
tallinity (figure 3.4a). The Fast Fourier Transform (FFT) pattern was used to index the
lattice planes in accordance to the monoclinic phase. The interplanar lattices observed
are (110), (111) and (020) planes, which are 6.3256, 6.0474 and 5.1311 Å, respectively.
The habit of nanocrystals was characterized from a TEM image and using a Shape
software based on the Wulff plot (figure 3.5b). According to their large interplanar
1 i.r = ionic radii with a coordination number = 8, Gd3+ (i.r)=1.053 Å, Yb3+ (i.r)= 0.985 Å, Er3+ (i.r)=1.004
Å and Eu3+ (i.r)=1.066 Å, [240]
61
dhkl forms and the PBCs parallel to them, it can be indexed the appeared forms as a
{110}, {111}, {020} and {310} [50].
F IGURE 3.5. Schemes of different crystallographic orientations of (a) KGdW nanocrystals and
(b) KYbW nanocrystals.

Particle size is one of the parameters that has most been studied in nanocrystals. The
properties of nanomaterials depend on it, so it must be determined accurately. Howe-
ver, the uncertainly in particle size measurements for nanomaterials is much greater
than the bulk materials derived directly from experimental data. Particle size can be
estimed by a number of experimental techniques. This study essentially used the elec-
tronic microscopy and Scherrer’s equation (eq. 2.10), which describes the dependence
of the broadening of the diffraction peak at θ on the crystalline size [241].
The TEM technique is ideal for directly measuring particle size and particle size
dispersion; however, a very large number of particles are required if the results are
to be considered statistically significant. Characteristic TEM images of KREW nano-
crystals are shown in figure 3.6. The particles were treated as a spherical, and it was
considered the particle diameter (nanocrystal width because of they have generally
irregular shape) as particle size. Taking into account the literature, the nanocrystals
formed by nucleation, condensation and particle growth the particle size histograms
have a lognormal distribution, fitted by the next (eq. 3.3) [242, 243]:
−(log d − log d0 )2

N (d) = A exp (3.3)
2σ2
where N(d) is the number of particles with a particular width (d), A is the ampli-
tude of the mode, d0 is the mean of the width and σ is the standard deviation of the
mode (2σ is the dispersion of the mode).
62
F IGURE 3.6. TEM images and particle size distribution of nanocrystals of: (a) KGdW, (b)
KYbW, (c) Er:KYbW and (d) Eu:KYbW.
63
TABLE 3.5. Summary of particle size and dispersion for KREW nanocrystals
Particle size (nm)

Nanocrystals TEM images References
Scherrer equation
d0 Dispersion
KGdW 90-100 15 — Paper I, II

KYbW 50-60 45 46 Paper I, IV
Er:KYbW 42 38 36.8 Paper III, IV
Eu:KYbW 20 8 45.5 Paper III, V
Table 3.5 summarizes the particle sizes of KREW nanocrystals determined by the
Scherrer equation and TEM analysis. Small particles predominated but larger par-
ticles or aggregates were also observed (see SEM images, figure 3.7), which show
a good homogeneity of the samples but also the presence of agglomerates of small
particles, leading to an increase in the particle size dispersion.
F IGURE 3.7. Representative SEM photographs of KREW nanocrystals.
64
3.2.5 Raman scattering of KRE(WO4 )2

The Raman spectroscopy of KREW nanocrystals was recorded at room temperature
from 17 to 1000 cm−1 and compared with unpolarized Raman spectra of KREW bulk
single crystals (figure 3.8). The most extensive study is published in Paper I. For
KREW, the irreducible representation is:
ΓN = 17A g + 19Bg + 17Au + 19Bu (3.4)
where Ag and Bg modes are Raman active, and Au and Bu are infrared active
modes, in all 72 vibrational modes. The phonon energies of KREW nanocrystals with
Raman spectroscopy and FTIR are shown in table 3, Paper I. Labels were assigned
to peaks on the basis of a previous study of KYbW bulk single crystal, taking as a
reference the original notation for CaWO4 [244, 245].
F IGURE 3.8. Raman spectroscopy of KREW nanocrystals and bulk single crystal.
The phonon energy and the linewidth (∆ν) for KREW nanocrystals and bulk sin-
gle crystal are shown in table 3.6. For KREW nanocrystals, ∆ν is bigger in the peaks
with higher phonon energies. The differences observed between nanocrystals and
bulk single crystal such as optical phonon confinement are due to the small particle
size [246].
65
TABLE 3.6. Vibrational frequencies and linewidths of spontaneous Raman peaks in KREW
KGdW nanocrystals KGdW bulk single crystals
Phonon Energy (cm−1 ) ∆ν (cm−1 ) Phonon Energy (cm−1 ) ∆ν (cm−1 )
86 2.4 84 3.0
772 12.5 769 7.0
903 8.7 902 6.54
KYbW nanocrystals KYbW bulk single crystals
Phonon Energy (cm−1 ) ∆ν (cm−1 ) Phonon Energy (cm−1 ) ∆ν (cm−1 )
87 2.4 90 3.8
758 18.2 763 14.6
908 9.16 911 8.4
3.3 Sesquioxides, RE2 O3

3.3.1 Determination of the crystallization temperature
The first studies to synthesize RE2 O3 nanocrystals were carried out with Lu2 O3 doped
with 50% Yb at. For the first time, Paper VI describes the methodology and the op-
timization of experimental parameters for the synthesis of Yb:Lu2 O3 nanocrystals as
shown in KREW nanocrystals.
F IGURE 3.9. DTA-TG thermogram of precursor powder in the synthesis of Yb:Lu2 O3 nano-
crystals.
The crystallization temperature was determined using the DTA-TG thermogram

of the precursor powder (figure 3.9), together with X-ray powder diffraction patterns
(figure 3, Paper VI ).
XRD revealed that the crystallization process begins in the temperature range 773-
873 K, and this was confirmed by DTA-TG analysis for the exothermic peak at 915.8
K (the shift in the crystallization temperature was attributed to different tempera-
ture calibrations in the equipment). On the other hand, the weak exothermic peak
66
at 1070.8 K corresponds to the growth of crystal particles [247]. In accordance with

these analyses, the experimental conditions to calcine these materials were 1073 K for
2 hours.
3.3.2 Structural characterization of RE2 O3 : variation of lattice pa-

rameters
X-Ray powder diffraction was used to structurally characterize the RE2 O3 nanocrys-
tals as a function of the active ion concentration (figure 3.10). These materials crys-
tallize a cubic system with the Ia3 space group. The shift observed to lower 2θ is
attributed to the increase in concentration of active ions because they have a higher
ionic radii than the host material 2 . The unit cell parameters refined with the Fullprof
software are shown in table 6.1. For each type of RE2 O3 , the shift in the unit cell pa-
rameters is attributed either to an increase in the active ion concentration or to the
fact that the ionic radii were different from those of the host material. The results of
EPMA enable the chemical composition for each doping are shown in table 6.1.
F IGURE 3.10. XRD patterns of RE2 O3 nanocrystals obtained by modified Pechini method and
its corresponding JCPDS.
One more reason for performing TEM studies is that they can show that individ-
ual nanocrystals are clearly part of the aggregates. Therefore, TEM images were taken
of RE2 O3 nanocrystals to identify the fringes of the lattice planes.
2 i.r = ionic radii wit a coordination number = 6, Lu3+ (i.r)=0.861 Å, Sc3+ (i.r)=0.745 Å, Yb3+ (i.r)=0.868 Å,
Ho3+ (i.r)=0.901 Å and Er3+ (i.r)=0.890 Å,

[240]
67
TABLE 3.7. Results data for sesquioxides nanocrystals
Nanocrystals Active Dopant concentration a (Å) V (Å3 ) L (nm) F Reference
Ion (%)
Lu2− x Ybx O3 50 Yb1.006 Lu0.994 O3 10.4136(3) 1129.28(6) 60 Paper VI

0.05 Yb:ScO3 9.8438(8) 953.9(1) 12.6
0.5 Sc1.990 Yb0.010 O3 9.8466(7) 954.7(1) 13.2
1 Sc1.981 Yb0.019 O3 9.8496(8) 955.6(1) 12.7
2 Sc1.961 Yb0.039 O3 9.8541(8) 956.9(1) 12
3 Sc1.944 Yb0.056 O3 9.8598(9) 958.5(1) 10.5
Sc2− x Ybx O3 Paper VII
4 Sc1.921 Yb0.079 O3 9.8657(9) 960.3(2) 10.1
5 Sc1.899 Yb0.101 O3 9.8711(11) 961.8(2) 10.7
68
10 Sc1.804 Yb0.196 O3 9.9080(17) 972.6(3) 8.7
25 Sc1.495 Yb0.506 O3 10.0090(5) 1002.67(9) 21.5
50 Sc1.015 Yb0.985 O3 10.1494(9) 1045.5(2) 10.8
0.5 Lu1.985 Ho0.015 O3 10.3898(7) 1121.5(1) 17.2
1 Lu1.975 Ho0.025 O3 10.3920(7) 1122.3(1) 15.3
Lu2− x Hox O3 Paper VIII
5 10.4010(8) 1125.2(1) 14.0
CHAPTER 3. SYNTHESIS AND CHARACTERIZATION OF OXIDE NANOCRYSTALS
Lu1.896 Ho0.104 O3
10 Lu1.789 Ho0.211 O3 10.4187(8) 1131.0(1) 14.3
Lu2− x−y Erx Yby O3 25/25 Lu0.990 Er0.520 Yb0.490 O3 10.4417(4) 1138.45(8) 14.9 —

Dopant concentration in the nanocrystals measured by EPMA, Dopant concentration is lower than the detection limit; it’s not possible to calculate by EPMA
F Estimated by Scherrer equation
JCPDS 43-1021 (Lu2 O3 ) a=10.39 Å, JCPDS 43-1028 (Sc2 O3 ) a=9.845 Å, JCPDS 43-1106 (Yb2 O3 ) a=10.4347 Å, JCPDS 44-1268 (Ho2 O3 ) a=10.6102 Å and JCPDS 43-1007
(Er2 O3 ) a=10.5480 Å
M. Galceran Mestres
F IGURE 3.11. TEM images of Yb:Lu2 O3 nanocrystals and respective FFT patterns.
Figure 3.11 shows the clear lattice fringes observed in the TEM images indicating
the high crystallinity of the nanocrystals. This was confirmed by the FFT patterns. The
diffraction corresponds to given (hkl) planes from several nanocrystals each of which
is oriented differently. Each ring in the FFT pattern is attributed to a crystallographic
plane, and in general the smaller rings correspond to the larger dhkl spacings.
In the case of Sc2− x Ybx O3 nanocrystals, electron diffraction was measured by two
methodologies: selected area electron diffraction (SAED) and convergent beam elec-
tron diffraction (CBED). Figure 3.12a shows the TEM image of the aggregates of the
Sc2− x Ybx O3 nanocrystals, and figure 3.12b shows its respective SAED, which con-
firms the non-preferential orientation of each nanocrystal. The incident beam covers a
broad sample area containing a large number of nanocrystals. Each ring corresponds
to one crystallographic plane, which can be indexed on the basis of its space group
(Ia3) and the smaller rings belong to the larger dhkl spacings.
The crystal structure was studied using an electron diffraction by a nanobeam
mode (CBED), where the incident beam is a convergent beam and the spots be-
come discs. Figure 3.12c and 3.12d depict a TEM image of an individual Sc2− x Ybx O3
nanoparticle and its CBED as a nanobeam mode (a 2 nm beam diameter), respec-
tively. The electron diffraction pattern shows the presence of four equivalent reflec-
tions (closest to the central beam) corresponding to (222) with an interplanar distance
of 2.8425 Å. Two other equivalent reflections correspond to (004) with an interplanar
distance of 2.4616 Å. The last one is (440) with an interplanar distance of 1.7406 Å.
From these reflections, the orientation of these nanocrystals can be indexed in the
[110] zone axis.
The same methodology was used to study another sesquioxide: Lu2− x Hox O3 . Fi-
gure 3.13a shows the characteristic TEM image, in which the interplanar lattice indi-
cating the high crystallinity degree can be observed. The FFT pattern (3.13b) makes it
possible to index the lattice planes d(200) = 5.1999 Å and d(211) = 4.2457 Å. To study
the possible preferential orientation of nanocrystals, a nanobeam electron diffraction
was performed (3.13c). Because of particle aggregates, it was very difficult to focalize
the beam in only one nanocrystal and to study his zone axis. In this sample, it was
69
possible to index the {200}, {211} and {400} with an interplanar distance of 5.1999,
4.2457 and 2.5999 Å, respectively.
F IGURE 3.12. (a)TEM image of the aggregate of Sc2− x Ybx O3 nanocrystals, (b) SAED pattern of
(a), (c) zoom of (a) showing a small nanocrystal with visible lattice planes and
(d) nanobeam electron diffraction pattern of (c).
F IGURE 3.13. (a)TEM image of Lu2− x Hox O3 nanocrystals, (b) FFT pattern of (a), (c) nanobeam
electron diffraction pattern of the Lu2− x Hox O3 nanocrystals.
70
Throughout the synthesis the nanocrystals were observed by electronic microscopy

to acquire information about the homogeneity and particle size. Paper VI explains the
methodology used during the synthesis of Lu2− x Ybx O3 nanocrystals. This method-
ology was extrapolated to the synthesis of sesquioxides in general.
The morphology and homogeneity were observed by scanning electronic microscopy.
Figure 3.14 shows representative SEM images of each type of RE2 O3 nanocrystals.
All these types present good homogeneity but they build aggregates that lead to high
particle size dispersion, as can be seen in KREW nanocrystals. On the other hand, the
particle size was estimated with Scherrer’s equation (eq. 2.10) and TEM analyses.
F IGURE 3.14. SEM images of RE2 O3 nanocrystals (a) Yb:Lu2 O3 , (b) Yb:Sc2 O3 and (c)
Ho:Lu2 O3 .
As mentioned above, the particle size dispersion was studied using TEM images
and software. Using equation 3.3, the histogram was fitted by a lognormal distri-
bution. Figures 3.15, 3.16 and 3.17 show the representative TEM images and their
histogram for sesquioxide nanocrystals.
F IGURE 3.15. TEM image of (a) Yb:Lu2 O3 nanocrystals and (b) (Er,Yb):Lu2 O3 nanocrystals.
The insets indicate the particle size distribution.
Table 3.8 summarizes the mean and the particle size dispersion of RE2 O3 nano-
crystals. For these materials, the particle sizes are in the range 10-60 nm. To sum up,
as shown above, the high dispersion is attributed to the particle agglomerates.
71
F IGURE 3.16. Several TEM images of Yb:Sc2 O3 nanocrystals and the total particle size distri-
bution.
F IGURE 3.17. Representative TEM image of Ho:Lu2 O3 nanocrystals and the total particle size
distribution.
TABLE 3.8. Mean particle size and dispersion for RE2 O3 nanocrystals estimated by TEM ana-
lysis
Nanocrystals d0 (nm) Dispersion (%) Reference
Lu2− x Ybx O3 76.6 81 Paper VI

Sc2− x Ybx O3 19.7 46 Paper VII
Lu2− x Hox O3 24.2 59 Paper VIII
Lu2− x−y Erx Yby O3 33.1 44 —
3.3.4 Raman scattering of RE2 O3

The C -type RE2 O3 has N = 40 translationally inequivalent positions with a number
of freedom degrees are 3N = 120 and 53 vibrational modes. As shown in the section
above there are three sites and the vibrational modes for each site are:
8b → Au + Eu + 3Fu (3.5)
24d → Ag + Au + Eg + Eu + 5Fg + 5Fu (3.6)
48e → 3Ag + 3Au + 3Eg + 3Eu + 9Fg + 9Fu (3.7)
Therefore, the total vibrational modes for RE2 O3 are represented as:
ΓN = 4A g + 4Eg + 14Tg + 5Au + 5Eu + 17Tu (3.8)
Taking into account the irreducible representation of the factor group and the se-
lection rules, the Raman active modes predicted for C -type structure RE2 O3 are 4Ag,
72
F IGURE 3.18. Raman spectra of (a) Yb:Lu2 O3 nanocrystals (b) Yb:Sc2 O3 nanocrystals and (c)
Ho:Lu2 O3 nanocrystals at room temperature.
4Eg and 14Fg [248]. The Raman spectroscopy of RE2 O3 nanocrystals was recorded at
room temperature from 100 to 2500 cm−1 (see figure 3.18).
The bands at low frequency are attributed to the Raman modes. However, the de-
tailed assignment of the peaks is not available in the literature, although the strongest
peak located around 390 cm−1 has been assigned as an Ag or Ag + Fg mode.
As the number of f electrons increases, the Raman peaks are shifted to a hig-
her wavenumber. This general tendency for the wavenumber to increase throughout
the period can be explained in terms of lanthanide contraction [249]. This effect can
be observed largely to the Raman spectra of Yb:Sc2 O3 nanocrystals because of the
difference of f electrons between ytterbium and scandium. On the other hand, the
difference intensity of the Raman peaks in the Yb:Sc2 O3 nanocrystals is related to the
experimental conditions needed to recorder the spectra caused by the high ytterbium
concentration.
3.4 Potassium Titanyl Phosphate, KTiOPO4

3.4.1 Determination of the crystallization temperature: phase tran-
sitions
KTP nanocrystals were synthesized by the modified Pechini method, and the most
interesting results are discussed in Paper V. In this section, the main results obtained
so far are discussed.
73
As can be seen in figure 3.19, the temperature at which the mixture of several ma-
terials transforms into a crystalline KTP orthorhombic structure (Pna21 space group)
is around 961 K. Together with figure 5, Paper IX, the calcination temperature was
established to be at 1073 K. If the temperature increases, phase transitions can be
observed at different temperatures:
cT o →c T
KTP (orthorhombic, Pna21 ) ←→ KTP (orthorhombic, Pnan) ←→ KTP (cubic, Fd3m)
T
d
−→ K2 O + P2 O5 + TiO2 (rutile)
where Tc , To→c and Td correspond to the Curie temperature (1221 K), the phase tran-
sition temperature for the orthorhombic phase to cubic phase (1446 K) and decompo-
sition temperature (1594 K), respectively (figure 3.19) [156, 250].
The shift temperature between KTP nanocrystals and bulk single crystal is attri-
buted to the effect the lower dimensions of nanocrystals have on the thermodynamics
properties [237, 251].
F IGURE 3.19. DTA-TG analysis of (blue) precursor powder in the synthesis of KTP nanocrys-
tals and (orange) powder from KTP bulk single crystal.

