structural and luminescence properties of magnesium boro-tellurite doped europium...

STRUCTURAL AND LUMINESCENCE PROPERTIES OF MAGNESIUM

BORO-TELLURITE DOPED EUROPIUM AND DYSPROSIUM ION CERAMIC

NUR ZU IRA BINTI BOHARI

A thesis submitted in fulfilment of the

requirements for the award of the degree of

Doctor of Philosophy (Physics)

Faculty of Science

Universiti Teknologi Malaysia

OCTOBER 2015

ii

To my husband, Muhammad Firdaus Ayob for your love and encouragement throughout my life

To my parents and parents in-law, for your amazing supports To all of my professors, and teachers for their strenuous efforts in molding me into the

educated person that I am today &

My Friends

iii

ACKNOWLEDGEMENTS

In the name of Allah, the Most Gracious and the Most Merciful,

Alhamdulillah, all praises to Allah for the strengths and His blessing in completing

this thesis.

I would like to express the deepest appreciation to my supervisor, Prof. Dr.

Rosli Hussin, for his invaluable guidance and constant encouragement during my

research. Without his guidance and persistent help this dissertation would not have

been possible. I would also like to extend my thanks to the other member of my

supervisory committee, Assoc. Prof. Dr. Zuhairi Ibrahim for the assistance he

provided at all levels of the research project. I am thankful to my friends and all

members of our research group for their great help and friendship.

My acknowledgement also goes to all the lab assistant of Faculty of Science,

Department of Physics and Ibnu Sina Institute for their co-operations. Thanks to

MyBrain15 that finance me since 2011. Also, I would like to thank Phosphor

Research Group, Physics Department, Universiti Teknologi Malaysia for the

equipment, the Ministry of Higher Education (MOHE), the Ministry of Science,

Technology and Innovation (MOSTI) and Universiti Teknologi Malaysia for their

financial support via Research University Grant Project Q.J13000.2526.03H97.

A special note of thanks goes to my family and dearest friends for their

precious friendship. I wish to express my deepest and most heartfelt gratitude to my

parents for their constant encouragement and love. My special thanks to go to my

husband for always being there for me with great love and constant support. This

thesis could not have been done without them. To those who indirectly contributed in

this research, your kindness means a lot to me.

Thank you very much.

iv

ABSTRACT

A series of xTeO2-(70-x)B2O3-30MgO samples with 0 ≤ x ≤ 70 mol% and doped samples with composition of 100-y(30TeO2-40B2O3-30MgO)-yEu

3+, 100-

z(30TeO2-40B2O3-30MgO)-zDy3+

, and 100-y-z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy

3+ with 0.2 ≤ y ≤ 2 mol% and 0.2 ≤ z ≤ 2 mol% were prepared via solid-state

reaction method. All the samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy, Raman spectroscopy, energy dispersive X-ray spectroscopy (EDX), field emission scanning electron microscopy (FESEM) and photoluminescence spectroscopy. The XRD results of the samples prepared at 650

oC

to 850oC showed that the major phase was Mg(Te2O5) while MgTe6O13, Mg2(B2O5)

and MgB4O7 were observed as a minor phase. The phases of Dy(BO2)3, Dy2Te4O11, EuB2O4 and Eu2Te4O11 were observed in the XRD patterns of doped samples. The EDX analyses confirmed the presence of boron (B), magnesium (Mg), tellurium (Te), oxygen (O), europium (Eu) and dysprosium (Dy) elements. In addition, the weight percentage of boron (B) decreases with the increase of x mol%. Based on the FESEM images, the xTeO2-(70-x)B2O3-30MgO samples with 0 ≤ x ≤ 70 mol% prepared at 750

oC consist basically of sub-micron size agglomerates of irregular

shape. The surface morphology of Eu3+

, Dy3+

and Eu3+

-Dy3+

doped samples is more agglomerated compared to the 30TeO2-40B2O3-30MgO samples. The grain sizes of samples doped with Eu

3+ (1.91 µm), Dy

3+ (1.87 µm) and Eu

3+-Dy

3+ (2.84 µm) are

smaller than the grain size of the undoped sample (2.99 µm). There were six main regions observed in IR spectra which are due to the B-O-B (400-590 cm

-1), Te-O-Te

(550 and 610 cm-1

), TeO2 (600-800 cm-1

), TeO3 (757 cm-1

), BO4 (840-1200 cm-1

) and BO3 (1300-1400 cm

-1) vibrations. The observed spectra also show greater bands for

tellurite network with the increase of x mol%. From the Raman spectra, the intensity of the peaks due to Te-O-Te, TeO2 and TeO3 groups increases with the increase of x from 0 to 30 mol%. The luminescence spectra of 100-y(30TeO2-40B2O3-30MgO)-yEu

3+ with 0.2 ≤ y ≤ 2 mol% showed that there was an increase in the emission

intensity which results in the enhancement of the red emission from the samples. All the spectra of 100-z(30TeO2-40B2O3-30MgO)-zDy

3+ samples with 0.2 ≤ z ≤ 2 mol%

show the main characteristic emission lines of Dy3+

, which consist of magnetic dipole transition,

4F9/2→

6H15/2 at 484.19 nm (blue), and hypersensitive electric dipole

transition, 4F9/2→

6H13/2 at 578.44 nm (yellow). The observed emission spectra of

100-y-z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy3+

samples with 0.2 ≤ y ≤ 2 mol% and 0.2 ≤ z ≤ 2 mol% exhibit three strong bands centered at 483.78 nm, 578.97 nm and 616.83 nm which correspond to the

