臺灣博碩士論文加值系統

本研究以溶膠凝膠法製備-Ga2O3作為螢光粉主體，並摻雜不同濃度之Dy3+離子作為發光中心，觀察摻雜濃度、煆燒溫度以及pH值對於螢光粉的晶體結構、表面型態以及發光特性之影響。
第一部分是以-Ga2O3作為螢光粉主體，摻雜不同濃度之Dy3+離子，由X-Ray結果顯示，煆燒1000 C持溫30分鐘條件下，可得知結構為單斜晶系-Ga2O3之結晶結構。隨著Dy3+離子濃度的增加，會觀察到二次相的產生，這是因為Ga3+離子半徑與Dy3+離子半徑差異性較大所造成之結果。而在SEM分析方面，螢光粉的表面型態皆為棒狀結構，而隨著Dy3+離子濃度增加，螢光粉顆粒尺寸有逐漸增加之趨勢。於260 nm激發下，其主要放射光波長坐落於460~510 nm和510~600 nm之間，屬於Dy3+離子之4F9/26H15/2和4F9/26H13/2之電子躍遷所造成，後者是屬於超靈敏躍遷(△J=2)，當Dy3+離子濃度為3 mol%時有最強的放射強度，CIE色度座標隨Dy3+離子摻雜濃度增加，由藍光區域至近白光區。
第二部分是以-Ga2O3作為螢光粉主體，固定Dy3+離子摻雜濃度3 mol%，改變煆燒溫度，由X-Ray分析結果顯示，在Ga2O3煆燒600~1200 C持溫30分鐘條件下，在煆燒800 C以上持溫30分鐘，可得結構為單斜晶系-Ga2O3之結晶結構。SEM分析方面，螢光粉的表面型態會隨著煆燒溫度的增加，從片狀結構轉變為棒狀結構。於260 nm激發下，其主要放射光波長坐落於460~510 nm和510~600 nm之間，屬於Dy3+離子之4F9/26H15/2和4F9/26H13/2之電子躍遷所造成，後者是屬於超靈敏躍遷(△J=2)，當煆燒溫度為1100 C持溫30分鐘時有最強的放射強度。CIE色度座標隨著煆燒溫度的增加，由藍光區域至近白光區域。
第三部分是以-Ga2O3作為螢光粉主體，固定Dy3+離子摻雜濃度3 mol%，改變溶液之pH值，由X-Ray分析結果顯示，在Ga2O3固定Dy3+離子摻雜濃度3 煆燒1100 C持溫30分鐘條件下，可得結構為單斜晶系-Ga2O3之結晶結構。SEM分析方面，螢光粉的表面型態會隨著pH值的增加，從棒狀結構轉變為顆粒結構，在pH值為9時螢光粉的表面型態為較平整的顆粒結構。於260 nm激發下，其主要放射光波長坐落於460~510 nm和510~600 nm之間，屬於Dy3+離子之4F9/26H15/2和4F9/26H13/2之電子躍遷所造成，後者是屬於超靈敏躍遷(△J=2)，當ph值為9時有最強的放射強度。CIE色度座標隨著pH值的增加，均位於近白光區域。
第四部分是以-Ga2O3作為螢光粉主體，固定溶液之pH值為9，摻雜不同濃度之Dy3+離子，由X-Ray結果顯示，在煆燒1100 C持溫30分鐘條件下，可得知結構為單斜晶系-Ga2O3之結晶結構。隨著Dy3+離子濃度的增加，會觀察到二次相的產生，這是因為Ga3+離子半徑與Dy3+離子半徑差異性較大所造成之結果。而在SEM分析方面，螢光粉的表面型態會由棒狀結構開始團聚再轉為顆粒結構。於260 nm激發下，其主要放射光波長坐落於460~510 nm和510~600 nm之間，屬於Dy3+離子之4F9/26H15/2和4F9/26H13/2之電子躍遷所造成，後者是屬於超靈敏躍遷(△J=2)，而350~450 nm是來自於主體晶格之放射峰，這裡並不會隨著Dy3+摻雜濃度之增加放射強度會隨之增強之現象。
當Dy3+離子濃度為3 mol%時有最強的放射強度，CIE色度座標隨Dy3+離子摻雜濃度增加，由藍光區域至近白光區。

In this study, -Ga2O3 phosphor was prepared as the host material and doped with different concentrations of Dy3+ ions as the activator using the sol-gel method.