The crystalline structure of KTP nanocrystals was determined by X-ray powder diffrac-
tion. Figure 3.20 shows the XRD powder patterns at room temperature of KTP nano-
crystals, bulk single crystal and the JCPDS associated to the orthorhombic phase with
the space group Pna21 . At the same time, the unit cell parameters were refined with
the Fullprof software, where the starting structure was KTP bulk single crystal XRD
data recorded by Thomas et al. [150]. The unit cell parameters obtained were a =
12.8166(7) Å, b = 6.4040(3) Å and c = 10.5809(4) Å, which agree well with the lattice
parameters reported for the bulk single crystal.
On the other hand, the characteristic absorption bands were studied by infrared
spectroscopy from 1200 to 600 cm−1 (figure 6, Paper IX ). The bands associated with
74
F IGURE 3.20. DRX powder patterns of KTP nanocrystals, bulk single crystal and the standard
JCPDS 80-0893.
the P-O vibrations of the PO4 group appear at 1124, 1100, 1041, 1021, 994, 958 and
632 cm−1 . Moreover, the bands that appear at 818, 785 and 693 cm−1 are attributed to
Ti-O vibrations of the distorted TiO6 octahedra [252].
F IGURE 3.21. HRTEM image of KTP nanocrystals with the corresponding FFT pattern.
As shown in the sections above, structural studies were also carried out by TEM
and electron diffraction. Figure 3.21 shows a HRTEM image with the corresponding
FFT pattern and the lattice planes can be indexed on the basis of their orthorhombic
phase. The nanocrystal aggregates make it very difficult to obtain a preferential ori-
entation. A clear interplanar {110} lattice can be seen with a value of 5.729 Å. Other
HRTEM image of these nanocrystals can also be seen in figure 9, Paper IX, where the
fringes of lattice plans can also be seen indicating the high degree of crystallinity of
KTP nanocrystals.
75
The electronic microscope was used to study the particle size distribution and the
morphology. Figure 3.22 shows an SEM image of KTP nanocrystals obtained after
calcination at 1073 K. The non-uniform particle size can be seen due to the formation
of KTP aggregates. On the other hand, Scherrer’s equation was used to estimate a
particle size around 72 nm.
F IGURE 3.22. SEM image of KTP nanocrystals.
The distribution of the particle size was estimated using a TEM image with Meta-
morph software (figure 3.23). In the histogram, it can be observed that the predom-
inance of small particles is centered in the range from 10 to 40 nm. However, large
particles are present because of the formation of KTP aggregates, which lead to high
particle size distribution. As in other studies of particle size, the size histogram of
KTP nanocrystals is well represented by a lognormal distribution with a mean of 25
nm and a dispersion of 58 % (eq. 3.3).
F IGURE 3.23. TEM images and particle size distribution of KTP nanocrystals.
76
3.5 Femtosecond laser ablation

3.5.1 Synthesis of KGd(WO4 )2 nanocrystals
The KGdW bulk single crystals used in the synthesis of nanocrystals were grown
by Top Seeded Solution Growth-Slow Cooling (TSSG-SG) [253, 254]. The bulk single
crystal was put on the bottom of the vessel and the laser beam was focused on the
crystal surface with an achromatic lens doublet (focal length f = 100 mm). Before
reaching the bulk crystal, the pulses passed through a column of deionized water 10
mm high. The vessel was placed in a motorized XYZ translation stage in order to
achieve optimal focusing on the target surface. The focused beam moved in straight
lines across the sample surface with a uniform speed of 50 µm/s, and iterative passes
along the same line were avoided.
The mean size and size dispersion of colloidal nanocrystals depend strongly on
the laser fluence (energy density per irradiated unit area). The technique used was
proposed by Dumitru et al. [255], and gave a threshold in air of 1.02 ± 0.27 J/cm2 for
100 pulses (multishot conditions). The sample was irradiated with fluences (in air)
that were around 15 times the ablation threshold fluence for a period of 8 hours. Other
studies have shown that the fluence affects particle size and distribution [213, 215].
Paper II reports this method of synthesis in greater detail. In particular, it discusses
the structure of nanocrystals, the particle size and the morphology of the nanocrystals
obtained by the modified Pechini method and femtosecond laser ablation.
3.5.2 Structural characterization of KGd(WO4 )2

Figure 3.24 shows the X-ray powder diffraction patterns of KGdW nanocrystals ob-
tained by femtosecond laser ablation and KGdW bulk single crystal grown by Top
Seed Solution Growth-Slow Cooling. The monoclinic phase with the C 2/c space
group has been obtained. When the unit cell parameters of KGdW nanocrystals were
refined, the values were similar to those of bulk single crystal: a = 10.6848(3) Å, b =
10.4411(3) Å, c = 7.6004(2) Å and β = 130.762(1)◦ [51].
F IGURE 3.24. XRD powder patterns of KGdW nanocrystals and the bulk single crystal.
77
Electronic microscopy showed that some KGdW nanocrystals have a crystalline

habit (figure 3.25). The habit model of KGdW was drawn using a Shape Program [256]
based on the Wulff plot to index the appeared faces (hkl ), of which {110}, {111} and
{010} develop most; at the same time, the poorly appeared are {021} and {221}.
These forms agree with their large interplanar dhkl and the parallel PBCs [51, 238].
F IGURE 3.25. Detailed TEM image and habit model drawn by Shape software on the basis of a
Wulff plot of KGdW nanocrystals obtained by femtosecond laser ablation.

Scherrer’s equation (eq. 2.10) was used to estimate the particle size, and found a mean
of around 86 nm. Particle size was also calculated from a TEM image (figure 3.26). In
this case, the mean was 55 nm with a dispersion of 49%.
F IGURE 3.26. TEM image of KGdW nanocrystals and size dispersion histogram.
78
Chapter 4
Synthesis and Characterization of
Nanostructures
4.1 PMMA, poly(methyl methacrylate), nanocomposites of oxide nanocrystals
4.1.1 Synthesis of PMMA nanocomposites of oxide nanocrystals
4.1.2 Structural characterization of nanocomposites
4.1.3 Distribution of oxide nanocrystals in the polymer matrix
4.2 PMMA microcolumns with embedded (Er,Yb):Lu2 O3 nanocrystals
4.2.1 Synthesis of PMMA microcolumns with embedded (Er,Yb):Lu2 O3 nanocrystals
4.2.2 Structural characterization of (Er,Yb):Lu2 O3 nanocrystals embedded in PMMA micro-
columns
4.2.3 Visualization of PMMA microcolumns by electron microscopy
4.3 (Er,Yb):Lu2 O3 nanowires
4.3.1 Synthesis of (Er,Yb):Lu2 O3 nanowires
4.3.2 Structural characterization of (Er,Yb):Lu2 O3 nanowires
4.3.3 Visualization of Er,Yb):Lu2 O3 nanowires by electron microscopy
H ischapter describes the synthesis and structural characterization of nanostruc-

T tures obtained from the nanocrystals synthesized in the previous chapter by the
modified Pechini method. The experiments were carried out in the laboratories of
the FiCMA-FiCNA group, at the Nanoelectronic and Photonic Systems (NePHoS) re-
search group at the Universitat Rovira i Virgili and at the Institute of Physics at the
University of Czestochowa in Poland.
79
CHAPTER 4. SYNTHESIS AND CHARACTERIZATION OF NANOSTRUCTURES M. Galceran Mestres
4.1 PMMA, poly(methyl methacrylate), nanocomposites

of oxide nanocrystals
4.1.1 Synthesis of PMMA nanocomposites of oxide nanocrystals
The nanocrystals obtained by the modified Pechini method characterized in the pre-
vious chapter were used to synthesize PMMA nanocomposites and to measure the
piezo-optical coefficients and the photoinduced second harmonic generation in the
case of KTP nanocomposites. The methodology and the results were published in
Paper III and Paper IX.
F IGURE 4.1. Scheme of the experimental procedure for obtaining PMMA nanocomposites.
First, the nanocrystals were mixed with PMMA polymer in the appropriate ratio
and then dissolved in the chloroform solvent. The solution was then deposited on the
glass plate and special rotation was applied to achieve a homogeneous distribution
of the nanocrystals (figure 4.1). The nanocomposites were fabricated at the Institute
of Physics at the University of Czestochowa in Poland.
These nanocomposites were used to measure the piezo-optical coefficients and
the photoinduced second harmonic generation of oxide nanocrystals, which will be
discussed in the next chapter.
81
4.1.2 Structural characterization of nanocomposites

The crystallinity of the agglomerates was studied by TEM using a JEOL 200EX micro-
scope with a LaB6 electron gun operating at 200 kV and a point resolution of ∼ 0.28
nm. TEM images were performed in bright field conditions with an objective aper-
ture and a size corresponding of 7 nm−1 in a back focal plane. These analyses were
made at the Institute of Physics at the University of Czestochowa.
F IGURE 4.2. Bright field TEM images of (a) a conglomerate of KREW nanoparticles, (b) one of
the smallest polycrystalline nanoparticles, (c) a zoom part of (a) showing ∼ 10 nm
size crystals with visible lattice planes and (d) a zoom part of (b).
The agglomerate consists of compact polycrystalline particles and nanocrystal

grains (see figure 4.2). To form the agglomerate, the particles are connected by frag-
ments of their surfaces. The agglomerates are in the range 30-120 nm and are formed
of nanocrystals 5-60 nm in size. One of this nanocrystal (25x10 nm) is shown in figure
4.2c. Figures 4.2b and 4.2d, on the other hand, show one of the smallest polycrys-
talline particles and a zoom part, respectively.
The particles can be divided into two main groups: (1) polycrystalline agglomer-
ates, and (2) isolated nanocrystals between 10 nm and 1 µm. TEM images shows that
the shapes and sizes of the nanocrystals are not regular and vary considerably; ho-
wever, this factor was not crucial for optical measurements, which will be discussed
in the next chapter.
4.1.3 Distribution of oxides nanocrystals into polymer matrix

The distribution of the nanocrystals embedded in the PMMA matrix was studied by
ESEM. The nanocrystals present a kind of alignment which leads to the assumption
that they are affected by the DC-electric field and/or by the rotation applied during
the sample preparation. Figure 4.3 shows the KYbW nanocrystals distributed in the
82
polymer matrix. It can be observed that bigger nanocrystals are present, which may
be polycrystalline aggregates.
F IGURE 4.3. ESEM image of the aligned KYbW nanocrystals embedded in the PMMA polymer
matrix.
F IGURE 4.4. TEM images of (a) the border of KREW nanocomposites and (b) the polycrys-
talline aggregates incorporated in the PMMA matrix obtained in the bright field
condition.
Figure 4.4a shows TEM images of the distribution nanocrystals embedded in the
PMMA matrix. They confirm the presence of a broad particle size distribution with
irregular shapes. The most regular shaped polycrystalline particles have 130, 320 and
35 nm in size. The dimensions of the irregular particles, on the other hand, are 68x20
nm. To sum up, the polycrystalline particles are formed of small nanocrystals bet-
ween 10 and 100 nm.
83
4.2 PMMA microcolumns with embedded (Er,Yb):Lu2 O3

nanocrystals
4.2.1 Synthesis of PMMA microcolumns with embedded (Er,Yb):Lu2 O3
nanocrystals
The synthesis and characterization of (Er,Yb):Lu2 O3 nanocrystals have been reported
and discussed in the previous chapter. The (Er,Yb):Lu2 O3 nanocrystals embedded in
PMMA microcolumns were prepared by vacuum infiltration. Figure 4.5 shows the
experimental procedure of the vacuum infiltration.
F IGURE 4.5. (a-c) Schematic diagram of the experimental procedure for obtaining micro-
columns using a disordered silicon template. Photographs of the silicon template
(d) general top-view and (e) cross section.
Firstly, in (a), the polymer solution formed by 5-7% weight of (Er,Yb):Lu2 O3 na-
nocrystals, poly(methyl) methacrylate and toluene is deposited on the surface of the
disordered silicon template. The diameter and height of pores are 1 µm and 90 µm,
respectively (d-e). The height of the template is around 350 µm. Then, in (b), the poly-
mer solution seeps into the pores to form the columns. Subsequently, the sample is
heated at 383 K during 3 h. Finally, the silicon template is removed in (c) with a KOH
solution. The silicon templates were fabricated and the vacuum infiltration was car-
ried out by the Nanoelectronic and Photonic Systems (NePHoS) research group at
the Departament d’Enginyeria Electrònica, Elèctrica i Autonomàtica at the Universi-
tat Rovira i Virgili in Tarragona.
84
4.2.2 Structural characterization of (Er,Yb):Lu2 O3 nanocrystals em-

bedded in PMMA microcolumns
The nanocrystals embedded in the PMMA matrix were structurally characterized by

micro X-ray diffraction (µXRD), which makes it possible to examine very small sam-
ple areas. The phase obtained corresponds to a cubic system with the Ia3 space group
(figure 4.9).
F IGURE 4.6. X-Ray diffraction of (Er,Yb):Lu2 O3 nanocrystals embedded in PMMA micro-

columns.
From ESEM images and energy dispersive X-ray analyses were also used to con-
firm the presence of erbium, ytterbium and lutetium of (Er,Yb):Lu2 O3 nanocrystals
in the pores after the surface of the silicon template had been polished (figure 4.7).
F IGURE 4.7. (a) ESEM image of the polished surface of the filled silicon template by PMMA
microcolumns embedded with (Er,Yb):Lu2 O3 nanocrystals (b) Energy Dispersive
X-ray analysis of Er, Yb and Lu in the composite.
85
4.2.3 Visualization of PMMA microcolumns by electron microscope
Environmental scanning electron microscopy was used to visualize the PMMA mi-
crocolumns after the silicon template had been removed. It can be observed that the
microcolumns are disorganized because they were grown on a disordered silicon
template. The diameter of the microcolumns was around 1 µm. It was difficult to
visualize the (Er,Yb):Lu2 O3 nanocrystals in the microcolumns using ESEM, so trans-
mission electron microscopy was used.
F IGURE 4.8. ESEM images of PMMA microcolumns with embedded (Er,Yb):Lu2 O3 nanocrys-
tals.
Figure 4.9 shows the TEM image of a piece of PMMA microcolumn. It can be
observed that the (Er,Yb):Lu2 O3 nanocrystals are distributed into the microcolumns.
F IGURE 4.9. TEM photographs of a fragment of PMMA microcolumns in which (Er,Yb):Lu2 O3

nanocrystals are embedded.
86
4.3 (Er,Yb):Lu2 O3 nanowires

4.3.1 Synthesis of (Er,Yb):Lu2 O3 nanowires
One of the most common methods used to synthesize nanostructures is the so-called
template-assisted method. This process involves synthesizing the desired material
within the pores of a porous membrane. Taking into account the synthesis of nano-
crystals by the modified Pechini method and using a alumina template fabricated
at the NePHoS research group, we can obtain the desired (Er,Yb):Lu2 O3 nanowires
(figure 4.10)
F IGURE 4.10. Experimental procedure for fabricating (Er,Yb):Lu2 O3 nanowires.
The alumina template was added to the solution formed by metal-EDTA com-
plexes and the ethylene glycol. This solution was stirred heated slowly for a given
period of time until the precursor resin was obtained. At this time, the sol was de-
posited on alumina pores. After heat treatment the desired nanowires were grown
within the pores. The experimental parameters and conditions used are shown in
table 3.2 (chapter 3).
4.3.2 Structural characterization of (Er,Yb):Lu2 O3 nanowires