4F9/2→

6H15/2 (Dy

3+),

4F9/2→

6H13/2 (Dy

3+) and

5D0→

7F2 (Eu

3+) transition respectively. The yellow emission (

4F9/2→

6H13/2) becomes

a dominant peak in the emission spectra compared to the other emissions. The longest decay time was observed from the transition in europium and dysprosium ions.

v

ABSTRAK

Satu siri sampel xTeO2-(70-x)B2O3-30MgO dengan 0 ≤ x ≤ 70 mol% dan sampel berdop dengan komposisi 100-y(30TeO2-40B2O3-30MgO)-yEu

3+, 100-


, dan 100-y-z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy

3+ dengan 0.2 ≤ y ≤ 2 mol% dan 0.2 ≤ z ≤ 2 mol% disediakan melalui kaedah

tindakbalas keadaan pepejal. Semua sampel dicirikan menggunakan pembelauan sinar-X (XRD), spektroskopi infra merah transformasi Fourier, spektroskopi Raman, spektroskopi sinar-X tenaga menyerak (EDX), mikroskopi pengimbasan elektron pancaran medan (FESEM) dan spektrokopi fotoluminesens. Keputusan XRD bagi sampel yang disediakan pada suhu 650

oC hingga 850

oC menunjukkan fasa major

ialah Mg(Te2O5) manakala MgTe6O13, Mg2(B2O5) dan MgB4O7 dilihat sebagai fasa minor. Fasa Dy(BO2)3, Dy2Te4O11, EuB2O4 dan Eu2Te4O11 dilihat dalam corak XRD bagi sampel berdop. Analisis EDX mengesahkan kehadiran elemen boron (B), magnesium (Mg), tellurium (Te), oksigen (O), europium (Eu) dan dysprosium (Dy). Tambahan pula, peratus berat bagi boron (B) berkurangan dengan peningkatan x mol%. Berdasarkan imej FESEM, sampel xTeO2-(70-x)B2O3-30MgO dengan 0 ≤ x ≤ 70 mol% disediakan pada 750

oC terdiri daripada bentuk bergumpal yang tidak tetap

bersaiz mikron. Morfologi permukaan bagi sampel berdopkan Eu3+

, Dy3+

dan Eu3+

-Dy

3+ adalah lebih bergumpal berbanding sampel 30TeO2-40B2O3-30MgO. Saiz

butiran bagi sampel yang didopkan dengan Eu3+

(1.91µm), Dy3+

(1.87µm) dan Eu3+

-Dy

3+ (2.84µm) adalah lebih kecil berbanding dengan saiz butiran sampel tidak

berdop (2.99 µm). Terdapat enam kawasan dapat dilihat dalam spektrum IR yang disebabkan oleh getaran B-O-B (400-590 cm

-1), Te-O-Te (550 and 610 cm

-1), TeO2

(600-800 cm-1

), TeO3 (757 cm-1

), BO4 (840-1200 cm-1

) dan BO3 (1300-1400 cm-1

). Spektrum yang diperhatikan juga menunjukkan jalur yang lebih besar bagi rangkaian tellurite dengan peningkatan x mol%. Daripada spektrum Raman, keamatan puncak yang disebabkan oleh kumpulan Te-O-Te, TeO2 dan TeO3 meningkat dengan peningkatan x daripada 0 kepada 30 mol%. Spektrum luminesens bagi sampel 100-y(30TeO2-40B2O3-30MgO)-yEu

3+ dengan 0.2 ≤ y ≤ 2 mol% menunjukkan wujudnya

peningkatan dalam keamatan pancaran yang menyebabkan peningkatan pancaran merah pada sampel. Semua spektrum bagi sampel 100-z(30TeO2-40B2O3-30MgO)-zDy

3+ dengan 0.2 ≤ z ≤ 2 mol% menunjukkan garis pancaran ciri utama bagi Dy

3+,

yang terhasil daripada peralihan dwikutub magnet 4F9/2→

6H15/2 pada 484.19 nm

(biru), dan peralihan dwikutub elektrik hipersensitif, 4F9/2→

6H13/2 pada 578.44 nm

(kuning). Pancaran spektrum bagi sampel 100-y-z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy

3+ dengan 0.2 ≤ y ≤ 2 mol% dan 0.2 ≤ z ≤ 2 mol% mempamerkan tiga jalur kuat

berpusat di 483.78 nm, 578.97 nm dan 616.83 nm yang masing masing merujuk kepada peralihan

4F9/2→

6H15/2 (Dy

3+),

4F9/2→

6H13/2 (Dy

3+) dan

5D0→

7F2 (Eu

3+).

