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UNIVERSITI PUTRA MALAYSIA
SHARUDIN BIN OMAR BAKI
FK 2013 61
PHYSICAL CHARACTERIZATION AND OPTICAL SPECTROSCOPY OF Er3/Yb3-DOPED MULTICOMPOSITION TELLURITE GLASS FOR
BROADBAND AMPLIFIERS
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PHYSICAL CHARACTERIZATION AND
OPTICAL SPECTROSCOPY OF Er3+/Yb3+-DOPED
MULTICOMPOSITION TELLURITE GLASS FOR
BROADBAND AMPLIFIERS
SHARUDIN BIN OMAR BAKI
DOCTOR OF PHILOSOPHY
UNIVERSITI PUTRA MALAYSIA
2013
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PHYSICAL CHARACTERIZATION AND OPTICAL SPECTROSCOPY OF
Er3+
/Yb3+
-DOPED MULTICOMPOSITION TELLURITE GLASS FOR
BROADBAND AMPLIFIERS
By
SHARUDIN BIN OMAR BAKI
Thesis Submitted to the School of Graduate Studies,
Universiti Putra Malaysia, in Fulfilment of the
Requirements for the Degree of
Doctor of Philosophy
June 2013
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Copyright Page
All material contained within the thesis, including without limitation text, logos,
icons, photographs and all other artwork, is copyright material of Universiti Putra
Malaysia unless otherwise stated. Use may be made of any material contained
within the thesis for non-commercial purposes from the copyright holder.
Commercial use of material may only be made with the express, prior, written
permission of Universiti Putra Malaysia.
Copyright © Universiti Putra Malaysia
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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment
of the requirement for the degree of Doctor of Philosophy
PHYSICAL CHARACTERIZATION AND OPTICAL SPECTROSCOPY OF
Er3+
/Yb3+
-DOPED MULTICOMPOSITION TELLURITE GLASS FOR
BROADBAND AMPLIFIERS
By
SHARUDIN BIN OMAR BAKI
June 2013
Chairman: Professor Mohd Adzir bin Mahdi, PhD
Faculty: Engineering
The erbium ion doped (Er3+
)-tellurite glasses have been extensively studied in recent
decades as a potential host material for broadband applications at 1.5 m band. As
compared to other host glasses they possess variety interesting physical and optical
properties which further can be exploited especially in optical communications.
Therefore continuous investigation of appropriate glass compositions is very
important in order to synthesis high performance tellurite glass.
In this dissertation, series of selected oxide based tellurite glasses (TeO2) were
synthesized and characterized. Three ternary TeO2-AmOn-BmOn; TZT:TeO2-ZnO-
TiO2, TTB:TeO2-TiO2-Bi2O3, TPB: TeO2-PbO- Bi2O3 and two multicomposition
TeO2-AmOn-BmOn-CmOn-DmOn-EmOn (more than three components); TZPTiN:TeO2-
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ZnO-PbO-TiO2-Na2O (with difference PbO concentration) tellurite glasses were
studied (AmOn, BmOn, CmOn, DmOn, EmOn represent the oxide components,
m,n=integer). Selected batch composition was chosen as a ‘host’ glass for Er3+
/Yb3+
doping by substituting selected batch component with the rare earth oxide dopants
Er2O3/Yb2O3. All oxide components were above 99.9% purity and a quantitative
glass batching procedure based on mol% formulation calculation was performed. A
standard melt-quenching technique around 1000 oC for an hour and followed by
annealing at 250 oC was done for all glass batches. The physical characterization of
the glass samples involved X-Ray diffraction (XRD), thermal analysis, density,
molar volume and refractive index while the spectroscopic properties were obtained
through Fourier Transform Infra Red spectroscopy, Ultraviolet-Visible-Near Infra
Red absorption spectroscopy, Raman spectroscopy and fluorescence spectra of the
visible upconversion and near infra red emission under 980 nm laser diode (LD)
excitation. All measurement were performed at room temperature.
The non distinguishable intensity peaks with broad ‘halo’ diffraction of the XRD
spectrogram confirmed the amorphous nature of the selected host glasses. The
density of the glasses was observed higher with the incorporation of heavier mass
component of PbO and Bi2O3 in both TTB and TPB glasses where higher n values
were obtained in both glasses. All host glasses TZT, TTB, TPB, TZPTiN and
TZPTiN indicated higher n > 2. The FTIR analysis revealed higher transmission infra
red cut-off beyond 6m with distinct water (OH-) absorption between 2000-3500 cm
-
1 in most of the studied glass samples. The optical absorption edge analysis in most
samples showed an appreciable formation of non-bridging oxygen with respect to the
calculated optical energy gap trend. This was clearly supported by the obtained
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intensity parameters values t(t=2,4,6) through the Judd-Ofelt analysis. The
reduction of 2 and 6 values were strongly associated with enhancement of the
symmetrical behaviour at the Er3+
site with the creation of higher electron density on
the oxygen ligand ion; as consequences strong Er-O covalency are formed with the
increasing of Er3+
doping concentration. In addition this factor has also contributed
structural deformation of TeO2 by transformation of [TeO4] trigonal bypiramid to
[TeO3] trigonal pyramid via [TeO3+1] polyhedral units which was confirmed through
the Raman spectroscopy analysis with obtained maximum phonon vibration energy
lies between 730-750 cm-1
slightly lower than reference TeO2 glass value at
780 cm-1
. The upconversion spectra exhibited significant both green and red
emission upon 980 nm LD excitation especially in Er3+
-TZT and Er3+
/Yb3+
-TZPTiN
glasses where indicated by two or/and three photon absorption processes. Intense
with broad near infra red 1.5 m emission above 70 nm width and gain bandwidth
within (500-1300) x 10-28
cm3 were obtained in most Er
3+/Yb
3+-doped glass samples .
These characteristics suggest that the synthesized multicomposition tellurite glass is
a potential optical material for the future broadband telecommunication technology.
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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai
memenuhi keperluan untuk ijazah Doktor Falsafah
PENCIRIAN FIZIKAL DAN SPEKTROSKOPIK
KACA TELURIT KEPELBAGAIAN KOMPOSISI TERDOP-Er3+
/Yb3+
UNTUK PENGUAT JALUR-LEBAR
Oleh
SHARUDIN BIN OMAR BAKI
Jun 2013
Pengerusi: Profesor Mohd Adzir bin Mahdi, PhD
Fakulti: Kejuruteraan
Kaca telurit terdop-ion erbium (Er3+
) telah dikaji dengan giatnya sejak beberapa
kurun kebelakangan ini setelah dikenal pasti sebagai bahan hos berpotensi untuk
aplikasi jalur lebar pada jalur 1.5 m. Sebagai perbandingan dengan hos kaca yang
lain, ianya mempunyai pelbagai sifat fizikal dan optikal yang menarik di mana perlu
diekploitasikan lebih lanjut khususnya di dalam teknologi komunikasi optik. Oleh
yang demikian penyelidikan yang berterusan bagi komposisi kaca yang tepat adalah
amat penting bagi mensintesis kaca telurit berprestasi tinggi.
