UNIVERSITI PUTRA MALAYSIA

HAMID-REZA BAHARI POOR FARKOOSH

FS 2012 51

STRUCTURAL, OPTICAL, AND PHYSICAL PROPERTIES OF GeO2-PbOBi2O3 GLASS

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STRUCTURAL, OPTICAL, AND PHYSICAL PROPERTIES OF GeO2-PbO-

Bi2O3 GLASS

By

HAMID-REZA BAHARI POOR FARKOOSH

Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia,

in Fulfilment of the Requirements for the Degree of Doctor of Philosophy

December 2012

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DEDICATION

Any beauty, harmony, and knowledge includes in this dissertation has been donated

to me from GOD and I pass to him with pleasure. This dissertation dedicated to the

only reality of universe, my merciful GOD.

It is dedicated to all merciful humans who tried honestly, bravely and persistently to

develop people’s realization of universe and help them to leave with happiness,

felicity and blessing.

I dedicate this thesis to my family who helped me during my study life. This

dissertation is dedicated to my Father who spiritually and financially supported me in

all of my study duration, especially in my PhD that which I was fully supported by

him. It is dedicated to my Mother because of her continues and deep spiritual

supports and encouragements. I dedicate also, this dissertation to my kind Sister who

patiently tolerated me and compassionately encouraged me during my stay in

Malaysia especially in onerous difficulties.

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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

STRUCTURAL, OPTICAL, AND PHYSICAL PROPERTIES GeO2-PbO-Bi2O3

GLASS

By

HAMID-REZA BAHARI POOR FARKOOSH

December 2012

Chair: Prof Sidek Abd. Aziz, PhD

Faculty: Faculty of Science

The lead bismuth germanate glasses are of growing interest, due to their low cut-off

optical phonon energy, high linear and nonlinear refractive index and excellent

infrared transmission. Fabrication of metallic nanostructures embedded in glass

matrix also attracts many researchers because of their enhancement ability of

photoluminescence and optical nonlinearity. However, fabrication of metallic

nanostructure other than sphere in glass matrix still is a challenge where met with a

very limited success. To achieve the research objectives, the undoped and Er3+

/Yb3+

doped germanate based glasses samples were prepared. This thesis reports the

preparation of GeO2-PbO-Bi2O3 ternary glass system with and without Er3+

/Yb3+

by

melt cast-quenching method. All samples are studied by a wide range of

characterization techniques which includes their structure, elastic and optical

properties. An attempt has been made to add silver nanostructures into the germanate

based glasses by thermal reduction of melt-quenched glass in order to study the

formation of nanostructures in the vitreous network.

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In the germanate based glasses system the bismuth atom will be substituted by the

lead atom to achieve almost mass independent properties due to their closeness of

atomic masses. Structure and physical properties were studied by X-ray diffraction,

Fourier transform infra-red (FTIR), density, ultrasonic velocities, UV-Visible

absorption, photoluminescence and transmission electron microscopy (TEM). All of

the samples were fully amorphous and their density, ultrasonic velocities and elastic

moduli are relatively low for high lead content samples. FTIR peaks related to PbO

covalent bond and bending Bi-O bond of BiO6 group which are formed when both

Pb and Bi act the role of former in glass network, were observed in high lead content

samples in contrast with low lead samples. The FTIR data also showed that

germanium participated in glass structure with both of four-fold and six-fold

coordination in all of samples. The UV-visible absorption of the glasses studied

showed highest energy of band-gap for Pb-rich samples and also showed

characteristic peaks of Er3+

/Yb3+

ions. The photoluminescence spectrum obtained by

excitation at wavelengths of highest absorption peaks, showed highest intensities for

samples with highest lead content which related to lowest non-radiative relaxation in

Pb-rich samples.

The GeO2-PbO glass dopped with Er2O3, Yb2O3 and AgNO3 were also prepared by

melt quenching method. Annealing of the glass were utilized for thermally reducing

of Ag+ ions to metallic silver. The TEM results showed that the annealing process at

450˚C caused the formation of silver nanoparticles of about 3 nm mean diameter

size. The samples which were annealed at 400˚C temperature showed the formation

of silver nanoplates with mean length size of 60 nm embedded in glass matrix. The

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UV-Visible absorption also confirmed the existence of metallic silver nanostructure.

The FTIR shows peaks at 470 cm-1

for 450˚C annealed samples, in contrast with

400˚C annealed samples, which suggest the existence of Pb-O chains in the

germanate glass network. This is the main source of difference in formation of

various nano structures due to different stabilizing medium and better physical

isolation of glass matrix in 450˚C annealed samples.

