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研究生：	黃光弘 Huang, Kuang-hung
論文名稱：	硫化鋅螢光粉披覆二氧化鈦和二氧化矽之製備與特性研究 Preparation and Characterization of SiO2 and TiO2 coated ZnS Phosphor Powders
指導教授：	陳引幹 Chen, In-Gann
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2006
畢業學年度：	94
語文別：	中文
論文頁數：	128
中文關鍵詞：	硫化鋅、二氧化矽、二氧化鈦、溶膠-凝膠法、化學氣相沉積法
外文關鍵詞：	TEM, X-ray diffraction, CVD nanocrystallites, Sol-Gel, ZnS, SiO2, TiO2
相關次數：	點閱：65 下載：2
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摘要
硫化鋅螢光粉體具有直接複合(direct recombination)能帶結構與寬能隙之特點，以及可調整可見光範圍段，是一理想的發光材料。目前商業上應用於陰極射線發光(cathodeluminescence)、場發射平面顯示器(field emission display)，以及發光二極體元件(UV-LED)。由於硫化鋅螢光粉在封裝過程中，易受到水氣的影響而造成其表面鈍化，結晶性變差，使得其量子發光效率降低。本研究利用化學沉積法披覆保護層TiO2 於ZnS:Cu,Cl 螢光粉體表面，改變TiCl4 與H2O 的比例與在不同退火溫度條件下，合成不同性質的TiO2。由實驗結果得知在快速升溫退火(RTA)800oC 條件下所沉積出的TiO2薄膜為金紅石(rutile)相結構，其吸收係數為2.5×103(cm-1)，此值與一般利用磁控濺鍍所沉積之薄膜相同。且在經過熱處理後可將殘存在螢光粉體的氯完全揮發，使螢光粉體的電致發光機率提升至100%。此外，在硫化鋅奈米級螢光粉體中，由於粉體團聚與表面缺陷會影響發光效率，披覆保護層於奈米級螢光粉體表面可提高其發光效率。故本研究利用共沉法合成ZnS: Mn 奈米級螢光粉體，及溶膠-凝膠法披覆 SiO2於螢光粉體上，達到表面修飾效果。由實驗結果得知添加分散劑六聚磷酸鈉具有修飾ZnS:Mn 表面之效果，改善顆粒團聚情況進而提升其發光效率，其光致發光強度相對於未添加分散劑之ZnS:Mn 螢光粉體可提升1.66 倍。同時以溶膠-凝膠法改質奈米粉體使其具有核層(core layer ZnS)和殼層(coating layer SiO2)之複合粉體。從TEM 的結果下顯示，SiO2 成功的包覆在ZnS:Mn 螢光粉體外圍，達到表面修飾效果，減少能量損失於表面上，其光致發光強度相對於未披覆之ZnS:Mn 螢光粉體可提升7.84 倍。

Abstract
Zinc sulfide (ZnS) phosphors exhibit direct recombination and wide band gap which can be applied for cathodeluminescence, field emission display and UV-LED. However, ZnS phosphors showed aging deterioration by moisture intrusion in the packing process of light emitting diode (LED). In this research, TiO2-coated ZnS:Cu,Cl phosphors are synthesized by chemical vapor deposition with different ratios of H2O/TiCl4 and annealing temperatures. The structure was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The optical properties were measured including photoluminescence spectroscopy (PL) and the absorbance. The XRD results revealed that the structure of TiO2 film is rutile under the annealing temperature of 800oC. The absorption coefficient of TiO2 by CVD is equal to 2.5×103 which is as that done by sputtering process. The residual Cl in the encapsulating film vanished by rapid thermal annealing (RTA) at 800oC. This elimination of Cl improves the electro-luminescence (EL) probabil to 100%, which is an indication of enhancement of the lifetime of the ZnS phosphor. Additionally, the nano-scaled ZnS:Mn phosphors were prepared by co-precipitation reaction. These nanoparticles are stabilized using polyphosphates of sodium hexametaphosphate (SHMP). The nano-scaled ZnS:Mn phosphors were coated with SiO2 via sol-gel reaction of TEOS. The TEM results showed that ZnS:Mn nanocrystallites were well-dispersed in SiO2. The PL intensity of SiO2-coated ZnS:Mn phosphors is 7.84 times to that of the non-coated ones. The enhancement was resulted from the reduction of surface non-radiation centers. Most importantly, we developed oxidant surfaces (TiO2- or SiO2-coated) ZnS phosphors with varied sizes that would enhance biological compatibility, mechanical , as well as high temperature chemical stability. At the same time, they changed properties of phosphors such as electricity, catalysis, hydrophilic or hydrophobic properties to enhance their durability and lifetime for various applications.