Di dalam disertasi ini, sesiri kaca berasaskan oksida telurit (TeO2) tepilih telah
disintesis dan dicirikan. Sebanyak tiga ternari TeO2-AmOn-BmOn; TZT:TeO2-ZnO-
TiO2, TTB:TeO2-TiO2-Bi2O3, TPB: TeO2-PbO- Bi2O3 dan dua pelbagai komposisi
TeO2-AmOn-BmOn-CmOn-DmOn-EmOn (lebih dari tiga komponen); TZPTiN:TeO2-
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ZnO-PbO-TiO2-Na2O (dengan kepekatan PbO berbeza) kaca-kaca telurit telah dikaji
(AmOn, BmOn, CmOn, DmOn, EmOn sebagai komponen-komponen oksida,
m,n=integer). Komposisi pengkelasan tertentu telah digunakan sebagai hos kaca
untuk pengedopan Er3+
/Yb3+
melalui penggantian komponen pengkelasan dengan
dopan oksida nadir bumi Er2O3/Yb2O3. Kesemua komponen oksida adalah
berketulinan melebihi 99.9% dan prosedur pengkelasan secara kuantitatif yang
dilakukan adalah berasaskan pengiraan formulasi mol%. Teknik sepuh lindap piawai
pada 1000 oC selama sejam dan diikuti penempaan pada 250
oC telah dilakukan ke
atas semua kelas kaca. Pencirian fizikal sampel-sampel kaca meliputi belauan sinar-
X (XRD), analisis terma, ketumpatan, isipadu molar dan indeks biasan manakala
sifat optik diperolehi melalui spektroskopi Transformasi Fourier Infra Merah,
spektroskopi penyerapan Ultra Lembayung-Sinar Nampak-Infra Merah Dekat,
spektroskopi Raman dan spektra floresen sinaran nampak perubahan-atas dan sinaran
infra merah dekat melalui pengujaan diode laser (LD) 980 nm. Kesemua pengukuran
dilakukan pada suhu bilik.
Ketiadaan puncak keamatan yang jelas dengan belauan ‘halo’ yang lebar
spectrogram XRD mengesahkan sifat amorfus hos kaca pilihan. Ketumpatan kaca
didapati tinggi dengan kehadiran komponen berat seperti PbO dan Bi2O3 untuk
kedua-dua kaca TTB dan TPB di mana n yang tinggi diperolehi untuk kedua-duanya.
Kesemua hos kaca TZT3, TTB3, TPB3, TZPTiN10 dan TZPTiN20 mencatatkan
yang tinggi iaitu n > 2. Analisis FTIR memperlihatkan penggalan ketelusan infra
merah melebihi 6 m dengan penyerapan air (OH-) yang ketara di antara 2000-3500
cm-1
di dalam kebanyakan sampel kaca yang dikaji. Analisis penyerapan optik
sempadanan di dalam kebanyakan sampel menunjukkan pembentukan sejumlah
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oksigen yang tidak-berkait yang saling bersandar dengan perubahan jurang tenaga
optic hitungan. Ini dengan jelasnya disokong oleh nilai parameter keamatan
t(t=2,4,6) yang diperolehi melalui analisis Judd-Ofelt. Pengurangan nilai 2 dan
6 adalah sangat berkait dengan peningkatan sifat simetri pada sekitaran Er3+
dengan
pembentukan ketumpatan electron yang tinggi pada ligan ion oksigen; atas kerana itu
sifat kovalen yang kuat Er-O terbentuk dengan peningkatan kepekatan pengedopan
Er3+
. Tambahan lagi faktor ini telah menyumbangkan perubahan struktur TeO2
melalui transformasi struktur [TeO4] piramid tiga-penjuru kepada [TeO3] piramid
dua-penjuru disamping perantaraan unit-unit polihedral [TeO3+1] yang dapat
ditentusahkan oleh analisis spektroskopi Raman yang turut mencatatkan tenaga
getaran maksimum fonon di antara 730-750 cm-1
lebih rendah sedikit berbanding
nilai rujukan TeO2 pada 780 cm-1
. Spektra floresen sinaran nampak perubahan-atas
dengan jelasnya memperlihatkan kedua-dua sinaran hijau dan merah setelah
pengujaan LD 980 nm terutamanya bagi kaca-kaca Er3+
-TZT dan Er3+
/Yb3+
-TZPTiN
yang dicirikan oleh proses penyerapan dua atau/dan tiga foton. Sinar infra merah 1.5
m berkeamatan tinggi dengan lebar melebihi 70 nm dan lebar-jalur pengganda
berjulat (500-1300) x 10-28
cm3 diperolehi di dalam kebanyakan sampel-sampel kaca
terdop Er3+
/Yb3+
. Ciri-ciri ini mencadangkan kaca telurit kepelbagaian komposisi
yang dihasilkan berpotensi sebagai bahan optik untuk teknologi komunikasi jalur-
lebar di masa hadapan.
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ACKNOWLEDGEMENTS
Bismillahirrahmanirrahim, In the name of Allah, the Most Beneficent, the Most
Merciful. Alhamdulillah, all the praises and thanks be to ALLAH the Almighty. All
blessing to Prophet Muhammad, Allah blessing be upon him.
First and foremost, I would like to express my gratitude to Professor Dr. Mohd Adzir
bin Mahdi , for his continuous guidance and advice directing me in this research. I
extended my appreciation also to both members of the supervisory committee, Dr
Ahmad Shukri bin Muhammad Noor and Dr Halimah binti Mohamed Kamari. My
gratitude also goes to the Universiti Putra Malaysia and Kementerian Pengajian
Tinggi Malaysia for providing the opportunity and allowing me to pursue my PhD
degree.
My thanks also goes to Low Dimensional Materials Research Center of Jabatan Fizik
Universiti Malaya Kuala Lumpur for the use of UVvis-NIR Spectrophotometer,
FTIR Spectrophotometer and X-ray diffractometer and NANO-SciTech Centre
UiTM Shah Alam Selangor for the use of microRaman-PL instruments. Also my
special thanks to Mr Azham (Ornets Sdn Bhd) and Ms Tan Loo Sing, Mr Kan Chee
Siong (Aseptec Sdn Bhd) for their kindly assistance in fluorescent measurements.
Not to forget as well to all my friends in Photonic and Fiber Optics System
Laboratory, Engineering Faculty, Universiti Putra Malaysia. Last and not least,
millions of loves and appreciations are bound for my parents and family, which I
dedicated this dissertation for the understanding and support.
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Members of the Examination Committee were as follows:
Date: 2 August 2013
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This thesis submitted to the Senate of Universiti Putra Malaysia and has been
accepted as fulfilment of the requirement for the degree of Doctor of Philosophy.
The members of the Supervisory Committee were as follows:
Mohd Adzir bin Mahdi, PhD
Professor
Faculty of Engineering
Universiti Putra Malaysia
(Chairman)
Ahmad Shukri bin Muhammad Noor, PhD
Senior Lecturer
Faculty of Engineering
Universiti Putra Malaysia
(Member)
Halimah binti Mohamed Kamari, PhD
Senior Lecturer
Faculty of Science
Universiti Putra Malaysia
(Member)
_________________________________
BUJANG BIN KIM HUAT, PhD
Professor and Dean
School of Graduate Studies
Universiti Putra Malaysia
Date:
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DECLARATION
I hereby declare that the thesis is based on my original work except for quotations
and citations, which have been duly acknowledged. I also declare that it has not been
previously or concurrently, submitted for any other degree at Universiti Putra
Malaysia or at any other institution.