Pancaran kuning (4F9/2→

6H13/2) menjadi puncak dominan dalam spektrum pancaran

berbanding pancaran yang lain. Masa pereputan paling lama berlaku daripada peralihan dalam ion europium dan dysprosium.

vi

TABLE OF CONTENTS

CHAPTER TITLE PAGE

DECLARATION ii

DEDICATION iii

ACKNOWLEDGEMENT iv

ABSTRACT v

ABSTRAK vi

TABLE OF CONTENTS vii

LIST OF TABLES xi

LIST OF FIGURES xiii

LIST OF SYMBOLS xx

LIST OF ABBREVIATIONS xxi

LIST OF APPENDICES xxiii

1 INTRODUCTION

1.1 Introduction

1.2 Background of Study

1.3 Problem Statement

1.4 Objectives of the Study

1.5 Scope of the Study

1.6 Significance of the Study

1.7 Outline of the Thesis

1

1

5

5

6

6

6

vii

2

LITERATURE REVIEW

2.1 Introduction

2.2 X-ray diffraction (XRD)

2.2.1 Undoped Sample

2.2.2 Doped sample (Eu3+

and Dy3+

)

2.3 Fourier Transform Infrared (FTIR)

Spectroscopy

2.3.1 Basic Principle

2.3.2 Borate Ceramic

2.3.3 Tellurite Ceramic

2.4 Raman Spectroscopy

2.4.1 Basic Principle

2.4.2 Borate Ceramic

2.4.3 Tellurite Ceramic

2.5 Energy Dispersive X-ray (EDX) Spectra

2.6 Field Emission Scanning Electron

Microscope (FESEM) Spectra

2.7 Luminescence Spectra

2.7.1 Doped Eu3+

2.7.2 Doped Dy3+

2.7.3 Doped Eu3+

and Dy3+

2.8 Lifetime Spectra

2.8.1 Doped Eu3+

2.8.2 Doped Dy3+

2.8.3 Doped Eu3+

and Dy3+

8

8

10

14

17

17

19

21

22

25

25

27

29

32

35

39

41

43

46

46

47

49

3

METHODOLOGY

3.1 Introduction

3.2 Sample Preparation

3.2.1 Materials

3.2.2 Preparation of Magnesium Boro-

51

52

52

viii

Tellurite Ceramic

3.2.3 Preparation of Magnesium Boro-

Tellurite doped with Eu3+

, Dy3+

and

(Eu3+

and Dy3+

) Ceramic

3.3 Sample Characterization

3.3.1 X-Ray Diffractometer

3.3.2 Fourier Transform Infrared (FTIR)

Spectrometer

3.3.3 Raman Spectrometer

3.3.4 Photoluminescence Spectroscopy

3.3.5 Field Emission Scanning Electron

Microscope (FESEM)

3.3.6 Energy Dispersive X-rays detector

(EDX)

52

56

59

60

61

61

63

64

64

4 RESULTS AND DISCUSSION

4.1 Introduction

4.2 X-ray Diffraction Studies

4.3 Energy Dispersive X-Ray (EDX) Studies

4.4 Surface Morphology Studies

4.5 Infrared Spectra Studies

4.5.1 Deconvolution IR Spectra of xTeO2

(70-x)B2O3-30MgO Ceramic

(x=30mol%)

4.6 Raman Spectra Studies

4.7 Photoluminescence Studies

4.8 Lifetime Studies

66

66

87

93

97

104

108

114

129

5 CONCLUSION

5.1 Conclusion

5.2 Suggestions for Future Work

134

136

ix

REFERENCES

Appendix

A: Calculation of Ceramic Composition

B: Publications

138

147

151

x

LIST OF TABLES

TABLE NO. TITLE PAGE

2.1 Raman shift (cm -1

) and possible assignment of the vibrations in

Mg2B2O5 (Li et al., 2012)

26

2.2 Approximate Wavelength the Colors of Visible Spectrum (Shinde

et al., 2013)

35

2.3 Hypersensitive Transitions of Rare Earths (Shinde et al., 2013) 37

2.4 Electronic Configurations of Trivalent Rare-Earth Ions

(Kano, 2006)

39

3.1 The preparation samples of magnesium boro-tellurite using

different solvent, raw materials and composition

53

3.2 Composition of xTeO2-(70-x)B2O3-30MgO 55

3.3 Composition of 100-y(30TeO2-40B2O3-30MgO)-yEu3+

58

3.4 Composition of 100-z(30TeO2-40B2O3-30MgO)-zDy3+

58

3.5 Composition of 100-y-z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy3+

59

4.1 Elemental analysis of xTeO2-(70-x)B2O3-30MgO with 0 ≤ x ≤ 70

mol% prepared at 750oC

91

4.2 Elemental analysis of 100-y(30TeO2-40B2O3-30MgO)-yEu3+

, 100-


and 100-y-z(30TeO2-40B2O3-

30MgO)-yEu3+

-zDy3+

with y, z = 1.5 mol%

93

4.3 Grain size values of xTeO2-(70-x)B2O3-30MgO with 0 ≤ x ≤ 70

mol%

94

4.4 Grain size values of (a) undoped, (b) 100-y(30TeO2-40B2O3-

30MgO)-yEu3+

; (c) 100-z(30TeO2-40B2O3-30MgO)-zDy3+

and (d)