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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai

memenuhi keperluan untuk ijazah Doktor Falasafah

STRUKTUR, SIFAT-SIFAT OPTIK DAN FIZIKAL KACA GeO2-PbO-Bi2O3

Oleh

HAMID-REZA BAHARI POOR FARKOOSH

Disember 2012

Pengerusi: Prof Sidek Abd. Aziz, PhD

Fakulti: Fakulti Sains

Kaca bismut germanat semakin diminati penyelidik disebabkan oleh tenaga optik

fonon bertenaga rendah, indeks pembiasan linear dan tak linear yang tinggi serta

proses penghantaran inframerah yang baik. Fabrikasi nanostruktur logam yang

berada dalam matrik kaca juga menarik perhatian ramai penyelidik kerana

keupayaannya dalam peningkatan fotoluminesen dan juga ketaklinearan optik. Walau

bagaimanapun, fabrikasi nanostruktur logam selain daripada sfera di kaca matrik

masih merupakan satu cabaran dengan sedikit kejayaan. Bagi mencapai objektif

kajian, kaca germanat yang didop dantanpa didop dengan Er3+

/Yb3+

telah berjaya

disediakan. Tesis ini melaporkan penyediaan sistem kaca ternari GeO2-PbO-Bi2O3

yang didop dan tanpa dengan Er3+

/Yb3+

menerusi kaedah acuan leburan pelindapan.

Kesemua sampel dikaji menerusi pelbagai teknik pencirian termasuklah struktur,

sifat elastik dan optik. Satu usaha telah dilakukan dengan menambah nanostruktur

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perak ke dalam kaca berasaskan germanat menerusi kaedah pengurangan terma

peleburan bagi mengkaji pembentukan nanostruktur dalam rangkaian kaca.

Bagi semua kaca germanat, atom bismut akan digantikan dengan atom plumbum

untuk mencapai kebebasan dari faktor jisim disebabkan jisim atom mereka yang

hampir sama. Struktur dan sifat fizikal dikaji menerusi pembelauan sinar-X, jelmaan

Fourier infra-merah (FTIR), ketumpatan, halaju ultrasonik, penyerapan UV-nyata,

fotoluminesen dan juga mikroskop elektron transmisi (TEM). Semua sampel

sepenuhnya amorfus dan ketumpatan, halaju ultrasonik dan modulus elastik adalah

agak rendah bagi sampel kaca berkandungan plumbum yang tinggi. Puncak FTIR

yang berkaitan dengan ikatan kovalen PbO dan ikatan kelenturan Bi-O bagi

kumpulan BiO6 terbentuk apabila kedua-dua Pb dan Bi berperanan sebagai

pembentuk rangkaian kaca; perkara ini telah diperhatikan bagi sampel berkandungan

plumbum yang tinggi berbanding dengan sampel berkandungan plumbum yang

rendah. Data FTIR juga menunjukkan bahawa germanium mengambil peranan dalam

struktur kaca dengan kedua-dua koordinasi iaitu empat dan enam –lipatan dalam

kesemua sampel. Penyerapan UV-nyata bagi kaca kajian menunjukkan jurang tenaga

tinggi bagi sampel yang kaya Pb dan juga menunjukkan puncak ciri bagi Er3+

/Yb3+

ion. Spektrum fotoluminesen diperolehi menerusi pengujaan pada jarak gelombang

puncak penyerapan, menunjukkan keamatan tertinggi bagi sampel dengan

berkandungan plumbum yang tinggi dan berkaitan dengan proses relaksasi terendah

bukan radiatif bagi sampel tersebut.

Kaca GeO2-PbO didop dengan Er2O3, Yb2O3 dan AgNO3 juga disediakan menerusi

kaedah leburan pelendapan. Proses penyepuhlindapan kaca telah dilaksanakan bagi

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menukar ion Ag+ kepada logam perak. Hasil kajian TEM menunjukkan bahawa

proses penyepuhlindapan pada 450˚C berupaya membentuk nanopartikel perak

bergarispusat purata kira-kira 3 nm. Sampel yang telah disepuhlindap pada suhu

400˚C menunjukkan pembentukan nanoplat perak bersaiz purata 60 nm panjang

tertanam dalam matrik kaca. Penyerapan UV nyata juga mengesahkan kewujudan

nanostruktur logam perak. Data FTIR menunjukkan puncak 470 cm-1

pada 450˚C

bagi sampel tersepuhlindap, berbanding pada suhu 400˚C ; hal ini mengesahkan

kewujudan rantaian rangkaian Pb-O kaca germanat. Ini adalah sumber utama

perbezaan dalam pembentukan pelbagai struktur nano kerana kelainan kestabilan

media dan pengasingan fizikal matrik kaca pada 450˚C bagi sampel yang

disepuhlindap.