The effects of doping concentration, calcination temperature and pH on the crystal structure, surface morphology and photoluminescence properties of the phosphor powder were observed.

In the first part was the host with -Ga2O3 doped Dy3+ different concentrations of Dy3+ ions. The X-ray diffraction analysis indicated that the structure belongs to monoclinic -Ga2O3 crystal structure under the calcination temperature of 1000 °C for 30 min. With the increase of the Dy3+ion concentration, secondary phase was observed which is due to the difference between the Ga3+ and the Dy3+ ionic radius. In the SEM analysis, the surface morphology of the phosphor powder is mostly rod structure. Under an excitation wavelength of 260 nm, the emission spectrum consists of 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transitions of Dy3+ ions. When the Dy3+ ion concentration is 3 mol%, the intensity of the 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transition for the Dy3+ ion is the strongest. The CIE chromaticity coordinates shift from blue region to near white region with the increase of the Dy3+ ion concentrations.

In the second part was the host with -Ga2O3 doped Dy3+ ion concentration was 3 mol% with various the calcination temperature. The X-ray diffraction analysis indicated that the structure belongs to monoclinic -Ga2O3 crystal structure under the calcination temperature of 800~1000 °C for 30 min. In the SEM analysis, the surface morphology of the phosphor powder changes from sheet structure to rod structure as the calcination temperature increases. Under an excitation wavelength of 260 nm, the emission spectrum consists of 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transitions of Dy3+ ions. When the calcination temperature is 1100 °C for 30 minutes, the intensity of the 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transition for the Dy3+ ion is the strongest. The CIE chromaticity coordinates shift from blue region to near white region with the increase of the calcination temperature.

In the third part was the host with -Ga2O3 doped Dy3+ ion concentration was 3 mol% and changed the pH value of the solution. The X-ray diffraction analysis indicated that the structure belongs to monoclinic -Ga2O3 crystal structure under the calcination temperature of 1100 °C for 30 min. In the SEM analysis, the surface morphology of the phosphor powder changes from rod structure to grain structure as the pH value increases. At pH value 9, the surface morphology of the phosphor powder is a relatively flat particle structure. Under an excitation wavelength of 260 nm, the emission spectrum consists of 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transitions of Dy3+ ions. When pH value 9, the intensity of the 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transition for the Dy3+ ion is the strongest. As the pH increases, the CIE chromaticity coordinates are located in the near white region.
The fourth part was the host with -Ga2O3 doped Dy3+ different concentrations of Dy3+ ions, and the fixed pH is 9. The X-ray diffraction analysis indicated that the structure belonged to monoclinic -Ga2O3 crystal structure under the calcination temperature of 1100 ° C for 30 min. With the increase of the Dy3+ ion concentration, secondary phase was observed which is due to the difference between the Ga3+ and the Dy3+ ionic radius. In the SEM analysis, the surface morphology of the phosphor powder will start to agglomerate from the rod structure and then transform into a granular structure. Under an excitation wavelength of 260 nm, the emission spectrum consists of 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transitions of Dy3+ ions. When the Dy3+ ion concentration is 3 mol%, the intensity of the 4F9/2→6H15/2 and 4F9/2→6H13/2 electronic transition for the Dy3+ ion is the strongest. The CIE chromaticity coordinates are all located in the blue region. When the Dy3+ doping concentration is 3 mol%, the luminescent position is located in the near white region.

