臺灣博碩士論文加值系統

在現今LED照明系統及其封裝材料追求高功率及高品質同時，提升效率、熱穩定性以及可靠度係為重要議題。傳統LED封裝材料以環氧樹脂及矽樹脂為主，但於高功率高效照明應用之LED晶片激發使用時，有機樹脂易因變質而產生黃化及老化現象。因此，追求高效率LED照明長使用壽命關鍵技術之一為開發優良光轉換螢光粉層。本研究開發低特性溫度之含鋅、鋰、鈉磷酸鹽玻璃系統，藉由功能性元素添加，玻璃轉換溫度(Tg)在310~320℃之間，玻璃軟化點(Td)在343~354℃，光學性質上，可見光區穿透率可達90%，並成功製作出光轉換層，利用CIE1931座標系統可得到最佳白光位置(0.3488,0.3639)及色溫4993K，同時符合美國能源之星(Energy Star)白光色溫5000K位置內之容許誤差範圍內。所開發之玻璃系統展現出低特性溫度及高光學性質。與其它螢光玻璃陶瓷製程專利文獻相比，本方法擁有較低的製備成本與較為簡便的製備程序，有利於生產製造，適合應用於高性能LED照明元件。

Nowadays LED lighting device and its package are requested for high performance, strengthened thermal and mechanical stability, and improved reliability for advanced applications. Conventional LED lighting package is based on epoxy and silicone for phosphor-conversion, PC, layer in which yellowing and degeneration occur significantly under high-power excitation and long term usage. Phosphor-containing glass layer instead of polymer-based composites is one of the important advances in the pursuit for high performance lighting. In present study, the developed phosphate glass system with functional elements (Al, Li, Na, and Zn) addition exhibits low characteristic temperatures and high optical performance. The glass has low characteristic temperatures of 310~320℃ and 343~354℃ for Tg and Td, namely glass transition and dilatometric softening points, respectively. The transmittance of the glasses is higher than 90% in visible region. A light conversion layer, glass-cermic phosphor, GCP, is successfully produced by phosphor embedding into softened glass at elevated temperature. The optimized white light position (0.3488, 0.3639) and color temperature of 4993K for the converted light from designed PC layer can be obtained using the CIE1931 coordinate system, which is within the tolerance range of the United States Energy Star white light color temperature of 5000K requirement. Compared with other fluorescent glass ceramic processes, this method has a lower preparation cost and a relatively simpler preparation procedure, which is advantageous to production and is suitable for application to high-performance LED lighting components.

摘要………i
Abstract………ii
誌謝………iii
目錄………iv
表目錄………vii
圖目錄………viii
第一章緒論………1
1.1前言………1
1.2研究動機與目的………2
1.3研究目標………2
第二章文獻探討………3
2.1 發光二極體………3
2.1.1發光二極體發光原理………3
2.1.2發光二極體特性及應用………3
2.2白色發光二極體………4
2.2.1白光………4
2.2.2白色發光二極體製造技術………4
2.2.白色發光二極體特性………5
2.3螢光粉物理機制………6
2.4玻璃介紹………6
2.4.1玻璃基礎理論………6
2.4.2玻璃網絡研究………6
2.4.3低溫玻璃………7
2.5磷酸鹽玻璃………8
2.5.1磷酸鹽玻璃基礎理論………8
2.5.2磷酸鹽玻璃網絡………8
2.5.3磷酸鹽玻璃添加其它元素之功能………9
第三章研實驗方法與步驟………23
3.1玻璃基板製造………25
3.2螢光玻璃體製造………27
3.3物理及化學性質特性………30
3.3.1 密度………30
3.3.2熱性質………30
3.3.3高溫老化測試………32
3.4結構分析………33
3.4.1紅外線光譜儀量測………33
3.4.2拉曼光譜儀量測………34
3.5光學性質………35
3.5.1折射率及阿貝數………35
3.5.2紫外-可見光光譜儀………36
3.6微觀結構及成分研究………36
3.7結構分析………36
3.8玻璃-陶瓷-螢光粉層研究………37
第四章結果與討論………39
4.1玻璃配方設計………39
4.2結構性質研究………39
4.2.1紅外線光譜儀分析………39
4.2.2拉曼光譜儀分析………41
4.3物理及化學性質研究………43
4.3.1密度及熱性質………43
4.4光學性質研究………46
4.4.1折射率及阿貝數分析………46
4.4.2紫外-可見光光譜儀分析………49
4.5.玻璃-陶瓷-螢光粉層製造及其分析………50
4.5.2微觀結構分析………50
4.5.3 X-射線繞射分析………54
4.5.4電子微探儀分析(EPMA)………57
4.6螢光玻璃體應用於發光二極體性能分析………58
第五章結論………65
第六章未來展望………67
參考文獻………68
Extended Abstract………75

[1]管鴻, 許進明, “LED 及 OLED照明,” 科學發展, 483期, (2013).