____________________________
SHARUDIN BIN OMAR BAKI
Date: 14 JUNE 2013
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TABLE OF CONTENTS
Page
ABSTRACT ii
ABSTRAK v
ACKOWLEDGEMENTS viii
APPROVAL ix
DECLARATION xi
LIST OF TABLES xii
LIST OF FIGURES xix
LIST OF ABBREVIATIONS xxx
CHAPTER
1 INTRODUCTION 1
1.1 Rare Earth Doped Tellurite Oxide Glasses 1
1.2 Problem Statement 2
1.3 Objectives 3
1.4 Thesis Outlines 4
2 LITERATURE REVIEW 7
2.1 Glass Forming Characteristics 7
2.1.1 Glass Definition 8
2.1.2 Glass Transformation Behaviour 9
2.2 Theories of Glass Formation 10
2.2.1 Structural Models 11
2.2.1.1 Goldschmidt’s- Ionic Radius Ratio 11
2.2.1.2 Zachariasen’s –The Random Network Model 12
2.2.1.3 Energetic based Models 14
2.2.2 Kinetic Models 18
2.3 Tellurite Glasses Overview 20
2.3.1 Structural and Physical Characteristics 20
2.3.2 Thermal Properties 26
2.3.3 Optical Properties 29
3 THEORY 32
3.1 Spectroscopy of rare earth ions 32
3.3.1 Energy level transitions 32
3.3.2 Electronic structure 36
3.3.3 The Crystal Field effect 38
3.2 Intensity Calculation: The Judd-Ofelt Theory 41
3.3.1 The Judd-Ofelt parameters 41
3.3.2 Transition Probabilities 44
3.3 Nonradiative transitions in rare earth ions 48
3.4 Energy transfer and ions interaction 50
3.4.1 Cross relaxation 51
3.4.2 Excited state absorption 52
3.4.3 Sensitization 53
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3.4.4 Concentration quenching effect 54
3.5 Upconversion 56
4 SAMPLE PREPARATION AND CHARACTERIZATION 58
4.1 Preparation of Glass Samples 58
4.1.1 Glass Composition 58
4.1.2 Glass Batching 61
4.1.3 Melting and Glass Formation 65
4.2 Structural Measurement 67
4.2.1 X-ray diffraction (XRD) 68
4.2.2 Thermal Profiling 68
4.2.3 Density and Molar Volume 70
4.3 Refractive Index Measurement 72
4.3.1 Method and instrumentation 73
4.3.2 Imaging Analysis 76
4.4 Optical Measurement 77
4.4.1 FTIR spectroscopy 78
4.4.2 Raman Spectroscopy 80
4.4.3 Uv-Vis-NIR Absorption 82
4.4.4 Upconversion Spectra 83
4.4.5 Near infra-red (NIR) Emission 85
5 EXPERIMENTAL RESULTS AND ANALYSIS 86
5.1 Structure Properties 86
5.1.1 X-Ray Diffraction (XRD) 91
5.1.2 Thermal Stability 93
5.1.3 Density and Molar Volume 101
5.2 Refractive Index Analysis 114
5.3 Hydroxyl Band Analysis 129
5.4 Raman Spectra Analysis 164
5.5 Optical Energy Gap and Tail Width Analysis 182
5.6 Judd-Ofelt Analysis 205
5.7 Upconversion Analysis 226
5.8 Near infra-red and Emission Cross Section Analysis 240
6 DISCUSSION
6.1 Judd-Ofelt Parameters: Er3+
Nature in Tellurite Glass Structure 257
6.2 Optical Transition Mechanism in Er3+
-doped Tellurite Glasses 266
6.3 1.5 m Emission of Er3+
-doped Tellurite Glasses 279
7 CONCLUSION AND SUGGESTIONS 296
REFERENCES 301
APPENDICES 310
BIODATA OF STUDENT 331
PUBLICATIONS 332
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LIST OF TABLES
Table Page
2.2.1 Classification of Cations as Network Formers, Network Modifiers,
and Intermediates
13
2.2.2 Pauling Electronegativities 15
2.2.3 Bond strength for selected oxides 16
2.3.1 Range (mol%) of glass formation in tellurite glass system 23
2.3.2 Types of coordination of TeO2 in crystalline and glass forms 24
2.3.3 Physical properties among potential glasses 25
2.3.4 Some of related physical properties for selected glass composition 26
2.3.5 The effects of RE dopants on Tg ,Tx and (Tx-Tg) on
[TeO2-ZnO- Na2O] glasses
28
2.3.6 Some of related optical properties for selected glass composition 29
2.3.7 Basic properties for EDTFA and EDSFA 31
3.1.1 The number of 4f electrons (n) in most common trivalent
lanthanides ions
33
4.1.1 (a) Ternary A-TZT (TeO2-ZnO-TiO2) glass compositions 59
(b) Ternary B-TTB (TeO2-TiO2-Bi2O3) glass compositions 59
(c) Ternary C-TPB (TeO2-PbO-Bi2O3) glass compositions 60
4.1.2 Multicomponent-TZPTiN (TeO2-ZnO-PbO-TiO2-Na2O) glass
compositions
60
4.1.3 Glass components and chemicals used to batch glasses, molecular
weight (MW), purity and sources
62
4.1.4 Batching calculation using Excel program 62
4.3.1 Reference table of tabulated d’ values for any possible range of
thicknesses versus the refractive indices
77
5.1.1 Summary of the thermal analysis parameters Tg, Tx, Tc, Tm and
glass stability
100
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5.1.2 Density and Molar Volume of Ternary A-TZT (TeO2-ZnO-TiO2)
glasses
103
5.1.3 Density and Molar Volume of Ternary B-TTB (TeO2-TiO2-Bi2O3)
glasses
106
5.1.4 Density and Molar Volume of Ternary C-TPB (TeO2-PbO-Bi2O3)
glasses
109
5.1.5 Density and Molar Volume of Multicompositions-TZPTiN (TeO2-
ZnO-PbO-TiO2-Na2O) glasses
112
5.2.1 Summarizes of the refractive indices analysis for the host glasses 128
5.3.1 Percentage of OH groups in glass series
(75-x)TeO2-20ZnO-5TiO2-xEr2O3 mol. %
(where x = 0, 0.2, 0.5, 1.0 and 1.5)
135
5.3.2 Er3+
contents, thickness, the free-OH absorption coefficients at
maximum peaks and the free-OH concentrations of (75-x)TeO2-
20ZnO-5TiO2-xEr2O3 mol. % glass series (where x = 0, 0.2, 0.5,
1.0 and 1.5)
137
5.3.3 Percentage of OH groups in glass series
85TeO2-10TiO2-(5-x)Bi2O3-xEr2O3 mol. %
(where x = 0, 0.2, 0.5, 1.0 and 1.5)
142
5.3.4 Er3+
contents, thickness, the free-OH absorption coefficients at
maximum peaks and the free-OH concentrations of 85TeO2-
10TiO2-(5-x)Bi2O3-xEr2O3 mol. % glass series
(where x = 0, 0.2, 0.5, 1.0 and 1.5)
143
5.3.5 Percentage of OH groups in glass series
60TeO2-35PbO-(5-x)Bi2O3-xEr2O3 mol. %
(where x = 0, 0.5, 1.0 and 1.5)
148
5.3.6 Er3+
contents, thickness, the free-OH absorption coefficients at
maximum peaks and the free-OH concentrations of 60TeO2-
35PbO-(5-x)Bi2O3-xEr2O3 mol. % glass series
(where x = 0, 0.2, 0.5, 1.0 and 1.5)
149
5.3.7 Percentage of OH groups in glass series
60TeO2-20ZnO-(3-x)PbO-5TiO2-5Na2O-xEr2O3-2Yb2O3 mol. %
(where x = 0.1, 1, 2 and 2.5)
154
5.3.8 Er3+
contents, thickness, the free-OH absorption coefficients at
maximum peaks and the free-OH concentrations of 60TeO2-
20ZnO-(3-x)PbO-5TiO2-10Na2O-xEr2O3-2Yb2O3 mol. % glass
series (where x = 0, 0.1, 1, 1and 2.5)
156
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5.3.9
Percentage of OH groups in glass series
60TeO2-20ZnO-(8-x)PbO-5TiO2-5Na2O-xEr2O3-2Yb2O3 mol. %
(where x = 0.1, 1, 2 and 2.5)
161
5.3.10 Er3+
contents, thickness, the free-OH absorption coefficients at
maximum peaks and the free-OH concentrations of 60TeO2-
20ZnO-(8-x)PbO-5TiO2-5Na2O-xEr2O3-2Yb2O3 mol. % glass
series (where x = 0, 0.5, 1.0, 2 and 2.5)
163
5.4.1 Summary of the Raman band assignments investigated by
different workers on TeO2 glass systems
166
5.4.2 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TTB3 host glass
168
5.4.3 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TTB22 glass
169
5.4.4 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TTB24 glass
170
5.4.5 Summary of the percentage area of the assigned Raman Gaussian
bands for the TTB glasses.
