臺灣博碩士論文加值系統

本研究以水熱合成法製備LaVO4螢光粉主體，摻雜稀土離子Dy3+ 和Eu3+當作發光中心並在pH固定等於8條件下改變不同的製程條件，探討摻雜濃度、退火溫度對其晶體結構、表面型態與發光特性之影響。
第一部分以LaVO4作為螢光粉主體，在煆燒溫度180℃持溫16小時固定pH=8條件下，製備(La1-xDyx)VO4 (x=0.01~0.03)，由XRD分析結果顯示，隨著Dy3+離子摻雜濃度的增加並沒有發現二次相的產生，均為正方晶系(tetragonal) LaVO4之結構。SEM分析結果顯示不同摻雜濃度之Dy3+離子條件下，螢光粉體皆為棒狀結構。在320 nm激發波長激發下，放射光譜主要由Dy3+離子的特徵峰組成，以4F9/2→6H15/2、4F9/2→6H13/2電子躍遷為主。當Dy3+離子摻雜濃度為0.025時，會有最強的放射強度。CIE色度座標顯示發光位置皆位在近白光區，其座標為(x=0.362, y=0.424)。

第二部分為在煆燒溫度180℃持溫16小時固定pH=8條件下，製備(La0.975-yDy0.025Euy)VO4 (y=0.005~0.03)。探討摻雜濃度對晶體結構、表面型態與發光特性之影響，由XRD結果，螢光粉均保持正方晶系結構，且無雜相產生。SEM結果顯示隨著Eu3+ 離子濃度增加螢光粉體並沒有太大的改變，螢光粉體皆為棒狀結構。在320 nm激發波長激發下，放射光譜主要由Dy3+離子和Eu3+離子的特徵峰組成，主要放射波長為482、573、618 nm，分別對應於Dy3+離子 4F9/2→6H15/2、4F9/2→6H13/2和618 nm處Eu3+離子5D0→7F2的電子躍遷，當Eu3+離子濃度為y=0.005時，CIE色度座標最接近於近白光區。

第三部分為(La0.97Dy0.025Eu0.005)VO4固定煆燒溫度180℃持溫16小時pH=8條件下，對其進行300℃~600℃ 熱退火4小時並探討其熱退火後晶體結構與發光特性之影響，從XRD結果可看出，300℃~600℃ 熱退火4 小時的條件下，均為正方晶系結構並沒有觀察到二次項的產生，SEM分析結果顯示所有樣品並無太大改變，皆為棒狀結構。當熱退火溫度在500℃ 時，在320 nm激發波長激發下，主要放射波長482、573、618 nm處有明顯的提升，具有最強的放射峰強度，當溫度達到550℃~600℃ 時放射峰強度有明顯的下降 。CIE色度座標顯示皆位於近白光區無明顯變化。

In this study, the LaVO4 phosphor host was prepared using the hydrothermal synthesis method, with rare earth ions Dy3+ and Eu3+ doped as luminescent centers. Different processing conditions were investigated under a fixed pH of 8, examining the effects of doping concentration and annealing temperature on the crystal structure, surface morphology, and luminescent properties.

he first part of the study uses LaVO4 as the host for the phosphor. Under the conditions of calcination at 180°C for 16 hours with a fixed pH of 8, (La1-xDyx) VO4 (x=0.01~0.03) was prepared. The XRD analysis results showed that with the increase in Dy3+ ion doping concentration, no secondary phases were found, and all structures were of the tetragonal LaVO4. SEM analysis showed that under different Dy3+ ion doping concentrations, the phosphor bodies all had a rod-like structure. Under the excitation wavelength of 320 nm, the emission spectrum was mainly composed of the characteristic peaks of Dy3+ ions, dominated by the 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transitions. When the Dy3+ ion doping concentration was 0.025, the strongest emission intensity was obtained. The CIE chromaticity coordinates showed that the luminescence positions were all located in the near white light area, with the coordinates being (x=0.362, y=0.424).

The second part of the study involves the preparation of (La0.975-yDy0.025Euy) VO4 (y=0.005~0.03) under the conditions of calcination at 180°C for 16 hours with a fixed pH of 8. The influence of doping concentration on the CIE chromaticity diagram was investigated. From the XRD results, the phosphor maintained a tetragonal structure with no secondary phases formed. SEM results showed that with the increase in Eu3+ ion concentration, there was no significant change in the phosphor body, which remained rod-like in structure. Under the excitation wavelength of 320 nm, the emission spectrum was mainly composed of the characteristic peaks of Dy3+ ions and Eu3+ ions, with the main emission wavelengths being 482, 573, and 618 nm. These corresponded to the 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transitions of Dy3+ ions, and the 5D0→7F2 electronic transition of Eu3+ ions at 618 nm. When the Eu3+ ion concentration was y=0.005, the CIE chromaticity coordinates were closest to the near-white light area.

