臺灣博碩士論文加值系統

本研究以固態反應法合成出一系列的鉬酸鹽紅光螢光粉，並以 X 射
線 繞 射 光 譜 分 析 儀 (x-ray diffraction, XRD) 、 螢光 光 譜 (fluorescence spectrophotometer，FL)、掃描式顯微鏡(scanning electron microscope, SEM)和顯微拉曼光譜儀(microscopes raman spectrometer)分析鉬酸鹽紅光螢光粉的晶體結構、發光特性及其形貌。結果顯示，從 XRD 分析鑑定其結構為白鎢礦結構，從螢光光譜來看，在 394 nm 和 465 nm 具有很強的吸收峰且在 616 nm 有很強的紅光放射，在不同燒結溫度中以900℃持溫 5 小時有最佳的發光強度。摻雜不同型態的釔方面，其中硝酸釔的效果較好，且在摻雜濃度在 50%有最佳強度。由於 Y 和 Eu 都是三價的離子，摻雜到二價的 Ca 離子中會造成電荷不平衡，而影響發光效率，本研究以一價金屬離子(Li+,Na+,K+)來達到電荷補償，結果發現電荷補償後放射強度增加，其中以 Na+ 效果最好。由此可見電荷補償可以改善螢光粉的發光特性。在複合鉬酸鹽螢光粉的部分當 Si 摻雜濃度為 2%時有最佳的發光強度，且也改善了 394 nm 和 465 nm 的強度比，這與近紫外光和藍光 LED 晶片有良好匹配性，由此可見鉬酸鹽紅光螢光粉未來應用在白光 LED 上是一個很好的選擇。

In this research, we use solid-state reaction methods to synthesize a serier of molybdate red phosphor. The crystal structure, luminescence properties and the morphology of molybdate red phosphor was analysised by x-ray diffraction, fluorescence spectrophotometer, scanning electron microscope and microscopes Raman spectrometer. XRD data shows that the molybdate phosphors are single phase with a tetragonal scheelite structure. From the result of fluorescence spectra, there is a strong absorption peak at 394 nm and 465 nm and a strong red radiation at 616 nm. In the part of different calcination temperatures, the samples sintering at 900℃ for 5 hours
have the best luminous intensity. For Yttrium doping effect, yttrium nitrate has better results in optimum intensity, when the doping concentration is about 50 %. Since both Y and Eu are trivalent ions, the divalent Ca ion replaced by Y and Eu which will cause charge imbalance affects the luminous efficiency. In this reseach, we achieve the charge compensation by doping monovalent metal ions (Li+, Na+, K+), the results showed that the charge compensation emission intensity increases, especially for Na+. According to these results, we can see that phosphor luminescence properties can be improved by charge compensation. In the other part of complex molybdate phosphor, 2 % silicon doping concentration in molybdate has the best optimum intensity, it also improves the 394 nm and 465 nm intensity ratio, which have a good matching with near ultraviolet and blue LED chips. According to the results, we can see that molybdate red phosphor is a good choice for white LED applications.