摘要...i
Abstract...iii
誌謝...vi
目錄...vii
表目錄...x
圖目錄...xi
第一章 緒論...1
1-1 前言...1
1-2 -Ga2O3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 螢光與磷光之關係...6
2-1-2 激發源的種類與應用...6
2-1-3 螢光材料簡介...7
2-2 螢光材料種類...7
2-2-1 有機螢光材料...7
2-2-2 無機發光材料...7
2-2-3 半導體發光材料...9
2-3 固態材料中的光致發光現象...9
2-3-1 本質型發光(Intrinsic Luminescence)...9
2-3-1-1 能帶發光(band-to-band luminescence)...9
2-3-1-2 激子發光(exciton luminescence)...10
2-3-1-3 交叉發光(cross-luminescence)...10
2-3-2 外質型發光(extrinsic luminescence)...10
2-3-2-1 侷限型(localized type)...10
2-3-2-2 非侷限型(unlocalized type)...11
2-4 發光機制簡介...11
2-4-1 發光原理與發光過程...11
2-4-2 組態座標(configuration coordination)...11
2-4-3 史托克位移(stokes shift)...12
2-4-4 能量轉移(energy transfer)...12
2-4-5 電子-聲子交互作用(electron-phonon interaction)...13
2-4-6 交叉緩解(cross relaxation)...13
2-4-7 非輻射躍遷(non-radiative transition)...13
2-5 影響發光性質的主要因素...13
2-5-1 主體晶格效應(host lattice effect)...14
2-5-2 熱淬滅效應(thermal quenching)...14
2-5-3毒劑效應(poisoning effect)...14
2-5-4 濃度淬滅效應(concentration quenching effect)...14
2-5-5 光游離效應(photoionization effect)...14
2-5-6 補償效應(offset effect)...15
2-6 螢光體的組成與選擇...15
2-7 螢光粉體之合成技術...16
第三章 實驗方法與步驟...32
3-1 實驗流程...32
3-2 實驗材料...32
3-3 成分與結構分析...32
3-3-1 X光繞射(X-ray diffraction analysis, XRD)分析...32
3-3-2 場發射掃描式電子顯微鏡(Field emission scanning electron microscopy, FE-SEM)分析...32
3-3-3 熱分析儀(Thermal analyzers，TGA)...33
3-4 螢光粉體之光學特性分析...33
3-4-1 吸收光譜(Absorption spectrum)...33
3-4-2 螢光光譜儀(Photoluminescence, PL)特性量測...33
3-4-3 衰減時間(Decay time)分析...33
3-4-4 CIE色度座標分析(analysis of C.I.E chromaticity diagram)...33
第四章 結果與討論...39
4-1 以溶膠-凝膠法製備Ga2O3:Dy3+之螢光粉...39
4-1-1 Ga2O3:Dy3+螢光粉之X-ray結構分析...39
4-1-2 場發射掃描式電子顯微鏡(FE-SEM)表面形態分析...39
4-1-3 Ga2O3:Dy3+螢光粉之吸收光譜分析...39
4-1-4 Ga2O3:Dy3+螢光粉之激發光譜分析...40
4-1-5 Ga2O3:Dy3+螢光粉之放射光譜分析...40
4-1-6 Ga2O3:Dy3+螢光粉之衰減曲線...40
4-1-7 CIE色度座標...41
4-1-8結論...41
4-2 煆燒溫度以溶膠-凝膠法製備Ga2O3:Dy3+螢光粉之影響...54
4-2-1 Ga2O3:Dy3+螢光粉之熱分析...54
4-2-2 Ga2O3:Dy3+螢光粉之X-ray結構分析...54
4-2-3 場發射掃描式電子顯微鏡(FE-SEM)表面形態分析...54
4-2-4 Ga2O3:Dy3+螢光粉之吸收光譜分析...54
4-2-5 Ga2O3:Dy3+螢光粉之激發光譜分析...55
4-2-6 Ga2O3:Dy3+螢光粉之放射光譜分析..55
4-2-7 Ga2O3:Dy3+螢光粉之衰減曲線...55
4-2-8 CIE色度座標...56
4-2-9結論...56
4-3 pH值對於以溶膠-凝膠法製備Ga2O3:Dy3+螢光粉之影響...70
4-3-1 Ga2O3:Dy3+螢光粉之X-ray結構分析...70