The third part of the study involves (La0.97Dy0.025Eu0.005) VO4 prepared under the conditions of calcination at 180°C for 16 hours with a fixed pH of 8, undergoing thermal annealing at 300°C to 600°C for 4 hours. The impact of post-annealing on the crystal structure and luminescent properties was examined. From the XRD results, it can be seen that under the conditions of thermal annealing at 300°C to 600°C for 4 hours, the structure remained tetragonal with no observation of secondary phase formation. SEM analysis results showed no significant changes in all samples, which remained rod-like in structure. When the annealing temperature reached 500°C, under the excitation wavelength of 320 nm, the main emission wavelengths at 482, 573, and 618 nm showed a significant increase, with the strongest emission peak intensity. When the temperature reached 550°C to 600°C, the emission peak intensity showed a significant decrease. The CIE chromaticity coordinates showed no significant changes, remaining in the near-white light area.

摘要.........i
Abstract.........iii
誌謝.........v
目錄.........vi
表目錄.........ix
圖目錄.........x
第一章 緒論.........1
1-1 前言.........1
1-2 LaVO4 主體晶體介紹.........1
1-3 研究動機與目的.........2
第二章 理論基礎與文獻回顧.........6
2-1 螢光粉材料簡介.........6
2-1-1 有機螢光材料.........6
2-1-2 無機螢光材料.........6
2-1-3 激發源種類及其應用.........8
2-2 發光的定義.........9
2-2-1 螢光(fluorescence)與磷光(phosphorescence).........9
2 -3 固態材料中的光致發光.........10
2-3-1本質行發光 (Intrinsic Luminescence).........10
2-3-2外質型發光 (Extrinsic Luminescence).........11
2-4 螢光粉發光機制簡介.........12
2-4-1 發光原理與發光過程.........12
2-4-2 組態座標 (configuration coordination).........12
2-4-3 史托克位移 (stokes shift).........13
2-4-4 能量轉移 (energy transfer).........14
2-4-5 電子-聲子交互作用 (electron-phonon interaction).........14
2-4-6 交叉緩解 (cross relaxation).........14
2-4-7 非輻射躍遷 (non-radiative transition).........14
2-5 影響發光效率及性質的主要因素.........15
2-5-1 主體晶格效應.........15
2-5-2 毒劑效應 (poisoning effect).........15
2-5-3 熱淬滅效應 (thermal quenching).........16
2-5-4 濃度淬滅效應 (concentration quenching effect).........16
2-5-5 光游離效應 (photoionization effect).........16
2-5-6 補償效應 (offset effect).........16
2-6 螢光體的組成與選擇.........17
2-7 螢光粉體之合成技術.........18
第三章 實驗方法與步驟.........34
