| 研究生: |
王郁婷 Yu-Ting Wang |
|---|---|
| 論文名稱: |
不同激發態三價銪化合物放射光譜及放射時間曲線之研究 |
| 指導教授: | 張伯琛 |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學學系 Department of Chemistry |
| 論文出版年: | 2020 |
| 畢業學年度: | 108 |
| 語文別: | 中文 |
| 論文頁數: | 81 |
| 中文關鍵詞: | 光譜學 、含三價銪化合物 、藍位移光譜 |
| 相關次數: | 點閱:7 下載:0 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
本論文使用激發(excitation)、光致放光(photoluminescence)及時間解析(time-resolved)光譜研究含Eu3+系列化合物,包含Eu(NO3)3、Eu2O3、R2(C8H10O4)3。其中配位聚合物R2(C8H10O4)3是以中溫水熱法所合成,配位基為1,4-cyclohexanedicarboxylate (C8H10O4,簡稱CHDC),而配位中心R是不同組成之三價銪(europium, Eu)或釔(yttrium, Y)。以單晶及粉末X光繞射實驗鑑定合成出的晶體其結構與純度,並利用感應耦合電漿原子發射光譜(ICP-AES)確認配位中心之稀土元素的準確比例。在Eu3+系列化合物以561 nm激發之放光光譜中皆觀測到藍位移(blue shift)放光,透過光功率依賴(power dependence)實驗及溫度依賴(temperature dependence)實驗得知,所觀測到的藍位移訊號為單光子熱譜帶躍遷(one-photon hot band transition)過程至5D1激發態所形成的放光。我們量測了這些化合物之Eu3+ 5D17FJ放光衰退曲線(emission decay curves)與5D07FJ放光上升曲線(emission rising curves),發現不同的Eu3+化合物有不同5D1激發態的放光生命期和強度,但5D0激發態的放光生命期和強度卻差不多,其原因可能為兩種(Eu3+-Eu3+和Eu3+-CHDC)交互遲緩(cross relaxation)過程發生,導致不同化合物中5D1緩解至5D0的速率不相同所致。
Excitation, photoluminescence, and time-resolved spectra of the Eu3+-containing compounds including Eu(NO3)3, Eu2O3, and R2(C8H10O4)3 were obtained. The coordination polymers, R2(C8H10O4)3, were synthesized by mid-temperature hydrothermal technique with various compositions of trivalent europium (Eu) or yttrium (Y) as the coordination center and 1,4-cyclohexanedicarboxylate (C8H10O4, CHDC) as the ligands. Single-crystal and powder X-ray diffraction data were collected for determining the structure and purity, while inductively coupled plasma atomic emission spectra (ICP-AES) were recorded for verifying the compositions. Blue shift emission signals are observed in the emission spectra of these Eu3+-containing compounds at 561 nm excitation. Power dependence and temperature dependence experiments indicate the blue shift emission results from one-photon hot band transition to the 5D1 excited state. We acquired the Eu3+ 5D17FJ emission decay curves and 5D07FJ emission rising curves of these compounds. The 5D1 state emission lifetimes and intensities are quite different in these compounds, whereas the 5D0 state emission lifetimes and intensities are roughly the same. This phenomenon could arise from two possible (Eu3+-Eu3+ and Eu3+-CHDC) cross relaxation processes that relax 5D1 to 5D0 at different rates among these compounds.
1. 資料來源: https://geology.com/articles/rare-earth-elements
2. Evans, R. C.; Carlos, L. D.; Douglas, P.; Rocha, J. Tuning the emission colour in mixed lanthanide microporous silicates: energy transfer, composition and chromaticity. Journal of Materials Chemistry 2008, 18, 1100-1107; Carlos, L. D.; Videira. Emission spectra and local symmetry of Eu3+ ion in polymer electrolytes. Physical Review B 1994, 49, 11721-11728
3. Ferreira, A.; Ananias, D.; Carlos, L. D.; Morais, C. M.; Rocha, J. Novel microporous lanthanide silicates with tobermorite-like structure. Journal of The American Chemical Society 2003, 125, 14573-14579.
4. Carnall, W. T.; Goodman, G. L.; Rajnak, K.; Rana, R. S. A systematic analysis of the spectra of the lanthanides doped into single crystal LaF3. The Journal of Chemical Physics 1989, 90, 3443-3457.
5. An, Y.; Schramm, G. E.; Berry, M. T. Ligand-to-metal charge-transfer quenching of the Eu3+ (5D1) state in europium-doped tris (2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium (III). Journal of Luminescence. 2002, 97, 7-12.
6. 洪士翔,含三價釤配位聚合物內特有淬熄過程之研究,國立中央大學化學系碩士論文(2019)。
7. 蕭郁如,以光譜學研究含稀土元素發光晶體內之能量轉移過程,國立中央大學化學系碩士論文(2014)。
8. 資料來源: https://www.hamamatsu.com/
9. 資料來源:http://andor.oxinst.com/learning/view/article/intensified-ccd-cameras
10. 陳逸翔,稀土元素配位聚合物和亞磷酸鹽之合成、晶體結構與發光性質研究,國立中央大學化學系碩士論文(2012)。
11. 李穗美,含三價稀土元素配位聚合物內能量轉移之研究,國立中央大學化學系碩士論文(2015)。
12. 陳湘婷,含單一三價銪或釤配位聚合物內淬熄過程之研究,國立中央大學化學系碩士論文(2019)。
13. Kaczkan, M. Luminescence from the 5D1,2,3 excited states of Eu3+ in Y4Al2O9 crystal. Optical Materials 2016, 59, 60-65.
14. Dexter, D. L.;Schulman, J. H. Theory of concentration quenching in inorganic phosphors. The Journal of Chemical Physics 1954, 22, 1063-1070.
15. Solarz, P.; Karbowiak, W. Optical spectra and cryatal field calculation for SrB4O7:Sm2+. Journal of Alloys and Compounds 2016, 661, 419-427.
16. 資料來源: http://webbook.nist.gov/chemistry.