171
5.4.6 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TPB3 host glass
172
5.4.7 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TPB22 glass
173
5.4.8 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TPB24 glass
174
5.4.9 Summary of the percentage area of the assigned Raman Gaussian
bands for the TPB glasses.
175
5.4.10 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TZPTiN10 host glass
177
5.4.11 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TZPTiN11 glass
178
5.4.12 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TZPTiN12 glass
179
5.4.13 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TZPTiN13 glass
180
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5.4.14 Peak position, width (FWHM) and integrated area
of the assigned Raman Gaussian bands for TZPTiN14 glass
181
5.4.15 Summary of the percentage area of the assigned
Raman Gaussian bands for the TZPTiN1 glasses.
182
5.5.1 Optical energy gap Eopt and Urbach energy EU for TZT glass series
((75-x)TeO2-20ZnO-5TiO2-xEr2O3 mol. %, x = 0, 0.2, 0.5, 1.0 and
1.5)
187
5.5.2 Optical energy gap Eopt and Urbach energy EU for TTB glass
series (85TeO2-10TiO2-(5-x)Bi2O3-xEr2O3 mol. % glass series
(where x = 0, 0.2, 0.5, 1.0 and 1.5)
191
5.5.3 Optical energy gap Eopt and Urbach energy EU for TPB glass series
(60TeO2-35PbO-(5-x)Bi2O3-xEr2O3mol. % ,x = 0, 0.5, 1.0 and 1.5)
195
5.5.4 Optical energy gap Eopt and Urbach energy EU for TZPTiN1 glass
series (60TeO2-20ZnO-(3-x)PbO-5TiO2-10Na2O-xEr2O3-2Yb2O3
mol. %, x = 0.1, 0.5, 1, 2 and 2.5)
199
5.5.5 Optical energy gap Eopt and Urbach energy EU
for TZPTiN2 glass series (60TeO2-20ZnO-(8-x)PbO-5TiO2-
5Na2O-xEr2O3-2Yb2O3 mol. %, x = 0, 0.5, 1.0, 2 and 2.5)
203
5.6.1 Density () and Er3+
concentration (N) for Er3+
doped TZT glasses 208
5.6.2 Tables of selected manifold integrated areas, dipole line strengths
S and calculated JO intensity parameters t=(t=2,4,6) value for
TZT21 glass
209
5.6.3 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZT22 glass
209
5.6.4 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZT23 glass
210
5.6.5 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZT25 glass
210
5.6.6 Summary of the calculated JO intensity parameters t=(t=2,4,6)
value for Er3+
doped TZT glasses
211
5.6.7 Density () and Er3+
concentration (N) for Er3+
doped TTB glasses 211
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5.6.8 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TTB21 glass
212
5.6.9 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TTB22 glass
213
5.6.10 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TTB23 glass
213
5.6.11 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TTB24 glass
214
5.6.12 Summary of the calculated JO intensity parameters t=(t=2,4,6)
value for Er3+
doped TTB glasses
214
5.6.13 Density () and Er3+
concentration (N) for Er3+
doped TPB glasses 215
5.6.14 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TPB22 glass
216
5.6.15 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TPB23 glass
216
5.6.16 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TPB24 glass
217
5.6.17 Summary of the calculated JO intensity parameters t=(t=2,4,6)
value for Er3+
doped TPB glasses
217
5.6.18 Density () and Er3+
concentration (N) for Er3+
doped
TZPTiN1 glasses
218
5.6.19 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZPTiN13 glass
219
5.6.20 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZPTiN14 glass
219
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5.6.21 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZPTiN15 glass
220
5.6.22
Summary of the calculated JO intensity parameters t=(t=2,4,6)
value for Er3+
doped TZPTiN1 glasses
220
5.6.23 Density () and Er3+
concentration (N) for Er3+
doped
TZPTiN2 glasses
221
5.6.24 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZPTiN22 glass
222
5.6.25 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZPTiN23 glass
222
5.6.26 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZPTiN24 glass
223
5.6.27 Table of selected manifold integrated areas, dipole line strengths S
and calculated JO intensity parameters t=(t=2,4,6) value for
TZPTiN25 glass
223
5.6.28 Summary of the calculated JO intensity parameters t=(t=2,4,6)
value for Er3+
doped TZPTiN2 glasses
224
5.6.29 Summary of the calculated JO intensity parameters
of Er3+
ion in different tellurite glass hosts
225
5.7.1 Summary of the total absorption photons in different
Er3+
doped tellurite glasses
239
5.8.1 Summary of the NIR spectroscopic parameters:
peak, Imax , FWHM, peak for selected Er3+
doped tellurite glasses
246
5.8.2 Table of ECS parameters (max , ECSmax), Effective
NIR width and gain bandwidth (GBW) for selected Er3+
doped
tellurite glasses
254
5.8.3 Calculated values for ACS and ECS parameters using McCumber
procedure: peak value (p and p), energy spread (E1, E2), net
free energy (ε) and scaling factor (K)
256
6.1.1 List of JO intensity parameters t (t = 2, 4 and 6) in selected
tellurite host glasses for comparison
265
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6.3.1 JO intensity parameters and related NIR emission parameters,
max, FWHM of the selected Er3+
/Yb3+
doped tellurite glasses
279
6.3.2
Comparison of the JO intensity parameters and related NIR
emission parameters, max, FWHM for Er3+
/Yb3+
doped tellurite
glasses
284
6.3.3 JO intensity parameters and related NIR emission parameters: Sed,
ARad and Rad values for 4I13/2
4I15/2 transition of Er
3+
in selected tellurite glasses
286
6.3.4 Er3+
/Yb3+
concentration and corresponding NR factor values for
free-OH, ET and CR (labelled as A, B/C/D and E columns
respectively)
290
6.3.5 NIR emission parameters: INIR-max, ARad, m, Rad and QE values
for 4I13/2
4I15/2 transition of Er
3+ in selected tellurite glasses
293
6.3.6 Comparison of the NIR emission parameters: ECS, FWHM
and GBW for Er3+
/Yb3+
doped tellurite glasses
295
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LIST OF FIGURES
Figure Page
2.1.1 Structural model molecular arrangement for crystal and glass 8
2.1.2 The glass transformation behaviour 9
2.2.1 Time–temperature-transformation (TTT) curve 20
2.3.1 Structural units in TeO2-ZnO glasses 21
2.3.2 The structural units type and mechanism that involved for M2O
addition
22
2.3.3 The coordination crystal structure of TeO2 24
2.3.4 The typical thermal profile of DSC/TGA 28
2.3.5 The stimulated emission cross section (e) of the 4I13/2-
4I15/2
transition of Er3+
ion in tellurite, fluoride and silica-based glasses
30
3.1.1 Transition mechanisms between two energy levels (a) absorption,
(b) spontaneous emission, and (c) stimulated emission
33
3.1.2 Transition rates between two energy levels at equilibrium 36
3.1-3 The energy levels of some of the trivalent lanthanide ions: Nd3+
,
Er3+
, Yb3+
, Eu3+
, Tb3+
, Sm3+
, Gd3+
, and Pr3+
38
3.2.1 Summary of overall steps for the Judd–Ofelt analysis 47
3.3.1 Non-radiative decay rate as a function of energy gap for glass and
crystal host materials
50
3.4.1 The cross relaxation between two ions 51
3.4.2 Excited state absorption (ESA) mechanism in Er3+
system 52
3.4.3 Direct and indirect excitation involving sensitizer on lanthanide
ions
53
3.4.4 The near infra red emission intensity at 1.5 m as a function of