3-1 實驗流程.........34
3-2 實驗材料.........34
3-3 成分與結構分析.........35
3-3-1 X光繞射 (X-ray diffraction analysis, XRD)分析.........35
3-3-2 場發射掃描式電子顯微鏡 (Field emission scanning electron microscopy, FE-SEM) 分析.........35
3-3-3 高解析穿透式電子顯微鏡 (High Resolution Transmission Electron Microscope, HR-TEM)分析.........36
3-4 螢光粉體之光學特性分析.........36
3-4-1 吸收光譜 (Absorption spectrum).........36
3-4-2 螢光光譜儀 (Photoluminescence, PL)特性分析.........36
3-4-3 衰減時間 (Decay time)分析.........36
3-4-4 CIE色度座標分析 (analysis of C.I.E chromaticity diagram).........36
第四章 結果與討論.........41
4-1 固定pH=8以水熱合成法製備(La1-xDyx)VO4螢光粉.........41
4-1-1 (La1-xDyx)VO4螢光粉之XRD結構分析.........41
4-1-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析.........41
4-1-3 (La1-xDyx)VO4固定pH=8螢光粉之吸收光譜分析.........41
4-1-4 (La1-xDyx)VO4固定pH=8螢光粉之激發光譜分析.........42
4-1-5 (La1-xDyx)VO4螢光粉之放射光譜分析.........42
4-1-6 (La1-xDyx)VO4螢光粉之衰減曲線.........42
4-1-7 CIE色度座標.........43
4-1-8 (La0.975Dy0.025)VO4螢光粉之熱淬滅分析.........43
4-1-9 結論.........43
4-2 固定pH=8以水熱合成法製備(La0.975-yEuyDy0.025)VO4之螢光粉.........60
4-2-1 (La0.975-yEuyDy0.025)VO4螢光粉之XRD結構分析.........60
4-2-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析.........60
4-2-3 (La0.975-yEuyDy0.025)VO4固定pH=8螢光粉之吸收光譜分析.........60
4-2-4 (La0.975-yEuyDy0.025)VO4固定pH=8之激發光譜分析.........60
4-2-5 (La0.975-yEuyDy0.025)VO4 (y=0.005~0.03)之放射光譜分析.........61
4-2-6 (La0.975-yEuyDy0.025)VO4 (y=0.005~0.03) 固定pH=8之衰減曲線.........61
4-2-7 CIE色度座標.........62
4-2-8 (La0.97Dy0.025Eu0.005)VO4固定pH=8之熱淬滅分析.........62
4-2-9 結論.........63
4-3 水熱合成法製備(La0.97Dy0.025Eu0.005)VO4之螢光粉熱退火分析.........79
4-3-1(La0.97Dy0.025Eu0.005)VO4螢光粉熱退火之XRD結構分析.........79
4-3-2 (La0.97Dy0.025Eu0.005)VO4螢光粉熱退火處理之晶格應變分析.........79
4-3-3 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析.........80
4-3-4 高解析穿透式電子顯微鏡 (HR-TEM)分析結構型態分析.........80
4-3-5 (La0.97Dy0.025Eu0.005)VO4螢光粉熱退火之吸收光譜分析.........80
4-3-6 (La0.97Dy0.025Eu0.005)VO4螢光粉熱退火之激發光譜分析.........80
4-3-7 (La0.97Dy0.025Eu0.005)VO4螢光粉熱退火之放射光譜分析.........80
4-3-8 (La0.97Dy0.025Eu0.005)VO4固定pH=8值螢光粉熱退火之衰減曲線.........82
4-3-9 CIE色度座標.........82
4-3-10 (La0.97Dy0.025Eu0.005)VO4螢光粉於500℃熱退火處理之熱淬滅分析.........82
4-3-11 結論.........82
第五章 總結論.........98
參考文獻.........99
Extended Abstract.........103