Figure 4.11 shows the micro X-ray diffraction pattern of (Er,Yb):Lu2 O3 nanowires. It
can be observed, that the phase obtained is the desired cubic system with Ia3 space
group (the same space group that the (Er,Yb):Lu2 O3 nanocrystals studied in the chap-
ter 3). The broadening of the peaks is attributed to the fact that the particles are small
because of the relatively small number of diffraction planes (dhkl ) that participate in
the diffraction in each nanocrystal.
87
F IGURE 4.11. X-Ray diffraction of (Er,Yb):Lu2 O3 nanowires grown on an alumina template.
4.3.3 Visualization of (Er,Yb):Lu2 O3 nanowires by electron micro-

scope
Electronic microscopy was used to observe the (Er,Yb):Lu2 O3 nanowires. In ESEM

studies (figure 4.12) it is possible to observe the formation of nanowires, which tend
to aggregate. The two pictures at the top show an aerial view of the (Er,Yb):Lu2 O3
nanowires, which tend to form aggregates with one another. This could be attributed
to a mechanism of sintering due to the calcination temperature. The photos of the bot-
tom are a lateral view, which differentiates the alumina template from the nanowires,
which tend to aggregate.
F IGURE 4.12. ESEM photographs of (Er,Yb):Lu2 O3 nanowires grown on an alumina template.
88
The theory of the sintering process is supported by the TEM images (figure 4.13),
which show compact nanowires formed by the sintering of different nanocrystals.
Therefore, the (Er,Yb):Lu2 O3 nanowires are polycrystalline.
F IGURE 4.13. ESEM images of a fragment of (Er,Yb):Lu2 O3 nanowires grown on an alumina

template.
89
Chapter 5
Spectroscopic and Optical
Characterizations
5.1 Spectroscopic properties of Yb3+ and Er3+ in KRE(WO4 )2 nanocrystals
5.1.1 Optical absorption
5.1.2 Optical emission
5.1.3 Lifetime measurements
5.2 Spectroscopic properties of Yb3+ and Eu3+ in KRE(WO4 )2 nanocrystals
5.2.3. Lifetime measurements
5.3 Spectroscopic properties of Yb3+ in RE2 O3 nanocrystals
5.3.3 Influence of the Yb3+ doping concentration in Sc2 O3 nanocrystals in the lifetimes mea-
surements
5.4 Spectroscopic properties of Ho3+ in Lu2 O3 nanocrystals
5.5 Piezo-optical measurements of oxide film nanocomposites
5.6 Photoinduced second harmonic generation of KTiOPO4 nanocomposites
Or optical applications, it is essential to fully characterize the host and the active
F ions. In this chapter, we summarize the experimental results about the effects
of doping on different host materials. Detailed spectroscopic and optical studies are
needed to accurately determine the energy level schemes of the lanthanide ions. The
spectroscopic and optical experiments were performed at the laboratories of the re-
search group Fı́sica i Cristal·lografia de Materials i Nanomaterials (FiCMA-FiCNA),
at the Instituto de Ciencia de Materiales of Madrid, at the Institute of Low Tempe-
rature and Structure Research of Wroclaw (Poland) and at the Institute of Physics of
Czestochowa (Poland).
91
CHAPTER 5. SPECTROSCOPIC AND OPTICAL CHARACTERIZATIONS M. Galceran Mestres
5.1 Spectroscopic properties of Yb3+ and Er3+ in KRE(WO4 )2

nanocrystals
The advantages of using ytterbium rather than neodymium as the active ion for the
laser operation in the 1 µm range have been extensively discussed in section 1.3.3 and
are largely the result of the simple energy level scheme of ytterbium, which consists
up of only two manifolds: the ground state 2 F7/2 and the excited state 2 F5/2 . On the
other hand, erbium has a rich energy level structure and it is used to obtain laser
radiation at several wavelengths. All these spectroscopic studies were reported in
Paper IV.

Ytterbium and erbium ions are located in a single site C 2 and are surrounded by eight
oxygen atoms to form a distorted square antiprism in the KYbW or Er:KYbW struc-
tures [50]. Figure 8, Paper IV depicts the optical absorption of KYbW nanocrystals
measured at room temperature and has been compared with the bulk single crystal
averaged among the three main polarizations (E //N g , E //N m and E //N p ). We ob-
served that the relation between the intensity peaks in the nanocrystals spectrum is
comparable to the average three polarization of the KYbW bulk single crystal. This is
logical because there is a non-preferential orientation of the nanocrystals.
F IGURE 5.1. Optical absorption and emission of Yb3+ in KYbW nanocrystals at low tempera-
ture.
Working at low temperature enabled that the electronic population to be at the

lowest sublevel of the ground energy level; therefore most of the energy was localized
in only transition and is better to study all the excited energy levels for each active
ion. For this reason, optical absorption of ytterbium (figure 5.1) and erbium (figure
10, Paper IV ) was performed at low temperature in order to determine the energy
values of the Stark sublevels.
93
Figure 5.1 shows the optical absorption of Yb3+ , and the transition bands can be
seen to be associated with the 2 F7/2 (0) → 2 F5/2 (n’) (n = 0’, 1’, 2’) electronic transitions.
In the case of Er3+ (figure 10, Paper IV ), the optical absorption at low temperature
was performed in the range 376-1500 nm (6400-26600 cm−1 ). As expected, the hyper-
sensitive transitions, are 4 I15/2 → 2 H11/2 , 4 I15/2 → 4 G11/2 , which show larger oscil-
lator strengths. The extra peaks observed were attributed to the transitions from a
thermal population in the first excited sublevels of the ground state 4 I15/2 multiplet.
The splitting of all energy levels for erbium and ytterbium was determined in
accordance with the Kramers levels (2J+1)/2 (see table 5.1). The values of the energy
levels in comparison with the Er:KYbW bulk single crystal are shown in table 2, Paper
IV, and no significant differences are observed [257].
TABLE 5.1. Energies of the Stark sublevels of Er3+ and Yb3+ in Er:KYbW nanocrystals
Active ion 2S+1 L
J Energy (cm−1 )
4I 0, 25, 104, 138, 241, 1 peak missing, 303
15/2
4I 6515, 6544, 6568, 6568, 6602, 6669, 6720, 6735
13/2
4I Not observed
9/2
4F 15179, 15204, 15281, 15331, 15366
9/2
4S 18310, 18377
3/2
Er3+ 2H
11/2 19035, 19056, 19129, 19170, 19194, 19219
4F 20432, 20472, 20497, 20575
7/2
4F 22107, 22138, 22177
5/2
4F 22388, 22452
3/2
2H 24485, 24524, 24543, 24571, 1 peak missing
9/2
4G 26205, 26218, 26325, 26388, 26437, 26459
11/2
2F 0, 152, 410, 561
7/2
Yb3+ 2F
5/2 10186, 10493, 10714

Optical emission was performed by exciting Yb3+ at 933 nm using a Ti:Sapphire con-
tinuous laser. The low temperature spectrum enabled the emission emission channel
and the Stark sublevels of the ground state to be determined. For trivalent ytterbium
(figure 5.1), the maximum appears at 10186 cm−1 , which corresponds to 2 F5/2 (0’)
→ 2 F7/2 (0) transition, and determines the energy of the 2 F5/2 (0’) sublevel. The other
peaks are associated with one transition from the lowest excited sublevel, 2 F5/2 (0’)
and with the ground state sublevels 2 F7/2 (3’), 2 F7/2 (2’), 2 F7/2 (1’) and the energy of
the Stark sublevels of the ground state has been determined (see table 5.1).
Trivalent erbium has a rich energy level structure that can be used to obtain sev-
eral laser radiations: for example, an interesting infrared emission located around 1.5
µm (4 I13/2 → 4 I15/2 transition). Because of the low absorption cross section of the
4I 3+ 3+ was used as a sensitizer ion. Yb3+ has a high absorption cross
11/2 (Er ), the Yb
section and its energy level 2 F5/2 can overlap with 4 I11/2 (Er3+ ). Therefore, a selec-
94
tive Yb3+ excitation at 933 nm, the electrons of 2 F5/2 (Yb3+ ) decay radiatively to the
ground state or transfer part of their energy to the 4 I11/2 (Er3+ ). Consequently, the
radiative decay to the ground state (4 I15/2 ) takes place late in the process. The energy
transfer scheme for this mechanism is shown in figure 5.2.
F IGURE 5.2. Energy level diagram and energy transfer from Yb3+ to Er3+ for the generation of
the emissions.
Figure 5.3 shows the optical emission of 4 I13/2 → 4 I15/2 transition (Er3+ ) at low
temperature. The values of the energy levels attributed to this 4 I13/2 → 4 I15/2 transi-
tion are shown in table 5.1. On the other hand, figure 5.4 shows the erbium emissions
at low temperature in the ultraviolet and visible regions (357-830 nm) under exci-
tation in the 2 F5/2 (Yb3+ ). The erbium emissions were generated by energy transfer
from 2 F5/2 (Yb3+ ) to 4 I11/2 (Er3+ ) (see figure 5.2).
F IGURE 5.3. Optical emission of Er3+ (4 I13/2 → 4 I15/2 transition) in Er:KYbW nanocrystals at
low temperature.
The up-conversion mechanism in the green emission (4 S3/2 → 4 I15/2 ) was studied
to measure the exciting power intensity (the green output intensity Igreen and I IR n
where n is the number of infrared photons). The relationship is described as Igreen ∝
I IR n and from a fit of the curve lnIgreen as a function of lnI IR , we obtained a slope, n,
95
around 1.5 that indicates two photons are involved in the up-conversion process (see
inset figure 5.4).
F IGURE 5.4. Optical emission of Er3+ in Er:KYbW nanocrystals in the ultraviolet and visible
range at low temperature.

The kinetic decays were measured for ytterbium (2 F5/2 → 2 F7/2 at 1025 nm) and
erbium (4 I13/2 → 4 I15/2 at 1533 nm). The high concentration of active ions meant
that reabsorption was also high. This was minimized by dispersing of KYbW and
Er:KYbW nanocrystals in ethylene glycol inside quartz cells.
The decays times were not fitted to a single exponential because of the resonance
energy transfer between Yb-Yb, Yb-Er and Er-Er ions. The Inokuti-Hiriyama model
describes this situation with the equation 2.16 [233]. Using this equation, the t/τ 0 +
ln[I(t)/I(0)] versus t3/s was plotted, and the linear behaviour was only obtained for s
= 6 in all cases.
For ytterbium ion, the sample was exiting at λ = 930 nm and the emission was
monitoring at λ = 1025 nm. Figures 5.5a and 5.5b show the Inokuti-Hiriyama repre-
sentations for Yb3+ ion in KYbW and Er:KYbW nanocrystals, respectively. The life-
time in KYbW nanocrystals was τ0 = 110 µs, which is shorter than the KYbW bulk
single crystal (τ0 = 270 µs) [244]. This decrease could be associated with non radia-
tive processes on their surface contaminants, adsorbed atmospheric CO2 and H2 O,
96
F IGURE 5.5. Representations of the Inokuti-Hiriyama model for fluorescence decay curves of
(a) Yb3+ transition in KYbW, (b) Yb3+ transition in Er:KYbW and (c) 4 I13/2 →
4I 3+
15/2 (Er ) transition in Er:KYbW.
or contaminants adsorbed during the combustion process [258]. For Er:KYbW nano-
crystals the linear behaviour was obtained by linear fit using the Yb properties of the
KYbW bulk single crystal (figure 5.5b). This shorter value is attributed to the fact that
the Yb-Er processes is more probable that the Yb-Yb process because of the critical
distance of Yb-Yb (KYbW) was 3.0 nm and from Yb to Yb and Er ions in Er:KYbW
nanocrystals was 4.9 nm. Figure 5.5c shows the Inokuti-Hiriyama representation for
the Er3+ ion for the 4 I13/2 → 4 I15/2 transition at 1533 nm after exciting resonantly at
1490 nm. The lifetime was τ0 = 1 ms which is the same order as the bulk single crystal.
5.2 Spectroscopic properties of Yb3+ and Eu3+ in KRE(WO4 )2

nanocrystals
Trivalent europium is a strong visible red emitter (5 D0 → 7 F0 ), which can be used as

a doping ion for applications in fluorescent lamps, colour lighting and optoelectronic
devices [124]. When Eu3+ is co-dopant with Yb3+ , the material presents interesting
features in the laser wavelengths of 1 micron (2 F5/2 → 2 F7/2 ). Spectroscopic studies of
europium-doped KYbW will extend what is known about this material as a solid laser
host, and also provide a new alternative material as a red emitter. Paper V describes
the optical characterization of this pair ions.
97

As shown in the above, the Yb3+ and Eu3+ ions are located in the C 2 symmetry site
and are surrounded by eight oxygen atoms to form a distorted square antiprism [50].
The optical absorption of Yb3+ in KYbW (figure 7, Paper V ) shows the same spectrum
as the Yb3+ in Eu:KYbW nanocrystals (figure 5.1), which we have discussed at length
in the section above.
The optical absorption of Eu3+ was performed in the infrared range 915-2150 nm
(10925-4700 cm−1 ) and the visible range 400-650 nm (25000-15300 cm−1 ). Figure 8,
Paper V shows the optical absorption bands of Eu3+ , which correspond to the elec-
tronic transitions from 7 F0 (ground state) to several excited states.
The broadening of the peaks indicates not only random distortion of the site sym-
metry and the possible presence of defects in the crystalline structure due to the rapid
formation of the nanocrystals, but also the anisotropic dilatation of the lattice and the
reduction in the degree of structural ordering [259].

The optical emission of Eu:KYbW nanocrystals was measured at room and low tem-
perature by excitation of the trivalent europium at 532 nm using the second harmonic
of the pulsed Nd:YAG laser. Despite the high europium concentration (3.16×1020
cm−3 ), there is no important quenching (figure 5.6). The emission bands of europium
are associated with the 5 D0 → 7 F J (J=0-4) transitions and the predominant emis-
sion band is located around 617 nm (5 D0 → 7 F2 red emission, hypersensitive electric
dipole transition), in which the final level is thermally populated at room tempera-
ture. The second transition, 5 D0 → 7 F1 is a magnetic-dipole transition.
F IGURE 5.6. Optical emission of Eu3+ in KYbW nanocrystals at room and low temperature in
the visible range.
The band related to the 5 D0 → 7 F0 transition must be forbidden by the Judd-

Ofelt theory [260,261]. However, Nieupoort and Blasse [262,263] reported that for the
98
low site symmetries such as Cs , Cn , or Cnv , the above transition is partially allowed
by group theory and is often observed. It is a pure electric dipole transiton and is
very interesting because of the strong dependence of its intensity on the nature of the
crystalline matrix.
The asymmetry parameter, R, defined as the ratio between the intensities of the
5 D → 7 F and 5 D → 7 F (eq. 5.1), is a good measure for the symmetry site of Eu3+
0 2 0 1
and can be used as an indicator for the relative magnitude of hypersensitivity.
I (5 D0 →7 F2 )
R= (5.1)
I (5 D0 →7 F1 )
A high R ratio indicates an enhancement of the electric dipole transition and an
increase in the crystal field strength. This fact could be related to an increase in the co-
valence or the distortion of the bonds surrounding the active ion. Pujol et al. reported
the study of the YbO8 environment in KYbW bulk single crystals [264]. On the other
hand, Zych et al. reported that the broadening of the emission lines may be related to
interaction between different Eu emitting centers [259].

The luminescence lifetimes of the europium 5 D0 → 7 F2 (613 nm) in Eu:KYbW na-
nocrystals were measured at room and low temperature after excitation at 532 nm
(figure 5.7). Despite the high europium concentration (3.16×1020 cm−3 ), no reabsorp-
tion was observed. In the both cases, the decays curves were fitted as single exponen-
tial with a lifetime of 227 and 258 µs at room and low-temperature, respectively. The
slight increase in the lifetime at low temperature is related to the reduction in energy
transfer mechanism between europium ions. These values are the same order (215
µs) as those reported for Eu-doped at 20 % at. in KYbW bulk single crystal [265].
On the other hand, Pazik et al. re-
ported lifetime measurements in the
range of 90-1600 µs for 2 % at. Eu:KGdW
nanocrystals with a particle size of
33-53 nm [266]. We observed a shorter
lifetime measurements in our smaller
nanocrystals. This fact may be due to
two reasons: (i) energy transfer phe-
nomena caused by the high europium
concentration and (ii) size effects of
the nanocrystals. The high europium
concentration leads to a minimum Eu-
Eu distance (0.42 nm using the ap-
proximation r=(4πN/3)−1/3 ). Conse- F IGURE 5.7. Decay curves for Eu3+ 5 D0 → 7 F2
quently, the probability that the ex- transition in Eu:KYbW nanocrystals
cited electron will encounter a defect at room- and low-temperature.
state will increase. This defect state will act as a quenching center and allow the elec-
tron to deexcite through a nonradiative process [259].
99
5.3 Spectroscopic properties of Yb3+ in RE2 O3 nanocrys-

tals
Spectroscopic studies of trivalent ytterbium-doped sesquioxides (Lu2 O3 and Sc2 O3 )
were reported in Papers VI and VII. some of the important features of ytterbium as
an active ion in the 1 µm range have been discussed in the introduction. Also, in the
chapter 1, RE2 O3 materials have two cation sites for RE3+ , one with C 2 symmetry
and another with C 3i . There is no preferential occupation of the RE3+ doping ions
in these two sites [71]. The electric dipole transitions associated with the C 3i site are
forbidden by the selection rules because of its inversion center. Therefore, the C 3i
transitions will be weaker than the C 2 transitions. On the other hand, the studies of
the fluorescence spectra of the C 3i site can only be studied by site-selective excitation
at low temperature [267]. In this thesis, we will study the bands associated with the
C 2 transitions.

