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研究生:傅珺怡
研究生(外文):Fu, Chuni
論文名稱:氧化鋱摻雜鋅鋁磷酸鹽玻璃性質與結構之研究
論文名稱(外文):The study of properties and structure of terbium oxide doped zinc aluminum phosphate glasses
指導教授:楊希文楊希文引用關係
指導教授(外文):Yang, Hsiwen
口試委員:金重勳施並裕張益新
口試委員(外文):Chin, Tsung-ShuneShin, PingyuChang, Yeeshin
口試日期:100/07/15
學位類別:碩士
校院名稱:國立聯合大學
系所名稱:材料科學工程學系碩士班
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2011
畢業學年度:99
語文別:中文
論文頁數:114
中文關鍵詞:發光玻璃螢光強度Tb 離子鋅鋁磷酸鹽玻璃
外文關鍵詞:Luminescence glassesFluorescence intensityTb3+ ionZinc aluminum phosphate glass
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本研究以P2O5-ZnO-Al2O3 玻璃系列作為基礎,改變ZnO 與P2O5間之比例,並摻雜稀土元素氧化鋱;探討其對本系列玻璃之影響,並分析其基本性質、結構和光學性質。隨著玻璃系列中氧化鋱摻雜含量的增加及ZnO 含量增加,玻璃之密度、玻璃轉換溫度(Tg)、玻璃軟化溫度(Td)、折射率及耐水性隨之增加,而莫爾體積及膨脹係數則下降。
在結構分析方面,使用傅立葉轉換紅外線光譜、拉曼光譜以及X光光電子能譜,探討此系列玻璃結構與玻璃組成的關係。當系列中P2O5 含量減少時,磷酸鹽鍵結隨之下降。而隨著系列中ZnO 含量及氧化鋱摻雜量增加,將打斷網絡結構中的架橋氧鍵結,產生非架橋氧鍵結。
在光學分析方面,鋅鋁磷酸鹽玻璃中,隨著氧化鋱摻雜含量增加,其Tb 離子的特徵吸收峰(545 nm)螢光相對強度隨之增加;相對在藍光部分(437 nm)會隨著摻雜含量超過2.5 mol%時,螢光相對強度會隨著摻雜量增加而下降,產生消光(Quenching)現象。當ZnO 含量增加,Tb 離子的特徵吸收峰(545 nm)螢光強度隨之增加,當ZnO 光生電子受困於缺陷能階,且缺陷能階位於在Tb3+之激發態,而能量將由無輻射過程轉移到Tb3+離子。
This study explores optical, physical and structure properties based on zinc aluminum phosphate glass system (P2O5-ZnO-Al2O3) doped with different amounts of (terbium oxide), which changed the composition ratio between ZnO and P2O5.
With increasing the terbium oxide and ZnO contents the density,refractive index and chemical durability of glasses increase, while the molar volume and thermal expansion coefficient decrease.
Structure of glasses was analyzed by Fourier-transformed-infrared spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy in glasses system. With decreasing P2O5 content and the increase of network modifier (ZnO) leak the bridge oxygen bonds and the non-bridging oxygen bonds increase.
In the optical analysis, with terbium oxide exceed 2.5 mol% the glasses exhibiters maximum intensity of blue emission from 5D3 to 7Fj level, while green emission from 5D4 level has increases linearly up to 9 mol% of Tb2O3. The concentration quenching of blue emission (5D3→7Fj) is attributed mainly to the cross-relaxation among the excited and nearest neighbor unexcited Tb3+ ions in the glass matrix. The fluorescence intensity increases with the increasing of ZnO content. The ZnO photogenerated electrons are trapped in the band gap defects which lie next to the Tb3+ excited states, and energy transferred to Tb3+ ion through radiation less process.
摘要............................................................................ I
Abstract...................................................................... II
目錄 .......................................................................... IV
表目錄 .........................................................................VI
圖目錄 ....................................................................... VII
第一章 緒論...................................................................... 1
1-1 前言 ............................................................................... 1
1-2 文獻回顧 ............................................................................... 2
1-3 研究目的 ............................................................................... 3
第二章 理論基礎 ............................................................................... 5
2-1 玻璃定義 ............................................................................... 5
2-2 玻璃的結構理論 ............................................................................... 6
2-3 磷酸鹽玻璃結構 .............................................................. 12
2-3-1 磷酸鹽玻璃之基本結構單元 .................................................... 14
2-3-2 磷酸鹽玻璃之分類 .......................................................... 17
2-4 玻璃之結構分析 .............................................................. 21
2-4-1 傅立葉紅外光譜 ............................................................ 21
2-4-2 拉曼光譜 ................................................................. 21
2-4-3 核磁共振能譜 ............................................................. 21
2-4-4 X 光光電子光譜 ........................................................... 22
2-4-5 化學耐久性質 ............................................................. 24
2-5 玻璃之光學分析 .............................................................. 25
2-5-1 發光原理與特性 ............................................................ 25
2-5-2 發光光譜量測 ............................................................. 26
2-5-3 發光性質研究 ............................................................. 26
2-5-4 Tb 離子發光性質 .......................................................... 27
第三章 實驗方法與步驟 ............................................................ 29
3-1 鋅鋁磷酸鹽玻璃之熔製 ......................................................... 29
3-1-1 實驗藥品 ................................................................. 29
3-1-2 實驗流程 ................................................................. 30
3-1-3 玻璃熔製 ................................................................. 30
3-2 玻璃結構分析 ............................................................... 32
3-2-1 FTIR 光譜分析 ............................................................ 32
3-2-2 Raman 光譜分析 .......................................................... 32
3-2-3 XPS 能譜分析 ............................................................. 32
3-2-4 NMR 分析 ................................................................ 33
3-3 玻璃性質量測 ............................................................... 34
3-3-1 密度及莫爾濃度 ............................................................ 34
3-3-2 耐水性 .................................................................. 34
3-3-3 熱分析 .................................................................. 35
3-3-4 折射率 .................................................................. 35
3-3-5 紫外-可見光譜 ............................................................ 35
3-3-6 激發、放射光譜 ........................................................... 36
第四章 結果與討論 ............................................................... 37
4-1 玻璃之結構分析 ............................................................. 38
4-1-1 FTIR 光譜分析 ........................................................... 38
4-1-2 Raman 光譜分析 .......................................................... 44
4-1-3 NMR 分析 ............................................................... 48
4-1-3-1 31P NMR 能譜分析....................................................... 48
4-1-3-2 27Al NMR 能譜分析 ..................................................... 51
4-1-4 XPS 能譜分析 ............................................................ 53
4-1-4-1O1s-XPS 能階分析 ....................................................... 53
4-1-4-2Tb 4d-XPS 能譜分析 ..................................................... 61
4-2 玻璃之性質檢測 .............................................................. 67
4-2-1 密度及莫爾濃度 ............................................................ 67
4-2-2 耐水性 .................................................................. 70
4-2-3 熱分析 .................................................................. 72
4-2-4 折射率 .................................................................. 76
4-2-5 紫外-可見光譜 ............................................................ 78
4-2-6 螢光光譜 ................................................................ 81
第五章 結論..................................................................... 89
參考文獻....................................................................... 90
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