concentration of Er3+
55
3.5.1 Upconversion mechanisms involves between energy levels and
types: (A) Sequential 2-photon absorption, (B) Energy transfer (ET)
and cross relaxation (CR)
57
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4.1.1 Steps of chemical batching procedures 64
4.1.2 Bench-top high temperature muffle furnace for melting process and
typical temperature profile
66
4.1.3 The mould used in the process of glass quenching 67
4.2.1 The typical glass thermal profile 69
4.2.2 DSC-Mettler Toledo thermal analyzer and aluminium crucibles for
thermal measurements
70
4.2.3 Density measurement via Archimedes’s principle 71
4.3.1 Measurement of glass refractive index (n) through an ‘apparent
depth’ method
74
4.3.2 The refractive index imaging analysis via Image Comparer 3.8
Build 711 (Copyright© 2002-2011 Bolide Software)
75
4.4.1 The configuration of an Fourier Transform InfraRed (FTIR)
Spectrometer by Michelson interferometer basis
80
4.4.2 The microRaman spectroscopy analysis via Horiba Jobin Yvon
micro Raman PL spectrometer
81
4.4.3 Schematic block diagram of the system set-up for the the absorption
spectra spectrophotometers
83
4.4.4 Experimental setup for the upconversion spectra measurements 84
4.4.5 Experimental setup for the near infra red spectra measurements 85
5.1.1 Ternary A-TZT (TeO2-ZnO-TiO2) glass compositions 87
5.1.2 Ternary B-TTB (TeO2-TiO2-Bi2O3) glass compositions 88
5.1.3 Ternary C-TPB (TeO2-PbO-Bi2O3) glass compositions 89
5.1.4 Multicomponent-TZPTiN (TeO2-ZnO-PbO-TiO2-Na2O) glass
compositions
90
5.1.5 XRD traces of TZT3, TTB3, TPB3, TZPTiN10 and TZPTiN20 92
5.1.6 Typical glass thermal profiles in this work 93
5.1.7 Thermal profile for glasses TZT3 (75TeO2–20ZnO-5TiO2 mol%)
and TZT23 (74TeO2–20ZnO-5TiO2-1Er2O3 mol%)
95
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5.1.8 Thermal profile for glasses TTB3 (85TeO2–10TiO2-5Bi2O3 mol%)
and TTB21 (85TeO2–10TiO2-4.8Bi2O3-0.2Er2O3 mol%)
96
5.1.9 Thermal profile for glasses TPB3 (60TeO2–35PbO-5Bi2O3 mol%)
and TPB22 (60TeO2–35PbO-4.5Bi2O3-0.5Er2O3 mol%)
97
5.1.10 Thermal profile for glasses TZPTiN10 (60TeO2–20ZnO2-5PbO-
5TiO2-10Na2O mol%) and TZPTiN12 (60TeO2–20ZnO2-2.5PbO-
5TiO2-10Na2O-0.5Er2O3-2Yb2O3 mol%)
98
5.1.11 Thermal profile for glasses TZPTiN20 (60TeO2–20ZnO2-10PbO-
5TiO2-5Na2O mol%) and TZPTiN22 (74TeO2–20ZnO-5TiO2-
1Er2O3 mol%)
99
5.1.12 Density and molar volume behaviours of TZT glasses as a function
of TiO2 concentration
102
5.1.13 Density and molar volume relationship for TZT3-Er3+
glasses as a
function of Er2O3 concentration
104
5.1.14 Density and molar volume behaviours of TTB glasses as a function
of Bi2O3 concentration
105
5.1.15 Density and molar volume relationship for TTB -Er3+
glasses as a
function of Er2O3 concentration
107
5.1.16 Density and molar volume behaviours of TPB glasses as a function
of Bi2O3 concentration
108
5.1.17 Density and molar volume relationship for TPB -Er3+
glasses as a
function of Er2O3 concentration
110
5.1.18 Density and molar volume relationships for multicomposition
TZPTiN1 glasses as a function of Er2O3 concentration
111
5.1.19 Density and molar volume relationships for TZPTiN2 glasses as a
function of Er2O3 concentration
113
5.2.1
(a)
(b)
The cumulative number of best image pairing (CNB Image Pairing)
at respective travelling microscope (TM) vernier positions for
Corning glass
Captured images comparison for Corning glass
115
116
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5.2.2
(a)
(b)
The cumulative number of best image pairing (CNB Image Pairing)
at respective travelling microscope (TM) vernier positions for
TZT3 host glass
Captured images comparison for TZT3 host glass
117
118
5.2.3
(a)
(b)
The cumulative number of best image pairing (CNB Image Pairing)
at respective travelling microscope (TM) vernier positions for
TTB3 host glass
Captured images comparison for TTB3 host glass
119
120
5.2.4
(a)
(b)
The cumulative number of best image pairing (CNB Image Pairing)
at respective travelling microscope (TM) vernier positions for
TPB3 host glass
Captured images comparison for TPB3 host glass
121
122
5.2.5
(a)
(b)
The cumulative number of best image pairing (CNB Image Pairing)
at respective travelling microscope (TM) vernier positions for
TZPTiN10 host glass
Captured images comparison for TZPTiN10 host glass
123
124
5.2.6
(a)
(b)
The cumulative number of best image pairing (CNB Image Pairing)
at respective travelling microscope (TM) vernier positions for
TZPTiN20 host glass
Captured images comparison for TZPTiN20 host glass
125
126
5.3.1 Infrared transmission spectrum for TZT3 glass 129
5.3.2 Infrared transmission spectra for erbium-doped TZT glasses 130
5.3.3 Infrared absorption spectra for TZT glasses 131
5.3.4 Gaussian deconvolution of OH bands in TZT3 host glass (75TeO2-
20ZnO-5TiO2 mol. %).
132
5.3.5 Gaussian deconvolution of OH bands in TZT21 glass
(74.8TeO2-20ZnO-5TiO2-0.2Er2O3 mol. %).
133
5.3.6 Gaussian deconvolution of OH bands in TZT22 glass
(74.5TeO2-20ZnO-5TiO2-0.5Er2O3 mol. %).
133
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5.3.7 Gaussian deconvolution of OH bands in TZT23 glass
(74 TeO2-20ZnO-5TiO2-1Er2O3 mol. %).
134
5.3.8 Gaussian deconvolution of OH bands in TZT24 glass
(73.5 TeO2-20ZnO-5TiO2-1.5Er2O3 mol. %).
134
5.3.9
OH percentage behaviour in TZT glasses as a function of Er3+
concentration
136
5.3.10 Calculated free-OH content in the TZT glasses with respect to Er3+
doping concentration
137
5.3.11 Infrared transmission and absorption spectra for TTB glasses 139
5.3.12 Gaussian deconvolution of OH bands in TTB3 glass
(85TeO2-10TiO2-5Bi2O3 mol. %)
140
5.3.13 Gaussian deconvolution of OH bands in TTB21 glass
(85TeO2-10TiO2-4.8Bi2O3-0.2Er2O3 mol. %)
140
5.3.14 Gaussian deconvolution of OH bands in TTB22 glass
(85TeO2-10TiO2-4.5Bi2O3-0.5Er2O3 mol. %)
141
5.3.15 Gaussian deconvolution of OH bands in TTB23 glass
(85TeO2-10TiO2-4Bi2O3-1Er2O3 mol. %)
141
5.3.16 Gaussian deconvolution of OH bands in TTB24 glass
(85TeO2-10TiO2-3.5Bi2O3-1.5Er2O3 mol. %)
142
5.3.17 OH percentage behaviour in TTB glasses as a function of Er3+
concentration
143
5.3.18 Calculated free-OH content in the TTB glasses with respect to Er3+
doping concentration
144
5.3.19 Infrared transmission and absorption spectra for TPB glasses 145
5.3.20 Gaussian deconvolution of OH bands in TPB3 host glass
(60TeO2-35PbO-5Bi2O3 mol. %)
146
5.3.21 Gaussian deconvolution of OH bands in TPB22 glass
(60TeO2-35PbO-4.5Bi2O3-0.5Er2O3mol. %)
146
5.3.22 Gaussian deconvolution of OH bands in TPB23 glass
(60TeO2-35PbO-4Bi2O3-1Er2O3mol. %)
147
5.3.23 Gaussian deconvolution of OH bands in TPB24 glass
(60TeO2-35PbO-3.5Bi2O3-1.5Er2O3mol. %)
147
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5.3.24 OH percentage behaviour in TPB glasses as a function
of Er3+
concentration
148
5.3.25 Calculated free-OH content in the TPB glasses with respect to Er3+
doping concentration
149
5.3.26
Infrared transmission and absorption spectra for TZPTiN1 glasses
(TZPTiN10, TZPTiN11, TZPTiN13, TZPTiN14, and TZPTiN15)
151
5.3.27 Gaussian deconvolution of OH bands in TZPTiN10 host glass
(60TeO2-20ZnO-5PbO-5TiO2-10Na2O mol. %)
152
5.3.28 Gaussian deconvolution of OH bands in TZPTiN11 glass
(60TeO2-20ZnO-2.9PbO-5TiO2-10Na2O-0.1Er2O3-2Yb2O3 mol.