摘要 ....................................................I
Abstract ...............................................II
誌謝 .................................................III
目錄 ..................................................IV
圖目錄 ...............................................VIII
表目錄 ...............................................XII
第一章 緒論 ........................................... 1
1.1 前言 .............................................. 1
1.2 研究目的 .......................................... 2
第二章 文獻回顧 ....................................... 4
2.1 螢光粉的介紹 ...................................... 4
2.1.1 螢光粉的發展 .................................... 4
2.1.2 螢光粉的發光原理................................. 4
2.1.3 螢光粉的材料組成機制 ............................ 5
2.1.4 影響發光效率之因素與定則 ........................ 9
2.1.5 固態螢光粉之分類............................... 11
2.1.6 稀土元素 ....................................... 13
2.2 紅光螢光粉 ....................................... 16
2.2.1 鹼土金屬硫化物體系紅色螢光粉 ................... 16
2.2.2 氮化物體系紅色螢光粉 ........................... 16
2.2.3 矽酸鹽體系紅色螢光粉 ........................... 17
2.2.4 硫氧化釔體系紅色螢光粉 ......................... 17
2.3 鉬酸鹽紅光螢光粉 ................................. 18
2.4 螢光粉之製備 ..................................... 22
2.4.1 溶膠凝膠法 ..................................... 23
2.4.2 水熱合成法 ..................................... 23
2.4.3 共沉澱法 ....................................... 24
2.4.4 固態反應法 ...................................... 24
2.4.5 球磨法 ......................................... 25
2.5 論文的研究背景及內容 .............................. 27
2.6 螢光粉的應用 ..................................... 28
第三章 實驗方法 ...................................... 29
3.1 實驗材料 ........................................ 29
3.2 實驗設備 ......................................... 30
3.3 實驗步驟 ......................................... 31
3.3.1 鉬酸鹽螢光粉製備製備 ........................... 31
3.3.2 樣品分析與鑑定.................................. 31
3.4 分析儀器 ......................................... 33
3.4.1 螢光光譜儀 (Fluorescence spectrophotometer，FL).33
3.4.3 顯微拉曼光譜儀(Microscopes Raman Spectrometer) . 36
3.4.4 掃描式顯微鏡 (Scanning Electron Microscope，SEM).37
第四章 結果與討論 .................................... 38
4.1 燒結溫度對鉬酸鹽螢光粉之影響...................... 38
4.1.1 XRD 分析 ........................................ 38
4.1.2 PL 分析 ......................................... 39
4.1.3 SEM 分析 ........................................ 42
4.2 摻雜釔和銪對鉬酸鹽螢光粉之影響.................... 43
4.2.1 Ca 0.99-x Y x MoO 4 :Eu3+0.01 (x=0.2~0.6)........ 43
4.2.2 Ca 0.95-x Y x MoO 4 :Eu3+0.05 (Y=氧化釔、硝酸釔，x=0.3~0.7)............................................. 45
4.2.3 Ca 0.45 Y 0.5 MoO 4 :Eu3+x(Y=硝酸釔，x=0.05~0.35).50
4.3 電荷補償對鉬酸鹽螢光粉的影響...................... 52
4.3.1 CaMoO 4 螢光粉電荷補償後的影響 .................. 52
4.3.2 CaY 0.3 MoO 4 螢光粉電荷補償後的影響 ............ 55
4.3.3 各個階段摻雜後對鉬酸鹽螢光粉的影響 ............. 63
4.4 矽摻雜對鉬酸鹽螢光粉的影響 ....................... 66
第五章 結論與未來展望 ................................ 69
5-1 結論 ............................................. 69
5-2 未來展望 ......................................... 70
參考文獻 ........................................... 71

[1] S. R. Chung, Application of Semiconducted Nanocrystal in White LED.
[2] N. Narendran, N. Maliyagoda, A. Bierman, R. M.Pysar, M. Overington, Proc. SPIE, 3938, 240, (2000).
[3] M. Brown, Proc. SPIE , 4445, 49, (2001).
[4] 田民波, 呂輝宗, 溫坤禮, 白光 LED 照明技術,(2011)。
[5] F. A. Ponce, D. P. Bour, Nature (London), 386, 351,(1997).
[6] S. Nakamura, T. Mukai, M. Senoh, J. Appl. Phys, 76, 8189, (1994).
[7] S. Nakamura, G. Fasol, The Blue Laser Diode, Springer, Berlin, (1997).
[8] F. B. Cao, Y. W. Tina, Y. J.Chen, L. J. Xiao, Y. Y. Liu, Acta Phys -Chim. February Sin., 25(2), 299-303,(2009).
[9] L. Liu, X. Yuan,A. Xie, Chin. J. Lumin. 32(7), 687-692, (2011).
[10] C. R. Ronda, J. Lumin., 72, 49, (1997).
[11] 賴炤銘, 李錫隆, 奈米材料的特殊效應與應用, 61, 4, (2003)。
[12] E. Y. Ivanol, C. Suryanarayana, B. D. Bryskin. Mater. Sciand Eng,A251:255~ 261, (1998).