100-y-z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy3+

with y, z = 1.5

xi

mol% 95

4.5 Peak position and types of the corresponding vibrational modes

(cm-1

) of xTeO2-(70-x)B2O3-30MgO with 0 ≤ x ≤ 70 mol%

103

4.6 FTIR characteristic band assignment of 30TeO2-40B2O3-30MgO,

doped Eu3+

, doped Dy3+

and doped Eu3+

-Dy3+

108

4.7 Raman characteristic band assignment of xTeO2-(70-x)B2O3-

30MgO with 0 ≤ x ≤ 70 mol% in the range of 0-1000 cm-1

113

4.8 Raman characteristic band assignment of 30TeO2-40B2O3-30MgO,

doped Eu3+

, doped Dy3+

and doped Eu3+

-Dy3+

115

4.9 Excitation characteristics of 100-y(30TeO2-40B2O3-30MgO)-yEu3+

with 0.2 ≤ y ≤ 2 mol% prepared at 750oC

118

4.10 Emission characteristics of 100-y(30TeO2-40B2O3-30MgO)-yEu3+

with 0.2 ≤ y ≤ 2 mol% prepared at 750 oC

120

4.11 Excitation characteristics of 100-z(30TeO2-40B2O3-30MgO)-zDy3+

with 0.2 ≤ z ≤ 2 mol% prepared at 750oC

122

4.12 Emission characteristics of 100-z(30TeO2-40B2O3-30MgO)-zDy3+

with 0.2 ≤ z ≤ 2 mol%

124

4.13 Excitation characteristics of 100-y-z(30TeO2-40B2O3-30MgO)-

yEu3+

-zDy3+

with 0.2 ≤ y ≤ 2 mol% and 0.2 ≤ z ≤ 2 mol%

127

4.14 Emission characteristics of 100-y-z(30TeO2-40B2O3-30MgO)-

yEu3+

-zDy3+


128

4.15 Decay times for 100-y(30TeO2-40B2O3-30MgO)-yEu3+

with 0.2 ≤

y ≤ 2 mol%

131

4.16 Decay times for 100-z(30TeO2-40B2O3-30MgO)-zDy3+

with 0.2 ≤

z ≤ 2 mol%

132

4.17 Decay times for 100-y-z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy3+


133

xii

LIST OF FIGURES

FIGURE NO. TITLE PAGE

2.1 Schematic Description of Bragg’s Diffraction Law

(Aditya and Andrew, 2013)

10

2.2 XRD patterns of the samples heat-treated at 5200C for

24 h in the hypermonotectic region of (1-x)TeO2-xB2O3

system (Yardimci et al., 2013)

11

2.3 XRD patterns of (1-x)TeO2-xB2O3 system (0.30 ≤ x ≤

0.40) in transparent phases (Yardimci et al., 2013)

12

2.4 XRD patterns of (1-x)TeO2-xB2O3 system (0.30 ≤ x ≤

0.40) in opaque phases (Yardimci et al., 2013)

13

2.5

X-ray diffractogram patterns of (TeO2)y[(PbO)x

(B2O3)1-x]1-y glasses (Mustafa et al., (2013)

14

2.6 X-ray diffraction pattern of Li2TiO3 doped with Dy3+

and Eu3+

(Kumar and Buddhudu, 2009)

15

2.7 XRD pattern of Li2TiO3 and Dy2Ti2O7 (Cheng et al.,

2014)

15

2.8 XRD profiles of Ca1-x EuxMgSi2O6 (Kunimoto et al.,

2013)

16

2.9 The Electromagnetic Spectrum 18

2.10 FTIR spectra of the (a) undoped (b) doped zinc borate

without sintering and (c) Eu3+

doped zinc borate with

sintering temperature at 400 ºC (Zheng et al., 2009)

19

2.11 FTIR spectra of NaSr1-x B5O9:Eux3+

(x = 0-9 at. %)

phosphors (Dillip et al., 2014)

20

xiii

2.12 IR Transmittance of the CZT crystals with different Te-

rich volume (Min et al., 2012)

21

2.13 FTIR spectra of xCdO-(1-x)TeO2 with 0.1 ≤ x ≤ 0.5

mol% doped 1 mol% Mn2+

(Hussin et al., 2009)

22

2.14 Diagram of the Rayleigh and Raman scattering process

(Smith and Dent, 2005)

24

2.15 The experimental and theoretical Raman spectra of

Mg2B2O5 micron-crystal rod (Li et al., 2012)

25

2.16 Raman spectra (at ambient temperature) of

(TeO2)y[(PbO)x(B2O3)1−x]1−y glasses with different

compositions (Mustafa et al., 2013)

27

2.17 Raman spectra of (a) Gd2Ti2O7, Eu2Ti2O7 and

GdEuTi2O7 pyrochlores (Garbout et al., 2013)

28

2.18 Raman spectra of (b) Dy2Ti2O7, Eu2Ti2O7 and

DyEuTi2O7 oxides (Garbout et al., 2013)

29

2.19 EDAX images of (MgCa)2Bi4Ti5O20:Eu3+

(Sailaja et al., 2011)

30

2.20 EDX spectra of Eu3+

: Li2TiO3 ceramics (Kumar and

Budduhudu, 2009)

31

2.21 EDX spectra of Dy3+

: Li2TiO3 ceramics (Kumar and

Budduhudu, 2009)

32

2.22 SEM micrographs of (a) GdEuTi2O7; (b) DyEuTi2O7

powders (magnification: 40X) (Garbout et al., 2013)