[2]J.E. Shelby, “Introduction to glass science and technology,” Royal Society of Chemistry, (2005)
[3]劉鎮洲,蕭銘芚,李豫芬,莊世琦, “應用藝術,” 台灣藝術教育網, (2006) 141.
[4]P.E. Gray and L.C. Klein, “The chemical durability of sodium ultraphosphate glasses,” Glass Technol., 24[4], (1983) 202.
[5]翁啟儒, 鋅磷酸鹽玻璃的去羥效應, 國立聯合大學材料科學工程學系碩士論文 (2008).
[6]M. Karabulut, E. Metwalli, and R.K. Brow, “Structure and properties of lanthanum-aluminum-phosphate Glasses,” Journal of Non-Crystalline Solids, 283 (2001) 21
[7]R.K. Brow, C.A. Click, and T.M. Alam, “Modifier coordination and phosphate glass networks,” Journal of Non-Crystalline Solids, 274 (2000) 9.
[8]Y. Lin, D.S. Wuu, K.F. Pan, S.H. Huang, C.E. Lee, W.K. Wang, S.C. Hsu, Y.Y. Su, S.Y. Huang, and R.H. Horng, “High-power GaN-mirror-Cu light-emitting diodes for vertical current injection using laser lift off and electroplating techniques,” IEEE Photo. Technol. Lett, 17,(9), 2005, 1809.
[9]H. Luo, J.K. Kim, E.F. Schubert, J. Cho, C. Sone, and Y. Park, “Analysis of high-power packages for phosphor-based white-light-emitting diodes,” Appl. Phys. Lett, 86, 2005, 2435.
[10]Y.R. Chung, C.K. Chang, J.H. Liao, and F.B. Wu, “Development in Phosphor Glass Ceramic Composites,” 61(26) (2014) 31.
[11]S. Yi, W.J. Chung, and J. Heo, “Stable and Color-Tailorable White Light from Blue LEDS Using Color-Converting Phosphor-Glass Composites,” J. Am Ceram. Soc. 97[2] (2014) 342.
[12]J.K. Gillham, G. Wisanrakkit, J.B. Enns, “The glass transition temperature as a parameter for monitoring the cure of an amine/epoxy system at constant heating rates ,” Journal of Applied Polymer Science, vol.41, Issue 7-8, Page 1895, 10 Mar 2003.
[13]陳繼弘, 低溫玻璃螢光體製程及均勻度分析, 國立中山大學光電工程研究所碩士論文 (2012).
[14]郭浩中, 賴芳儀, 郭守義, LED原理與應用, 五南圖書出版公司 (2012).
[15]A. Mills, “High-Brightness LEDs lighting up the future,” 14 (1) (2001) 32
[16]I. Niki, Y. Narukawa, D. Mortita, S. Sonobe, T. Mitani, H. Tamaki, Y. Murazaki, M. Yamata, and T. Mukai, “White LED for solid state lighting,” Proceedings of SPIE, 5187, (2004).
[17]L. Kim, J.H. Choi, S.H. Jang, and M.W. Shin, “Thermal analysis of LED array system with heat pipe,” Thermochimica Acta, 455, (2006), 21.
[18]M. Arik, C. Becker, C. Becker, S. Weaver, and J. Peroski, “Thermal management of LEDs: package to system,” Proceedings of SPIE, 5187, (2004), 64.
[19]M. Arik, C. Becker, J. Peroski, and S. Weaver, “Thermal challenges in the future generation solid state lighting applications,” Inter Society Conference on Thermal Phenomena, (2002), 113.
[20]J.K. Gillham, G. Wisanrakkit, and J.B. Enns, “The glass transition temperature as a parameter for monitoring the cure of an amine/epoxy system at constant heating rates,” Journal of Applied Polymer Science, 41, (2003), 1895.
[21]張詒安, “白光二極體的發展,” 科學研習, No53-5 (2014).