[13] X. X. Zhao, X. J. Wang, B. J. Chen, Q. Y. Meng, B. Yan, W. H. Di, Opt. Mater., 29, 1680, (2007).
[14] F.B. Cao, Y.W. Tian, Y.J. Chen, L.J. Xiao, Q. Wu, J. Alloys Compd., 475, 387, (2009).
[15] 王書任, 林仁鈞, 讓LED發光的功臣-螢光粉, (2009)。
[16] 楊素華, 螢光粉在發光上的應用, 358期, (2002) 。
[17] 鄧昌蔚, 科學教育月刊, 246, 32, (2002) 。
[18] R. M. Clegg, X. F. Wang, B. Herman, Chemical Analysis Series, 137, 196, (1996).
[19] T. Justel, H. Nikol, C. R. Ronda, Angew. Chem. Int. Ed. , 37, 3084, (1998).
[20] C. Feldmann, T. Justel, C. R. Ronda, P. J. Schmidt, Adv. Funct. Mater. , 13, 7 (2003).
[21] A. H. Kitai, Solid state Luminescence, Chapman &Hail: New York, (1993).
[22] P. W. Atkins, Physical Chemistry-six ed. , Oxford University Press: Tokyo, (1998).
[23] 方容川, 固體光譜學, 中國科技大學出版社, (2001) 。
[24] 楊俊英, 電子產業用螢光材料之應用調查, (1992)。
[25] Phosphor Research Society, Phosphor Handbook, CRC Press: New York, (1999).
[26] B. E. Douglas, D. H. McDaniel, J. J. Alexander, Concepts and Models of Inorganic Chemistry-3rd ed, Jhon Wiley & Son , Inc. : New York, (1994).
[27] 蘇鏘, 稀土元素, 清華大學出版社: 北京, (2000) 。
[28] 徐光石, 神奇之土, 清華大學出版社: 長沙, (1995) 。
[29] G. Blasse , B. C. Grabmaier, Luminescent Materials., Springer-Verlag: New York, (1994).
[30] Y. Hu, W. Zhuang, H. Ye, J. Lumin., 111(3), 139-145, (2005).
[31] X. Piao, Horikawa, H. Takashi, Appl. Phys. Lett., 88(16), 1619-1623, (2006).
[32] Y. Q. Li, J. E. Steen, J. W. Krevel, J. Alloys Compd., 417(1-2), 273-279, (2006).
[33] S. Nakamura, T. Mukai, M. Senoh, Appl. Phys. Lett., 64(13), 1687-1689, (1994).
[34] 柯韋志, 林群哲, 劉如熹, 藍光LED激發產生白光之鋁酸鹽與矽酸鹽螢光粉特性比較, 76, 68-70, (2008).
[35] Z. Wang, Y. Wang, J. Fun. Mater., 9(36), 1328-1330,(2005).
[36] X. X. Wang, Optical Materials, 30(4), 521-526,(2007).
[37] Y. Jin, J. Zhang, S. Lu, J. Phys. Chem. C. 112(15), 5860-5864, (2008).
[38] Y. Hu, W. Zhuang, H.Ye, D. Wang, S. Zhang, X. Huang, Journal of Alloys and Compounds ,390, 226–229, (2005).
[39] F. Gao, L. F. Liang, C. F. Cuo, Chin. J. Lumin. 30, 611, (2009).
[40] M. M. Haque, H. I. Lee, D. K. Kim, J. Alloys Compd. 481, 792, (2009).
[41] Y. L. Yang, X. M. Li, W. L. Feng, W. L. Li, C. Y. Tao, Journal of Alloys and Compounds, 505, 239–242, (2010).
[42] B. Yan, J. H. Wu, Mater. Chem. Phys., 116, 67-71, (2009).
[43] Z. Ci, Y. Wang, J. Zhang, Y. Sun, Physica B, 403, 670–674, (2008).
