희토류 이온이 첨가된 산화물 박막 제조 및 형광특성 연구
- Alternative Title
- Synthesis and Luminescent Properties of Rare Earth Ions-doped Oxide Thin Film
- Abstract
- The thesis reports the correlation between the synthesis and crystallization and luminescent properties of YVO4:Eu3+, YVO4:Sm3+, GdVO4:Eu3+, CaTiO3:Pr3+, YAG:Eu3+, ZnSiO4:Mn2+, and BaSi2O5:Eu2+ powder ceramic, and thin film phosphors.
The oxide materials based ceramic and thin film phosphors were prepared by solid state reaction, high-energy ball milling, pulsed laser deposition methods, respectively.
For the thin film phosphors, the crystallinity, surface roughness, and photoluminescence of the thin-film phosphors are highly dependent on substrate temperature, oxygen pressure and substrate kind. The surface roughness and PL intensity of the films also behave similarly as a function and condition of substrate temperature, oxygen pressure and substrate kind.
For the Li-doped phosphors, the improvement in PL performance with the Li-doping may result not only from improved crystallinity leading to higher oscillating strengths for the optical transitions but also from enlarged grain size inducing rougher surfaces. For the enhanced PL intensity, it can also be suggested that the incorporation of Li+ ions creates the oxygen vacancies, which might act as a sensitizer for the effective energy transfer due to the strong mixing of charge transfer states.
For the phosphors synthesized by high-energy ball milling, the most important advantage of the high-energy ball milling process is that it can be used to synthesize the designed compounds at room temperature with a grain size on the nanometer scale. Compared to the solid state reaction method, synthesis by high-energy ball milling is simple, easy to carry out and the raw materials are commercially available. The reported oxide powder, ceramic, and thin film phosphors can give a promise for fluorescence lamp, laser emitting diode, and display technologies.
- Issued Date
- 2010
- Awarded Date
- 2010. 2
- Type
- Dissertation
- Keyword
- Photoluminescence Rare Earth Thin Film Phosphors PLD
- Publisher
- 부경대학교
- Alternative Author(s)
- Yang, Hyun Kyoung
- Affiliation
- 부경대학교 물리학과
- Department
- 대학원 물리학과
- Advisor
- 정중현
- Table Of Contents
- 1. Introduction 1
1.1 Trends in the research of phosphor 1
1.1.1 LCD(liquid crystal display) 3
1.1.2 PDP(plasma display panel) 5
1.1.3 FED(field emission display) 8
1.1.4 VFD(vacuum fluorescent display) 9
1.2 Definition of phosphor 11
1.3 Specific luminescence properties of Rare Earth Ions 14
1.3.1 Pr3+ ion 14
1.3.2 Sm3+, Sm2+ ion 16
1.3.3 Eu3+ ion 16
1.3.4 Eu2+ ion 21
1.4 Studied phosphor materials 23
1.4.1 YVO4:RE3+ phosphors 23
1.4.2 CaTiO3:Pr3+ phosphors 24
1.4.3 YAG:Eu3+ phosphors 25
1.4.4 GdVO4:Eu3+ phosphors 26
1.4.5 Zn2SiO4:Mn3+ phosphors 27
1.4.6 BaSi2O5:Eu2+, Eu3+ phosphors 28
1.5 Research purpose ？ 30
2. Theory of luminescence 31
2.1 Luminescence mechanism of phosphors 33
2.2 Energy level analysis of rare earth ions(4f n) 37
3. Experimental 39
3.1 Powder sample and ceramic target preparation 39
3.2 Nanopowder samples preparation 40
3.3 Thin films preparation 41
3.3.1 Main Advantages of PLD 41
3.3.2 PLD Mechanisms 43
3.4 Composition of PLD device 49
3.4.1 Vacuum device 50
3.4.2 Substrate heating device 53
3.5 Characterizations 54
3.5.1 X-ray diffractrometer 54
3.5.2 FTIR 56
3.5.3 SEM and FE-SEM 57
3.5.4 X-ray photoelectron spectrometer 59
3.5.5 Scanning prove microscope 60
3.5.6 Luminescence spectrometers 61
3.5.7 Fluorescence dynamics spectrometer 63
3.5.8 Cathodoluminescence spectrometer 63
4. Results and Discussion 64
4.1 YVO4:Eu3+ phosphors 64
4.1.1 YVO4:Eu3+ ceramic phosphors by Li doping 64
4.1.1.1 Synthesis 64
4.1.1.2 XRD patterns 65
4.1.1.3 The correlation between PL intensity and I(200)/I(101) peak ratio 66
4.1.1.4 Surface morphology 68
4.1.1.5 PL and PLE spectra 69
4.1.1.6 Luminescence decay 72
4.1.2 YVO4:Eu3+ thin film phosphors by Li doping 73
4.1.2.1 Deposition conditions 73
4.1.2.2 PL characteristics dependent on deposition conditions 74
4.1.2.3 XRD patterns 75