Spectroscopic studies at room temperature are necessary for the evaluation of the
laser parameters of the crystals. Figure 5.8 shows the optical absorption and emission
at room temperature of the Yb3+ in RE2 O3 nanocrystals.
F IGURE 5.8. Optical absorption and optical emission of Yb:Lu2 O3 and Yb:Sc2 O3 nanocrystals
at room temperature.
The optical absorption spectra show three main lines associated with 2 F7/2 →
2F transition; a small one around 900 nm, a broader one around 940 nm and the
5/2
strongest one for the 0-line around 975 nm. Sc2 O3 has smaller lattice parameters than
Lu2 O3 and, as a result, the RE-O distance is smaller and the crystal field stronger. This
fact can be seen in the splitting of the main absorption line.
The optical absorption was performed al low temperature for Yb:RE2 O3 to de-
termine the Stark sublevels, since the electronic population is at the lowest sublevel
of the ground state (2 F7/2 ). Figure 5.9a shows the 2 F7/2 (0) → 2 F5/2 (n´), n = 0 - 2,
electronic transitions for Yb3+ in Lu2 O3 and Sc2 O3 nanocrystals. Figure 10a (Paper
100
F IGURE 5.9. (a) Optical absorption and (b) optical emission of Yb3+ in Lu2 O3 and Sc2 O3 nano-
crystals at low temperature.
VI ) and figure 7 (Paper VII ) depict the comparison between the optical absorption
at room and low temperature for Yb:Lu2 O3 and Yb:Sc2 O3 , respectively. The absorp-
tion bands at low temperature are slightly sharper than at room temperature in both
graphs and are also broader than the bulk counterpart, which may be due to oxygen
vacancies or surface disorder [268]. The splitting of all the energy excited levels of
Yb3+ (2 F5/2 ) was determined using Kramers levels (2J+1)/2, and is shown in table
5.2.
TABLE 5.2. Energy levels of trivalent ytterbium in Yb:Lu2 O3 and Yb:Sc2 O3 nanocrystals
Energy (cm−1 )
Yb:Lu2 O3 Yb:Sc2 O3
Nanocrystals Bulk single Nanocrystals Bulk single
crystal [47] crystal [88]
(2’) 11074 11073 11151 11195
2F (1’) 10539 10666 10629 10630
5/2
(0’) 10246 10244 10256 10260
(3) 947 903 1090 1116
2F (2) 556 514 646 650
7/2
(1) — 427 586 594
(0) 0 0 0 0
101

The optical emission was carried out by pumping with a Ti:Sapphire continuous la-
ser around 900 nm. The optical emissions at room and low temperature for Yb:Lu2 O3
and Yb:Sc2 O3 are shown in figure 10b (Paper VI ) and figure 8 (Paper VII ), respec-
tively. The room temperature emission was slightly affected by the reabsorption of
ytterbium ions (figure 8) and by some thermal quenching induced by energy transfer
from active centers to default levels [115].
The optical emission at low temperature can be found in figure 5.9b. The four
main peaks correspond to the 2 F5/2 (0’) → 2 F7/2 (n), n = 1 - 3 transitions. The values
of the Stark sublevels of the ground state of Yb3+ for each material are shown in table
5.2.
5.3.3 Influence of the Yb3+ doping concentration in Sc2 O3 nano-

crystals on the lifetime measurements
The radiative lifetime of the electronic transitions of an ion embedded in a medium
is described by the formula:
1 1 λ20
= τrad ∼ 2 (5.2)
ΣAi f f ( ED )
1 2
3 (n + 2) n
where f( ED ) is the oscillator strength for the electric dipole transition, λ0 is the
wavelength in vacuum and n is the refractive index. The nanoparticles occupy only a
small fraction of the total volume, so it is necessary to introduce an effective refraction
index for the medium (ne f f ), which replace n in the equation 6.1.
ne f f ( x ) = xn p + (1 − x )nm (5.3)
where n p and nm are the refractive indices of the nanoparticles and of the sur-
rounding medium, respectively, and x is the fraction of space filled with nanoparti-
cles [25]. We used a medium with an nm =n p because it is very difficult to experimen-
tally control x and it is also necessary to fully overcome light trapping by multiple
internal reflections in the particle. This latter effect combined with the fluorescence
reabsorption helps to lengthen the measured lifetime.
We studied the influence of the dispersed medium on the measured 2 F5/2 Yb3+
lifetime. For this reason, we dispersed 0.5 % at. Yb:Sc2 O3 nanocrystals in EG (n = 1.52)
and in poly(chloro-trifluoro-ethylene) (PCE) (n = 1.94) to minimize the fluorescence
reabsorption. On the other hand, the refractive index of the Sc2 O3 bulk single crystal
is 1.965 (at λ = 1050 nm). Figure 9 (Paper VII ) shows the Yb3+ fluorescence decay at
λ EMI = 990 nm after excitation at λ EXC = 940 nm in EG and PCE dispersive media
measured at room temperature. We observed that the fluorescence decays for 0.5 %
at. Yb:Sc2 O3 nanocrystals did not depend on the surrounding medium. Therefore, for
our studies, we concluded that the medium does not modify the radiative lifetime. In
further experiments, we used EG to match particle dispersion with refractive indices.
102
Ytterbium-doped bulk single crystals are often described as being free of con-
centration fluorescence quenching. For example, the lifetime obtained for Yb3 Al5 O12
(YbAG) crystals (τ = 980 µs) was found to be similar to < 15 % at. Yb:YAG (τ = 1050
µs) [47]. It is known that in the most common case of ytterbium-doped bulk single
crystals, the lifetime decreases as the Yb concentration increases. In the case of Yb-
doped Lu2 O3 , the lifetime obtained in 0.46 % at. Yb:Lu2 O3 was τ = 820 µs which
decreased to τ = 13 ns in 90 % at. Yb:Lu2 O3 [47]. These reductions can be attributed
to the presence of uncontrolled impurities or defects in the material. Yb2 O3 is with-
out doubt a source of contamination of other lanthanides, unless very high purity
(99.999 %) products are used. Defects, surfaces and atmospheric pollution are com-
monly found in nanopowders leading to inhomogeneous broadening of the optical
transitions (see figure 5.9).
We studied the effect of the
Yb3+ concentration on lifetime mea-
surements. Figure 10 (Paper VII )
compares the decay times for sev-
eral ytterbium dopings, and it was
seen that the decays were faster
as the Yb3+ concentration increased.
This result rules out the possibil-
ity that fluorescence reabsorption
increases the lifetime in our mea-
surements. For the 0.05 % at. Yb3+
(figure 10a, Paper VII ), the decay
curve was not a pure single ex- F IGURE 5.10. Yb+3 fluorescence lifetime of Yb:Sc2 O3
ponential. We observed two dif- nanocrystals immersed in EG (points)
ferent decay times, the first was versus Yb concentration dependence at
room temperature.
the faster (τ = 680 µs) than the
3 +
second (τ = 810 µs). For larger Yb concentrations, very fast decays were observed
with lifetimes ranging from τ = 16 µs in 10 % at. Yb:Sc2 O3 to τ = 1.3 µs for 50 % at.
Yb:Sc2 O3 .
Figure 5.10 summarizes the evolution of the 2 F5/2 Yb3+ lifetime as a function of
the Yb3+ concentration. The largest lifetime obtained for 0.05 % at. Yb:Sc2 O3 , τ = 810
µs, is very similar to that obtained in Yb-doped Sc2 O3 single crystals [269]. At low
Yb concentrations, the energy transfer between Yb-Yb ions or from Yb to unknown
impurities can be ignored because of the long distances involved. Therefore, the first
fast component must be related to the nanoscopic character of the particles, perhaps
due to Yb3+ ions on the surface close to adsorbed atmospheric radicals.
5.4 Spectroscopic properties of Ho3+ in Lu2 O3 nanocrys-

tals
As mentioned above (section 5.3), Lu2 O3 as a host material presents two different
symmetry sites (C 2 and C 3i ) and there is no preferential occupation of the RE3+ dop-
ing ions in these two sites [71]. These studies on the nanocrystals are the previous
103
results in order to study the nanoceramics, which will be discussed in the next chap-
ter. Some of these results are reported and studied in depth Paper VIII.

The optical absorption of the Ho:Lu2 O3 nanocrystals was measured at room and low
temperature in the 350-2000 nm range (28500-5000 cm−1 ) range in order to determine
the transition bands from the ground state (5 I8 ) to the excited states (figure 5.11). The
spectroscopic selection rules do not allow electric dipole transitions for ions at the C 3i
site because of its inversion center. The holmium transitions associated with C 3i sites
are therefore weaker than the C 2 transitions. Because of their the high multiplicity,
each manifolds is split into a large number of quite closely spaced Stark components
and this makes it difficult to determine the energy levels of trivalent holmium. The
energy level values of Ho:Lu2 O3 bulk single crystals was reported by Peters [47].
F IGURE 5.11. Optical absorption of Ho:Lu2 O3 nanocrystals at low temperature.

The room and low-temperature luminescence spectra of Ho:Lu2 O3 nanocrystals re-
corded after pumping at 355 nm are shown in figure 5.12. The spectra exhibit three
emission bands: green emission (5 F4 + 5 S2 ) → 5 I8 (532-564 nm), red emission 5 F5 → 5 I8
(650-700 nm) and NIR transition (5 F4 + 5 S2 ) → 5 I7 (745-780 nm). The transition bands
in the nanocrystals have no significant shifting of peaks but the intensity is reduced
by about one order of magnitude respect to the bulk single crystal [270]. This behav-
ior could be attributed to an increase in multiphonon relaxation (yields vibrational
quanta of higher wavenumbers), due to adsorbed CO2 or H2 O on the surface [271].
104
F IGURE 5.12. Optical emission of Ho:Lu2 O3 nanocrystals at room and low temperature.
The room and low-temperature decay curves of the (5 F4 + 5 S2 ) → 5 I8 transition for

nanocrystals were measured at an excitation wavelength of 355 nm. The decay curves
were fitted by a double-exponential attributed to the distribution of the dopants ions
within the nanocrystals. This distribution leads to a nonexponetial decay: one portion
of ions is located close to the surface and another inside the nanocrystals because of
the small particle size. For this reason, the curves of the nanocrystals can be fitted a
double-exponential model because two time constants can be expected for each type
of ions: close to the surface or inside the nanocrystal (figure 12, Paper VIII ).
The value of the first lifetime is lower than the second lifetime and they are both
faster than in the bulk single crystal. For example, Y1.98 Ho0.02 O3 bulk single crys-
tal was found at 135 µs which is higher than in the similarly doped nanocrystals
Lu1.985 Ho0.015 O3 (table 6.2). The lifetime of one transition is given by the radiative
and nonradiative transition probabilities (energy transfer between ions and multi-
phonon relaxation) [272]. The high energy phonons present in the nanocrystals pro-
duce a rapid relaxation in the nonradiative transitions from (5 F4 + 5 S2 ) level to 5 F5
level and consequently lifetimes are shorter.
TABLE 5.3. Decay times obtained for Lu1.985 Ho0.015 O3 nanocrystals at room and low-
temperature for (5 F4 + 5 S2 ) → 5 I8 transition after excitation an 355 nm
RT LT
First decay lifetime (µs) 1.4 1.0

Second decay lifetime (µs) 34.7 37.7
105
5.5 Piezo-optical measurements of oxide film nanocom-

posites
Paper III discusses the piezo-optical (PO) measurements of oxide nanocrystals (in the
range of 80-120 nm) embedded in PMMA nanocomposites, which the synthesis and
characterization of which were discussed in the previous chapter . The experiments
were conducted by simultaneously applying a DC 50 Hz pulsed electric field within
the 1-10 kV cm−1 and the polarized UV light with wavelength 371 nm, 10 ns laser
pulses and 1 MW power. As a reference, we used quartz bulk single crystal, which
the piezo-optical coefficients of which are known.
TABLE 5.4. Principal parameters of the oxide film nanocomposites

NC Wt. % NC Film thickness % Transmission PO (before UV) PO (after UV)
(µm) (λ=633 nm) (10−14 m2 N−1 ) (10−14 m2 N−1 )
Er:KYbW 11.4 750 72.6 2.42 6.98
Eu:KYbW 11.8 770 73.5 3.5 3.01
KYbW 10.5 790 72 0.92 1.36
KGdW 11.8 740 75 1.15 1.22
KTP 11.7 760 73.2 0.42 0.56
NC = Nanocrystals
Figure 7 (Paper III ) shows the evaluation of the piezo-optical coefficients as a func-
tion of nanocrystals content. Values are maximum for nanocomposites with 10-12 %
of nanocrystals. The upper limit is determined by the initial nanocrystalline aggre-
gation and leads to substantial suppression of the optical susceptibilities (including
non-linear optical susceptibilities). On the other hand, table 5.4 summarizes the prin-
cipal experimental parameters of the film nanocomposites studied. The changes in
the light transparency due to the scattering were attributed to the fact that the nano-
crystals and PMMA matrix had different refractive indices.
F IGURE 5.13. Dependence of the diagonal piezo-optical coefficient versus the treatment time
by the polarized UV light at 0.4 GW cm−2 and DC-field directed along x at 300
K.
106
Figure 5.13 shows the piezo-optical coefficients of oxide nanocrystals incorpo-

rated into PMMA matrix. Rare earths ions have different piezo-optical coefficients
because their ionic radii are different, which leads to differences in polarizability. The
polarizability of rare earth ions, then, depends on their piezo-optical coefficients, and
this dependence, in turn, will depend on the influence of the external DC-field and
polarized light. The DC-electric field aligns the state dipole moments of the nano-
sheets and the electronic states of the PMMA, which enhances the non-linear optical
susceptibilities. The UV-polarized light also enhances the corresponding susceptibil-
ities caused by the additional polarization of the trapping nanosheets levels, which
separate the nanocrystals and the surrounding PMMA matrix.
To sum up, the maximum piezo-optical coefficients were maximum for Er:KYbW
and Eu:KYbW nanocomposites at 7.1·10−14 and 3.2·10−14 m2 N−1 , respectively.
5.6 Photoinduced second harmonic generation of KTiOPO4

nanocomposites
The enhancement of the nonlinear optical phenomena in nanocomposites has been
described above in section 1.1.3. Paper IX reports the study of the photoinduced sec-
ond harmonic generation in KTP nanocomposites. The synthesis of KTP nanocrystals
embedded in a PMMA matrix has been discussed in the chapter 4.
F IGURE 5.14. (a) Dependence of the second-order optical susceptibility of KTP nanocom-
posites with DC-electric field at different temperatures at 1064 nm generated
by Nd:YAG laser. (b) Second-order susceptibilities stimulated by 371 nm UV-
stimulated polarized light of KTP nanocomposites at 391 nm.
The dependence of the second order susceptibilities (χ2 ) at a laser wavelength

of 1064 nm and a pulse duration 10 ns at several temperatures are shown in figure
5.14a. The optimal conditions for the generation of the frequency doubled light were
observed at 391 K (near the glass transition temperature of PMMA), which indicates
that the local ordering of the PMMA has a large influence on the photoinduced non-
centrosymmetry. The enhancement of de f f was observed at an electric field strength
107
of 2.8 kVcm−1 . Additional treatment with polarized UV light provided increased the
second-order susceptibility to 3.23 pm V−1 (figure 5.14b), which is the same order
as the de f f measured in KTP bulk single crystal by Vanherzeele and Bierlein [162]
and also agreed with the measurements by Eckardt and Byer [273]. For bulk single
crystals, the second-order susceptibility is a fixed value and can only be measured
in large crystalline. For our measurements, however, the same nanocomposites were
used many times and the optical susceptibility was varied in the desired direction us-
ing the appropriate dc- and UV-induced fields. Another research group has recently
published the second-order optical susceptibility of KTP nanocomposites prepared
by mechanical crushing with a value around 2.2 pm V−1 , substantially less than that
obtained in our study [274].
Figure 5.15 shows the quick re-
laxation of the second-order sus-
ceptibility after switching off the
external electric fields and the UV
laser light. For example, after 1500
minutes, a a decrease of up to 0.3
pmV−1 is observed. The influence
of the UV-laser light is crucial to
the enhancement of the output sus-
ceptibility but the most important
factor in increasing the output sus-
ceptibility is the trapping levels at
the interfaces between a nanocrys-
F IGURE 5.15. Relaxation of the second-order suscep- tal and the polymer matrix. This
tibility at 391 K after switching off the
effect originates from the thin nano-
ce-electric field and the UV treatment.
sheets that separate the crystallites
and the polymers and has been shown in previous investigations [275, 276]. These
nanosheets (with a thickness of several nanometers) possess substantially large dipole
moments that determine their large hyperpolarizabilities.
108
Chapter 6
Fabrication and characterization
of Ho:Lu2O3 nanoceramics
6.1 Fabrication of Ho:Lu2 O3 laser nanoceramics
6.2 Structural characterization of Ho:Lu2 O3 nanoceramics
6.3 Raman scattering of Ho:Lu2 O3 nanoceramics
6.4 Morphology and particle size of Ho:Lu2 O3 nanoceramics
6.5 Physical characterization of Ho:Lu2 O3 nanoceramics
6.6 Spectroscopic properties of Ho3+ in Lu2 O3 nanoceramics
H is chapter describes the synthesis of Lu2− x Hox O3 nanoceramics by the high