摘要........................................... I
Abstract.......................................II
致謝...........................................IV
目錄............................................V
表目錄.......................................VIII
圖目錄.........................................IX
第一章 緒論.....................................1
1-1 前言........................................1
1-2 研究動機與目的..............................3
第二章 理論基礎與文獻回顧.......................5
2-1 螢光材料簡介................................5
2-2 螢光體材料組成..............................5
2-3 發光中心之種類與原理........................7
2-4 發光機制與應用..............................9
2-5 螢光體發光原理.............................11
2-5.1 螢光體能量之激發與吸收...................11
2-5.2 螢光放射和非輻射轉移（nonradiative transition） ..................................13
2-6 硫化鋅型螢光體之簡介.......................14
2-6.1 發展歷史.................................14
2-6.2 硫化鋅性質與應用.........................15
2-6.3 硫化鋅晶體結構介紹.......................15
2-6.4 ZnS:Mn 螢光光譜介紹......................16
2-7 奈米材料...................................16
2-7.1 奈米材料簡介.............................16
2-7.2 奈米材料之基本性質.......................17
1. 小尺寸效應..................................18
2. 表面效應....................................18
3. 量子尺寸及量子穿隧效應......................19
2-7.3 奈米粉末表面改質.........................19
2-7.4 奈米粉體的分散...........................21
2.8 螢光體製程技術及原理.......................22
2-9 奈米粉末表面改質製程技術及原理.............23
2-9.1 溶膠-凝膠法..............................23
2-9.2 化學氣相沉積法...........................24
2-10 螢光體發光時特性測量......................25
2-10.1 亮度量測................................25
2-10.2 放射光譜量測............................25
第三章 實驗方法及步驟..........................45
3-1 實驗藥品...................................45
3-2 實驗步驟...................................46
3-2.1 共沈法 (Coprecipitation) ................46
3-2.2 奈米硫化鋅螢光粉表面改質sol-gel 製程.....46
3-2.3 奈米硫化鋅螢光粉表面改質化學氣相沉積法(CVD) .........................................47
3-2.4 螢光粉表面改質之腐蝕研究.................47
3-2.5 電激發光元件的製作.......................47
3-3 儀器設備...................................48
第四章 結果與討................................57
4-1 奈米硫化鋅摻錳螢光粉合成與發光性質之研究...57
4-1.1 ZnS:Mn 奈米螢光粉體之合成與結構分析......58
4-1.2 Mn 添加量對ZnS:Mn 發光特性之影響.........59
4-1.3 分散劑添加與ZnS:Mn 之粒徑之發光影響......61
4-2 螢光粉體ZnS 表面改質之研究.................73
4-2.1 化學沉積法披覆TiO2 於螢光粉體............73
4-2.1.1 TiO2 之結構與穿透分析..................73
4-2.1.2 ZnS:Cu,Cl 披覆TiO2 表面型態分析........77
4-2.1.3 表面改質對ZnS: Cu,Cl 螢光粉體之發光特性影響.............................................78
4-2.2 凝膠-溶膠法披覆 SiO2 於螢光粉體..........91
4-2.2.1 SiO2 之合成與批覆研究..................91
4-2.2.2 表面改質對ZnS:Mn 奈米粉體之發光特性影響93
4-2.2.3 ZnS:Mn 披覆SiO2 之FTIR 與結構分析......94
4-2.2.4 ZnS:Mn 披覆SiO2 表面型態分析...........95
4-2.2.5 表面改質對ZnS:Mn 奈米粉體之光吸收特性影響.............................................96
4-3 螢光粉表面改質NaOH 之腐蝕研究.............111
4-3.1 不同腐蝕時間之表面型態SEM 分析..........111
4-3.2 表面蝕刻對ZnS:Cu,Cl 粉體之發光特性影響..112
4-4 綜合討論..................................113
第五章 結論...................................120
參考文獻......................................122
自述..........................................128
                                    

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校內：2008-07-26公開
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