4-3-2 場發射掃描式電子顯微鏡(FE-SEM)表面形態分析...70
4-3-3 Ga2O3:Dy3+螢光粉之吸收光譜分析...70
4-3-4 Ga2O3:Dy3+螢光粉之激發光譜分析...70
4-3-5 Ga2O3:Dy3+螢光粉之放射光譜分析...71
4-3-6 Ga2O3:Dy3+螢光粉之衰減曲線...71
4-3-7 CIE色度座標...71
4-3-8結論...71
4-4 以溶膠-凝膠法製備Ga2O3:Dy3+之螢光粉..83
4-4-1 Ga2O3:Dy3+螢光粉之X-ray結構分析...83
4-4-2 場發射掃描式電子顯微鏡(FE-SEM)表面形態分析..83
4-4-3 Ga2O3:Dy3+螢光粉之吸收光譜分析...83
4-4-4 Ga2O3:Dy3+螢光粉之激發光譜分析...83
4-4-5 Ga2O3:Dy3+螢光粉之放射光譜分析..84
4-4-6 Ga2O3:Dy3+螢光粉之衰減曲線...84
4-4-7 CIE色度座標...84
4-4-8結論...84
第五章 總結論...97
參考文獻...99

[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]劉如熹、劉宇桓，2006年，“發光二極體用氮氧螢光粉介紹”，全華科技，台北。
[3]S.Shionoya and W. M. Yen, 1999, “Phosphor Handbook”, CRC press, Boca Raton.
[4]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.
[5]Z. Liu, Y. Li, Y. Xiong, D. Wang, Q. Yin, “Electroluminescence of SrAl2O4:Eu2+ phosphor”, Microelectronics Journal 35 (2004) 375.
[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，“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，民國100年。
[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]D. Gourier a , L. Binet a & E. Aubay, ” Magnetic bistability and memory of conduction electrons released from oxygen vacancies in gallium oxide” Radiation Effects and Defects in Solids, Vol. 134, 99. 223-228(1995).
[12]楊明輝，”金屬氧化物半導體的材料特性與Ga2O3的研發近況”，工業材料雜誌，365期。
[13]William C. Herbert, Henry B. Minnier, and Jesse J. Brown, Jr , “Self-Activated Luminescence of -Ga2O3” J. Electrochem (1969).
[14]Y.P. Qian, D.Y. Guo, X.L. Chu, H.Z. Shi, W.K. Zhu, K. Wang, X.K. Huang, H.Wang, S.L. Wang, P.G. Li, X.H. Zhang, W.H. Tang, “Mg-doped p-type β-Ga2O3 thin film for solar-blind ultraviolet photodetector” Materials Letters (2017).
[15]Y. Chun, Z. Junying, X. Daoqi, W. Ximing, W. Tianmin “Red-Emitting Ga2O3 : Eu3+ Powder Derived by Sol-Gel Processing” , JOURNAL OF RARE EARTHS Vol.25, Suppl., Jun. 2007, p.90.
[16]Kenji S., Toshihiro N., and Sadao A. “(Tb3+, Eu3+)-Codoped Ga2O3 Phosphors: Synthesis and Photoluminescence Properties” ECS Journal of Solid State Science and Technology, 5 (5) R67-R73 (2016).
[17]Xiaoming L., Cuicui Y., Chunxia L., and Jun Lina, “Comparative Study of Ga2O3:Dy3+ Phosphors Prepared by Three Methods” Journal of The Electrochemical Society, 154 (6) P86-P91 (2007).