33

2.23 SEM micrographs of a) Ca2SiO4:Eu3+

, b) Sr2SiO4:Eu3+

and c) Ba2SiO4:Eu3+

phosphors (Liu et al., 2012)

34

2.24 Schematic Diagram of (a) direct excitation of the

activator and (b) indirect excitation followed by energy

transfer from the sensitizer or host to the activator

(Bamfield and Hutching, 2010)

36

2.25 Positions of the Rare Earth Element (Righini and

Ferrari, 2005)

38

2.26 Excitation and emission spectra of CBTO: 0.15Eu3+

(Cui et al., 2013)

40

xiv

2.27 Emission spectra of Ca1–yBi2Ta2O9:yEu3+

(0.05 ≤ y ≤

0.25 mol%) (Cui et al., 2013)

41

2.28 Excitation spectra of YPxV1−xO4:Dy3+

with 0.2 ≤ x ≤ 0.8

mol% (Su et al., 2005)

42

2.29 Emission spectra of YVO4:Dy3+

under 223 nm emission

(Su et al., 2005)

43

2.30 PL emission spectra of Y2O3 phosphor particles

codoped with different Eu3+

and Dy3+

contents with 254

nm excitation (Atabaev et al., 2012)

44

2.31 PL emission spectra of Y2O3 phosphor particles

codoped with different Eu3+

and Dy3+

contents with 350

nm excitation (Atabaev et al., 2012)

45

2.32 Concentration-dependent Eu-doped KNbO3 powders

luminescence decay curves (Fang et al., 2006)

47

2.33 Decay Curve of Sr3Gd2(BO3)4:xDy3+

phosphors (Zhang

et al., 2011)

48

2.34 Decay Curve of BaLa1.75-xWO7:0.25Dy3+

: xEu3+

phosphors (Deng et al., 2014)

50

3.1 a) before heating and b) after heating of xTeO2-(70-

x)B2O3-30MgO ceramic pellets

56

3.2 xTeO2-(70-x)B2O3-30MgO ceramic in powder form 56

3.3 Flow diagram of the Sample Preparation Procedure 57

3.4 X-Ray Diffractometer 60

3.5 Perkin-Elmer Spectrum One FT-IR Spectrometer 61

3.6 Raman Spectrometer 62

3.7 Raman Accessory Kit 62

3.8 Fluorescence spectrophotometer 63

3.9 Sample holder Jasco Fluorescence spectrometer 63

3.10 FESEM instrument 65

3.11 The SUPRA 55VP with EDX detectors 65

4.1 X-ray diffraction pattern of 30TeO2-40B2O3-30MgO

using methanol as solvent prepared at 500ºC

68


xv

using H2O as solvent prepared at 650ºC 69


using (MgCO3)4.Mg(OH)2.5H2O) as raw material

prepared at 650ºC

70


prepared at 750ºC

71

4.5 (a) X-ray diffraction pattern of xTeO2-(70-x)B2O3-

30MgO with 0 ≤ x ≤ 30 mol% prepared at 650oC

74

4.5 (b) X-ray diffraction pattern of xTeO2-(70-x)B2O3-


75



76



77



78



79


30MgO with 0≤ x ≤ 30 mol% prepared at 800oC

80



81



82



83

4.10 X-ray diffraction pattern of (a) 30TeO2-40B2O3-30MgO,

(b) pure B2O3, (c) pure TeO2 and (d) TeO2-B2O3

prepared at 750oC

85

4.11 X-ray diffraction pattern of (a) 30TeO2-40B2O3-30MgO

(b) 100-y(30TeO2-40B2O3-30MgO)-yEu3+

, (c) 100-


and (d) 100-y-

z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy3+

with y, z = 1.5

xvi

mol% prepared at 750 oC 86

4.12 (a) EDX spectrum (a) x = 0, (b) x = 10 mol% and (c) x =

20 mol% of xTeO2-(70-x)B2O3-30MgO

88

4.12 (b) EDX spectrum (d) x = 30, (e) x = 40 mol% and (f) x

= 50 mol% of xTeO2-(70-x)B2O3-30MgO

89

4.12 (c) EDX spectrum (g) x = 60 and (h) x = 70 mol% of

xTeO2-(70-x)B2O3-30MgO

90

4.13 EDX spectrum of (a)100-y(30TeO2-40B2O3-30MgO)-

yEu3+

; (b) 100-z(30TeO2-40B2O3-30MgO)-zDy3+

and

(c) 100-y-z(30TeO2-40B2O3-30MgO)-yEu3+

-zDy3+

with

y, z = 1.5 mol%

92

4.14 (a): FESEM images (a) x = 0, (b) x = 10 mol%, (c) x =

20 mol% and (d) x = 30 mol% of xTeO2-(70-x)B2O3-

30MgO prepared at 750oC (magnification: 50X)

95

4.14 (b): FESEM images (e) x = 40, (f) x = 50 mol%, (g) x =

60 mol% and (h) x = 70 mol% of xTeO2-(70-x)B2O3-

30MgO prepared at 750oC (Magnification: 50X)

96

4.15 FESEM images of (a) undoped, (b) 100-y(30TeO2-

40B2O3-30MgO)-yEu3+

; (c) 100-z(30TeO2-40B2O3-

30MgO)-zDy3+

and (d) 100-y-z(30TeO2-40B2O3-

30MgO)-yEu3+

-zDy3+

with y, z = 1.5 mol%

(magnification: 5K X)