[22]楊淑惠, LED產業新版圖, 財訊出版社 (2006).
[23]K. Sakuma, K. Omichi, N. Kimura, M. Ohashi, D. Tanaka, N. Hirosaki, Y. Tamamoto, R.J. Xie, and T. Suehiro, “Warm-white light-emitting diode with yellow wish Orange SiAlON ceramic phosphor,” Optical Letter, 29, (2004) 2001.
[24]史光國, 半導體發光二極體集固態照明, 全華科技圖書 (2005).
[25]J.K. Sheu, S.J. Chang, C.H. Kuo, Y.K. Su, L.W. Wu, Y.C. Lin, W.C. Lai, J.M. Tsai, G.C. Chi and R.K. Wu, “White-light emission from near UV InGaN-GaN LED chip precoated with blue/green/red phosphors”, IEEE Photonics Technology Letters, 15, (2003), 18.
[26]S. Muthu, F.J. Schuurmans, and M.D. Pashley, “Red, green, and blue LED for based white light generation: issues and control,” IEEE, (2002), 327.
[27]郭子菱,呂紹旭, “白光LED技術法展演進近況”, 光連雙月刊, 72期, (2007).
[28]M.X.Chen, X.B.Luo, MA Z.T.Ma, S. Liu, “ ,” SEMICONDUCTOR OPTOELECTRONICS, vol.27, No.6, (2006).
[29]劉偉仁, 姚中業, 黃健豪, 鍾淑茹, 金風, LED 螢光粉技術, 五南圖書出版 (2014).
[30]N. Narendran, “Improved performance of white LED,” SPIE, vol.5941, (2005).
[31]科銳應用工程師M.Leung, “白光LED和非接觸式螢光粉的比較,” CTIMES, (2014).
[32]陳仙瑋, 高演色性白光發光二極體封裝, 國立臺灣科技大學光電工程研究所碩士論文 (2007).
[33]E. Radkov, A. Setlur, Z. Brown, and J. Reginelli, “High CRI phosphor blends for near-UV LED lamps,” Fourth International Conference on Solid State Lighting, Denver, CO, Unite State, (2004), 260.
[34]Y. Narukawa, J. Narita, T. Sakamoto, T. Yamada, H. Narimastsu, M. Sano, and T. Mukai, “Recent progress of high efficiency white LEDs,” Physica Status Solidi (a), 204, (2007), 2087.
[35]廖晉宏, 照明應用之低特性溫度磷酸鹽玻璃開發, 國立聯合大學材料科學工程學系碩士班碩士論文 (2005).
[36]王柏彬, 李燕如, 楊文都, “鋯酸鋇摻雜錳（BaZrO3：Mn2+）與四氧化三錳（Mn3O4）之螢光粉合成及其發光特性研究,” 工程科技與教育學刊, 第八卷, 第四期, (2011).
[37]A.K. Varshenya, “Fundamentals of inorganic glasses,” Gulf Professional Publishing, New York, (1994).
[38]L. Abbas, L. Bih, A. Nadiri, Y. El Amraoui, D. Mezzane, and B. Elouadi, “Properties of mixed Li2O and Na2O molybdenum phosphate glasses,” Journal of Molecular Structure, 876(2008) 194.
[39]A. Dietzel, “Die Kationenfeldstӓrken und ihre Beziehungen zu Entglasungsvorgӓngen, zur Verbindungsbildung und zu den Schmelzpunkten von Silikaten,” Z. Elektrochem., 48 (1942) 9.
[40]K.H. Sun, “Fundamental condition of glass formation,” Journal of American Chemical Society, 30 (1947) 277.
[41]W.H. Zachariasen, “The atomic arrangement in glass,” Journal of American Chemical Society, 54 (1932) 3841.
[42]R.H. Doremus, “Glass Science,” Wiley Interscience, New York, 1994.
[43]H. Scholze, “Glass-nature, structure, and properties,” Springer-Verlage, New York, (1991).
[44]M. Karabulut, E. Metwalli, and R.K. Brow, “Structure and properties of lanthanum-aluminum-phosphate Glasses,” Journal of Non-Crystalline Solids, 283 (2001) 211.
[45]R.K. Brow, C.A. Click, and T.M. Alam, “Modifier coordination and phosphate glass networks,” Journal of Non-Crystalline Solids, 274 (2000) 9.
[46]張紅耀, “無鉛銲料的發展概況,” 雲南冶金, 2002.
