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研究生：	陳貞融 Chen, Chen-Jung
論文名稱：	高演色性PiG型白光發光二極體之開發: 紅色Li2MgTiO4:Mn4+螢光粉及碲玻璃:Eu3+、Sm3+之製備 Development of PiG -Type WLEDs with High CRI: Preparation of Red Phosphor Li2MgTiO4:Mn4+ and TeO2 Glass: Eu3+, Sm3+
指導教授：	朱聖緣 Chu, Sheng-Yuan
學位類別：	碩士 Master
系所名稱：	電機資訊學院 - 電機工程學系 Department of Electrical Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	英文
論文頁數：	71
中文關鍵詞：	紅色螢光粉、稀土離子、低溫熔點碲玻璃、白光LED
外文關鍵詞：	red phosphor, rare earth ions, low melting TeO2-based glass, WLED
相關次數：	點閱：93 下載：1
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本論文針對兩種改善白光LED (blue chip+ YAG: Ce3+)之演色性(CRI)及相關色溫(CCT) 的方式進行探討，將白光LED調整至人眼可接受及舒適的範圍。第一種方法首先製備紅色螢光粉Li2MgTiO4:Mn4+結合助熔劑MgF2使整體分散性佳且粒子大小分布呈現均一。我們發現加入助熔劑MgF2可提升紅色螢光粉Li2MgTiO4:Mn4+的發光強度及熱穩定性由於助熔劑可以幫助粒子減少團聚及讓粒子大小一致，使其在燒結過程中能讓粉體更加緻密得到結晶性較佳的螢光粉。除此之外，外部量子效率也從9%提高至17%，之後利用熔融淬火法合成低熔點玻璃(TeO2-B2O3-ZnO-Na2CO3-WO3)。將紅色螢光粉及商用黃色螢光粉加入玻璃進行封裝並結合波長468nm的藍光晶片形成PiG型白光LED。紅色螢光粉的添加使得白光LED的演色性從74.97提高至82.50，而相關色溫從6285K降低至5487K。
第二種方法，將發橘紅光的稀土元素Eu3+及Sm3+共摻入碲玻璃(TeO2-based)中，並結合黃色螢光粉及波長465nm的藍光晶片形成白光LED。可發現將稀土離子摻入玻璃中可提升白光LED的演色性從74.97增加至78.33，且降低相關色溫從5623K減少至5113K。最終，我們會針對兩種PiG形式的變電流與熱穩定性進行比較。

In this thesis, two ways of improving color rendering index (CRI) and correlated color temperature (CCT) of WLED (blue chip+ YAG: Ce3+) adjust to the comfortable range to human eyes are investigated. First, well-dispersed red phosphors Li2MgTiO4:Mn4+ combined with the flux MgF2 are first prepared and shown good size distribution uniformity. The flux MgF2 is found to promote emission intensity and thermal stability of the proposed phosphors, besides the external quantum efficiency of the phosphors increases from 9% to 17%. Then, TeO2-B2O3-ZnO-Na2CO3-WO3 glass with low melting point is synthesized by melt-quenching method and PiG-based WLEDs are fabricated by encapsulating the proposed red phosphors, commercial YAG phosphors and glass with 468nm blue chips. The addition of red phosphors caused the CRI of WLED increasing from 74.97 to 82.50; in addition, the CCT of WLED is decreasing from 6285K to 5487K. On the other hand, TeO2-based glass: Eu3+, Sm3+ which emits orange-red are prepared and combined with yellow phosphor YAG: Ce3+ and 465nm blue chips to fabricate WLEDs. It is found that mixing rare earth ions into glass helps to increase the CRI of WLED from 74.97 to 78.33 and lower the CCT of WLED from 5623K to 5113K. Finally, the current-dependent and thermal stability of these two devices are compared.

