臺灣博碩士論文加值系統

本研究以水熱合成法來製備LaVO4螢光粉體，添加稀土離子Pr3+當作發光中心並改變不同的製成條件，探討摻雜濃度對晶體結構、粉體形態及發光特性之影響。
在LaVO4共摻Pr3+,Y3+離子螢光粉中，固定Pr3+離子濃度2 mol%，共摻不同濃度的Y3+離子，由XRD分析結果顯示，在水熱處理180 oC持溫16小時條件下，可得知結構為正方晶系(tetragonal) LaVO4之結構，隨著Y3+離子摻雜濃度的增加也並沒有二次相的生成。SEM分析方面，隨著Y3+離子濃度增加，螢光粉顆粒逐漸變小且不一致。在315nm激發下，當Y3+離子濃度為3 mol%時，(La0.98-yPr0.02Yy)VO4螢光粉位於607nm強度的放射峰為最強，是屬於Pr3+離子的1D2→3H4電子躍遷。吸收光譜圖分析顯示，200~330 nm為主體晶格吸收帶，在440~500 nm和580~620 nm為Pr3+離子4f-5d軌域的特性吸收。當Y3+離子摻雜濃度為3 mol%時，會出現最佳的發光強度，發光位置為近白光區，而CIE的座標為(x=0.326, y=0.266)。
LaVO4螢光粉體摻雜固定Pr3+離子濃度0.2 mol%和在pH值為8會出現形態改變並且發光特性有明顯改善。由XRD觀察在180oC持溫16小時會維持正方晶系(tetragonal)LaVO4之結構且無雜相。由SEM圖顯示當pH=8時螢光粉表面形態由顆粒轉變為棒狀且成長一致。在激發波長為315 nm放射光譜得知到當pH=8具有最強的放射強度，其色度座標為(x=0.396, y= 0.228)，座落於紅光區域。

In this study, LaVO4 was prepared by hydrothermal method and doped with different concentrations of Pr3+ ion as the luminescent center for the phosphor. The effects of the Pr3+ ion concentrations, the crystal structure and photoluminescence properties of the phosphor were investigated.
In order to enhance the photoluminescence properties of LaVO4:Pr3+ phosphors, the Pr3+ ion concentration was fixed for 2 mol% and doped with different Y3+ ion concentrations. The XRD results show that the crystal structure of (La0.98-yPr0.02Yy)VO4 phosphor prepared by the hydrothermal method at 180°C for 16 h can be attributed to the tetragonal structure of LaVO4 and no secondary phases appear when the Y3+ ion doping concentration increased.
The SEM results show that the phosphor particles become smaller and inconsistent as the Y3+ ion concentrations increase. Under an excitation of 315 nm, when the Y3+ ion concentration is 3 mol%, the emission spectra of (La0.98-yPr0.02Yy)VO4 phosphors show a maximum intensity of emission peak at 607 nm which is corresponding to the 1D2→3H4 electron transition of Pr3+ ion. The Absorption analysis show that an absorption band between 200 ~ 330 nm is due to the lattice absorption, and the Pr3+ ion 4f-5d characteristic transition is located between in the 440 ~ 500 nm and 580 ~ 620 nm region. The optimal PL intensity is obtained when Y3+ ion concentration is 3 mol%, and which is located in the white region with the CIE chromaticity coordinates of (x=0.326, y=0.266).
LaVO4 phosphor powder doped with fixed Pr3+ ion concentration of 0.2 mol% and at pH=8 exhibited morphological changed and significantly improved luminescence properties. The XRD patterns show that the crystal structure keeps a tetragonal crystal structure. The SEM images show that when pH=8, the surface morphology of the phosphor powder changes from a particle to a rod and grows uniformly. At the excitation wavelength of 315 nm, it was found that when pH=8 had the strongest emission intensity, and which is located in the red region with the CIE chromaticity coordinates of (x=0.396, y= 0.228).