T pressure low temperature method. It is necessary to characterize the structure
and the morphology to determine how they are affected by the sintering method.
Detailed spectroscopic studies of lanthanide ions in the nanoceramics will be dis-
cussed. The experimental work was performed at the laboratories of the Fı́sica i
Cristal·lografia de Materials i Nanomaterials (FiCMA-FiCNA) and the Institute of
Low Temperature and Structure Research of Wroclaw.
109
CHAPTER 6. FABRICATION AND CHARACTERIZATION OF HO:LU2 O3 NANOCERAMICS M. Galceran Mestres
6.1 Fabrication of Ho:Lu2 O3 laser nanoceramics
Laser ceramics were sintered by means of the high pressure low temperature (HPLT)
method at the Department of Spectroscopy of Excited States at the Institute of Low
Temperature and Structure Research, which is located at the Polish Academy of Sci-
ences in Wroclaw. The fabrication process can be divided into three steps (6.1):
Step 1 Synthesis of the nanocrystals: Ho:Lu2 O3 nanocrystals were synthesized

using the modified Pechini method (see section 3.1).
Step 2 Preparation of the green body: The green body was obtained from Ho:Lu2 O3
nanocrystals; the shape was modulated by cold pressing in a cylindrical cell
under pressure (5 MPa) and vacuum. The green body had a diameter of 5 mm
and a height of approximately 2 mm.
Step 3 Sintering: Ho:Lu2 O3 nanoceramics were prepared under a pressure of 8
GPa for 1 hour. Then, the temperature was increased until 723 K in 30 seconds
and this hot-pressure was applied for 1 minute; then the temperature was
decreased at room temperature in 30 seconds Finally, the sample is polished
with SiC to remove the impurities, such as graphite or boron nitride.
F IGURE 6.1. Schematic of experimental method for sintering Ho:Lu2 O3 nanoceramics.
A Logitech PM5 polisher with an oscillating arm and an Alumina abrasive pow-
der was used to polish the samples. These features allow the samples to be rotated
and pressurized according with their hardness (figure 6.2).
111
F IGURE 6.2. Polished nanoceramics (a) 0.5 % at. Ho and (b) 10 % at. Ho.
6.2 Structural characterization of Ho:Lu2 O3 nanoceram-

ics
Micro X-ray diffraction (µXRD) was used to structurally characterize the Ho:Lu2 O3
nanoceramics (figure 6.3). However, the high pressure applied during the sintering
process, Ho:Lu2 O3 nanoceramics maintain the same crystalline phase with cubic sys-
tem with the Ia3 space group as the Ho:Lu2 O3 nanocrystals studied in chapter 3.
F IGURE 6.3. X-Ray diffraction of the Lu2− x Hox O3 nanoceramics.
Table 6.1 summarizes the unit cell parameters of the Lu2− x Hox O3 nanoceramics,
which were refined with the same methodology as the nanocrystals; a slight increase
in the unit cell parameters respect to the Ho:Lu2 O3 nanocrystals was observed. This
slight increase in the unit cell parameters and the apparent decrease in the parti-
cle size could be attributed to the high pressure applied during the sintering pro-
cess, which leads an increase in the nanoparticle’s surface tension and prevents their
growth [91, 277].
112
TABLE 6.1. Unit cell parameters of Lu2− x Hox O3 nanoceramics

Nanoceramics Active Ion (%) a (Å) V (Å3 ) L (nm) F Reference
0.5 10.411(3) 1128.5(5) 8
Lu2− x Hox O3 1 10.419(3) 1131.0(6) 8.4 Paper VIII
10 10.422(2) 1131.9(5) 11.2
F Estimated by Scherrer equation
JCPDS 44-1268 (Ho2 O3 ) a = 10.6102 Å, and JCPDS 43-1021 (Lu2 O3 ) a = 10.39 Å
6.3 Raman scattering of Ho:Lu2 O3 nanoceramics
The Raman studies of RE2 O3 nanocrystals were widely discussed in section 3.3.4.
Taking into account the irreducible representation of the factor group and the selec-
tion rules, the Raman active modes that are predicted for the C -type structure RE2 O3
are 4Ag , 4Eg and 14Fg [248]. Now, we will discussed the Raman measurements of
the Ho:Lu2 O3 nanoceramics and which changes that were induced by the pressure.
Figure 6.4 shows the Raman spectrum of the Ho:Lu2 O3 nanoceramics and has been
compared with the spectrum from both the green pellet and the nanocrystals. No
significant differences were observed between the nanocrystals and the green pellet.
On the contrary, the high pressure that was applied during the sintering process pro-
duced broader and lower intensity bands. These facts are related to the increase in
the surface tension, to the reduced particle size and to the apparent decrease in the
degree of crystallinity. On the other hand, doped sesquioxides can present two new
Raman peaks around 520 and 650 cm−1 , which are associated with oxygen vacancies
that were created by doping [278].
F IGURE 6.4. Raman spectra of the Lu2− x Hox O3 nanocrystals, green pellet and nanoceramics.
113
As observed in XRD patterns, the pressure that was applied does not induce a
structural phase change. Wang et al. reported that the pressure to transform the C -
type structure into an A-type structure is up to 12.1 GPa [279].
6.4 Morphology and particle size of Ho:Lu2 O3 nanoce-

ramics
Figure 6.5a shows a confocal image of the Ho:Lu2 O3 nanoceramics surface. On the
other hand, an ESEM photograph of the Ho:Lu2 O3 nanoceramics polished surface is
shown in figure 6.5b. The sample consisted of nanocrystals or nanocrystal aggregates
that measured in the tens of nanometers. As mentioned in the chapter 2, the HPLT
method is expected to prevent grain growth. Figure 6.5c shows a fracture of the fully
dense nanoceramics, where the nanocrystal-boundary and aggregate-boundary are
clearly observed. These nanocrystals aggregates are formed by nanocrystals measur-
ing tens of nanometers. A schematic representation of the nanocrystals, aggregates
and packing aggregates (which are present in a ceramic materials) is shown in figure
6.5d.
F IGURE 6.5. (a) Confocal image,(b) ESEM image of the Ho:Lu2 O3 nanoceramics surface, (c)
ESEM image of the fracture surface of the Ho:Lu2 O3 nanoceramics and (d)
schematic illustration of the nanocrystals, an aggregate and the packing of ag-
gregates.
114
6.5 Physical characterization of the Ho:Lu2 O3 nanoce-

ramics
One of the most important parameters in ceramic materials is the degree of the trans-
parency, which is mainly affected by the residual pores, inclusions, secondary phases
and grain boundaries. These effects have been reported for Nd:YAG ceramics [280].
Figure 8, Paper VIII, shows the optical transmission of Ho:Lu2 O3 nanoceramics with
a thickness of 730 µm in the range of 0.2-2.2 µm. A maximum transparency observed
was observed around 60 % in the region of 1.9 µm.
The refractive index is another important physical parameter to study because
it will be later used to spectroscopically characterize the ceramic materials in more
detail. The refractive index of the nanoceramics was calculated using the total inter-
nal reflection angle law that couples the light from a prism (prism coupler Metricon
2010). The measure was recorded at room temperature by pumping at 632.8 nm; the
measured value was n = 1.9146, which is of the same order as the bulk single crystal,
n = 1.91 (λ =1050 nm) [47].
6.6 Spectroscopic properties of Ho3+ in Lu2 O3 nanoce-

ramics
The optical absorption of Ho:Lu2 O3 nanoceramics was measured at room tempera-
ture (figure 6.6). We studied two of the most important bands of trivalent holmium,
which are attributed to electronic transitions from 5 I8 → 5 I7 (1775-2175 nm) and 5 I8
→ 5 F4 +5 S2 (525-560 nm).
F IGURE 6.6. Absorption cross section of Ho3+ in Lu2 O3 nanoceramics at room temperature.
With holmium concetration of 2.2x1021 cm−3 , the highest measured value of the
absorption cross section was 0.52x10−20 cm2 (at 1963.6 nm). These values are similar
to other Ho3+ -doped bulk single crystals [281, 282]. For the 5 I8 → 5 F4 +5 S2 transition,
the value of the maximum cross section at 542.5 nm was 1.76x10−20 cm2 .
115

Figure 6.7 shows the luminescence spectra of the Ho:Lu2 O3 nanoceramics that were
excited at 355 nm. We observed a two characteristic bands that are attributed to the
5 F + 5 S → 5 I (532-564 nm) and 5 F + 5 S → 5 I (745-780 nm) transitions. These tran-
4 2 8 4 2 7
sitions are in agreement with the bulk single crystal and the nanocrystals measure-
ments that were studied in the above chapter and that were reported by Capobianco
et al. [270]. As expected, the broadening of the bands is related to strain and surface
tension from the high pressure applied during the sintering process.
F IGURE 6.7. Optical emission of the Ho:Lu2 O3 ceramics at room and low temperature.
The emission cross section of the 5 I7 → 5 I8 transitions in the 2 µm region was

calculated using the reciprocity method and the energy levels that were reported by
Peters [47,272]. Figure 6.8a shows the maximum emission cross section of 0.52x10−20
cm2 , which was located at 1936 nm; moreover, we also observed a broad band around
2020 nm. One the other hand, we calculated the dependence on the wavelength for
the gain cross section using different values for the Ho3+ population inversion (figure
6.8b). At lower inversion levels, the maximum optical gain was located around 2120
nm. As a remark, the large width of the gain optical band is suitable for tunable or
pulsed laser operation.

The decay curves of the 5 F4 + 5 S2 → 5 I8 transition in Ho:Lu2 O3 nanoceramics were
measured at room and low temperature after excitation at 355 nm (third harmonic of
the pulsed Nd:YAG). Decay curves were fitted by a double-exponential that could be
related to the presence of ions, which were located near to the surface and on other
inside the nanoceramics due to their small particle size. For this reason, we observed
two different lifetimes (see figure 12, Paper VIII ). The calculated lifetimes are summa-
116
F IGURE 6.8. (a) Absorption and emission cross section of the Ho:Lu2 O3 nanoceramics for the
5 I ↔ 5 I transition and (b) the gain cross section at different population inversion
7 8
rates in the 5 I7 → 5 I8 transition.
rized in table 6.2. We observed shorter luminescence lifetimes at room temperature

than low temperature; however, both lifetimes were faster than in the bulk single
crystal. The lifetime of one transition is given by the radiative and nonradiative tran-
sition probabilities (energy transfer between ions and multiphonon relaxation) [272].
Nanocrystals present phonons with a higher energy due to the residual components
of the synthesis. For this reason, there is an increased the probability for the non-
radiative transition 5 F4 + 5 S2 → 5 F5 because a lower order multiphonon process is
required, which results in rapid relaxation and a shorter lifetime for the 5 F4 + 5 S2
level.
TABLE 6.2. Decay times for the Lu1.985 Ho0.015 O3 nanoceramics at room and low-temperature
for the 5 F4 + 5 S2 → 5 I8 transition after an excitation of 355nm
RT LT
First decay lifetime (µs) 1.8 1.4

Second decay lifetime (µs) 34.7 46.0
The radiative lifetime value of the 5 I7 level in the Ho:Lu2 O3 nanoceramics was
determined from the spontaneous emission probability (Ai f ) using the relationship
that was proposed by Weber [283]:
gf 8πn2

1
Z
= Ai f = α(ν)dν (6.1)
τrad gi Nλ2
where g f and gi are the degeneracies of the final and initial states (17 and 15, re-
spectively), n is the refractive index, N is the holmium concentration and α(ν) is the
absorption coefficient. The calculated value is equal to 14.9 ms; this value is consid-
ered to be a long lifetime and indicates a consequent low laser threshold.
117
The main spectroscopic parameters for the two micron emission of trivalent holmium
have been tabulated in table 3, Paper VIII, and compared with different host laser ma-
terials.
118
Conclusions
He main results of this study from part of, on the one hand, the synthesis of the
T optical nanomaterials and on the other, the structural, optical and spectroscopic
characterizations of the active ions and host materials in the nanometer range.
The most important results from this work are the successful synthesis of the mon-
oclinic with with C 2/c space group KYb(WO4 )2 , Er:KYb(WO4 )2 and Eu:KYb(WO4 )2 ,
the cubic with Ia3 space group Yb:Lu2 O3 , Yb:Sc2 O3 and Ho:Lu2 O3 , and the orthorhom-
bic with Pna21 space group KTiOPO4 nanocrystals using the modified Pechini method.
In order to obtain a small size particle and good sample homogeneity, thee experi-
mental variables that have been optimized were molar ratio, molar ratio, calcination
temperature and calcination time.
The particle size and its dispersion were estimated for each type of nanocrystals
using Scherrer’s equation and electronic microscopy. Good homogeneity and small
particle predominated but we also observed aggregates leading to an increase in the
particle size dispersion. As a remark, higher particle size has been seen for KREW and
KTP nanocrystals than in sesquioxides, this fact could be related to the more complex
compound.
Raman spectroscopy studies in nanocrystals showed broad peaks and slight red
or blue shift with respect to bulk single crystals.
The spectroscopic studies on the rare earth ions (Yb3+ , Er3+ , Eu3+ and Ho3+ ) in
these oxide nanocrystals reveal that their optical absorption and luminescence mea-
surements are closely those of bulk single crystals. Mainly, broadening of the peaks
have been observed.
The fluorescent decay times are often shorter than in bulk crystals, and in some
cases, two decays times were observed due to the presence of ions located near to the
surface and other inside the nanocrystals.
Piezo-optical (elasto-optic) properties were studied for the oxide nanocrystals in-
corporated into poly(methyl methacrylate) (PMMA) in order to evaluate the acoustic
parameters. Moreover, the incorporation of rare earths implies an additional contri-
bution, which possess large polarizabilities and the occurrence of porous-like space
regions.
The photoinduced second harmonic generation was investigated for KTP nano-
composites and the value achieved is similar to that reported for KTP bulk single
crystals.
In the last part of this work, Ho:Lu2 O3 nanoceramics were obtained by the high
pressure low temperature method and using the Ho:Lu2 O3 nanocrystals synthesized
by the modified Pechini method. The structural characterization reveals that, ho-
119
wever the high pressure applied, this does not induce a structural phase change.
The maximum transparency was around 60 % in the range of 1.9 µm for trivalent
holmium. The spectroscopical and optical results suggest that the Ho:Lu2 O3 nanoce-
ramics could be used as aa solid state laser material for 2 microns emission with good
performance
References
[1] Rao, C. N. R.; Cheetham, A. K. Journal of Materials Chemistry 2001, 11, 2887-2894.
[2] Poole, C. P.; Owens, F. J. Introduction to Nanotechnology; Ed. Whiley-

Interscience: 2003.
[3] Feynman, R. Engineering and Science. In ; 1960; Chapter There’s Plenty of room
at the bottom: An invitation to enter a new fiels of physics.
[4] Feynman, R. Miniaturization; New York: Reinhold: 1961.
[5] Taniguchi, N. On the Basics Concept of Nano-Technology. In Procedings of the

International Conference of Production Engineering, Vol. part II; 1974.
[6] Drexler, K. E. Engines of Creation: The Coming Era of Nanotechnology; Doubleday:

1986.
[7] Binnig, G.; H.Rohrer, “Scanning tunneling microscope”, 1982.
[8] Binnig, G.; Quate, C. F.; Gerber, C. Physical Review Letters 1986, 56, 930-933.
[9] Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. Nature 1985,
318, 162-163.
[10] Fulton, T. A.; Dolan, G. J. Physical Review Letters 1987, 59, 109-112.
[11] Steigerwald, M. L.; Alivisator, A. P.; Gibson, J. M.; Harris, T. D.; Korton, R.;
Multer, A. J.; Thayer, A. M.; Duncan, T. M.; Douglas, D. C.; Brus, L. E. Journal
of American Chemical Society 1988, 110, 3046-3050.
[12] Eigler, D. M.; Schweitzer, E. K. Nature 1990, 344, 524-526.
[13] Iijima, S. Nature 1991, 345, 56-58.
[14] Drexler, K. E. Nanosystems: Molecular Machinery, Manufacturing, and Computa-

tion; Whiley: New York ed.; 1992.
[15] Cao, G. Nanostructures and Nanomaterials - Synthesis, Properties and Applications;