[18]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)756-758
[19]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.
[20]張中太、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。
[21]G. Blasse and B. C. Grabmaier, “Luminescent Materials”, Springer. Verlag Berlin Heidelberg, (1994) 1-3.
[22]徐敘瑢編著，“光電材料與顯示技術”，五南圖書，2004年8月，pp33~284。
[23]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.
[24]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。
[25]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。
[26]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.
[27]楊俊英著，民國81年，“電子產業用螢光材料之應用調查”，工研院。
[28]S. Shionoya and W. M. Yen, 1999, “Phosphor Handbook”, CRC press, Boca Raton.
[29]J. A. Deluca, “An Introduction to Luminescence in Inorganic Solids”, J. Chem. Edu. 57 (1980) 541-545.
[30]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.
[31]G. Blasse and B. C. Grabmaier,1991 , “Luminescence Materials”, Springer Verlag, Berlin Heidelberg, p.245.
[32]S. Taminizu, 1999, “Luminescence center of ns2-type ions”, Phosphor Handbook, CRC press, Florida, 141-152.
[33]M. Tamatani, 1999, “Luminescence center of transition metal ions”, Phosphor Handbook, CRC press, Florida, 153-176.
[34]M. Morita, 1999, “Luminescence centers of complex ions, Phosphor Handbook”, CRC press, Florida, 201-212.
[35]T. Kano, 1999, “Luminescence centers of rare-earth ions, Phosphor Handbook”, CRC press, Florida, 177-200.
[36]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。
[37]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。
[38]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。
[39]D. R. Vij, 1998, “Luminescence in Solids”, Plenum press, New York.
[40]A. H. Kitai, 1993, “Solid State Luminescence”, Chapman & Hall press, Cambridge.
[41]方客川，2001年，“固態光譜學”，中國科技大學出版社，中國。
[42]H. Yamamoto, “IIa-VIb compounds＂, Phosphor Handbook, CRC press (1999) 217-230).
[43]劉如熹、王健源，“白光發光二極體用製作技術”，全華科技，(2001)。
[44]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.
[45]G. Blasse, 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.
[46]R. C. Ropp, “Luminescence and the Solid State”, Elsevier Science Publishers, The Netherlands, (1991).
[47]E. Cavalli, P.Boutinaud, M. Grinberg, 2014, “Luminescence dynamics in CaWO4:Pr3+ powders and single crystals”, Elsevier B.V. All rights reserved.
[48]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技研究所碩士論文。
[49]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.
[50]M. L. Pang, W. Y. Shen, and J. Lin, “ Enhanced photoluminescence of phosphor films by doping” , Journal of Applied Physics 97, 033511 (2005).
[51]Rafaela T. Alves, Camyla M. Trindade, Weslley Q. Santos, Artur S. Gouveia-Neto, Luciano A. Bueno, Caio F. Mathias, and Marcelo Nalin, “Dy3+/ Tb3+-codoped tunable warm light-emitting fluorogermanate glass phosphor”, Optical Engineering 55(11), 117103 (November 2016).
[52]W. Y. Shen, M. L. Pang, J. Lin, and J. Fang, “Host-Sensitized Luminescence of Dy3+ in Nanocrystalline -Ga2O3 Prepared by a Pechini-Type Sol-Gel Process”, Journal of The Electrochemical Society, 152(2) H25-H28 (2005).
[53]C. H. Liang, Y. C. Chang, Y. S. Change, 2009, “Enhancement of luminescence porperties by Sr2+ Substituting Ba2+ in Red-Emitting Phosphor:Ba1-xSryLa2-xZnO5:xEu(x=0-1, y=0-0.7)”, J Electrochem. Soc., 156(10), J303-J307.
[54]Roy, R., Hill, V. G., & Osborn, E. F., “Polymorphism of Ga2O3and the System Ga2O3—H2O”, Journal of the American Chemical Society, (1952)74(3), 719–722.