[44] W. F. Yao, J. H. Ye, J. Phys. Chem. B, 110, 11188, (2006).
[45] S. H. Yang, M. Yokoyama, Jpn. J. Appl. Phys, 37, 6429, (1988).
[46] J. Wang, X. Jing, C. Yan, J. Lin, Journal of The Electrochemical Society, 152, G186-G188, (2005).
[47] J. Liu, H. Lian, C. Shi, Opt. Mater, 29 1591–4,(2007).
[48] 劉如熹, 紀喨勝, 紫外光發光二極體用螢光粉介紹, (2003)。
[49] Y. Liao, W. Zhu, X. Li, Y. Mo, X. A. Hao, X. Ma, Materials Review, 21 (8), 321, (2007).
[50] Y. Zhang, H. L. Gong, S. K. Shi, J. Zhou, J. P. Ye, Chinese Journal of inor ganic Chemistry, 25, 563-566, (2009).
[51] C. Zhao, Y. Hu, A. W. Zhuang, X. W. Huang, T. He, Journal of Rare Earths, 27, 5, (2009).
[52] 汪建民, 粉末冶金技術手冊, 中華民國粉末冶金協會, (1999)。
[53] 西田廣泰, 研磨用粒子與研磨材, 經濟部中央專利, (2003)。
[54] H. Way, Grinding And Dispersing Nanoparticles, Manager of Customer Service Lab, 224-226, (2001).
[55] 陳永芳, 以四異丙醇鈦為前區物利用化學器相沉積法和水解法置備二氧化鈦, ( 2003)。
[56] R. Roy, J. Am. Ceram. Soc., 44-52, (1969).
[57] 松尾尚典 , 和田雄高 , 研磨裝置及整修方法 , 經濟鄰中央專利 , (2000)。
[58] 汪建民, 材料分析, 中國材料科學學會, (1998)。
[59] J. A. DeLuca, J. Chem. Educ., 57, 541, (1995).
[60] A. Beiser, Concepts of Modern Physics, 6e, (2002).
[61] 王瑜, 科儀新知, 5, 25, (2005)。
[62] 吳泰伯, 許樹恩, X光繞射原理與材料結構分析, 中國材料科學學會, (1993)。
[63] 國立成功大學微奈米中心, 設備名稱-顯微拉曼光譜儀, (2007)。
[64] 林宏一, SEM/EDS構造與原理探討, (2006)。
[65] Shionoya Shigeo, Yen William M, Phosphor Hand-book. New York, (1989).
[66] X. G. Wang, S. L. Bo, X. Qi, M. L. Na, L. M. Li, Chinese Journal Inorganic Chemistry. , 25(2), 350-353, (2009).
[67] Z. L. Wang, H. B. Liang, M. L. Gong, Q. Su, J. Alloys Compd. 432, 308, (2007).
[68] F. Lei, B. Yan, J. Solid State Chem. 181, 855,(2008).
[69] J. Y. Sun, H. Y. Du, W. X. Hu, Solid-state Luminescence Marterials. , (2003).
[70] G. Q. Yao, Y. E, Feng, J. E. Duan, Acta Phys. –Chim. Sin. 19(3), 226-229, (2003).
[71] R. A. Swalin, John Wiley& Sons. 355, (1972).
[72] J. Liu, H.Z. Lian, C.S. Shi, Opt. Mater., 29, 1591, (2007) .
[73] A. Xie, X. Yuan, F. Wang, Y. Shi, Z. Mu, J. Phys. D: Appl. Phys. 43, 055101, (2010).
[74] X. Li, Z. Yang, L. Guan, J. Guo, Y. Wang, Q. Guo, Journal of Alloys and Compounds. 478, 684–686, (2009).
[75] J. F. Banfield, S. A. Welch, H. Zhang, T. T. Ebert, R. L. Peen, Science, 289, 751, (2000).
[76] A.N. Lasarev, A.P. Mirgorodskii, I.S. Ignatiev, Vibronic Spectra of Complex Oxides, (1975).