Imperial College Press (World Scientific): 2004.
121
REFERENCES M. Galceran Mestres
[16] Murray, C. B.; Norris, D. J.; Bawendi, M. G. Journal of the American Chemical
Society 1993, 115, 8706-8715.
[17] Goldstein, A. N.; Echer, C. M.; Alivisatos, A. P. Science 1992, 256, 1425-1427.
[18] Ishikawa, K.; Yoshikawa, K.; Okada, N. Physical Review B 1988, 37, 5852-5855.
[19] Herring, C.; Galt, J. K. Physical Review 1952, 85, 1060-1061.
[20] Lyuttsau, V. G.; Fishman, Y. M.; Svetlov, I. L. Soviet Physics - Crystallography

1966, 10, 707.
[21] Nohara, A. Japanese Journal of Applied Physics 1982, 21, 1287-1292.
[22] Bayer, P. D.; Cooper, R. E. Journal of Materials Science 1967, 2, 233-237.
[23] Brenner, S. S. Growth and perfection of crystals; John Whiley & Sons, New York:
1958.
[24] Rossetti, R.; Nakahara, S.; Brus, L. E. Journal of Chemical Physics 1983, 79, 1086-
1088.
[25] Meltzer, R. S.; Feofilov, S. P.; Tissue, B.; Yuan, H. B. Physical Review B 1999, 60,
R14012-R14015.
[26] Hong, K. S.; Meltzer, R. S.; Biharib, B.; Williams, D. K.; Tissue, B. M. Journal of
Luminescence 1998, 76-77, 234-237.
[27] Williams, T. M.; Hunter, D.; Pradhan, A. K.; Kityk, I. V. Applied Physics Letters
2006, 89, 043116-043118.
[28] Sun, Y.; Riggs, J. E.; Henbest, K. B.; Martin, R. B. Journal of Nonlinear Optical
Physics and Materials 2000, 9, 481-503.
[29] Kityk, I. V.; Demianiuk, M.; Majchrowski, A.; Ebothe, J.; Siemion, P. Journal of
Physics: Condensed Matter 2004, 16, 3533-3544.
[30] Kityk, I. V.; Liu, Q.; Sun, Z.; Fang, J. The Journal of Physical Chemistry B 2006,
110, 8219-8222.
[31] Feller, F.; Geschke, D.; Monkman, A. P. Journal of Applied Physics 2003, 93, 2884-
2889.
[32] Gruhn, W.; Kityk, I. V.; Sahraoui, B. Journal of Applied Physics 2003, 93, 2912-
2916.
[33] Kityk, I. V. Journal of Non-Crystalline Solids 2001, 292, 184-201.
[34] Einstein, A. Physikalische Zeitschrift 1917, 18, 121-128.
[35] Gordon, J. P.; Zeiger, H. J.; Towns, C. H. Physical Review 1954, 95, 282-284.
[36] Shallow, A. L.; Townes, C. H. Physical Review 1958, 112, 1940-1949.

122
[37] Maiman, T. H. Nature 1960, 187, 493-494.
[38] Sorokin, P. P.; Stevenson, M. J. Physical Review Letters 1960, 5, 557-559.
[39] Johson, L. E.; Nassau, L. Proceedings of the Institute of Radio Engineers 1961, 49,
1704-1706.
[40] Geusic, J. E.; Marcos, H. M.; Uitert, L. G. V. Applied Physics Letters 1964, 4,
182-184.
[41] Kaminskii, A. A. Crystalline Lasers: Physical processes and operating schemes; CRC
Press, New York: 1996.
[42] Kaminskii, A. A. Laser Crystals, Their Physics and Properties; Springer Berlin:
1990.
[43] McDevitt, N. T.; Davidson, A. D. Journal of the Optical Society of America 1996,
56, 636-638.
[44] Hurrel, J. P.; Porto, S. P. S.; Chang, I. F.; Mitra, S. S.; Bauman, R. P. Physical
Review 1968, 173, 851-856.
[45] Weber, M. J. Handbook of Laser Science and Technology. In , Vol. 1; Press Inc.,
Boca Raton, Florida: 1982; Chapter Laser and Maser.
[46] Nigara, Y. Japanese Journal of Applied Physics 1968, 7, 404-408.
[47] Peters, V. Growth and Spectroscopy of Ytterbium-doped Sesquioxides, Thesis, Uni-

versität Hamburg, 2001.
[48] Kaminskii, A. A.; Bagayev, S. N.; Oka, K.; Shibata, H.; Ueda, K.; Takaichi, K.;
Eichler, H. J.; Rhee, H. Laser Physics Letters 2006, 3, 263-267.
[49] Kevtsov, P. V.; Kozeeva, L. P.; Kharchenko, L. Y. Soviet Physics - Crystallography

1974, 20, 732-735.
[50] Pujol, M. C.; Mateos, X.; Solé, R.; Massons, J.; Gavaldà, J.; Solans, X.; Dı́az, F.;
Aguiló, M. Journal Applied Crystallography 2002, 35, 108-112.
[51] Pujol, M. C.; Solé, R.; Massons, J.; Gavaldà, J.; Solans, X.; Zaldo, C.; Dı́az, F.;
Aguiló, M. Journal Applied Crystallography 2001, 34, 1-6.
[52] Basiev, T. T.; Sobol, A. A.; Zverev, P. G.; Osiko, V. V.; Powell, R. C. Applied
Optics 1999, 38, 594-598.
[53] Ustimenko, N. S.; Gulin, A. V. Instruments and experimental techniques 1998, 41,
386-387.
[54] Lagatsky, A. A.; Abdolvand, A.; Kuleshov, N. V. Optics Letters 2000, 25, 616-618.
[55] Kaminskii, A. A.; Pavlyuk, A. A.; Agamalyan, N. R.; Sarkisov, S. E.;

Bobovich, L. I.; Lukin, A.; Lyubchencko, V. Inorganic Materials 1980, 15, 1649.
123
[56] Pujol, M. C.; Solé, R.; Gavaldà, J.; Massons, J.; Dı́az, F.; Aguiló, M. Journal of
Materials Research 1999, 14, 3739-3745.
[57] Wang, G.; Luo, Z. Journal of Crystal Growth 1992, 116, 505-506.
[58] Tu, C.; Huang, Y.; Luo, Z.; Chen, G. Journal of Crystal Growth 1999, 135, 636-638.
[59] Kaminskii, A. A.; Li, L.; Butashin, A. V.; Mironov, V. S.; Pavlyuk, A. A.;
Bagayev, S. N.; Ueda, K. Japanese Journal of Applied Physics Part 2 Letters 1997,
36, L107-L109.
[60] Kushawaha, V.; Michael, A.; Major, L. Applied Physics B 1994, 58, 533-535.
[61] Avsievich, T. S.; Verenik, V. N.; Pavlyuk, A. A.; Puko, R. A.; Shkadare-
vich, A. P.; Yarzhemkovskii, V. D. Journal of Applied Spectroscopy 1986, 44, 248-
251.
[62] Kaminskii, A. A.; Pavlyuk, A. A.; Bobovich, L. I.; Lukin, A.;

Lyubchencko, V. V. Inorganic Materials 1979, 15, 1182-1183.
[63] Kuleshov, N. V.; Lagastky, A. A.; Mikhailov, V. G.; Heumann, E.; Jensen, T.;
Diening, A.; Huber, G. Applied Physics B 1997, 64, 409-413.
[64] Petrov, V.; Güell, F.; Massons, J.; Gavalda, J.; Solé, R. M.; Aguilo, M.; Dı́az, F.;
Griebner, U. IEEE Journal of Quantum Electronics 2004, 40, 1244-1251.
[65] Mateos, X.; Petrov, V.; Liu, J.; Pujol, M.; Griebner, U.; Aguiló, M.; Dı́az, F.;
Galan, M.; Viera, G. IEEE Journal of Quantum Electronics 2006, 42, 1008-1015.
[66] Lagastky, A. A.; Kuleshov, N. V.; Mikhailov, V. G. Optics Communication 1999,

165, 71-75.
[67] Klopp, P.; Griebner, U.; Petrov, V.; Mateos, X.; Busrsukova, M. A.; Pujol, M. C.;
Solé, R.; Gavaldà, J.; Aguiló, M.; Güell, F.; Massons, J.; Kirilov, T.; Dı́az, F.
Applied Physics B 2002, 74, 185-189.
[68] Mateos, X.; Petrov, V.; Aguiló, M.; Solé, R. M.; Gavaldà, J.; Massons, J.;
Dı́az, F.; Griebner, U. IEEE Journal of Quantum Electronics 2004, 40, 1056-1059.
[69] Coutures, J.; Rouanet, A.; Verges, R.; Foex, M. Journal of Solid State Chemistry
1976, 17, 171-182.
[70] Powell, C. Physics of Solid-State Laser Materials; Springer Berlin: 1998.
[71] Pauling, L.; Shapell, M. D. Zeitschrift für Kristallographie 1930, 75, 138-142.
[72] Morrison, C. A.; Leavitt, R. P. Handbook on the Physics and Chemistry of Rare
Earths; New York: 1982.
[73] Ermeneux, F.; Sun, Y.; Cone, R. L.; Equall, R. W.; Hutchison, R. L.; Moncorge,
Advanced Solid State Lasers; volume 26 OSA TOPS: 1999.
124
[74] Mix, E.; Fornasiero, L.; Diening, A.; Petermann, K.; Hutchison, R. L. Advanced
Solid State Lasers; volume 19 OSA TOPS: 1998.
[75] Klein, P. H.; Croft, W. J. Applied Physics 1967, 38, 1603-1607.
[76] Lu, J.; Takaichi, K.; Uematsu, T.; Shirakawa, A.; Musha, M.; Ueda, K.;
Yagi, H.; Yanagitani, T.; Kaminskii, A. A. Applied Physics Letters 2002, 81, 4324-
4326.
[77] Coble, R. L. “Transparent alumina and method of preparation”, 1962.
[78] Carnall, E.; Hatch, S. E.; Parson, W. F. Optical Studies on hot-Pressed Polycrys-
talline CaF2 with Clean Crain Boundaries; volume 3 New York: 1966.
[79] Hatch, S. E.; Parsons, W. F.; Weagley, R. J. Applied Physics Letters 1964, 5, 153-
154.
[80] Greskovich, C.; Chernoch, J. P. Journal of Applied Physics 1973, 44, 4599-4606.
[81] Ikessue, A.; Kinoshita, T.; Kamata, K.; Yoshida, K. Journal of the American Ce-
ramic Society 1995, 7, 1033-1040.
[82] Ikessue, A. Optical Materials 2002, 19, 183-187.
[83] Yanagitani, T.; Yagi, H.; Ichikawa, M. “Production of yttrium-aluminium-

garnet fine powder”, 1998.
[84] Yanagitani, T.; Yagi, H.; Yamasaki, Y. “Production of yttrium-aluminium-

garnet fine powders for transparent YAG ceramic”, 1998.
[85] Lu, J.; Murai, T.; Takaichi, K.; Uematsu, T.; Ueda, K.; Yagi, H.; Yanagitani, T.;
Kaminskii, A. A. Japanese Journal of Applied Physics part 2 Letters 2001, 40, L1277-
L1279.
[86] Lu, J.; Ueda, K.; Yagi, H.; Yanagitani, T.; Akiyama, Y.; Kaminskii, A. A. Journal
Alloys and Compounds, 2002, 341, 220-225.
[87] Lu, J.; Takaichi, K.; Uematsu, T.; Shirakawa, A.; Musha, M.; Bisson, J. F.;
Ueda, K.; Yagi, H.; Yanagitani, T.; Kaminskii, A. A. Laser Physics 2003, 13,
940-942.
[88] Lu, J.; Bisson, J. F.; Takaichi, K.; Uematsu, T.; Shirakawa, A.; Musha, M.;
Ueda, K.; Yagi, H.; Yanagitani, T.; Kaminskii, A. A. Applied Physics Letters
2003, 83, 1101-1103.
[89] Takaichi, K.; Yagi, H.; Shirakawa, A.; Ueda, K.; Hosokowa, S.; Yanagitani, T.;
Kamisnkii, A. A. Physica status solidi (a) 2005, 202, R1-R3.
[90] Hreniak, D.; Strek, W. Journal of Alloys and Compounds 2002, 341, 183-186.
[91] Fedyk, R.; Hreniak, D.; Lojkowski, W.; Strek, W.; Matysiak, H.; Grzanka, E.;
Gierlotka, S.; Mazur, P. Optical Materials 2007, 29, 1252-1257.
125
[92] Strek, W.; Bednarkiewicz, A.; Hreniak, D.; Mazur, P.; Lojkowski, W. Journal of
Luminescence 2007, 122-123, 70-73.
[93] Pazik, R.; Gluchowski, P.; Hreniak, D.; Strek, W.; Ros, M.; Fedyk, R.; Lo-
jkowski, W. Optical Materials 2008, 30, 714-718.
[94] Gazza, G. E.; Dutta, S. K. “Hot pressing ceramic oxides to transparency by

heating in isothermal increments”, 1973.
[95] de With, G.; Dijk, H. J. A. V. Materials Research Bulletin 1984, 19, 1669-1674.
[96] Sekita, M.; Haneda, H.; Yanagitani, T.; Shirasaki, S. Journal of Applied Physics
1990, 67, 453-458.
[97] Hong, K. S.; Meltzer, R. S.; Bihari, B.; Williams, D. K.; Tissue, B. Journal of
Luminescence 1998, 76-77, 234-237.
[98] Soo, Y. L.; Huang, S. W.; Ming, Z. H.; Kao, Y. H.; Smith, G. C.; Goldburt, E.;
Holdel, R.; Kulkarni, B.; Veliadis, J. V. D.; Bhargava, R. N. Journal of Applied
Physics 1998, 83, 5404-5409.
[99] Kruppe, W. F. IEEE Journal of Selected Topics in Quantum Electronics 2000, 6, 1287-
1296.
[100] Zou, X.; Toranti, H. Physical Review B 1995, 52, 15889-15897.
[101] Deloach, L. D.; Payne, S. A.; Chase, L. L.; Smith, L. K.; Kway, W. L.;
Kruppe, W. F. IEEE of Quantum Electronics 1993, 29, 1179-1191.
[102] Montoya, E.; Capmany, J.; Bausá, L. E.; Kellner, T.; Diening, A.; Huber, G.
Applied Physics Letters 1999, 74, 3113-3115.
[103] Dieke, G. H. Spectra and Energy Levels of Rare Earth Ions in Crystals; Wiley Inter-
science, New York: 1968.
[104] Carnall, W. T.; Crosswhite, H.; Crosswhite, H. M. “Energy Level Structure and
Transition probabilities of the trivalent lanthanides in LaF3 ”, Technical Report,
Argonne National Laboratory Report, 1977.
[105] Pollack, S. A. Journal of Chemical Physics 1964, 40, 2751-2767.
[106] Krupke, W. F.; Gruber, J. B. Journal of Chemistry Physics 1964, 41, 1225-1232.
[107] Weber, M. J.; Bass, M.; de Mars, G. A. Journal of Applied Physics 1971, 42, 301-
305.
[108] de Souza, D. F.; Zonetti, L. F.; Bell, M. J. V.; Sampaio, J. A.; Nunes, L. A. O.;
Baeso, M. L.; Bento, A. C.; Miranda, L. C. M. Applied Physics Letters 1999, 74,
908-910.
[109] Dwyer, R. M.; Bass, M. Lasers in Medicine; volume 3 Academic New York: 1977.
[110] Kincade, K. Laser Focus World; 1996.