[1]. 劉如熹、王建元、石景仁，2001年8月， “白光發光二極體之螢光粉材料介紹”，光訊第91期，p.30。
[2]S. Shionoya and W. M. Yen, 1999, “Phosphor Handbook”, CRC press, Boca Raton.
[3]Y. S. Chang, H. J. Lin, Y. L. Chai, Y. C. Li, “Preparation and luminescent properties of europium-activated YInGe2O7 phosphors” J. Alloy. Compd. 460 (2008) 421.
[4]Z. Liu, Y. Li, Y. Xiong, D. Wang, Q. Yin, “Electroluminescence of SrAl2O4:Eu2+ phosphor”, Microelectronics Journal 35 (2004) 375
[5]W. T. Hsu, W. H. Wu, C. H. Lu, “Synthesis and luminescence properties of nano-sized Y3Al5O12:Eu3+ phosphors” Mater. Sci Eng. B104 (2003) 40.
[6]Y. C. Li, Y. H. Chang. Li, Y. F. Lin, Y. S. Chang, Y. J. Lin, “Synthesis and luminescent properties of Ln3+(Eu3+, Sm3+, Dy3+)-doped lanthanum aluminum germinates LaAlGe2O7 phosphors” J. Alloy. Compds. 439 (2007) 367
[7]S. D. H., S. P. Khatkar, V. B. Taxak, G. S., D. K., “Synthesis, luminescence and effect of heat treatment on the properties of Dy3+-doped YVO4 phosphor” Mater. Sci. Eng. B 129 (2006) 126.
[8]V. Bachmann, C. Ronda, A. Meijerink, Chem. Mater. 21 (2009) 2077-2084
[9]戴品綸，民國98年，“Y1-xInGe2O7:Mx3+(M=Bi, Sm, Er, Dy)之合成與光致發光特性研究”， 國立成功大學材料科學及工程學系碩士論文。
[10]Structure and stability of monazite- and zircon-type LaVO4 under hydrostatic pressure
[11]Rice C.E, Robinson W.R, Acta Cryst., B 32 (1976) 2232
[12]S.Cho,J.Nanosci.Nanotechnol.13(11)(2013)7546
[13]S.W.Park,H.K Yang,J.W.Chung, B.K.Moon,B.C Choi,J. H. Jeong, Korean Phys.Soc.57[6] (2010) 1764
[14]G.C. Liu ,X.C. Duan, H.B. Li,H. Dong, L.G. Zhu, J. Cryst. Geowh 310 (2008) 4689
[15]C. J. Jia. L. D. Sun, F. Luo, X. C. Jiang. L. H. Wei, C. H. Yan, Appl. Phys. Lett. 84 (2004) 5305
[16]F.C. Palilla, A.K. Levine, M.J. Rinkevics, J. Electrochem. Soc. 112 (1965) 776
[17]U. Rambabu, D.P. Amalnerkar, B.B. Kale, S. Buddhudu, Mater. Res. Bull. 35 (2000) 929
[18]C. J. Jia, L. D. Sun, L. P. You, X. C. Jiang, F. Luo, Y. C. Pang, C. H. Yan, J. Phys. Chem. B 109 (2005) 3284
[19]W. L. Fan, W. Zhao, L. P. You, X. Y. Song, W. M. Zhang, H. Y. Yu, S. X. Sun, J. Solid State Chem. 177 (2004) 4399
[20]B.Mercier, C. Dujardin, G. Ledoux, D. Nicolas, B. Masenelli, P. Melinon, "Effect of the quantum confinement on the luminescent properties of sesquioxydes" J.Lumin. 122-123
[21]J. A. Deluca, "An Introduction to Luminescence in Inorganic Solids", J. Chem. Edu. 57
[22]N. I. Meyer and F. P, Jeasen, 1996, "Hot electron from silicon p-n junctions produced by ion implantation/. J. Appl. Phys,37 (11), 4297.
[23]G. Blasse and B.C. Grabmaier, 1991 , "Luminescence Materials", Springer Verlag, Berlin Heidelberg, p.245.
[24]S. Tanimizu, 1999, "Luminescence center of ns?-type ions", Phosphor Handbook, CRC press, Florida, 141-152.
[25]M. Tamatani, 1999, "Luminescence center of transition metal ions",Phosphor Handbook
[26]M. Morita, 1999, "Luminescence centers of complex ions, Phosphor Handbook", CRC press, Florida, 201-212.
[27]T. Kano, 1999, "Luminescence centers of rare-earth ions, Phosphor Handbook", CRC press, Florida, 177-200.
[28]Lauren E. SheaRohwer and Robert J. Walko, “Synthesis and Characterization of Phosphors for Flat-Panel Displays”, Handbook of Luminescence, Display Materials, and Devices Volume 3 Display Devices, American Scientific Publishers (2003) 158-160.
[29]張太中、張俊英編著， “無機光致發光材料及應用”，北京：化學工業出版社，2005年2月，pp68~192。
[30]G. Blasse and B. C. Grabmaier, “Luminescent Materials”, Springer. Berlag Berlin Heidelberg (1994) 1-3.
[31]徐敘瑢編著， “光電材料與顯示技術”，五南圖書，2004年8月，pp33~284。
