有機染料分子及鈣鈦礦量子點薄膜化之雙光子吸收性質研究;Two-photon Absorption Properties of Neat-Films of Organic Dyes and Perovskite Quantum Dots

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题名:	有機染料分子及鈣鈦礦量子點薄膜化之雙光子吸收性質研究;Two-photon Absorption Properties of Neat-Films of Organic Dyes and Perovskite Quantum Dots
作者:	劉岳青;Liu, Yueh-Ching
贡献者:	化學學系
关键词:	有機染料分子薄膜化;鈣鈦礦量子點薄膜化;雙光子吸收性質研究;Two-photon Absorption Properties;Neat-Films of Organic Dyes;Neat-Films of Perovskite Quantum Dots
日期:	2019-01-23
上传时间:	2019-04-02 14:14:51 (UTC+8)
出版者:	國立中央大學
摘要:	本論文主要比較各類型分子製成薄膜後與其溶液態的雙光子光學性質。其中包括了本實驗室所合成之四類系統染料分子，以及一個與清華大學合作的鈣鈦礦量子點樣品。另外，我們也測量了一個來自日本廣島大學的染料小分子於溶液態中的雙光子性質。上述四類本實驗室所合成分子系統簡介如下：第一系列：以Carbazole為中心之樹枝狀分歧型分子；第二系列：以Oxadiazole或Thiazole作為核心之對稱與不對稱型分子；第三系列：以三鍵為中心之啞鈴型分子以fluorene或carbazole替換其芳香環位置；第四系列：多取代位置及取代方式變換之含quinoxaline單元為中心之染料分子；從上述系統所作實驗可得結論如下： (1)於薄膜態時的雙光子吸收截面值較於溶液態時高。 (2)於薄膜態與溶液態時所呈現之雙光子吸收截面光譜譜形相似。我們推測可能原因為當分子於薄膜態時接近固態，分子堆疊較緊密，使分子之共平面性較高進而提高薄膜態樣品之雙光子吸收截面。另外與清華大學林皓武教授實驗室合作之鈣鈦礦量子點薄膜以及廣島大學Manabu Abe教授所合作之染料小分子系統也得到以下結論： (1)來自清華大學林皓武老師實驗室的鈣鈦礦量子點薄膜，我們觀察到了很高的雙光子螢光強度。另外我們也發現了一個有趣的現象，此系統薄膜在經過高強度雷射照射後螢光強度雖會大幅下降，但在短時間內卻能恢復至原始螢光強度之85 %。 (2)與廣島大學合作測量之染料小分子系統，是承襲我們在2017年兩間實驗室共同研究發表之coumarin衍生物分子(出處：Org. Lett. 2017, 19, 2622−2625)並延伸其共軛長度；使其由過去的D-π-D型結構延展至D-π-π-D型。隨著共軛結構的延伸，在實驗中也觀察到了雙光子吸收截面提高了數十倍，這項結果對未來將caged-compound應用於醫療上將會是一大助益。 ;This thesis mainly studies the optical properties of neat-films that fabricated by using our newly synthesized two-photon chromophores in comparison to their optical properties in solution phase. In addition, we also studied the two-photon properties of a film of perovskite quantum dot and a coumarin-containing chromophore in solution phase in order to evaluate its applicability for two-photon uncaging. We have used four different types of our new chromophore for the film fabrication: Series1: Carbazole-cored multi-branched structure. Series2: Symmetric and asymmetric chromophores derived from oxadiazoles and thiazoles. Series3: Bisarylacetylene-type chromophores based on quinoxaline, fluorene and carbazole units. Series4: Multi-substituted quinoxalinoid chromophores. For the film samples made from the above-mentioned chromophores, we have found the following optical properties: (1)The two-photon absorption cross-section values of film-phase are generally higher than those of the solution-phase for each chromophore. (2)The two-photon absorption spectra are similar for film and solution samples for each chromophore. We postulate that the close-stacking of molecules has led to a better coplanarity of the molecules, therefore, the two-photon activity values would be higher. The other two systems of the studied samples are from our collaborators-Prof. Hao-Wu Lin in National Tsing Hua University and Prof. Manabu Abe in Hiroshima University. We have found the following interesting properties: (1)The sample from National Tsing Hua University is a film of perovskite quantum dot. This film exhibits very high fluorescence quantum efficiency. In addition, this film shows a recoverable fluorescence intensity under intermittent irradiation of laser light. (2)The sample from Hiroshima University is an extended version of our previously published chromophore (from: Org. Lett. 2017, 19, 2622−2625). We have modified the conjugated structure from D-π-D to D-π-π-D. We have observed that with the extension of the structure, the two-photon absorption cross-section value can be enhanced over ten times. Such a result has pointed out a possibility to use this structure as a caged-compound for medical application.
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