126
[111] Auzel, F. E. Proceedings of the IEEE 1973, 61, 758-786.
[112] Dieke, G. H.; B.Pandey, Journal of Chemical Physisics 1964, 41, 1952-1969.
[113] Caspers, H. H.; Rast, H. E.; Fry, J. L. The Journal of Chemical Physics 1970, 53,
3208-3216.
[114] Zhang, X.; Liu, X. G.; Jouart, J. P.; Mary, G. Journal of Luminescence 1998, 78,
289-293.
[115] Zhang, X.; Liu, X.; Jouart, J. P.; Mary, G. Chemical Physicas Letters 1998, 287,
659-662.
[116] Patel, D. N.; Reddy, B. R.; Nashstevenson, S. K. Optical Materials 1998, 19, 225-
234.
[117] Malinowski, M.; Piramidowicz, R.; Frukacz, Z.; Chadeyron, G.; Mahiou, R.;
Joubert, M. F. Optical Materials 1999, 12, 409-423.
[118] Martin, I. R.; Rodriguez, V. D.; Lavin, V.; Mendoza, U. R. R. Journal of Alloys
and Compounds 1998, 277, 345-348.
[119] Rustad, G.; Stenersen, K. IEEE Journal of Quantum Electronics 1996, 32, 1645-
1656.
[120] Ranieri, I. M.; Baldochi, S. L.; Santo, A. M. E.; Gomes, L.; Currol, L. C.;
Tarelho, L. V. G.; Derossi, W.; Berretta, J. R.; Costa, F. E.; Nogueira, G. E. C.;
Wetter, N. U.; Zezell, D. M.; Vieria, N. D.; Morato, S. P. Journal of Crystal Growth
1996, 166, 423-428.
[121] Rothacher, T.; Luthy, W.; Weber, H. P. Optics Communications 1998, 155, 68-72.
[122] Sharma, B.; Singh, V. B.; Rai, D. K.; Rai, S. B. Journal of Physics 1998, 50, 405-418.
[123] Blasse, G.; Grabmeier, B. Luminescent Materials; Springer-Verlag, New York:

1994.
[124] Nazarov, M. V.; Jeon, D. Y.; Kang, J. H.; Popovici, E. J.; Muresan, L. E.;
Zamoryanskaya, M. V.; Tsukerblat, B. S. Solid State Communications 2004, 131,
307-311.
[125] Chang, N. Journal of Applied Physics 1963, 34, 3500-3504.
[126] Reintjies, F. Encyclopaedia of Physical sciences and Technology. In , Vol. 11;
[127] Franken, P. A. Physics Review Letters 1961, 7, 118-119.
[128] Brenier, A. Journal of Luminescence 2000, 91, 121-132.
[129] Johnson, L. F.; Ballman, A. A. Journal of Applied Physics 1969, 40, 297-302.
[130] Dmitriev, V. G.; Raevskii, E. V.; Rubina, N. M.; Rashkovich, L. N.;

Silichev, O. O.; Fomichev, A. A. Soviet Technical Physics Letters 1979, 5, 590-591.
127
[131] Zumsteg, F. C.; Bierlein, J. D.; Gier, T. E. Journal of Applied Physics 1976, 47,
4980-4985.
[132] Bierlein, J. D.; Vanherzeele, H. Journal of the Optical Society of America B 1989, 6,
622-633.
[133] Belt, R. F.; Gashurov, G.; Liu, Y. S. Laser Focus 1985, 21, 110-114.
[134] Fan, T. Y.; Huang, C. E.; Hu, B. Q.; Eckardt, R. C.; Fan, Y. X.; Byer, R. L.;
Feigenlson, R. Applied Optics 1987, 26, 2390-2394.
[135] Brown, A. J. W.; Bowers, M. S.; Kangas, K. W.; Fisher, C. H. Optics Letters 1992,
17, 109-111.
[136] Satyanarayan, M. N.; Deepty, A.; Bhat, H. L. Critical Reviews in Solid State Ma-
terials and Science 1999, 24, 103-191.
[137] Hargeman, M. E.; Poeppelmeier, K. R. Chemistry of Materials 1995, 7, 602-621.
[138] Kurokawa, K.; Nakazawa, M. Applied Physics Letters 1989, 55, 7-9.
[139] Shen, H. Y.; Zhou, Y. P.; Lin, W. X.; Zheng, Z. D.; Zheng, R. R.; Yu, G. F.;
Huang, C. H.; Jiang, A. D.; Jia, S. Q.; Shen, D. Z. IEEE Journal of Quantum
Electronics 1992, 28, 48-51.
[140] Stolzenberger, R. A. IEEE Photonics Technology Letters 1989, 1, 446-448.
[141] Chung, J.; Siegman, A. E. Journal of the Optical Society of America B 1993, 10,
2201-2210.
[142] Kato, K. IEEE Journal of Quantum Electronics 1991, 27, 1137-1140.
[143] Grasser, C.; Wang, D.; Beigang, R.; Wallestein, R. Journal of the Optical Society
of America B 1993, 10, 2218-2221.
[144] Lin, J. T.; Montgomery, J. Optics Communication 1990, 75, 315-320.
[145] Lotshaw, W. T.; Unternahrer, J. R.; Kukla, M. J.; Miyaka, C. I.; Braun, F. D.
Journal of the Optical Society of America B 1993, 10, 2191-2194.
[146] Wachman, E. S.; Edelstein, D.; Tang, C. L. Optics Letters 1990, 15, 136-138.
[147] Mangin, J.; Khodjaoui, A.; Marnier, G. Physica Status Solidi (a) 1990, 120, K111-
K116.
[148] Baumert, J. C.; Schellenberg, F. M.; Lenth, W.; Risk, W. P.; Bjorklund, G. C.
Applied Physics Letters 1987, 51, 2192-2194.
[149] Tordjman, I.; Masse, R.; Guitel, J. C. Zeitschrift für Kristallographie 1974, 139,
103-115.
[150] Thomas, P. A.; Glazer, A. M.; Watts, B. E. Acta Crystallographica Section B: Struc-
tural Science 1990, 46, 333-343.
128
[151] Masse, R.; Grenier, J. C. Bulletin de la Société Française de Minéralogie et de Cristal-

lographie 1971, 94, 437.
[152] Phillips, M. L. F.; Harrison, W. T.; Stucky, G. D. SPIE-The International Society

for Optical Engineering 1991, 1561, 84-92.
[153] Cheng, L. K.; Bierlein, J. D. Ferroelectrics 1993, 142, 209-228.
[154] Xue, D.; Zhang, S. Applied Physics Letters 1997, 70, 943-945.
[155] Sasaki, T.; Miyamoto, A.; Yokotani, A.; Nakai, S. Journal of Crystal Growth 1993,
128, 950-955.
[156] Angert, N.; Tseitlin, M.; Yashchin, E.; Roth, M. Applied Physics Letters 1995, 67,
1941-1943.
[157] Cheng, L. K.; Bierlein, J. D.; Ballman, A. A. Journal of Crystal Growth 1991, 110,
697-703.
[158] Damazyan, G. S.; Esayan, S. K.; Manukyan, A. L. Soviet Physics - Crystallography

1986, 31, 239.
[159] Thomas, P. A.; Mayo, S. C.; Watts, B. E. Acta Crystallographica Section B 1992,
48, 401-407.
[160] Bierlein, J. D.; Arweiler, C. B. Applied Physics Letters 1986, 49, 917-919.
[161] R.J. Bolt, M. V. d. M. Optics Communications 1993, 100, 399-410.
[162] Vanherzeele, H.; Bierlein, J. D. Optics Letters 1992, 17, 982-984.
[163] Reid, D. T.; Ebrahimzadeh, M.; Sibbett, W. Journal of the Optical Society B 1995,
12, 2168-2179.
[164] Watson, G. H. Journal of Raman Spectroscopy 1991, 22, 705-713.
[165] R. I. Mashkovtsev, L. I. I. Physica Status Solidi (b) 1996, 198, 577-585.
[166] Wang, M.; Wang, J. Y.; Liu, Y. G.; Wei, J. Q. Ferroelectrics 1991, 115, 13-20.
[167] Delarue, P.; Lecomte, C.; Jannin, M.; Marnier, G.; Menaert, B. Physical Review
B 1998, 58, 5287-5295.
[168] Bierlein, J. D.; Vanherzeele, H.; Ballman, A. A. Applied Physics Letters 1989, 54,
783-785.
[169] Mayo, S. C.; Thomas, P. A.; Teat, S. J.; Loiacono, G. M.; Loiacono, D. N. Acta
Crystallographica Section B: Structural Science 1994, 50, 655-662.
[170] Cheng, L. K.; Cheng, L. T.; Galperin, L.; Hotsenpiller, P. A. M.; Bierlein, J. D.
Journal of Crystal Growth 1994, 137, 107-115.
[171] Kung, A. H. Applied Physics Letters 1994, 65, 1082-1084.

129
[172] Oseledchik, Y. S.; Pisarevsky, A. I.; Prosvirnin, A. L.; Lopatko, V. N.; Titkov, L.
E. K. E. F.; Demidovich, A. A.; Shkadarevich, A. P. Procedings of Laser Optics
Concerence; Leninigrad University Press: 1990.
[173] Wang, J. Y.; Liu, Y. G.; Wei, J. Q.; Shi, L. P.; Wang, M. Zeitschrift für Kristallo-
graphie 1990, 191, 231-238.
[174] J.Han,; Liu, Y.; Wang, M.; Nie, D. Journal of Crystal Growth 1990, 128, 864-866.
[175] Risk, W. P.; Loiacono, G. M. Applied Physics Letters 1996, 69, 311-313.
[176] Protas, J.; Marnier, G.; Boulanger, B.; Menaert, B. Acta Crystallographica Section
C: Crystal Structure Communications 1989, 45, 1123-1125.
[177] Loiacono, G.; Loiacono, D.; Stolzenberger, R. Journal of Crystal Growth 1993,
131, 323-330.
[178] Cheng, L. K.; Cheng, L. T.; Zumsteg, F. C.; Bierlein, J. D.; Galperin, J. Journal
of Crystal Growth 1993, 132, 289-296.
[179] Anderson, M. T.; Phillips, M. L. F.; Sinclair, M. B.; Stucky, G. D. Chemistry of

Materials 1996, 8, 248-256.
[180] Sole, R.; Nikolov, V.; Koseva, I.; Peshev, P.; Ruiz, X.; Zaldo, C.; Martin, M.;
Aguilo, M.; Diaz, F. Chemistry of Materials 1997, 9, 2745-2749.
[181] Rico, M.; Zaldo, C.; Massons, J.; Diaz, F. Journal of Physics: Condensed Matter
1998, 10, 10101-10113.
[182] Martin, C. R.; Parthasarathy, R. Advanced Materials 1995, 7, 487-488.
[183] Martin, C. Advanced Materials 1991, 3, 457-459.
[184] Cai, Z.; Lei, J.; Liang, W.; Menon, V.; Martin, C. R. Chemistry of Materials 1991,
3, 960-967.
[185] Foss, C. A.; Hornyak, G. L.; Stockert, J. A.; Martin, C. R. Advanced Materials
1993, 5, 135-136.
[186] Brumlik, C. J.; Menon, V. P.; Martin, C. R. Journal Materials Research 1994, 9,
1174-1183.
[187] Parthasarathy, R. V.; Phani, K. L. N.; Martin, C. R. Advanced Materials 1995, 7,

896-897.
[188] Lakshmi, B. B.; Dorhout, P. K.; Martin, C. R. Chemistry of Materials 1997, 9,

857-862.
[189] Ulhir, A. Bell System Technology Journal 1956, 35, 333-337.
[190] Hirschman, K. D.; Tsybeskov, L.; Duttagupta, S. P.; Fauchet, P. M. Nature 1996,
384, 338-341.
130
[191] Marsal, L. F.; Formentı́n, P.; Palacios, R.; Trifonov, T.; Ferré-Borrull, J.; Ro-
driguez, A.; Pallarés, J.; Alcubilla, R. Physica Status Solidi (a) 2008, 205, 2437-
2440.
[192] Trifonov, T.; Garı́n, M.; Rodrı́guez, A.; Marsal, L. F.; Alcubilla, R. Physica Status
Solidi (a) 2007, 204, 3237-3242.
[193] Loni, A.; Canham, L. T.; Berger, M. G.; Arens-Fischer, R.; Munder, H.;
Luth, H.; Arrand, H. F.; Benson, T. M. Thin Solid Films 1996, 276, 143-146.
[194] Ferrand, P.; Romestain, R. Applied Physics Letters 2000, 77, 3535-3537.
[195] Rossi, A. M.; Amato, G.; Camarchia, V.; Boarino, L.; Borini, S. Applied Physics
Letters 2001, 78, 3003-3005.
[196] Dorvee, J.; Sailor, M. J. Physica Status Solidi (a) 2005, 202, 1619-1623.
[197] Ouyang, H.; Striemer, C. C.; Fauchet, P. M. Applied Physics Letters 2006, 88,
163108-163109.
[198] Keller, F.; Hunter, M. S.; Robinson, D. L. Journal of the Electrochemical Society
1953, 100, 411-419.
[199] Marsal, L. F.; Vojkuvka, L.; Ferré-Borrull, J.; Trifonov, T.; Pallarès, J. Physica
Status Solidi (c) 2007, 4, 1918-1922.
[200] Brinker, C. J.; Scherrer, G. W. Sol-Gel Science. The physics and chemistry of Sol-Gel
processing; Academic Press, San Diego: 1990.
[201] Liu, W.; Farrington, G. C.; Dunn, B. Journal of the Electrochemical Society 1996,
143, 879-884.
[202] Pechini, M. P. “Method of preparing lead and alkaline earth titanates and nio-
bates and coating method using the same to form capacitor”, 1967.
[203] Kodaira, C. A.; Brito, H. F.; Malta, O. L.; Serra, O. A. Journal of Luminescence
2003, 101, 11-21.
[204] Kakihama, M. Journal of Sol-Gel Science and Technology 1996, 6, 7-55.
[205] Lessing, P. A. American Ceramic Society Bulletin 1989, 68, 1002-1007.
[206] Dolgaeva, S. I.; Simakina, A. V.; Voronova, V. V.; Shafeeva, G. A.; Bozon-
Verduraz, F. Applied Surface Science 2002, 186, 546-551.
[207] Henglein, A. Journal of Physics Chemistry 1993, 97, 5457-5471.
[208] Mafuné, F.; Kohno, F. J.; Takeda, Y.; Kondow, T.; Sawabe, H. Journal of Physical
Chemistry B 2000, 104, 8333-8337.
[209] Sibbald, M. S.; Chumanov, G.; Cotton, T. M. Journal of Physical Chemistry 1996,
100, 4672-4678.
131
[210] Tsuji, T.; Iryo, K.; Watanabe, N.; Tsuji, M. Applied surface Science 2002, 202,
80-85.
[211] Tsuji, T.; Kakita, T.; Tsuji, M. Applied surface Science 2003, 206, 314-320.
[212] Yeh, M. S.; Yang, Y. S.; Lee, Y. P.; Lee, H. F.; Yeh, H. Y.; Yeh, C. S. Journal of
Physical Chemistry B 1999, 103, 6851-6857.
[213] Kabashin, A. V.; Meunier, M. Journal of Applied Physics 2003, 94, 7941-7943.
[214] Kabashin, A. V.; Meunier, M.; Kingston, C.; Luong, J. T. Journal of Physical
Chemistry B 2003, 107, 4527-4531.
[215] Moreno, P.; Méndez, C.; Garcı́a, A.; Torchia, G.; Delgado, D.; de Aldana, J. V.;
Arias, I.; Roso, L. Journal of Nanoscience and Nanotechnology 2006, 6, 1961-1967.
[216] Sugioka, K. Laser precision microfabrication (LPM2002); Ed RIKEN Review 50:

2003.
[217] Ferkel, H.; Hellmig, R. J. Nanostructured Materials 1999, 11, 617-622.
[218] Qin, G.; Lu, J.; Bisson, J. F.; Feng, Y.; Ueda, K. I.; Yagi, H.; Yanagitani, T. Solid
State Commun 2004, 132, 103-106.
[219] Chaoudhury, S.; Gandhi, A. S.; Jayaram, V. J. American Ceramic Society 2003, 86,
247-251.
[220] Liao, S.-C.; Pae, K. D.; Mayo, W. E. Materials Science and Engineering A 1995,
204, 152-159.
[221] Urbanovich, V. S.; Shkatulo, G. G. Powder Metallurgy and Metal Ceramics, Vol.
42, Nos. 1-2, 2003 2003, 42, 19-23.
[222] Bragg, W. L. Nature 1912, 90, 410.
[223] Glusker, J. P.; Trueblood, K. N. Crystal structure analysis: A premier; Oxford Uni-
versity press, New York: 1985.
[224] Solans, X. Introducció a la cristal·lografia; Edicions de la Universitat de Barcelona:

1999.
[225] “JCPDS-ICDD. Joint Comitte for Powder Diffraction Standards International,

Center of Diffraction Data”, 1997.
[226] Birks, L. S.; Friedman, H. Journal of Appled Physics 1946, 17, 687-692.
[227] Cullity, B. D. Element X-Ray diffraction; Addison-Wesley: 1978.
[228] Rodriguez-Carvajal, J. Reference guide for the computer program Fullprof; Labora-
torie León Brillouin. CEA-CNRS. Saclay, France: 2000.
[229] Rietveld, H. M. Journal of Appied Crystallography 1969, 2, 65-71.