%)
152
5.3.29 Gaussian deconvolution of OH bands in TZPTiN13 glass
(60TeO2-20ZnO-2PbO-5TiO2-10Na2O-1Er2O3-2Yb2O3 mol. %)
153
5.3.30 Gaussian deconvolution of OH bands in TZPTiN14 glass
(60TeO2-20ZnO-1PbO-5TiO2-10Na2O-2Er2O3-2Yb2O3 mol. %)
153
5.3.31 Gaussian deconvolution of OH bands in TZPTiN15 glass
(60TeO220ZnO-0.5PbO-5TiO2-10Na2O-2.5Er2O3-2Yb2O3 mol. %)
154
5.3.32 OH percentage behaviour in TZPTiN1 glasses as a function of Er3+
concentration
155
5.3.33 Calculated free-OH content in the TZPTiN1 glasses with respect to
Er3+
doping concentration
156
5.3.34 Infrared transmission and absorption spectra for TZPTiN2 glasses
(TZPTiN20, TZPTiN22, TZPTiN23, TZPTiN24, and TZPTiN25)
158
5.3.35 Gaussian deconvolution of OH bands in TZPTiN20 host glass
(60TeO2-20ZnO-10PbO-5TiO2-5Na2O mol. %)
159
5.3.36 Gaussian deconvolution of OH bands in TZPTiN22 glass (60TeO2-
20ZnO-7.5PbO-5TiO2-5Na2O-0.5Er2O3-2Yb2O3 mol. %)
159
5.3.37 Gaussian deconvolution of OH bands in TZPTiN23 glass (60TeO2-
20ZnO-7PbO-5TiO2-5Na2O-1Er2O3-2Yb2O3 mol. %)
160
5.3.38 Gaussian deconvolution of OH bands in TZPTiN24 glass
(60TeO220ZnO-6PbO-5TiO2-5Na2O-2Er2O3-2Yb2O3 mol. %)
160
5.3.39 Gaussian deconvolution of OH bands in TZPTiN25 glass (60TeO2-
20ZnO-5.5PbO-5TiO2-5Na2O-2.5Er2O3-2Yb2O3 mol. %)
161
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5.3.40 OH percentage behaviour in TZPTiN2 glasses as a function of
Er3+
concentration
162
5.3.41 Calculated free-OH content in the TZPTiN2 glasses with respect to
Er3+
doping concentration
163
5.4.1 Typical Raman spectra for TeO2 glass system 165
5.4.2 Gaussian deconvolution of Raman spectra for
TTB3 host glass (85TeO2-10TiO2-5Bi2O3 mol. %)
168
5.4.3 Gaussian deconvolution of Raman spectra for
TTB22 glass (85TeO2-10TiO2-4.5Bi2O3-0.5Er2O3 mol. %)
169
5.4.4 Gaussian deconvolution of Raman spectra for
TTB24 glass (85TeO2-10TiO2-3.5Bi2O3-1.5Er2O3 mol. %)
170
5.4.5 Gaussian deconvolution of Raman spectra for
TPB3 host glass (60TeO2-35PbO-5Bi2O3 mol. %)
172
5.4.6 Gaussian deconvolution of Raman spectra for
TPB22 glass (60TeO2-35PbO-4.5Bi2O3-0.5Er2O3mol. %)
173
5.4.7 Gaussian deconvolution of Raman spectra for
TPB24 glass (60TeO2-35PbO-3.5Bi2O3-1.5Er2O3mol. %)
174
5.4.8 Gaussian deconvolution of Raman spectra for TZPTiN10 host
glass (60TeO2-20ZnO-5PbO-5TiO2-10Na2O mol. %)
177
5.4.9 Gaussian deconvolution of Raman spectra for TZPTiN11 glass
(60TeO2-20ZnO-2.9PbO-5TiO2-10Na2O-0.1Er2O3-2Yb2O3 mol.
%)
178
5.4.10 Gaussian deconvolution of Raman spectra for TZPTiN12 glass
(60TeO2-20ZnO-2.5PbO-5TiO2-10Na2O-0.5Er2O3-2Yb2O3 mol.
%)
179
5.4.11 Gaussian deconvolution of Raman spectra for TZPTiN13 glass
(60TeO2-20ZnO-2PbO-5TiO2-10Na2O-1Er2O3-2Yb2O3 mol. %)
180
5.4.12 Gaussian deconvolution of Raman spectra for TZPTiN14 glass
(60TeO2-20ZnO-1PbO-5TiO2-10Na2O-2Er2O3-2Yb2O3 mol. %)
181
5.5.1 Tauc’s plot of (h)1/2
vs. hfor TZT3 host glass 185
5.5.2 Tauc’s plot of (h)1/2
vs. hfor Er3+
doped glasses:
TZT21, TZT22, TZT23 and TZT24
185
5.5.3 Plot of ln() vs. hfor TZT3 host glass 186
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5.5.4 Plot of ln() vs. h for Er3+
doped glasses:
TZT21, TZT22, TZT23 and TZT24
186
5.5.5 Eopt variation with respect to Er3+
content for TZT glasses 188
5.5.6 Tauc’s plot of (h)1/2
vs. hfor TTB3 host glass 189
5.5.7 Tauc’s plot of (h)1/2
vs. hfor Er3+
doped glasses:
TTB21, TTB22, TTB23 and TTB24
189
5.5.8 Plot of ln() vs. hfor TTB3 host glass 190
5.5.9 Plot of ln() vs. h for Er3+
doped glasses:
TTB21, TTB22, TTB23 and TTB24
190
5.5.10 Eopt variation with respect to Er3+
content for TTB glasses 192
5.5.11 Tauc’s plot of (h)1/2
vs. hfor TPB3 host glass 193
5.5.12 Figure 5.5-12. Tauc’s plot of (h)1/2
vs. hfor Er3+
doped glasses:
TPB22, TPB23 and TPB24
193
5.5.13 Plot of ln() vs. hfor TPB3 host glass 194
5.5.14 Plot of ln() vs. h for Er3+
doped glasses:
TPB22, TPB23 and TPB24
194
5.5.15 Eopt variation with respect to Er3+
content for TPB glasses 196
5.5.16 Tauc’s plot of (h)1/2
vs. hfor TZPTiN10 host glass 197
5.5.17 Tauc’s plot of (h)1/2
vs. hfor Er3+
doped glasses: TZPTiN11,
TZPTiN12, TZPTiN13, TZPTiN14, and TZPTiN15
197
5.5.18 Plot of ln() vs. hfor TZPTiN10 host glass 198
5.5.19 Plot of ln() vs. h for Er3+
doped glasses:
TZPTiN11, TZPTiN12, TZPTiN13, TZPTiN14, and TZPTiN15
198
5.5.20 Eopt variation with respect to Er3+
content for TZPTiN1 glasses 200
5.5.21 Tauc’s plot of (h)1/2
vs. hfor TZPTiN20 host glass 201
5.5.22 Tauc’s plot of (h)1/2
vs. hfor Er3+
doped glasses:
TZPTiN22, TZPTiN23, TZPTiN24and TZPTiN25
201
5.5.23 Plot of ln() vs. hfor TZPTiN20 host glass 202
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5.5.24 Plot of ln() vs. h for Er3+
doped glasses:
TZPTiN22, TZPTiN23, TZPTiN24and TZPTiN25
202
5.5.25 Eopt variation with respect to Er3+
content for TZPTiN2 glasses 204
5.6.1 Typical absorption spectra of the Er3+
doped glass in the visible and
near-infrared region
206
5.6.2 Typical Gaussian fitting for measuring the integrated area
of the Er3+
absorption bands
207
5.6.3 The UV-VIS-NIR absorption spectra for Er3+
doped TZT glasses
208
5.6.4 The UV-VIS-NIR absorption spectra for Er3+
doped TTB glasses 212
5.6.5 The UV-VIS-NIR absorption spectra for Er3+
doped TPB glasses 215
5.6.6 The UV-VIS-NIR absorption spectra for Er3+
doped TZPTiN1
glasses
218
5.6.7 The UV-VIS-NIR absorption spectra for Er3+
doped TZPTiN2
glasses
221
5.7.1 Upconversion spectra for TZT21 glass 227
5.7.2 Log-log plot of power dependence analysis for TZT21 glass 228
5.7.3 Normalized upconversion spectra of TZT glasses
in different concentration of Er3+
229
5.7.4 Upconversion spectra for TTB22 glass 230
5.7.5 Log-log plot of power dependence analysis for TTB22 glass 230
5.7.6 Normalized upconversion spectra of TZT glasses in different
concentration of Er3+
231
5.7.7 Upconversion spectra for TPB24 glass 232
5.7.8 Log-log plot of power dependence analysis for TPB24 glass 233
5.7.9 Normalized upconversion spectra of TPB glasses in different
concentration of Er3+
234
5.7.10 Upconversion spectra for TZPTiN15 glass 235
5.7.11 Log-log plot of power dependence analysis for TZPTiN15 glass 235
5.7.12
Normalized upconversion spectra of TZPTiN1 glasses
in different concentration of Er3+
236
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5.7.13 Upconversion spectra for TZPTiN25 glass 237
5.7.14 Normalized upconversion spectra of TZPTiN25 glasses