97

4.16 (a): FTIR spectra of xTeO2-(70-x)B2O3-30MgO with 0 ≤

x ≤ 30 mol% at 750oC range 4000 – 1400 cm

-1

99

4.16 (b): FTIR spectra of xTeO2-(70-x)B2O3-30MgO with 40

≤ x ≤ 70 mol% at 750oC range 4000 – 1400 cm

-1

100

4.17 (a) FTIR spectra of xTeO2-(70-x)B2O3-30MgO with

0≤x≤30 mol% at 750oC range 1400 – 400 cm

-1

101

4.17 (b): FTIR spectra of xTeO2-(70-x)B2O3-30MgO with 40

≤ x ≤ 70 mol% at 750oC range 1400 – 400 cm

-1

102

4.18 Deconvoluted IR spectra of xTeO2-(70-x)B2O3-30MgO

with x = 30 mol%

104

4.19 (a) FTIR spectra of 30TeO2-40B2O3-30MgO, doped

xvii

Eu3+

, doped Dy3+

and doped Eu3+

-Dy3+

range 4000 –

1400 cm-1

106

4.19 (b): FTIR spectra of 30TeO2-40B2O3-30MgO, doped

Eu3+

, doped Dy3+

and doped Eu3+

-Dy3+

range 1400 –

400 cm-1

107

4.20 (a) Raman spectra of xTeO2-(70-x)B2O3-30MgO with 0

≤ x ≤ 30 mol%

110

4.20 (b): Raman spectra of xTeO2-(70-x)B2O3-30MgO with

40 ≤ x ≤ 70 mol%

111

4.21 Raman spectra of 30TeO2-40B2O3-30MgO, doped Eu3+

,

doped Dy3+

and doped Eu3+

-Dy3+

112

4.22 Excitation spectra of 100-y(30TeO2-40B2O3-30MgO)-

yEu3+

with 0.2 ≤ y ≤ 2 mol% prepared at 750oC

117

4.23 Emission spectra of 100-y(30TeO2-40B2O3-30MgO)-

yEu3+

with 0.2 ≤ y ≤ 2 mol% prepared at 750 oC

119

4.24 Energy level of Eu3+

in 100-y(30TeO2-40B2O3-

30MgO)-yEu3+

119

4.25 Excitation spectra of 100-z(30TeO2-40B2O3-30MgO)-

zDy3+


122

4.26 Emission spectra of 100-z(30TeO2-40B2O3-30MgO)-

zDy3+


124

4.27 Energy level of Dy3+

in 100-z(30TeO2-40B2O3-

30MgO)-zDy3+

125

4.28 Excitation spectra of 100-y-z(30TeO2-40B2O3-30MgO)-

yEu3+

-zDy3+

with 0.2 ≤ y ≤ 2 mol% and 0.2 ≤ z ≤ 2

mol%

127

4.29 Emission spectra of 100-y-z(30TeO2-40B2O3-30MgO)-

yEu3+

-zDy3+

with 0.2 ≤ y ≤ 2 mol% and 0.2 ≤ z ≤ 2

mol%

128

4.30 Energy level of Eu3+

and Dy3+

in 100-y-z(30TeO2-

40B2O3-30MgO)-yEu3+

-zDy3+

129

4.31 Lifetime spectra of 100-y(30TeO2-40B2O3-30MgO)-

yEu3+

with 0.2 ≤ y ≤ 2 mol%

131

xviii

4.32 Lifetime spectra of 100-z(30TeO2-40B2O3-30MgO)-

zDy3+

with 0.2 ≤ z ≤ 2 mol%

132

4.33 Lifetime spectra of 100-y-z(30TeO2-40B2O3-30MgO)-

yEu3+

-zDy3+

with 0.2 ≤ y ≤ 2 mol% and 0.2 ≤ z ≤ 2

mol%

133

xix

LIST OF SYMBOLS

m - Mili

µ - Mikro

n - Nano

τ - Decay time

n - Diffraction order

θ - Diffracted angle of the X-ray beam

λ - Wavelength

S - Spin angular momentum

L - Orbital angular momentum

J - Total angular momentum

dhkl - Interplanar spacing of the crystal planes

f - Frequency

c - Speed of light

h - Planck’s constant

xx

LIST OF ABBREVIATIONS

B2O3 - Borate

B - Boron

H3BO3 - Boric Acid

Ce3+

- Cerium ion

CL - Cathodoluminescence

CTB - Charge transfer band

CTS - Charge transfer state

Dy3+

- Dysprosium ion

Dy2O3 - Dysprosium oxide

EDX - Energy Dispersive X-Ray

EL - Electroluminescence

Eu3+

- Europium ion

Eu2O3 - Europium oxide

Er3+

- Erbium ion

H2O - Water

FESEM - Field Emission Scanning Electron Microscope

FTIR - Fourier Transform Infrared

Gd - Gadolinium

HAB - Host absorption band

IR - Infrared

KBr - Kalium bromide

La3+

- Lanthanum ion

Lu3+

- Lutetium ion

LED - Light Emitting Diode

Mg - Magnesium

xxi

MgO - Magnesium Oxide

(MgCO3)4.Mg(OH)2.