132
[230] Young, R. A. International union of crystallography, monografs on crystal-

lography 5. In ; Oxford University Press, Oxford: 1995; Chapter The Rietveld
Method.
[231] Ozawa, T. Thermochimica Acta 2000, 355, 35-42.
[232] Pouchou, J. L.; Pichoir, F. Recherche aerospatiale 1984, 215, 253.
[233] Inokuti, M.; Hirayama, F. The Journal of Chemical Physics 1965, 43, 1978-1989.
[234] Korpel, A. Proceedings of the IEEE 1981, 69, 48-53.
[235] Andrushchak, A. S.; Bobitski, Y. V.; Kaidan, M. V.; Mytsyk, B. G.; Kityk, A. V.;
Schranz, W. Optics & Laser Technology 2005, 37, 319-328.
[236] Klevtsov, P. V.; Kozeeva, L. P.; Kharchenko, L. Y.; Pavlyuk, A. A. Soviet Physics
- Crystallography 1974, 19, 342-346.
[237] Jiang, Q.; Zhang, Z.; Hsu, D. T.; Tong, H. Y.; Iskandar, M. Journal of Materials
Science 1999, 34, 5919-5922.
[238] Pujol, M. C.; Mateos, X.; Solé, R.; Massons, J.; Gavaldà, J.; Dı́az, F.; M.Aguiló,
Materials Science Forum 2001, 710-715, 378-381.
[239] Borowiec, M. T.; Dyakonov, V. P.; Wózniak, K.; Dobrzycki, L.; Berkowski, M.;
Zubov, E. E.; Michalski, E.; Szewczyk, A.; Gutowska, M. U.; Zayarnyuk, T.;
Szymczak, H. Journal of Physics: Condensed Matter 2007, 19, 056206-056222.
[240] Shannon, R. D. Acta Crystallographica 1976, A32, 751-767.
[241] Klug, P.; Alexandre, L. E. X-Ray Diffraction Procedures; Wiley-Interscience: 1974.
[242] Granqvist, C. G.; Buhrman, R. A. Journal of Applied Physics 1976, 47, 2200-2219.
[243] Söderlund, J.; Kiss, L. B.; Niklasson, G. A.; Granqvist, C. G. Physical Review
Letters 1998, 80, 2386-2388.
[244] Pujol, M. C.; Bursukova, M. A.; Guell, F.; Mateos, X.; solé, R.; Gavaldà, J.;
Aguiló, M.; Massons, J.; Dı́az, F.; Klopp, P.; Griebner, U.; Petrov, V. Physical
Review B 2002, 65, 165121-11.
[245] Porto, S. P. S.; Scott, J. F. Physical Review B 1967, 157, 716-719.
[246] E. P. Pokatilov, S. N. Klimin, V. M. F. J. T. D. Physical Review B 2002, 65, 075316-1.
[247] Guo, H.; Yin, M.; Dong, N.; Xu, M.; Lou, L.; Zhang, W. Applied Surface Science
2005, 243, 245-250.
[248] White, W. B.; Keramidas, V. G. Spectrochimica Acta 1972, 28A, 501-509.
[249] Urben, M. W.; Cornilsen, B. C. The Journal of physics and chemistry of solids 1984,
48, 475-479.
[250] Yanovskii, V. K.; Voronkova, V. I. Physica Status Solidi (a) 1986, 93, 665-668.
133
[251] Wu, Y.; Yang, P. Advanced Materials 2001, 13, 520-523.
[252] Jacco, J. C. Materials Research Bulletin 1986, 21, 1189-1194.
[253] Solé, R.; Nikolov, V.; Ruiz, X.; Gavaldà, J.; Solans, X.; Aguiló, M.; Dı́az, F.
Journal of Crystal Growth 1996, 169, 600-603.
[254] Pujol, M. C.; Aguiló, M.; Dı́az, F.; Zaldo, C. Optics Materials 1999, 13, 33-40.
[255] Dumitru, G.; Romano, V.; Weber, H. P.; Sentis, M.; Marine, W. Applied Physics
A 2002, 74, 729-739.
[256] Dowty, E. “Shape for Windows, version 5.0.1”, 1995.
[257] Mateos, X.; Güell, F.; Pujol, M. C.; Bursukova, M. A.; Solé, R.; Gavaldà, J.;
Aguiló, M.; Dı́az, F.; Massons, J. Applied Physics Letters 2002, 80, 4510-4512.
[258] Vetrone, F.; Boyer, J. C.; Capobianco, J. A.; Speghini, A.; Bettinelli, M. The
Journal of Physical Chemistry B 2002, 106, 5622-5628.
[259] Zych, E.; Hreniak, D.; Strek, W. Journal of Physical Chemistry B 2002, 106, 3805-
3812.
[260] Judd, B. R. Physical Review 1962, 127, 750 - 761.
[261] Ofelt, G. S. The Journal of Chemical Physics 1962, 37, 511-520.
[262] Nieuwpoort, W. C.; Blasse, G. Solid State Communications 1966, 4, 227.
[263] Blasse, G.; Bril, A. Philips Research Reports 1966, 21, 368.
[264] Pujol, M. C.; Mateos, X.; Aznar, A.; Solans, X.; Suriñach, S.; Massons, J.;
Dı́az, F.; Aguiló, M. Journal of Applied Crystallography 2006, 39, 230-236.
[265] Strek, W.; Derén, P. J.; Bednarkiewicz, A.; Kalisky, Y.; Boulanger, P. Journal of
Alloys and Compounds 2000, 300-301, 180-183.
[266] Pazik, R.; Zych, A.; Strek, W. Materials Chemistry and Physics 2009, 115, 536-540.
[267] Petermann, K.; Huber, G.; Fornasiero, L.; Kuch, S.; Mix, E.; Peters, V.; Ba-
sun, S. A. Journal of Luminescence 2000, 87-89, 973-975.
[268] Eilers, H.; Tissue, B. M. Chemical Physics Letters 1990, 251, 74-78.
[269] Fornasiero, L.; Mix, E.; Peters, V.; Petermann, K.; Huber, G. Crystal Research
and Crystal Technology 1999, 34, 255-260.
[270] Capobianco, J. A.; Boyer, J. C.; Vetrone, F.; Speghini, A.; Bettinelli, M. Chem-
istry of Materials 2002, 14, 2915-2921.
[271] Capobianco, J. A.; Vetrone, F.; Boyer, J. C.; Speghini, A.; Bettinelli, M. Physical
Chemistry Chemical Physics 2000, 2, 3203-3207.
[272] Layne, C. B.; Lowdermilk, W. H.; Weber, M. J. Physical Review B 1977, 16, 10–20.
134
[273] Eckardt, R. C.; Byer, R. L. Measurement of nonlinear optical coefficients by

phase-matched harmonic generation. In , Vol. 1561; Bordui, P. F., Ed.; SPIE:
1991.
[274] Faugeroux, O.; Majchrowski, A.; Rutkowski, J.; Klosowicz, S.; Caussanel, M.;
Tkaczyk, S. Physica E: Low-dimensional Systems and Nanostructures 2008, 41, 6 -
8.
[275] Kityk, I. V. Semiconductor Science and Technology 2003, 18, 1001-1009.
[276] Plucinski, K.; Kityk, I. V.; Wang, C.; Kasperczyk, J. Molecular Crystals and Liquid
Crystals Science and Technology Section B: Nonlinear Optics 2000, 24, 311-317.
[277] Ye, X.; Sha, J.; Jiao, Z.; Zhang, L. Nanostructured Materials 1997, 8, 945-951.
[278] McBride, J. R.; Hass, K. C.; Poindexter, B. D.; Weber, W. H. Journal of Applied
Physics 1994, 76, 2435-2441.
[279] Wang, L.; Pan, Y.; Ding, Y.; Yang, W.; Mao, W. L.; Sinogeikin, S. V.; Meng, Y.;
Shen, G.; Mao, H. Applied Physics Letters 2009, 94, 061921-3.
[280] Ikesue, A.; Yoshida, K.; Yamamoto, T.; Yamaga, I. Journal of the American Ce-
ramic Society 1997, 80, 1517-1522.
[281] Gheorghe, C.; Lupei, A.; Lupei, V.; Gheorghe, L.; Ikesue, A. Journal of Applied
Physics 2009, 105, 123110.
[282] So, S.; Mackenzie, J. I.; Shepherd, D. P.; Clarkson, W. A.; Betterton, J. G.;
Gorton, E. K.; Terry, J. A. C. Optics Express 2006, 14, 10481-10487.
[283] Weber, M. Physical Review B 1971, 4, 3153-3159.
135
List of Errata
U ringthe redaction of this thesis work, we have observed some errata in the
D published papers. We summarize here a list of errata.
⇒ Paper I
• Figure 4a (pag. 84), KGdW should be instead of KGdW bulk single crystal.
• Figure 4b (pag. 84), KYbW should be instead of KYbW bulk single crystal.
• Table 2 (pag. 86), KGdW∗∗ should be instead of KGdW bulk single crystal∗∗ .
• Table 2 (pag. 86), KYbW∗∗ should be instead of KYbW bulk single crystal∗∗ .
• Figure 8 (pag. 87), KGdW should be instead of KGdW bulk single crystal.
• Figure 48 (pag. 87), KYbW should be instead of KYbW bulk single crystal.
⇒ Paper II
• Line 91, (pag. 719), should be measured hkl peak and K is a constant equal
to 0.9 for L.
• Figure 2a (pag. 720), KGdW should be instead of KGdW bulk.
• Figure 2b (pag. 720), KGdW should be instead of KGdW bulk single crystal.
• Table 1 (pag. 721), KGdW should be instead of KGdW bulk crystal.
⇒ Paper III
• Figure 3 (pag. 5681), KNP should be instead of KNP bulk single crystal.
• Figure 3 (pag. 5681), KTP should be instead of KTP bulk single crystal.
• Table 1 (pag. 5681), KYbW the b = 10.2597(6) Å should be instead of b =
10.297(6) Å.
⇒ Paper IV
• Line 43, (pag. 15499), the two endothermic peaks at 1322 and 1327 K should
be instead of the two exothermic peaks at 1322 and 1327 K.
• Table 1 (pag. 15501), KYbW the b = 10.2597(6) Å should be instead of b =
10.297(6) Å.
• Figure 10 (pag. 15502), Erb3+ absorption transition 4 I15/2 → 4 S3/2 should be
instead of 4 I15/2 → 2 S3/2 .
• Figure 11 (pag. 15503), Yb3+ energy level, 2 F5/2 should be instead of 2 F7/2 .
• Figure 11 (pag. 15503), Yb3+ energy level, 2 F7/2 should be instead of 2 F5/2 .
137
⇒ Paper IX
• Figure 4, (pag. 035705-4), DTA (KTP) should be instead of DTA (KTP bulk
single crystal).
• Table 1 (pag. 035705-5), KTP should be instead of KTP bulk single crystal.
• Table 5 (pag. 035705-5), KTP should be instead of bulk single crystal.
• Table 6 (pag. 035705-5), KTP should be instead of bulk single crystal.
Paper I
Pechini method for obtaining nanocrystalline KRE(WO4 )2 (RE = Gd and Yb)
M. Galceran, M. C. Pujol, M. Aguiló, F. Dı́az

Journal of Sol-Gel Science and Technology
2007, 42(1), 79-88
139
Paper II
Synthesis of monoclinic monoclinic KGd(WO4 )2 nanocrystals by two

preparations methods
M. Galceran, M. C. Pujol, C. Méndez, A. Garcı́a, P. Moreno, L. Roso, M. Aguilo´, F.

Dı́az,
Journal of Nanoparticle Research
2009, 11(3), 717-724
151
Paper III
UV- operated piezooptical effects in oxide nanocrystals incorporated into the

PMMA matrices
S. Tkaczyk, M. Galceran, S. Kret, M. C. Pujol, M. Aguiló, F. Dı́az, I. V. Kityk

Acta Materialia
2008, 56(1-3), 5677-5684
161
Paper IV
Size dependence of structural and optical properties in monoclinic Er:KYb(WO4 )2

nanocrystals
M. Galceran, M. C. Pujol, C. Zaldo, M. Aguiló, F. Dı́az

Journal Physical Chemistry C
2009, 113, 15497-15506
171
Paper V
Synthesis, structural and optical characterization of Eu:KYb(WO4 )2 nanocrystals.

A promising red phosphor
M. Galceran, M. C. Pujol, P. Gluchowski, W. Strek, J. J. Carvajal, X. Mateos, C. Zaldo,

M. Aguiló and F. Dı́az
submitted to Journal of Solid State Chemistry
—, —(—), —-
183
Paper VI
Synthesis and characterization of nanocrystalline Yb:Lu2 O3 by modified Pechini

Method
M. Galceran, M. C. Pujol, M. Aguiló, F. Dı́az

Materials Science and Engineering B-Solid State Materials for Advanced Technology
2008, 146(1-3), 7-15
201
Paper VII
Structural and spectroscopic characterization of Yb:Sc2 O3 by modified Pechini

Method
M. Galceran, M. C. Pujol, J. J. Carvajal, X. Mateos, C. Zaldo, M. Aguiló and F. Dı́az

submited to Journal of Luminescence
—, —(—), —-
213
Paper VIII
A promising Lu2− x Hox O3 laser nanoceramics: Synthesis and characterization
M. Galceran, M. C. Pujol, P. Gluchowski, W. Strek, J. J. Carvajal, X. Mateos, C. Zaldo,

M. Aguiló and F. Dı́az
submitted to Journal of Physical Chemistry C
—, —(—), —-
231
Paper IX
Synthesis and characterization of KTiOPO4 nanocrystals and their PMMA

nanocomposites
M. Galceran, M. C. Pujol, J. J. Carvajal, S. Tkaczyk, I. V. Kityk, F. Dı́az, M. Aguiló

Nanotechnology
2008, 20(3), 035705-035715
255

Tesi

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Tesi

Uploaded by

Copyright:

Available Formats

Synthesis and characterization of optical

nanocrystals and nanostructures. An approach

Montserrat Galceran Mestres

Departament de Quı́mica Fı́sica i Inorgànica

Fı́sica i Cristal·lografia de Materials i Nanomaterials (FiCMA-FiCNA)

Que aquest treball, titulat ”Synthesis and characterization of optical nanocrystals

Tarragona, 26 de novembre de 2009

Montserrat Galceran Mestres

Everyone else whom I have forgotten.

Paper I: M. Galceran, M. C. Pujol, M. Aguiló, F. Dı́az, ”Sol-gel modified Pechini

List of Publications xiii

1.5 Fundamentals of template-based methods . . . . . . . . . . . . . . . . . 26

3 Synthesis and Characterization of Oxide Nanocrystals 55

3.4.2 Structural characterization . . . . . . . . . . . . . . . . . . . . . 74

4 Synthesis and Characterization of Nanostructures 79

5 Spectroscopic and Optical Characterizations 91

6 Fabrication and characterization of Ho:Lu2 O3 nanoceramics 109

List of Errata 137

Paper III 161

Paper VII 213

Paper VIII 231

1.1 Nanoscience and Nanotechnology

TABLE 1.1. Typical nanomaterials.

(a) 1D Nanocrystals and clus- Metals, semiconductors, magne-

To put nanoscale in context, we could be say that a nanometer is to a meter what

1.1.2 A brief history of nanotechnology

F IGURE 1.1. Approach of the macroscale to nanoscale.

Later, in 1977, E. Drexler promoted the concept of the Molecular Nanotechnology

1.1.3 Characteristics of nanomaterials

1. A large fraction of surface atoms

A representative scheme of LSNC is shown in figure 1.2. Region I corresponds to

1.1.3.1 Melting point and phase transition temperature

nanoparticles, the Curie temperature appears at lower temperatures and decreases as

1.1.3.2 Mechanical properties

Generally, the mechanical properties of nanomaterials such as hardness, elastic mo-

1.1.3.3 Optical properties

1.1.4 Nanotechnology applications

1.2 Overview of the laser history. Solid-state lasers

1. Solid active media consist of a crystals, glasses or ceramics as a host materials

2. A pump source to excite the gain medium

1.3 Solid active laser media materials

1.3.1 Host materials

TABLE 1.3. Some examples of the monoclinic solid state tungstates.

KLu(WO4 )2 Ho3+ 2.08µm, 2.99µm Kaminskii et al. (1980) [55]

1.3.1.2 Sesquioxides (RE2 O3 )

F IGURE 1.7. Polymorphic forms and transition temperatures of sesquioxides [69].

1.3.2 Transparent laser ceramics

1.3.2.1 Introduction to laser ceramics

2. Green-body formation: A ceramic green body is a molded shape made from

F IGURE 1.9. Schematic diagram of transparent ceramic processing.

1.3.2.2 State of the art

1.3.2.3 Advantages of transparent laser ceramics

1. They are easier to fabricate.

1.3.3 Active ions

1.4 Nonlinear optical materials: Potassium titanyl phos-

Potassium titanyl phosphate, KTiOPO4 (KTP) was described as a non-linear opti-

1.5 Fundamentals of template-based methods

1.5.1 Porous silicon templates

TABLE 1.5. Several properties of KTP and its important isostructurals.

1.5.2 Porous alumina templates

1.6 Aims of this doctoral thesis

H ischapter discusses the fundamentals and basics principles of the characteri-

2.1 Synthesis of nanocrystals: the modified Pechini method