[47]郭宏偉, 劉新年, 趙彦釗, 高檔妮, “低熔封接玻璃的研究進展[J] ,” 材料導報, 2005, 11(19):專輯V.
[48]R.J. Kirkpatrick and R.K. Brow, “Nuclear magnetic resonance investigation of the structures of phosphate and phosphate-containing glasses: a review,” Solid State Nuclear Magnetic Resonance, 5 (1995) 9.
[49]J.J. Hudgens, R.K. Brow, D.R. Tallant, and S.W. Martin, “Raman spectroscopy study of the structure of lithium and sodium ultraphopshate glasses,” Journal of Non-Crystalline Solids, 223 (1998) 21.
[50]R.K. Brow, “Section 1. Structure of simple phosphate glasses,” J. Non-Cryst. Solids, 4, 263&264 (2000) 1.
[51]J.R. van Wazer, “Phosphorus and its Compounds (vol. 1) ,” Interscience, New York, 1958.
[52]U. Hoppe, “A structural model for phosphate glasses,” Journal of Non-Crystalline Solids, 195 (1996) 138.
[53]U. Hoppe, G. Walter, R. Kranold, D. Stachel, and A. Barz, “The dependent of structural peculiarities in binary phosphate glasses on their network modifier content,” Journal of Non-Crystalline Solids, 192&193 (1995) 28.
[54]R.K. Brow, “Review: the structure of simple phosphate glasses,” Journal of Non-Crystalline Solids, 263&264 (2000) 1.
[55]T. Kanazawa, “Inorganic phosphate materials”, Printed-Japan, Tokyo, (1989).
[56]J. van Wazer, “The phosphate and its compounds,” Interscience, New York, (1958).
[57]J.O. Byum, B.H. Kim, K.S. Hong, H.J. Jung, S.W. Lee, A.A. Izyneev, “Properties and structure of RO-Na2O-Al2O3-P2O5 (R=Mg, Ca, Sr, Ba ) ,” Journal of Non-Crystalline Solids 190 (1995) 288.
[58]L. Koudelka, and P. Mo˘sner, Materials Letters, “Borophosphate glasses of the ZnO–B2O3–P2O5 system,” 42 (2000) 194.
[59]L. Abbas, L. Bih, A. Nadiri, Y. El Amraoui, D. Mezzane, and B. Elouadi, “Properties of mixed Li2O and Na2O molybdenum phosphate glasses,” Journal of Molecular Structure, 876(2008) 194.
[60]X.Y. Yu, D.E. Day, G.J. Long, and R.K. Brow, “Properties and structure of sodium-iron phosphate glasses,” Journal of Non-Crystalline Solids, 215 (1997) 21.
[61]F. Moreau, A. Duran, and F. Munoz, “Structure and properties of high Li2O-containing aluminophosphate glasses,” Journal of European Ceramic Society (2009).
[62]R.K. Brow, “Nature of Alumina in Phosphate Glass: I, Properties of Sodium Aluminophosphate Glass,” J. Am. Ceram. Soc, 76[4] (1993) 913.
[63]F. Mun˜oz, F.A.Rueda, L.Montagne, R. Marchand, and A.Dura´n, L.Pascual, “Structure and properties of (25-x/2)Li2O-(25-x/2)Na2O-xPbO-50P2O5 metaphosphate glasses,” Journal of Non-Crystalline Solids 347 (2004) 153.
[64]A. Shain, M. Et-tabirou, L. Montagne, and G. Palavit, “Role of bismuth and titanium in Na2O-Bi2O3-TiO2-P2O5 glasses and a model of structure unit”, Materials Research Bulletin 37 (2002) 2459.
[65]A. Chahine, and M. Et-tabirou, “Structure study of (50-x)Na2O-xCuO-10Bi2O3-40P2O5 glasses,” Materials Research Bulletin 37 (2002) 1973.
[66]Y.B. Peng, and D.E. Day, “High Thermal Expansion Phosphate Glass Part 1,” Glass Technology, 32 (1991) 166.
[67]L.M. Senovilla, S. Venkatachalam, F. Muñoz and L. V. Wüllen, “ Relationships between fragility and structure through viscosity and high temperature NMR measurements in Li2O–ZnO–P2O5 phosphate glasses,” Journal of Non-Crystalline Solids, vol. 428, pp. 54-61 (2015).