in different concentration of Er3+
238
5.7.15 Normalized upconversion spectra of TZPTiN2 glasses
in different concentration of Er3+
239
5.8.1 Near infrared (NIR) fluorescence emission for TZT21 glass 240
5.8.2 Near infrared (NIR) fluorescence emission for TZT24 glass 241
5.8.3 Near infrared (NIR) fluorescence emission for TTB21 glass 241
5.8.4 Near infrared (NIR) fluorescence emission for TTB22 glass 242
5.8.5 Near infrared (NIR) fluorescence emission for TPB23 glass 242
5.8.6 Near infrared (NIR) fluorescence emission for TPB24 glass 243
5.8.7 Near infrared (NIR) fluorescence emission for TZPTiN13 glass 243
5.8.8 Near infrared (NIR) fluorescence emission for TZPTiN15 glass 244
5.8.9 Near infrared (NIR) fluorescence emission for TZPTiN23 glass 244
5.8.10 Near infrared (NIR) fluorescence emission for TZPTiN25 glass 245
5.8.11 Absorption and emission cross sections spectra for TZT21 glass 249
5.8.12 Absorption and emission cross sections spectra for TZT24 glass 249
5.8.13 Absorption and emission cross sections spectra for TTB21 glass 250
5.8.14 Absorption and emission cross sections spectra for TTB22 glass 250
5.8.15 Absorption and emission cross sections spectra for TPB23 glass 251
5.8.16 Absorption and emission cross sections spectra for TPB24 glass 251
5.8.17 Absorption and emission cross sections spectra for TZPTiN13 glass 252
5.8.18 Absorption and emission cross sections spectra for TZPTiN15 glass 252
5.8.19 Absorption and emission cross sections spectra for TZPTiN23 glass 253
5.8.20 Absorption and emission cross sections spectra for TZPTiN25 glass 253
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6.1.1 Relationship between the t (t=2, 4, 6) parameters as a function of
Er3+
concentration (NEr3+
) in ternary TZT, TTB and TPB glass
composition
263
6.1.2 Relationship between the t (t=2, 4, 6) parameters as a function of
Er3+
concentration (NEr3+
) in multicomposition TZPTiN1 and
TZPTiN2 glass composition
264
6.2.1 Simplified energy level scheme and optical transition of the Er3+
under 980 nm excitation
266
6.2.2 Schematic optical transition mechanisms for Er3+
-doped TZT
glasses
271
6.2.3 Schematic optical transition mechanisms for Er3+
-doped
TTB glasses
273
6.2.4 Schematic optical transition mechanisms for Er3+
-doped TPB
glasses
275
6.2.5 Schematic optical transition mechanisms for
multicomposition Er3+
-Yb3+
doped TZPTiN glasses
278
6.3.1 Relationship between 6 and max for the
selected Er3+
/Yb3+
doped tellurite glasses 281
6.3.2 Relationship between 2 and FWHM for the
selected Er3+
/Yb3+
doped tellurite glasses 283
6.3.3 Relationship between intensity parameter 6 parameter, line
strength Sed, and radiative lifetime Rad of Er3+
in selected tellurite
glasses
286
6.3.4 Proposed quenching mechanism between the Er3+
ions and free-OH
group
288
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LIST OF ABBREVIATIONS
CN Coordination number
CNB Cumulative number of best image pairing
CR Cross relaxation
DSC Differential scanning calorimetry
DTA Differential thermal analysis
ECS Emission cross section
ED Electric dipoles
EDSFA Silica based erbium-doped fiber amplifier
EDTFA Tellurite-based erbium-doped fiber amplifier
ESA Excited state absorption
ET Energy transfer
FTIR Fourier Transform Infra Red Spectroscopy
FWHM Emission width /Full width at half maximum
GBW Optical gain bandwidth
GSA Ground state absorption
HMO Heavy metal oxide
HR Hruby’s parameter (or ratio)
IR Infrared
JO Judd-Ofelt
LD Laser diode
MD Magnetic dipole line strength
MRP Multiphonon relaxation process
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MW Molecular weight
NBO Non-bridging oxygen
NIR Near infra red
OD Optical density
RE Rare earth
RNM Random Network Model
TM Travelling microscope
TTT Time–temperature-transformation
UV Ultraviolet
VIS Visible
XRD X-ray diffraction
ε Net free energy required to excite one Er3+
from the 4I15/2 to
4I13/2
Wnr Nonradiative rate
VM Molar volume
Tx Crystallization onset temperature
tp Trigonal pyramid
Tm Melting temperature
Tg Glass transformation/transition temperature
tbp Trigonal bipyramid
Smeas Measured line strength
Sed Electric dipole line strength
Scalc Theoretically/calculated electric dipole line strength
n Refractive index
k(λ) Absorption coefficient
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Imax Maximum intensity
EU Urbach energy
Er3+
erbium ions
Eopt Optical energy gap
AT Spontaneous transition probabilities
t JO intensity parameters
Rad Radiative lifetimes
peak/max Peak wavelength
exp Experimental/Measured lifetime
e Emission cross section
a Absorption cross section
peak Effective width of the emission band
Lifetime
Quantum efficiency
Branching ratios
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CHAPTER 1
INTRODUCTION
1.1 Rare Earth Doped Tellurite Oxide Glasses
Tellurite oxide (TeO2) glasses have been identified an attracted optical glass
materials due to their interesting properties as compared to other glass types. The
glasses have advantages of good combination of physical and thermal stability,
mechanical strength and chemical durability. Among oxide based glasses such as
germinate, phosphate, borate and silicate glasses, TeO2 based glasses posses
comparatively smaller phonon energies [1]. Moreover, they also exhibit low optical
attenuation between 0.4 and 5 μm range, broad infrared transmission (as low from 4
um to 6 um range), high refractive index and excellence rare earth (RE) solubility,
which promoted better radiative transitions mechanism in the RE ions. Erbium ion
(Er3+
) has been identified as an ideal and excellence existing candidate RE ions as it
emits both in visible (upconversion) and infrared by excitation of 800 and 980 nm
laser diodes (LD) [2-3]. Due to the above factors, much efforts has been focused to
exploit them as prospect photonic materials for the applications of optical fiber
amplifiers and upconversion lasers, nonlinear optical devices, optical data storage
and sensors [4-6]. Today with the intensive computer networks development
especially in data transmission services of the wavelength division multiplexing
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(WDM) system has prompted much investigation into extending the bandwidth
which can be addressed by optical amplification [7-9].