摘要.....i
Abstract.....ii
誌謝.....iv
目錄.....v
表目錄.....ix
圖目錄.....x
第一章 緒論.....1
1-1前言.....1
1-2 LaVO4晶體介紹.....2
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發光的定義.....6
2-1-1螢光材料簡介.....6
2-1-2螢光與磷光.....6
2-1-3激發源的種類及應用.....7
2-2 螢光材料種類.....8
2-2-1有機螢光材料.....8
2-2-2無機發光材料.....8
2-3 固態材料中的光致發光現象.....10
2-3-1 本質型發光(Intrinsic Luminescence).....11
2-3-1-1能帶發光 (band-to-band luminescence).....11
2-3-1-2 激子發光 (exciton luminescence).....11
2-3-1-3交叉發光 (cross-luminescence).....11
2-3-2 外質型發光(extrinsic luminescence).....12
2-3-2-1 侷限型(localized type).....12
2-3-2-2 非侷限型(unlocalized type).....13
2-4 發光機制簡介.....13
2-4-1 發光原理與過程.....13
2-4-2組態座標 (configuration coordination).....14
2-4-3能量轉移 (energy transfer).....14
2-4-4電子-聲子交互作用(electron-phonon interaction).....14
2-4-5交叉緩解(cross relaxation).....15
2-4-6史托克位移(stokes shift).....15
2-4-7 非輻射躍遷(non-radiative transition).....16
2-5 影響發光性質的主要因素.....17
2-5-1 主體晶格效應 (host lattice effect).....17
2-5-2濃度淬滅效應(concentration quenching effect).....17
2-5-3毒劑效應(poisoning effect).....18
2-5-4熱淬滅效應(rhermal quenching).....18
2-5-5 螢光共振能量轉移(FRET, fluorescence resonance energy transfer.....18
2-6 螢光體的組成與選擇.....18
2-6-1 主體晶格的選擇.....19
2-6-2 活化劑的選擇.....19
2-6-3 增感劑的選擇.....19
2-6-4 抑制劑的避免.....20
2-7 螢光粉體之合成技術.....20
第三章 實驗方法與步驟.....37
3-1 實驗流程.....37
3-2實驗材料.....37
3-3 成分與結構分析.....37
3-3-1 X光繞射 (X-ray diffraction analysis, XRD)分析.....37
3-3-2 場發射掃描式電子顯微鏡 (field emission scanning electron microscopy, FE-SEM)分析.....38
3-4 螢光粉體之光學特性分析.....38
3-4-1 吸收光譜 (absorption spectrum).....38
3-4-2 螢光光譜儀(photoluminescence, PL)特性量測.....38
3-4-3 CIE色度座標分析 (analysis of C.I.E chromaticity diagram).....39
第四章 結果與討論.....43
4-1以水熱合成法合成La0.98-yPr0.02YyVO4 (y=0~0.1)之螢光粉.....43
4-1-1 La0.98-yPr0.02YyVO4螢光粉之XRD分析.....43
4-1-2 場發射掃描式電子顯微鏡(FE-SEM)表面形態分析.....44
4-1-3 La0.98-yPr0.02YyVO4螢光粉之吸收光譜分析.....44
4-1-4 La0.98-yPr0.02YyVO4螢光粉之激發光譜分析.....44
4-1-5 La0.98-yPr0.02YyVO4螢光粉之放射光譜分析.....45
4-1-6 CIE色度座標.....46
4-1-7結論.....46
4-2 對水熱合成La0.998Pr0.002VO4之螢光粉分析.....61
4-2-1 La0.998Pr0.002VO4之合成與分析.....61
4-2-2 La0.998Pr0.002VO4之XRD結構分析.....61
4-2-3 FE-SEM表面形態分析.....62
4-2-3 La0.998Pr0.002VO4螢光粉之吸收光譜分析.....62
4-2-4 La0.998Pr0.002VO4螢光粉之激發光譜分析.....62
4-2-5 La0.998Pr0.002VO4螢光粉之放射光譜分析.....63
4-2-6 CIE色度座標.....63
4-2-7結論.....64
第五章 總結論.....77
5-1以水熱合成法合成La0.98-yPr0.02YyVO4 (y=0~0.1)之螢光粉.....77
5-2以水熱合成法合成La0.998-yPr0.002VO4之螢光粉.....77
參考文獻.....79
Extended Abstract.....85
Abstract.....85

[1]劉如熹、王健元、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 germinate LaAlGe2O7 phosphors” J. Alloy. Compds. 439 (2007) 367
[7]項鈺軒，民國100年，“以溶膠-凝膠法製備BaY2-xLaxZnO5:Eu3+ (x=0~0.36)螢光粉及其光致發光性質研究”，國立虎尾科技大學光電與材料科技研究所碩士論文。
[8]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。
[9]林暉然，“鍺酸鹽YxInGe2O7:R1-x(R＝Eu, Tb, Tm)之螢光特性研究”，國立成功大學材料科學及工程學系碩士論文，pp11~42，民國95年。
[10]戴品綸，“Y1-xInGe2O7:Mx3+(M = Bi, Sm, Er, Dy)之合成與光致發光特性研究”，國立虎尾科技大學光電與材料科技研究所碩士論文，民國98年。
[11]Rice C. E., Robinson W. R., ActaCryst., B 32 (1976) 2232
[12]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