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ACKNOWLEDGEMENTS

I thank my supervisory committee for any supports during my stay in UPM. The

financial support from Universiti Putra Malaysia, under the Research University

Grant Scheme, vote no. 91748, the faculty of science for sample preparation and for

XRD, FTIR, Ultrasonic, UV-Visible absorption and PL facilities and also institute of

bioscience for TEM service are gratefully acknowledged.

I would like to thank my friends who helped me to have a nice and friendly

environment convenient for study. My sincere and deepest thanks are due to my

friend Dr Reza Zamiri because of his insight, honesty and encouragement in my

research work.

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This thesis was 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:

Sidek Haji Abd Aziz, PhD

Professor

Faculty of Science

Universiti Putra Malaysia

(Chairman)

Halimah Mohamed Kamari, PhD

Senior Lecturer

Faculty of Science

Universiti Putra Malaysia

(Member)

Wan Mahmood Wan Yunus, PhD

Professor

Faculty of Science

Universiti Putra Malaysia

(Member)

Faisal Rafiq Bin Mohamd Adikan, PhD

Senior Lecturer

Faculty of Engineering

University of Malaya

(Member)

______________________

BUJANG BIN KIM HUAT, PhD

Professor and Dean

School of Graduate Studies

Universiti Putra Malaysia

Date:

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DECLARATION

I declare that the thesis is my original work except for quotations and citations which

have been duly acknowledged. I also declare that it has notbeen previously, and is

not concurrently, submitted for any other degree at Universiti Putra Malaysia or at

any other institution.

______________________

Hamid-Reza Bahari Poor Farkoosh

Date: 13 December 2012

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TABLE OF CONTENTS

Page

DEDICATION ii

ABSTRACT iii

ABSTRAK vi

ACKNOWLEDGEMENTS x

APPROVAL xi

DECLARATION xii

LIST OF TABLES xv

LIST OF FIGURES xvii

LIST OF ABBREVIATIONS xxiii

CHAPTER

1 INTRODUCTION 1

1.1. General Introduction 1

1.2.Problem statement 4

1.3.Research objectives 8

1.4.Chapter organization 9

2 LITERATURE REVIEW 10

2.1.GeO2 glass system 10

2.2.GeO2-PbO-Bi2O3 glass system 13

2.3.Rare-Earth doped glass 16

2.4. Nanoparticles embedded in glass matrix 23

3 METHODOLOGY 28

3.1.Sample preparation 28

3.1.1. Sample coding and formula 31

3.1.2. Melt-cast-quenching technique 34

3.1.3. Weighing 36

3.1.4. Cutting, polishing and grounding 38

3.2.Sample characterization 39

3.2.1. XRD 39

3.2.2. Density 40

3.2.3. Ultrasonic velocities and elastic properties 41

3.2.4. FTIR 44

3.2.5. UV-Visible Absorption 46

3.2.6. Photoluminescence 48

3.2.7. TEM 50

4 RESULTS AND DISCUSSION 51

4.1.Structure and elastic properties 51

4.1.1. Set A: Primary series 51

4.1.1.1.Density and ultrasonic velocity 52

4.1.2. Set B: GPB5XX series 56

4.1.2.1. XRD, density and molar volume 56

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4.1.2.2.Ultrasonic velocities and elastic moduli 60

4.1.2.3.Power law of bulk modulus and ring

deformation model 64

4.1.2.4.Poisson’s ratio, Fractal bond connectivity 68

4.1.2.5.FTIR 70

4.1.3. Set C: GPB6XX series 75

4.1.3.1.XRD and FTIR 75

4.1.3.2.Density, ultrasonic velocities and

elastic moduli 81

4.1.3.3.Poisson’s ratio, Fractal bond

connectivity and Debye temperature 85

4.2.Optical properties 88

4.2.1. Set C: GPB6XX series 88

4.2.1.1.Debye temperature 89

4.2.1.2.UV-Visible absorption 90

4.2.1.3.Photoluminescence 95

4.2.1.4.Dependence of PL intensities to glass host 104

4.3.In-situ fabrication of Nanostructures in glass matrix

and its properties 107

4.3.1. Set D:GP55-T450 series 107

4.3.1.1.UV-Visible absorption results 107

4.3.1.2.TEM results 109

4.3.1.3.FTIR results 117

4.3.1.4.Discussion 119

4.3.2. Set E: GP55-T400 series 121

4.3.2.1.TEM results 121

4.3.2.2.FTIR results 130

4.3.2.3.UV-Visible absorption results 132

4.3.2.4.Discussion 133

5 CONCLUSION 135

REFERENCES/BIBLIOGRAPHY 139

BIODATA OF STUDENT 144

LIST OF PUBLICATIONS 147