[68]E. Metwalli, and R.K. Brow, “Modifier effects on the properties and structures of aluminophasphate glasses,” Journal of Non-Crystalline Soliids 289 (2001) 113.
[69]S.H. Im, Y.H. Na, N.J. Kim, D.H. Kim, C,W. Hwang, and B.K. Ryu, “Structure and properties of zinc bismuth phosphate glass,” Thin Solid Film 518 (2010) e46.
[70]盧依宣, 聚酪胺酸和聚(4-乙烯比基吡啶)之相容性與螺旋性胜肽二級結構對分散捲曲和鏈聚集行為之影響, 國立中山大學材料與光電科學系碩士論文 (2012).
[71]謝非, 吳瓊水, 曾立波, “面向生物過程的在線式傅立葉變換紅外光譜儀,”光譜學與光譜分析, 第35卷, 第8期, (2015).
[72]劉鈞元, 利用射頻磁控濺鍍系統製備BiFeO3薄膜及其物性研究, 國立高雄大學應用物理學系碩士班碩士論文 (2012).
[73]張子才, “阿貝折射儀實驗的探討,” 實驗室科學, No.4, (2005).
[74] 黃宏勝, 林麗娟, “ FE-SEM/CL/EBSD分析技術簡介” , 工業材料雜誌, 第201期, (2003).
[75]林佳民, ZnIn2S4螢光粉製備與發光特性之研究及其在單晶矽太陽能電池應用, 國立虎尾科技大學光電與材料科技研究所碩士論文(2003).
[76]謝雅佶, 基於彩色線陣CCD的色選技術研究, 哈爾濱理工大學自動化學院碩士論文 (2015).
[77] L. Koudelka, J. Jirák, P. Mošner, L. Montagne and G. Palavit, “Study of lithium–zinc borophosphate glasses,” Journal of Materials Science, vol.41, pp. 4636-4642, (2006).
[78] L.M. Senovilla, S. Venkatachalam, F. Muñoz and L. V. Wüllen, “ Relationships between fragility and structure through viscosity and high temperature NMR measurements in Li2O–ZnO–P2O5 phosphate glasses,” Journal of Non-Crystalline Solids, vol. 428, pp. 54-61 (2015).
[79] X. Li, A. Lu and H. Yang, “Structure of ZnO–Fe2O3–P2O5 glasses probed by Raman and,” Journal of Non-Crystalline Solids 389, pp. 21-27, (2017).
[80]張文華, 鉍鋅磷酸鹽玻璃性質與結構影響之研究, 國立聯合大學材料科學工程學系碩士論文 (2007).
[81]B. George, P. Mclntyer, 紅外線光譜分析法, 高立圖書有限公司出版 (2001).
[82]吳國禎, 分子振動光譜學概論原理與研究, 高立圖書有限公司出版 (2002)
[83]R.C. Bunker, G.W. Arnold, and J.A. Wilder, “Phosphate glass dissolution in aqueous solutions”, Journal of Non-Crystalline Solids, 64 (1983) 291.
[84]張濤, “光與電子的電磁感應相互作用,” 世界科技研究與發展, 第30捲, 第6期, 791-795頁, (2008).
[85]李浩偉, 結合數位微鏡晶片之全域式彩色共焦顯微量測系統研發, 國立臺北科技大學自動化科技研究所碩士論文 (2011).
[86]林育澍, 含芳香環之高折射環氧樹脂之特性研究, 國立交通大學應用化學系所碩士論文 (2004).
[87]中村淳一, 北村直之, 日高達雄, 橋間英和, 真弓禎隆, 福味幸平, 西井準治, “光學玻璃,” 中華人民共和國專利, 公布號: CN101970368A (2011).
[88]李英春, 劉文泰, 侯建偉, 閆冬成, 李俊鋒, 李兆廷, “一種輕質觸屏蓋板玻璃配方,” 中華人民共和國專利, 公布號: CN102701586B (2012).
[89]A. S. Budi, A. H. Permana, H Nasbey and Y. Fujii, “The Characterization ZnO-Na2O-P2O5 Glass System for Dental Restorative Materials,” Journal of Technology and Social Science, Vol.1, No.3, 2017.
[90]朱樹恭, 工業化學概論上冊, 台灣商務印書館 (1991).
[91]黃韻潔, 散射光子萃取技術於白光發光二極體空間色偏之改善, 國立臺灣科技大學色彩與照明科技研究所碩士論文 (2014).