[13]S. Cho, J. Nanosci. Nanotechnol.13(11) (2013)7546
[14]S. W. Park, H. K. Yang, J. W. Chung, B. K. Moon, B. C. Choi, J. H. Jeong, J. Korean Phys. Soc. 57 [6] (2010) 1764
[15]F. Zhang, G. Q. Li, W. F. Zhang, Y. L. Yan, Inorg. Chem. 54 (2015) 7325
[16]G. C. Liu, X. C. Duan, H. B. Li, H. Dong, L. G. Zhu, J. Cryst. Growth 310 (2008) 4689
[17]G. S. R. Raju, J. Y. Park, H. C. Jung, R. Balarkrishnaiah, B. K. Moon, and J. H. Jeong, 2011, “Synthesis, structural and luminescent properties of Pr3+ activated GdAlO3 phosphors by solvothermal reaction method”, Curr. Appl. Phys., 11, S292-S295
[18]C. J. Jia, L. D. Sun, F. Luo, X. C. Jiang, L. H. Wei, C. H. Yan, Appl. Phys. Lett. 84 (2004) 5305
[19]F.C. Palilla, A.K. Levine, M.J. Rinkevics, J. Electrochem. Soc. 112 (1965) 776
[20]U. Rambabu, D.P. Amalnerkar, B.B. Kale, S. Buddhudu, Mater. Res. Bull. 35 (2000) 929
[21]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
[22]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
[23]D.R. Vij ,“Luminescence in Solids”, Plenum press, New York (1988).
[24]徐敘瑢、蘇勉增，發光學與發光材料 , p2，2004年。
[25]羅浚仁，“照明用螢光粉”，電機月刊，第十二卷，五期，pp.165-175，2002年5月。
[26]楊富涵，“氧化鋁添加軟鋁石之混合漿料懸浮與流變行為及其應用研究”，南台科技大學化學工程研究所碩士論文，pp.29-61，民94年6月。
[27]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 (2007)220-222--0607
[28]柯以侃、吳明珠，“儀器分析”，新文京開發出版有限公司，2003。
[29]劉如熹、劉宇桓，2006年，“發光二極體用氧氣螢光粉介紹”，全華科技。
[30]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 (2007)220-222
[31]J. A. Deluca, “An Introduction to Luminescence in Inorganic Solids”, J. Chem. Edu. 57 (1980) 541-545.
[32]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.
[33]G. Blasse and B.C. Grabmaier,1991 , “Luminescence Materials”, Springer Verlag, Berlin Heidelberg, p.245.
[34]T. Kano, 1999, “Luminescence centers of rare-earth ions, Phosphor Handbook”, CRC press, Florida, 177-200.
[35]M. Tamatani, 1999, “Luminescence center of transition metal ions”,Phosphor Handbook, CRC press, Florida, 153-176.
[36]M. Morita, 1999, “Luminescence centers of complex ions, Phosphor Handbook”, CRC press, Florida, 201-212.
[37]S. Tanimizu, 1999, “Luminescence center of ns2-type ions”, Phosphor Handbook, CRC press, Florida, 141-152.
[38]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。
[39]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。
[40]方客川，2001年，“固態光譜學”，中國科技大學出版社，中國。
[41]A. H. Kitai, 1993, “Solid State Luminescence”, Chapman & Hall press, Cambridge.
[42]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。
[43]H. Yamamoto, “IIa-VIb compounds＂, Phosphor Handbook, CRC press (1999) 217-230).
[44]S. Kuboniwa, H. Kawain and T. Hoshima, “Cathodoluminescence Saturation and Decay Characteristics of ZnS: Cu,Al Phosphor”, Jpn. J. Appl. Phys. 19 (1980) 1647.
[45]M. Tabei, S. Shionoya and H. Ohmatsu, “Mechanism of the Killer Effect of Iron-Group Ions on the Green Luminescence in ZnS:Cu,Al phosphors”, Jpn. J. Apply. Phys.14 (1975) 240.
[46]R. C. Ropp, “Luminescence and the Solid State”, Elsevier Science Publishers, B.V., The Netherlands, (1991) p.245.