5H2O

- Magnesium Carbonate Hydroxide

Pentahydrate

NAT - Sodium aluminum tellurite

NBO - Non Bridging Oxide

O - Oxygen

PbO - Plumbum Oxide

PL - Photoluminescence

Pr3+

- Praseodymium ion

RE - Rare Earth

SEM - Scanning electron microscope

Sc3+

- Scandium ion

Te - Tellurium

Tb - Terbium

TeO2 - Tellurium Oxide

UV - Ultraviolet

XRD - X-ray Diffraction

Y3+

- Yttrium ion

Yb3+

- Ytterbium ion

xxii

LIST OF APPENDICES

APPENDIX TITLE PAGE

A

B

Samples Calculation

Publications

147

151

1

CHAPTER 1

INTRODUCTION

1.1 Introduction

This chapter presents the pertinent introduction covering the brief description

and a review of the materials studied. It includes the problem statement, objectives of

study, scope of study, significance of study and the outline of the thesis.

1.2 Background of Study

Ceramic is defined as inorganic nonmetallic material and the atomic structure

of ceramic can be crystalline, non-crystalline or partially crystalline. Typically,

ceramics are very hard, brittle, high melting point materials with low electrical and

thermal conductivity, good chemical and thermal stability, and high compressive

strengths (Barsoum, 1997 and Minh et al., 1995). Also, the ceramic can be fabricated

at lower cost and in much speedy processes in a large variety of sizes and shapes

(Lupei et al., 2005; Mohr et al., 2008).

2

Ceramics are of tremendous interest primarily because of their wide range of

applications especially in high temperature environment. They are also extensively

used in fuel technology, oxygen sensor (Ciacchi et al., 1994), magnets ceramics

(Valenzuela, 2005), all electronic equipments including integrated-chips, capacitors

and digital alarms (Miller et al., 2002), telecommunication (Bhargava, 2005),

ceramic crystal-glass (Carter and Norton, 2007). Ceramic insulators are widely used

in the electrical power transmission system (Chowdhury, 2010), ceramic

superconductors (David and Bruce, 1992) and other pharmaceuticals industries (Rice

et al., 2002).

Ceramic materials can be classified into four main groups (Rajendran, 2004)

that were the amorphous ceramics, which are generally referred to as glasses,

crystalline ceramics, which are single phase materials like alumina, or mixtures of

such materials, bonded ceramics, where individual crystals are bonded together by a

glassy matrix, such as clay products and the cements, these are crystalline, and also

amorphous materials.

Recently ceramic material has been study for luminescent material

applications. Ceramics have the potential to become good luminescence material due

to its opaque characteristic which enhances the absorption efficiency of rare earth

ions (Yang et al., 2008). Sailaja and Reddy (2011) introduced the luminescence

properties of Eu3+

(MgCa)2Bi4Ti5O20 and Tb3+

(MgCa)2Bi4Ti5O20 ceramic has shown a

strong red and green emission. Ceramics can be incorporate with high concentrations

of dopant ions such as rare earth and transition metal ions. The ceramic doped also

have attracted much for their applications such as cathode ray tubes, lamps, X-ray

detectors, electroluminescence, laser materials and fluorescent tubes (Yan et al.,

2007 and Sastri et al., 2003).

Borate has been the subject of intensive investigations because of their

technological and scientific importance. It offers promising choice especially for

thermoluminescence applications due to its high sensitivity, low cost and easy

3

preparation (Krongh-Moe, 1969). Borate crystals have been used as optical materials

for second harmonic generation and fluorescence. The spectroscopy of borates doped

with Eu3+

, Pr3+

and Er3+

has been studied (Ambrosi et al., 1994; Thulasiramudu et

al., 2007; Pozza et al., 1996). Borate has been incorporated with various types of

modifier metal oxide in order to obtain the desired physical and chemical properties

(Yano et al., 2003). In terms of luminescence, borate doped rare earth has more

attention because it has high luminescence, great color coordinate and low thermal

degradation (Wang et al., 2008).

Over the past years, the use of tellurite as a host material was focused in

fundamental research and in an optical device fabrication as TeO2 host show

relatively low phonon energy. The tellurite have lower operating temperature and

mostly prepared by solid state reaction method with heating temperature of 800-

1000oC (Kumar et al., 2002; Lin et al., 2006 and Zambelli, 2004). On the other hand,

TeO2 have been extensively studied due to good properties such as high refractive

indices, good transparency, low melting point and high dielectric constant which are

essential for good UV and IR transmission. Hence, TeO2 is then very attractive and

interesting for a range of different applications (Mallawany et al., 1992; Babu et al.,

2007). The addition of TeO2 into the samples may result in strong modifications of

the structure as compared to that of the pure B2O3.

Many papers worked based on the silicate and aluminate system with higher

operating temperature (Srivasta, 2009; Kuang, 2005 and Aitasalo, 2004). For the host

materials, borate and tellurite also known as boro-tellurite prepared in ceramic have

not been reported yet. Ceramic based on boro-tellurite host matrices doped with rare

earth have applications in lasers, optical amplifier, photo sensitivity, optical storage,

and bio-ceramics materials (Mallawany, 1992; Babu et al., 2007; Joshi et al., 2008;

Sudhakar, 2008; Rada et al., 2008; Konijnendijk, 1975; Bhargava et al., 1987;

Pascuta et al., 2008).