Table of contents
Abstract	I
中文摘要	II
致謝	III
Table of contents	IV
List of Tables	VII
List of Figures	VIII
Chapter 1: Introduction	1
1 Background	1
2 Motivation	1
2.1 Improvement of CRI	1
2.2 Promotion of encapsulant	3
Chapter 2: Theory and Literature Review	5
1 Introduction to luminescence [18-20]	5
1.1 Excitation	5
1.2 Emission	6
1.2.1 Emission processing	6
1.2.2 Stokes shift	7
1.2.3 Concentration quenching	8
1.3 Nonradiative transitions	9
1.3.1 Multiphonon emission	9
1.3.2 Energy transfer	10
2 Luminescent centers [18-21]	11
2.1 Transition metal ions	11
2.2 Rare earth ions	12
3 Theory of glass [22-23]	13
3.1 Glass transformation behavior	14
3.2 Glass melting	15
3.3 Network connectivity	16
3.4 Optical property	17
3.4.1 Refractive index	17
3.4.2 Molar and ionic refractivity	18
4 Literature review of phosphor and glass encapsulant	19
4.1 Overview of Li2MgTiO4:Mn4+ phosphor	19
4.2 Overview of rare earth ions doped glass	21
4.3 Overview of phosphor in glass (PiG)	24
Chapter 3: Experimental Procedure	25
1 Introduction	25
2 The proposed red phosphors with low melting point TeO2 glass of PiG-based WLEDs	25
2.1 Synthesis of red-emitting phosphor Li2MgTiO4:Mn4+ with flux MgF2	25
2.2 Preparation of TeO2-based glass	26
2.3 Fabrication of phosphor in glass (PiG) of WLED	27
3 TeO2-based glass: Eu3+, Sm3+ of PiG-based WLEDs	28
3.1 Preparation of TeO2-based glass doping Eu3+, Sm3+	28
3.2 PiG-based with rare earth ions Eu3+/Sm3+ of WLED	29
4 Instrumental analysis of characterization	30
4.1 X-ray diffraction (XRD)	30
4.2 Scanning electron microscopy (SEM)	30
4.3 Photoluminescence spectra, thermal stability and quantum efficiency	31
4.4 UV-VIS spectra	31
4.5 Decay time	31
4.6 Color rendering index (CRI), correlated color temperature (CCT) and luminous efficiency of WLED	31
Chapter 4: Results and Discussion	32
1 Red-emitting phosphor Li2MgTi(1-x)O4:xMn4+	32
1.1 XRD analysis of Li2MgTi(1-x)O4:xMn4+	32
1.2 Photoluminescence spectra of Li2MgTi(1-x)O4:xMn4+	33
2 Effect of flux MgF2 addition on photoluminescence characteristic of Li2MgTi0.997O4:0.003Mn4+	35
2.1 XRD analysis of flux MgF2 addition to Li2MgTi0.997O4:0.003Mn4+	35
2.2 Photoluminescence spectra of MgF2 addition to Li2MgTi0.997O4:0.003Mn4+	37
2.3 Thermal stability of Li2MgTi0.997O4:0.003Mn4+ with MgF2 and without MgF2	38
2.4 SEM observation of Li2MgTi0.997O4:0.003Mn4+ with MgF2 and without MgF2	40
2.5 Decay time of Li2MgTi0.997O4:0.003Mn4+ with MgF2 and without MgF2	41
3 Rare earth ions Eu3+ doped TeO2-based glass	42
3.1 XRD analysis of Eu3+ doped TeO2-based glass	42
3.2 Photoluminescence spectra of Eu3+ doped TeO2-based glass	43
3.3 Transmittance of Eu3+ doped TeO2-based glass	44
3.4 Decay time of Eu3+ doped TeO2-based glass	45
4 Rare earth ions Eu3+/Sm3+ co-doped TeO2-based glass	47
4.1 XRD analysis of Eu3+/Sm3+ co-doped TeO2-based glass	47
4.2 Photoluminescence spectra of Eu3+/Sm3+ co-doped TeO2-based glass	48
4.3 Transmittance of Eu3+/Sm3+ co-doped TeO2-based glass	50
4.4 Decay time of Eu3+/Sm3+ co-doped TeO2-based glass	51
5 White light-emitting diodes fabrication by using PiG disk with InGaN chip emitting blue light	53
5.1 Weight ratio of Pure YAG: Ce3+ and glass	53
5.2 PiG-based white light-emitting diode composed of Li2MgTi0.997O4:0.003Mn4+ and YAG	54
5.2.1 WLED characteristics of Li2MgTi0.997O4:0.003Mn4+ and YAG of PiG	54
5.2.2 XRD pattern of Li2MgTi0.997O4:0.003Mn4+ and YAG of PiG	55
5.2.3 Photoluminescence spectra of Li2MgTi0.997O4:0.003Mn4+ and YAG of PiG	56
5.3 PiG-based white light-emitting diodes composed of Eu3+/Sm3+doped glass and YAG	57
5.3.1 WLED characteristics of rare earth ions Eu3+/ Sm3+ and YAG of PiG	57
5.3.2 XRD pattern of rare earth ions Eu3+/ Sm3+ and YAG of PiG	58
5.3.3 Photoluminescence spectra of rare earth ions Eu3+/ Sm3+ and YAG of PiG	59
5.4 WLED characteristics stability of LMTPiG3 and ESPiG2 by changing current	60
5.5 Thermal stability of LMTPiG3 and ESPiG2	62
Chapter 5: Conclusions and Future Work	64
1 Conclusions	64
2 Future Work	65
References	66


                                    

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