1.2 Problem Statement
The searching for novel glass composition for this low phonon oxides is a challenge
for both material and optical glass designer due to the current demand for low loss
broadband and flat gain amplifiers applications. Due to rapid development of
broadband erbium-doped fiber amplifiers (EDFA) in recent years, broader bandwidth
above 50 nm than silica-based EDFA at the 1.5 μm optical telecommunication
window for erbium-doped tellurite oxide glasses are expected could be obtained.
Several proposed oxide glass components such as ZnO, TiO2, Bi2O3, PbO, and WO3
are among potential candidates for this purpose. Thus selection of appropriate
composition is very crucial task since it will affect the physical, chemistry and
optical properties of the glass host. ZnO has been known an excellent glass modifier
which facilitate easy glass formation in parent TeO2 glass matrix [10]. The addition
of TiO2 on the other hand will enhance both linear and nonlinear optical properties
of the glass [11]. Recently Bi2O3, PbO, and WO3 which are also referred as heavy
metal oxides (HMO) form an important class of glass materials for photonic
devices. These oxides would contribute significant structural and optical glass
properties since they comprise of heavy, low field strength and high polarizability
behaviour [12]. In this study differentxxcompositions of ternary and
multicomposition tellurite based glasses were fabricated. It is to note that in the
realization of the desired end glass host properties, selection of the right glass
formulation or batching procedure and glass fabrication parameter: melting
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temperature, time and surrounding ambient condition (open/closed-circulated gasses
feeding) are seriously taken into consideration. It is to ensure glassy, transparency,
homogeneity and contamination-free of the fabricated glass samples are fulfilled.
1.3 Objectives
The features exhibited by rare-earth ions especially Er3+
-doped tellurite oxide based
glasses as mentioned above have been recognised as factors that triggered the
motivation to exploit the potential of this materials in the area of telecommunication
technology. The main goals of this study are to formulate and fabricate a new
tellurite based multicomponent (ternary and above) glass compositions which posses
better glass stability and optical performance. The roles of each glass constituent in
this complex amorphous structure, expected to provide an interesting physical and
optical characteristic are to be explored.
In order to obtain high performance broad and intense 1.5 m emission due to
transition of 4I13/2
4I15/2 of Er
3+ in tellurite based glasses, nature of the dopant site of
the glass matrix need to be well understood. Both theoretical and experimental
techniques are adopted in this work to explore the fascinating Er3+
behaviour in the
amorphous nature of glass. The theoretical Judd-Ofelt (JO) approach is a
comprehensively spectroscopic analysis attribute to the intensity of RE ions. The
analytical calculation procedure of the intensity parameters which also referred to JO
intensity parameters, t(t=2,4.6) involve tedious multiple equation solving has
allowed for the calculation of manifold to manifold transition probabilities, from
which the radiative lifetimes and branching ratios of emission can be determined
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[13]. In addition the absorption-emission probabilities or cross section relationship
due to 4I13/2
4I15/2 of Er
3+ may also be predicted through the reciprocity relation of
the McCumber theory. Furthermore the optical performance of Er3+
-doped tellurite
based glasses are often compromise with luminescence quenching factors attributed
to nature of the glass host, rare-earth doping concentration and existing hydroxyl
(OH-) groups. All these factors are commonly referred to the contribution from non-
radiative processes which compete with the radiative counterpart and reflected by the
quantum efficiency of studied glass. Finally through the fluorescence spectra
observation an optical transition mechanism could be proposed in explaining the
physical mechanism processes that probably involved in the corresponding glass.
1.4 Thesis Outlines
Chapter 2 of this thesis presents a review on the principle of glass formation which
defines and explains some basic structural and kinetic theories of glass. The model of
glass theories and its formation mechanisms are fundamental elements to understand
glasses behaviour even more better. It then followed by a detail review specifically
on tellurite glasses which describe some of its special physical and optical features
as compared to other glasses.
The rare-earth ions in glasses phenomena and some of its fundamental
characteristics are very important resources in this study especially the role of Er3+
ions in the tellurite glass host are presented in Chapter 3. It begins with the basic rare
earth spectroscopic theory which account for the observed intensity absorption
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spectra of the rare-earth ions in solids. This is followed by the theory of Judd-Ofelt
where the related absorption intensity parameters t(t=2,4.6) are obtained through a
comprehensive numerical calculation procedure. Also included in this chapter some
of the nonradiative factors that may affect glass optical performance. A special topic
on upconversion process is given at the end of the chapter, attribute to anti-Stokes
emission phenomenon which known strongly exhibited in most Er3+
doped glasses.
The glass sample preparation and method of characterizations shall be highlighted in
Chapter 4. The steps of important procedure together with details of preparation
conditions are described here. Beginning with glass sample formulation, then the
batching procedure and glass fabrication are mentioned in lengthy. Both structural
and optical characterization techniques that utilized in the present study are
illustrated in detail. The particulars of the material characterization and
instrumentation are also specified in this chapter.
Chapter 5 presents the experimental data and result analysis of the measurements
described in Chapter 4. Section 5.1 describes the amorphous nature and thermal
properties of glass are investigated. The glass refractive index is determined in
Section 5.2. Details of the analytical techniques involved in the determining of
water (OH-) content and TeO2 structural units ([TeO4] tbp, [TeO3] tp, [TeO3+1]
polyhedral) are presented clearly in section 5.3 and 5.4 respectively. Section 5.5
is describing the optical energy gap (Eopt) behaviour in the present glass and its
variation upon different compositions. This is follows by comprehensive JO
result analysis in Section 5.6 describing the nature of the Er3+
ions inside the glass
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host where related intensity parameters are obtained. The upconversion spectra at
different excitation laser diode (LD) power of wavelength 980 nm are analyzed in
Section 5.7. Finally the near infrared (NIR) 1.5 m emission due to the transition of
4I13/2
4I15/2 of Er
3+ for selected glasses are presented in Section 5.8.
In Chapter 6 the nature of the Er3+
ions vicinity in the glass matrix corresponding to
interaction with surrounding ligands are interpreted in details through the obtained
t(t=2,4,6) values which are strongly related to structural modification of the
constituent glass composition. Details proposed optical transition mechanisms of
Er3+
ions which possibly involved in the present glasses are also elaborated in length
based on both fluorescence upconversion and NIR spectra. Further discussion
specifically focused on the NIR 1.5 m emission due to the transition of 4I13/2
4I15/2
of Er3+
for selected glasses are presented here. The prospect for photonic device
materials and its potential are explored through the obtained t(t=2,4,6) values,
electric dipole line strength (Sed), spontaneous transition probabilities (AT),
absorption and emission cross section (a and e), emission width (FWHM), lifetime
and quantum efficiency ().
Finally, Chapter 7 summarizes the results obtained in the present studies and
explores the possibility of further works in this area of research.
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301
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