4

Meanwhile, adding of alkali oxide (magnesium oxide) into the host can

increase the stability and chemical strength of the samples (Duverger et al., 1997).

Also, an addition of alkali oxide has a strong influence on the luminescence

properties (Dayang et al., 2010). Magnesium oxide doping has effectively

inhibit grain growth in ceramics and it can improve the fracture toughness (Hussin

et al., 2009). Also, magnesium oxide is well-known for its luminescent properties

which are being utilized in sensors (Li et al., 2003). This oxide also can be as a

network former (Doweidar et al., 2012).

Doped rare earth (RE) ions have attracted research interests in the field of

luminescence. Many researchers have been carried out in order to investigate the

potential of doped rare earth ion especially Eu3+

and Dy3+

-doped boro tellurite. Eu3+

-

doped are commonly used as red emitting materials for field emission technology

and LEDs, which exhibit higher luminescence efficiency compared with other

luminous materials (Oikawa and Fujihara, 2005). Meanwhile, luminescence materials

doped with Dy3+

have drawn much interest because of its white emission. Dy3+

is

known as a good activator due to the two dominated band in the emission spectra and

its position depends strongly on the crystal field of the lattice used. Hence,

luminescence materials doped with Dy3+

can produce white emission by adjusting the

yellow to blue intensity ratio value, which can be used as potential white phosphors

(Hussin et al., 2009). Doped materials have potential applications for phosphors,

display monitor, x-ray imaging, and scintillators (Blasse and Grabmaier, 1994).

Moreover, the luminescence properties of the ceramic could be improved by doping

with rare earth (RE) ions as an activator.

http://en.wikipedia.org/wiki/Doping_(semiconductor)http://en.wikipedia.org/wiki/Grain_growthhttp://en.wikipedia.org/wiki/Ceramic_materialshttp://en.wikipedia.org/wiki/Fracture_toughness

5

1.3 Problem Statement

Currently, a great deal of research has been focused on rare earth (RE) doped

boro-tellurite glasses owing to their extensive applications (Maheshvaran et al., 2011;

Selvaraju et al., 2011). But, the investigation on the luminescence properties of rare

earth doped boro-tellurite ceramic is not many. In the meantime, there was limited

structural information regarding effect in the boro-tellurite as the host that can be

reasoned to find a good luminescence material. Thus, in this study, magnesium boro

tellurite doped Eu3+

and Dy3+

present to synthesize the ceramic materials by using

solid state reaction method. The investigation of structural features was important in

order to study the structures changes in the undoped and doped samples. Also, the

luminescence emission and decay curve induced by addition of rare earth dopant

were characterized for developing a new luminescence material.

1.4 Objectives of the Study

The objectives of this study are as follows:

i. To synthesize magnesium boro-tellurite ceramic and magnesium boro-

tellurite doped with Eu3+

and Dy3+

ceramic

ii. To determine the crystalline phases of magnesium boro-tellurite ceramic and

magnesium boro-tellurite doped with Eu3+

and Dy3+

ceramic

iii. To determine the structural properties of ceramic in term of their vibrational

band, elemental analysis and surface morphology using the IR and Raman,

EDX and FESEM spectroscopy.

iv. To determine the luminescence excitation, emission and decay curve of

magnesium boro-tellurite doped with various dopant of Eu3+

and Dy3+

6

1.5 Scope of the Study

In order to achieve the objectives of the study, magnesium boro-tellurite

ceramic and magnesium boro-tellurite ceramic doped with Eu3+

and Dy3+

ions have

been prepared using solid state reaction method. The crystalline phase of the obtained

ceramics was determined using x-ray diffraction (XRD). The surface morphology of

the ceramics was measured using Field Emission Scanning Electron Microscope. The

presence of elemental composition in the prepared samples was measured using

Energy Dispersive X-Ray (EDX). Also, the vibrations mode of the prepared sample

was measured using FTIR and Raman spectroscopy. The luminescence spectra and

decay curves of the doped ceramics was measured using photoluminescence

spectroscopy.

1.6 Significance of the Study

In this research, the significance of the study is to develop a new

luminescence material that can show an enhancement of the luminescence

characteristic and have a long decay time. So, this new material can produce a high

potential application in solid-state lighting devices.

1.7 Outline of the Thesis

Chapter 1 gives a brief description related to the magnesium boro-tellurite

ceramic and magnesium boro-tellurite doped Eu3+

and Dy3+

ceramic. Chapter 2

provides an overview of the work done on the magnesium boro-tellurite ceramic with

7

emphasis on its structural and luminescence properties. Chapter 3 presents some

background materials on the theoretical aspect of the thesis. It also discusses about

the mechanism of luminescence and the principles of X-Ray Diffractogram (XRD),

Fourier Transform Infrared (FTIR) and Raman properties. Chapter 4 describes in

detail the preparation of the magnesium boro-tellurite ceramic and magnesium boro-

tellurite doped Eu3+

and Dy3+

ceramic. Chapter 5 presents the result, analysis and

discussion for experiments on XRD, surface morphology, elemental composition of

the samples, IR and Raman, luminescence and lifetime. The last chapter, Chapter 6

contains the conclusion of the study and suggestions for future work.

138

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