臺灣博碩士論文加值系統

本論文旨在研究改變不同的摻雜濃度與製程溫度來合成Er3+-doped
Y2Ti2O7 薄膜與粉末，並探討其螢光特性。
我們使用溶膠凝膠法製備Er3+ (0, 5, 10%)-doped Y2Ti2O7、Er2Ti2O7薄膜，在980 nm 紅外線雷射激發下，研究其薄膜型態與上轉換發光特性，由實驗結果可得到ErxY2-xTi2O7 薄膜擁有高的平均穿透率(~77%)、高折射率(>1.93 at λ=550nm) 和高能階(>4.06 eV) 等特性，由於晶格的對稱性、[OH-]與濃度粹滅效應互相競爭之原因，Er3+ (5%)–doped Y2Ti2O7薄膜經700℃退火後，在1540nm (4I13/2→4I15/2) 有最強的躍遷。另外，我們也製作晶粒大小約為36~46nm 的Er3+ (3, 5, 7, 10%)–doped Y2Ti2O7 粉末，經380、980nm 雷射激發，具有下與上轉換發光特性，其發光峰值為526nm (2H11/2→4I15/2 )、547 nm(4S3/2→4I15/2)、660 nm(4F9/2→4I15/2)。Er3+(5%)-doped Y2Ti2O7 所得之綠光，其上轉換機制為雙光子吸收，Er3+(10%)-doped Y2Ti2O7 則因為短的鉺離子間距，進而增強了energy-transfer up-conversion 及energy-transfer cross- relaxation 機制，所以得到較強的紅光。

Er3+-doped Y2Ti2O7 thin films with the thickness of ~375 nm thin films were fabricated by the sol-gel spin-coating method. A pyrochlore phase ErxY2-xTi2O7 was observed with a strong (222) preferred orientation while the annealing temperature exceeded 800 °C. Below 800 °C annealing, thin films exhibited amorphous structure. The average visible transmittance calculated in the wavelength range 200–1100 nm of the Er3+-doped Y2Ti2O7 thin films annealed at 400 to 900 °C reduced from ~87 to ~77% because of the increase of grain size and surface roughness. The variation of refractive indexes and optical band gaps of Er3+-doped Y2Ti2O7 thin films strongly depend on the Er3+ concentrations and annealing temperatures. Higher annealing temperatures result in the increase of refractive indexes but the decease of optical band gaps. In addition, higher Er3+ concentrations lead to a decrease in both refractive indexes and optical band gaps. The variation of these basic optical properties can be attributed to the evolution of grain size, crystallinity, lattice constant, and composition of Er3+-doped Y2Ti2O7 thin films. Because the competition between the [OH-], concentration quenching effect, as well as the diversity and symmetry of Er3+ lattice sites, the Er3+ (5%)-doped Y2Ti2O7 thin films annealed at 700 °C for 1 h possessed the largest intensity of ~1.5μm PL and FWHM ~ 60 nm.
Er3+-doped Y2Ti2O7 nanocrystals with pyrochlore phase were fabricated by the Pechini sol-gel method and the average crystal size increased from ~34 to ~46 nm under 800 to 1000 °C/1 h annealing. The amorphous Er3+-doped Y2Ti2O7 nanocrystals was obtained at ≦700°C annealing temperature. The Er3+-doped Y2Ti2O7 nanocrystals possess the dual down- and up-converted luminescent properties, which convert the 380 and 980 nm photons to the visible green light (~526, and ~547 nm; 2H11/2→4I15/2 and 4S3/2→4I15/2) and red light (~660 nm; 4F9/2→4I15/2). For both high (10 mol%) and low (5 mol%) Er3+ doped concentration, the mechanism of up-converted green light is two-photon excited-state absorption; however, much stronger intensity of red light relative to green light is observed for sample with high Er3+ doped concentration (10 mol%), attributed to the reduced distance between Er3+-Er3+ ions resulting in the enhancement of the energy-transfer up-conversion and energy-transfer cross-relaxation mechanisms.

摘要 II
英文摘要 III
致謝 Ⅴ
目次 Ⅵ
表目錄 Ⅸ
圖目錄 Ⅹ
第一章 緒論 1
1-1 研究動機 1
1-2 前言 2
第二章 文獻回顧與理論基礎 5
2-1 螢光材料簡介 5
2-2 螢光材料的分類 5
2-2-1 以螢光材料組成分類 5
2-2-2 以螢光材料發光物性分類 6
2-2-3 以螢光材料特性分類 8
2-2-4 以激發源種類及其應用特性分類 9
2-3 發光機制簡介 10
2-3-1 發光原理 10
2-3-2 螢光與磷光 11
2-3-3 史托克位移 12
2-3-4 固態材料中的發光 14
2-3-4-1 本質發光 14
2-3-4-2 異質發光 15
2-4 影響發光行為與效率主要的因素 18
2-4-1 主體晶格效應 18
2-4-2 濃度淬滅效應 19
2-4-3 熱淬滅 20
2-4-4 毒化 20
2-5 螢光材料之組成與設計 21
2-6 螢光材料製程 23
2-6-1 固相反應法 23
2-6-2 溶膠凝膠法 24
2-6-3 水熱法 25
2-6-4 共沉澱法 25
2-6-5 其他製程 25
2-7 稀土元素的發光特性 26
2-7-1 鑭系元素之性質 26
2-7-2 稀土離子的電子躍遷 27
2-8 Pyrochlore主體結構 29
第三章 實驗方法 47
3-1 實驗藥品 47
3-2 儀器設備 47
3-2-1 掃描式電子顯微鏡 48
3-2-2 X光單晶繞射儀 48
3-2-3 UV-VIS光譜 49
3-2-4光致發光光譜儀 50
3-2-5 高溫爐 50
3-3 實驗步驟 51
3-3-1 以溶膠凝膠法製備Er3+- doped Y2Ti2O7薄膜 51
3-3-2 以溶膠凝膠法合成Er3+- doped Y2Ti2O7粉末 52
第四章 結果與討論 58
4-1 薄膜分析 58
4-1-1 SEM分析 58
4-1-2 XRD分析 58
4-1-3 穿透光譜分析 59
4-1-4 光譜分析 64
4-2 粉末分析 66
4-2-1 XRD分析 66
4-1-2 光譜分析 67
第五章 結論 87
參考文獻 89

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