含單一三價銪或釤配位聚合物內淬熄過程之研究

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姓名

陳湘婷(Shiang-Ting Chen) 查詢紙本館藏

畢業系所

化學學系

論文名稱

含單一三價銪或釤配位聚合物內淬熄過程之研究
(Investigation of Quenching Processes in the Coordination Polymers Containing Single Trivalent Europium or Samarium)

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摘要(中)

本論文利用光致放光光譜、激發光譜及時間解析光譜分析以中溫水熱法合成之單一三價鑭系配位聚合物(R2(C8H10O4)3, R = Tb, Eu, Sm)與不同比例之混合三價釔鑭配位聚合物(YXR2-x(C8H10O4)3, R = Tb, Eu, Sm)。配位中心為三價稀土離子(Y, Tb, Eu, Sm)，配位基為1,4-cyclohexanedicarboxylate (C8H10O4，簡稱CHDC)。單晶及粉末X光繞射實驗鑑定合成之晶體結構與純度，再經由感應耦合電漿原子發射光譜分析儀確認配位中心之稀土元素的實際比例。先前研究發現YxTb2-x(CHDC)3中並不存在濃度淬熄效應，但Tb2(CHDC)3仍有較快的放光衰退行為，為能夠徹底闡明含單一三價鑭系配位聚合物(R2(CHDC)3¬, R = Tb, Eu, Sm)中此一機制，本論文以激發至三價鑭系最低上能階的激發波長取得R2(CHDC)3¬ and YxR2-x(CHDC)3 (R = Eu, Sm)之新的光致放光光譜與放光衰退曲線，發現新的能量轉移及淬熄現象，藉由分析這些放光衰退曲線成功地建立單一三價鑭系配位聚合物內之能量轉移與淬熄模型來闡明其較快的發光速率。但Sm2(CHDC)3中可能存在著較為複雜的淬熄行為，可由觀測到的光譜資料推測其原因。

摘要(英)

Photoluminescence (PL), excitation, and time-resolved spectra were obtained for the coordination polymers including R2(C8H10O4)3 and YxR2-x(C8H10O4)3 (R = Tb, Eu, Sm) synthesized by mid-temperature hydrothermal method. The ligand is 1,4-cyclohexanedicarboxylate (C8H10O4, CHDC). Single and powder X-ray diffraction data confirm the structure and purity of these compounds. Inductively-coupled plasma atomic emission spectroscopy (ICP-AES) verifies the elemental compositions of coordination centers. Previous study found no concentration quenching in the YxTb2-x(CHDC)3 compounds, but Tb2(CHDC)3 still has a faster emission decay rate. This thesis adopts the excitation wavelengths which respectively pump trivalent lanthanides to lowest upper states to record new PL spectra and emission decay curves of R2(CHDC)3¬ and YxR2-x(CHDC)3 (R = Eu, Sm). New energy transfer and quenching phenomena were observed. Based on the analysis of these new data, a model of the energy transfer and quenching processes in the R2(CHDC)3 compounds is successfully established for elucidating the faster emission decays. On the other hand, more complicated quenching behaviors were discovered in Sm2(CHDC)3 and the observed spectroscopic data reveal the possible factors.

關鍵字(中)

★ 稀土元素
★ 光致放光光譜
★ 激發光譜
★ 時間解析光譜
★ 淬熄機制

關鍵字(英)

★ Rare earth elements
★ Photoluminescence spectra
★ Excitation spectra
★ Time-Resolved spectra
★ Quenching mechanism

論文目次

中文摘要 I
英文摘要 II
謝誌 III
目錄 IV
圖目錄 VII
表目錄 X
第一章緒論1
1-1稀土元素及發光材料 1
1-2稀土元素發光原理 3
1-3研究動機與目標 4
第二章實驗 9
2-1 實驗目標 9
2-2 合成方法 9
2-2-1 中溫水熱合成法 10
2-2-2 藥品使用 12
2-2-3 R2(CHDC)3晶體製備 12
2-3 樣品鑑定方法 13
2-3-1 單晶X光繞射實驗 13
2-3-2 粉末X光繞射實驗 15
2-3-3 感應耦合電漿原子發射光譜 16
2-4 光譜技術簡介 17
2-5 光譜分析技術及其儀器裝置 18
2-5-1 激發光譜(Excitation Spectra) 19
2-5-2 光致放光光譜(Photoluminescence Spectra) 21
2-5-3 時間解析光譜(Time-Resolved Spectra) 23
2-6 光譜量測元件介紹 26
2-6-1 光源 26
2-6-2 單光儀(Monochromator) 28
2-6-3 偵測器(Detector) 28
2-6-4 示波器(Oscilloscope) 31
第三章結果與討論 32
3-1 R2(CHDC)3 32
3-2 晶體結構分析 32
3-3 晶體純度鑑定 34
3-4 稀土離子能階分布 36
3-4-1 鋱離子發光原理 36
3-4-2 銪離子發光原理 37
3-4-3 釤離子發光原理 38
3-5 光致放光光譜 39
3-6 Tb2(CHDC)3放光衰退曲線分析 40
3-6-1 兩段式放光衰退曲線分析 41
3-7 Eu2(CHDC)3與YxEu2-x(CHDC)3放光衰退曲線分析 44
3-7-1 濃度淬熄現象 46
3-7-2 Eu3+淬熄物種分析 50
3-7-3 衰退行為之探討 53
3-7-4 與YxTb2-x(CHDC)3及Tb2(CHDC)3之差異 54
3-8 Sm2(CHDC)3與YxSm2-x(CHDC)3放光衰退曲線分析 57
3-8-1 Sm2(CHDC)3中淬熄物種之分析 59
第四章結論 68
參考文獻 70

參考文獻

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指導教授

張伯琛(Bor-Chen Chang)

審核日期

2019-7-26

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