4.1.2.5 Surface morphology 76
4.1.2.6 PL and PLE spectra 77
4.1.2.7 PL intensity and I(200)/I(101) peak ratio 81
4.2 YVO4:Sm3+ phosphors 82
4.2.1 Surface morphology and phoroluminescence characteristics of Sm-doped YVO4:Sm3+ thin films 82
4.2.1.1 Deposition conditions 82
4.2.1.2 XRD patterns 83
4.2.1.3 Surface morphology 84
4.2.1.4 PL and PLE spectra 87
4.2.1.5 PL intensity and I(101)/I(200) peak ratio 89
4.2.1.6 PL intensity and rms surface roughness 89
4.2.2 Crystalline and photoluminescence characteristics of YVO4:Sm3+ thin films 91
4.2.2.1 Deposition conditions 91
4.2.2.2 PL characteristics dependent on deposition conditions 92
4.2.2.3 XRD patterns 93
4.2.2.4 Surface morphology 94
4.2.2.5 PL and PLE spectra 96
4.2.2.6 The correlation between PL intensity and I(101)/I(200) peak ratio 97
4.2.2.7 The correlation between PL intensity and rms surface roughness 97
4.2.3 Photoluminescence and cathodoluminescence of YVO4:Sm3+ thin films prepared by PLD with various substrates 100
4.2.3.1 Deposition conditions100
4.2.3.2 XRD patterns 101
4.2.3.3 Surface morphology 102
4.2.3.4 PL and PLE spectra 103
4.2.3.5 CL spectra 103
4.3 CaTiO3:Pr3+ phosphors 106
4.3.1 Luminescent characteristics of CaTiO3:Pr3+ thin films prepared by PLD with various substrate 106
4.3.1.1 Deposition conditions 106
4.3.1.2 PL intensity dependent on Pr3+ contents 107
4.3.1.3 PL characteristics dependent on deposition conditions 108
4.3.1.4 FTIR spectra 110
4.3.1.5 XRD patterns 111
4.3.1.7 Surface morphology 112
4.3.1.8 PL and PLE spectra 113
4.3.2 Li-doped CaTiO3:Pr3+ thin films grown on Si(100) substrate 116
4.3.2.1 Deposition conditions 116
4.3.2.2 XRD patterns 117
4.3.2.3 Surface morphologyE 118
4.3.2.4 PL and PLE spectra 119
4.3.2.5 The correlation between PL intensity and lattice parameter 121
4.3.2.6 The correlation between PL intensity and rms surface roughness 122
4.3.3 Li-doped CaTiO3:Pr3+ thin films grown on Al2O3(0001) substrate under Li+ ion contents 123
4.3.3.1 Deposition condition 123
4.3.3.2 XRD patterns 124
4.3.3.3 FTIR spectra124
4.3.3.4 Surface morphology 126
4.3.3.5 PL and PLE spectra 126
4.3.4 Enahncement of the luminescent characteristics of Li-doped CaTiO3:Pr3+ thin films 129
4.3.4.1 Deposition condition 129
4.3.4.2 XRD patterns 130
4.3.4.3 Surface morphology 131
4.3.4.4 PL and PLE spectra 131
4.3.4.5 X-ray diffraction of the thin films grown on different oxygen pressure 132
4.3.4.6 PL spectra of the thin films grown on different oxygen pressure 133
4.3.4.7 The correlation between PL intensity and grain size 135
4.3.4.8 The correlation between PL intensity and rms surface roughne -ss 136
4.4 Sillicate phosphors 138
4.4.1 Mn2+-doped Zn2SiO4 thin films 138
4.4.1.1 Deposition conditions 138
4.4.1.2 XRD patterns 139
4.4.1.3 Surface morphology 140
4.4.1.4 PL and PLE spectra 142
4.4.1.5 The correlation between PL intensity and rms surface roughne-ss 144
4.4.2 Eu2+-and Eu3+-doped BaSi2O5 thin film phosphors 145
4.4.2.1 Deposition conditions 145
4.4.2.2 FTIR spectra 146
4.4.2.3 Surface morphology 146
4.4.2.4 PL and PLE spectra 148
4.4.2.5 The correlation between PL intensity and rms surface roughne -ss 150
4.5 Comparison of solid-state reaction and high-energy ball milling 151
4.5.1 Synthesis and luminescent properties of Eu3+-doped nanocrystalline and bulk GdVO4 phosphors by high-energy ball milling and solid state reaction method 152
4.5.1.1 Synthesis 152
4.5.1.2 Surface morphology 154
4.5.1.4 PL brightness 154
4.5.1.5 XRD patterns 157
4.5.1.6 FE-SEM images 159
4.5.1.7 PL and PLE spectra 160
4.5.2 Synthesis, crystal growth and photoluminescence properties of YAG:Eu3+ phosphors by high-energy ball milling and solid-state reaction 162
4.5.2.1 Synthesis 162
4.5.2.2 XRD patterns 164
4.5.2.3 FTIR diffraction 165
4.5.2.4 FE-SEM images 167
4.5.2.5 PL and PLE spectra 169
4.5.2.6 PL intensity function of sintering temperature 172
4.5.2.7 Time resolved spectroscopy 172
5. Conclusion175
6. References 181
7. Publication List 194
8. Acknowledgement 200
- Degree
- Doctor
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