[47]劉如熹、王健源，”白光發光二極體用製作技術”，全華技術，(2001)。
[48]G. Blasse and B. C. Grabmaier,“Luminescence Materials”, Springer-Verlag Berlin Heidelberg (1994) 1-3
[49]R. C. Ropp, “Luminescence and the Solid State”, Elsevier Science Publishers, The Netherlands, (1991).
[50]R. C. Ropp, “Luminescence and the Solid State”, Elsevier Science Publishers, The Netherland, Chapter 8
[51]L. Ge, M. Xu, H. Fang, “Synthesis and characterization of the Pd/InVO4– TiO2 co-doped thin films with visible light photocatalytic activities” App. Sur. Sci. 253 (2006) 2257-2263
[52]B. Yan, X. Q. Su “Chemical co-precipitation synthesis and photoluminescence of LnPxV1-xO4:Dy3+(Ln = Gd, La) derived from assembling hybrid precursors”, Journal of Alloys and Compounds 431 (2007) 342-347.
[53]張祐嘉，民國102年，“(Y1-x-yPrxLay)InGe2O7 (x=0~0.2, y=0~0.2)系之光致發光特性研究”，國立虎尾科技大學電子工程研究所碩士論文。
[54]E. Botcharovaa, M. Heilmaiera, J.Freudenbergera, G. Drewa, D. Kudashowb, U. Martinb, “Supersaturated solid solution of nibium in copper by mechanical alloying”, J. Alloy. Compd., 351, 119-125 (2003).
[55]D. Sarkar, M. C. Chu, S. J. Cho, Y. I. Kim, “Synthesis and Morphological Analysis of Titanium Carbide Nanopowder”, J. Am. Ceram. Soc., 92, 2877-2882 (2009).
[56]Joshua D. Sayre, Kris T. Delaney, Nicola A. Spaldin, “Interplay between strain and oxygen vacancies in lanthanum aluminate”, Mater. Sci., 1202.1431 (2012).
[57]Mu Gu*, Lihong Xiao, Xiaolin Liu, Rui Zhang, Bingjie Liu, Xin Xu, “Highly enhanced luminescence of GdTaO4:Eu3+ phosphors by codoping with Zn2+ ions”, J. Alloy. Compd., 426, 390–394 (2006).
[58]Bingjie Liu, Mu Gu, Xiaolin Liu, Chen Ni, Di Wang, Lihong Xiao, Riu Zhang, “Effect of Zn2+ and Li+ codoping ions on nanosized Gd2O3：Eu3+ phosphor”, J. Alloy. Compd., 440, 341-345 (2007).
[59]Baogeng Xie, Guanzhong Lu*, Yanqin Wang, Yun Guo, Yanglong Guo, “Selective synthesis of tetragonal LaVO4 with different vanadium soures and its luminescence performance”, J. Alloy. Compd.,544,173-180 (2012).
[60]Weiliu Fan, Xinyu Song, Sixiu Sun, Xian Zhaoa*, “Microemulsion-mediated hydrothermal synthesis and characterization of zircon-type LaVO4 nanowires”, Journal of Solid State Chemistry 180 (2007) 284-290.
[61]Li Tian*, Qiliang Sun, Xijun Xu, Yaolin Li, Yunfei Long, Guangshan Zhu, “Controlled synthesis and formation mechanism of modispersive lanthanum vanadate nanowires with monoclinic structure”, Journal of Solid State Chemistry 200 (2013) 123-127.
[62]J. S. Kim, J. Y. Kang, P. E. Jeon, J. C. Choi, H. L. Park, and T. W. Kim, 2004, “GaN-based white-light-emitting diodes fabricated with a mixture of Ba3MgSi2O8：Eu2+ and Sr2SiO4：Eu2+ phosphors”, Jpn. J. Appl. Phys., 43 [3], 989-992.
[63]C. de Mello Donega, A. Meijerink, G. Blass, 1995, “Non-Radiative relaxation processes of the Pr3+ ion Solid”, J. Phys. Chem. Solids, 56, 673-685.
[64]Li Tian, Ruini Zhao, Jinjing Wang, Qiliang Sun, Lin Chen, Qiaoguo Xiao, Shengli Liu, “Faclie synthesis and luminescence of hollow Eu3+-doped LaVO4 nanspheres”, Materials Letters 156 (2015) 101-104.
[65]A.J. Kenyon, “Recent developments in rare-earthdoped materials for optoelectronics”, Progress in Quantum Electronics 26 (2002) 225.
[66]Robert M Clegg, “Fluorescence resonance energy transfer”, Current Opinion in Biotechnology 1995, 6:103-l 10.