[32]H. Zhang, X. Fu, S. Niu, G. Sun, Q Xin, 2004, “Photoluminescence of YVO4:Tm phosphor prepared by a polymerizable complex method”, Solid State Commun., 132, 527-531.
[33]柯以侃、吳明珠，民國92年6月， “儀器分析”，新文京開發出版有限公司。
[34]劉如熹、劉宇桓， “發光二極體用氧氮螢光粉介紹”，全華科技(2006)。
[35]蔡濱祥， “尖晶石(MgxZn1-x)(In2-yGay)O4:Eu3+, Tb3+螢光粉體製備及其光致發光特性研究”，國立成功大學材料科學及工程學系博士論文，2005。
[36]陳昱霖， “柘榴石(Y3Al5O12)螢光體之合成與性質研究”，國立成功大學材料科學及工程學系碩士論文，2001。
[37]李育群，“鍺酸鹽LaAlGe2O7螢光粉光致發光特性研究”，國立成功大學材料科學及工程學系博士論文，2007。
[38]D R Vij, 1998, “Luminescence in Solids”, Plenum press, New York.
[39]G. Blasse and B. C. Grabmaier, 1991, “Luminescence Marterials”, Springer Verlag, Berlin Heidelberg, p.245.
[40]楊素華，“螢光粉在發光上的應用”，科學發展358期，2002年10月，pp.67~68
[41]A. H. Kitai, 1993, “Solid State Luminescence”, Chapman & Hall press, Cambridge.
[42]S. Shionoya and W. M. Yen, 1999, “Phosphor Handbook”, CRC press, Boca Raton.
[43]方客川，2001年，“固態光譜學”，中國科技大學出版社，中國。
[44]H. Yamamoto, “IIa-VIb compounds”, Phosphor Handbook, CRC press (1999) (217-230).
[45]劉如熹、王健源，“白光發光二極體用製作技術”，全華科技，(2001)。
[46]G. Blasse, W Schipper and J. J. Hamelink, 1991, “On the quenching of the luminescence of the trivalent cerium ion”, Inorg. Chim. Acta, 189, 77.
[47]G. Blass, C de Mello Donega, N. Efryushina, V. Dotsenko and I Berezovskaya, 1994, “Luminescence of Pr3+ in indium borate (InBO3)”, Solid State Commun., 92(8), 687.
[48]R. C. Ropp, “Luminescence and the Solid State”, Elsevier Science Publishers, The Netherlands, (1991).
[49]E. Cavalli, P.Boutinaud, M. Grinberg, 2014, “Luminescence dynamics in CaWO4:Pr3+ powders and single crystals”, Elsevier B. V. All rights reserved.
[50]X. Cheng, D.J. Guo, S.Q. Feng, K. Yang, Y.Q. Wang, Y.F. Ren, Y. Song “Structure and stability of monazite- and zircon-type LaVO4 under hydrostatic pressure”, Optical Materials 49 (2015) 32-38.
[51]施昭榮，民國99年，“釩酸鹽 InVO4:Eu3+螢光粉之製備與光致發光特性研究”，國立虎尾科技大學光電與材料科
[52]L. Ge, M. Xu, H. Fang, 2006, “Synthesis and characterization of the Pd/InVO4-TiO2 co-doped thin films with visible light photocatalytic activities” Appl. Surf. Sci., 253, 2257-2263.
[53]Fei He, Piaoping Yang, Dong Wang, Na Niu, Shili Gai, Xingbo Li and Milin Zhang, “Hydrothermal synthesis, dimension evolution and luminescence properties of tetragonal LaVO4:Ln (Ln = Eu3+, Dy3+, Sm3+) nanocrystals”, Dalton Trans., 2011, 40, 11023.
[54]林柏學，民國109年，“雙鈣鈦礦型Ba2LaNbO6：Dy3+,Eu3+,Sm3+螢光粉之製備與發光特性研究”，國立虎尾科技大學電子工程系研究所碩士論文。
[55]E. Botcharova, M. Heilmaier, J. Freudenberger, G. Drew, D. Kudashow, U. Martin, L. Schultz, “Supersaturated solid solution of niobium in copper by mechanical alloying”, J. Alloys Compd 351 (2003) 119-125.
[56]Debasish Sarkar, Mincheol Chu, Seong-Jai Cho, Yong Il Kim, “Synthesis and Morphological Analysis of Titanium Carbide Nanopowder”, J. Am. Ceram. Soc., 92 [12] 2877-2882 (2009).
[57]Mu Gu*, Lihong Xiao, Xiaolin Liu, Rui Zhang, Bingjie Liu, Xin Xu, "Highly enhanced luminescence of GdTaO.:Eu3+ phosphors by cooping with Zn2+ ions", J. Alloy. Compd., 426, 390-394 (2006).
[58]Bingie Liu, Mu Gu, Xiaolin Liu, Chen Ni, Di Wang, Lihong Xiao, Riu Zhans, "Effec: of, Zm2+ and Lit codoping ions on nanosized Gd203 Eu3+ phosphor", J. Alloy Compd., 440, 341-345 (2007)
[59]Bing Yan Xue-Qing Su "Chemical co-precipitation synthesis and photoluminescence of LnPxV1 − xO4:Dy3+ (Ln = Gd, La) derived from assembling hybrid precursors" Journal of Alloys and Compounds
Volume 431, Issues 1–2, 4 April 2007, Pages 342-347
[60]王敬文，民國112年，“混和助熔劑對於Ba2(La0.9575Dy0.04Eu0.0025)NbO6螢光粉體之結構與光致發光特性研究”，國立虎尾科技大學電子工程系研究所碩士論文。