A Density Functional Theory Study of the Electronic Transition of Squaraine-Derived Dye Sensitizer in Solution and Adsorbed on TiO2 Cluster

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：43

、訪客IP：18.223.125.110

姓名

曾文新(Wen-hsin Tseng) 查詢紙本館藏

畢業系所

化學學系

論文名稱

(A Density Functional Theory Study of the Electronic Transition of Squaraine-Derived Dye Sensitizer in Solution and Adsorbed on TiO2 Cluster)

相關論文

★ 嗜甲烷菌內甲烷單氧化酵素中催化反應中心三核銅模擬分子之合成與光譜分析	★ 烷烴氧化菌及氧化酵素之純化與功能性探討
★ 以電腦模擬研究香蕉型液晶元的分子交互作用力	★ 利用時間相關的電子密度泛函理論研究反式-二苯乙烯胺的光化學行為
★ 以生物資訊法研究穩定Asparagine在左手螺旋形下的交互作用力	★ 葛蘭氏陰性菌脂質A之結構研究
★ 五苯荑衍生之苯乙炔寡聚物之合成與光物理性質研究	★ 紫質三元件系統的金屬化作用對遠端氫鍵調控的影響
★ 非鍵結作用力的理論研究： (1)質子化與氧化三元件系統遠端調控氫鍵的比較 (2)π- π與CH- π作用力的取代基效應	★ 利用時間相關的密度泛涵理論研究HBI分子及其衍生物在第一激發態的位能曲線
★ Replica-Exchange分子動態模擬法研究類澱粉胜肽25-35 嵌入膜與折疊的行為	★ 抗菌胜肽資料庫分析及利用分子動態模擬法探討抗菌胜肽Indolicidin於生物膜上的行為
★ 網頁圖形界面在分子模擬上的應用	★ 類澱粉胜肽Abeta(25-35) 序列影響該類胜肽在水-膜環境下的組態: 強調多樣性的神經毒性
★ 以分子動態模擬法研究陽離子-負電磷脂質雙層的配位網絡結構：延伸應用於膜融合機制	★ 染料敏化太陽能電池吸光性質的計算研究

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

[檢視]

[下載]

本電子論文使用權限為同意立即開放。
已達開放權限電子全文僅授權使用者為學術研究之目的，進行個人非營利性質之檢索、閱讀、列印。
請遵守中華民國著作權法之相關規定，切勿任意重製、散佈、改作、轉貼、播送，以免觸法。

摘要(中)

Squaraine (SQ) 染料因在遠紅光/近紅外光區具有很強的吸光能力而備受矚目，其光譜特性與太陽光光譜吻合程度高，對太陽光的利用率好，是應用於太陽能電池的理想染料。本研究使用電子密度泛函理論 (Density Functional Theory, DFT) 以及time dependent的電子密度泛函理論(TD-DFT) 計算七個非對稱SQ染料分子，探討染料分子在溶劑中，以及吸附於銳鈦礦相 (TiO2)38 cluster (101)面兩種狀態下的分子結構、光學性質及與電荷轉移性質，並進一步分析染料吸附於(TiO2)38的系統，在被光激發後，電子重新分布的情形。在計算結果中，SQ染料的LUMO能階高於(TiO2)38 conduction band者，在激發後行direct electron injection 機制；而LUMO能階低於(TiO2)38 conduction band者，以及在激發後，電子密度流動方向遠離anchoring 端者，則行indirect electron injection 機制。有兩個吸收帶的SQ染料 (JD10及YR6)，同時進行direct 及indirect electron injection：較低能量的吸收帶[(SQ) →*(SQ) transition] 行indirect electron injection 機制，較高能量的吸收帶，則在激發後行direct electron injection 機制。
最後，我們將計算出的電荷轉移量與電池裝置測得的短路電流密度產生關聯。本計算研究使我們對SQ染料吸附在TiO2時，被光激發後所產生的電荷轉移現象有更詳盡的了解。

摘要(英)

Squaraine (SQ) dyes are well-known for their intense absorption in the red/near-IR spectral regions, which closely match the spectral response of the sun light. Thus, the SQ dye seems to be promising for light absorption in the red/near-IR spectral region. In this study, we employ density functional theory (DFT) as well as time dependent DFT to investigate the structural, optical and electron transfer properties of seven SQ-derived dyes in solution and adsorbed on a (TiO2)38 cluster with an anatase (101) surface, as a model for the corresponding DSCs. We calculate the absorption spectra of dye-(TiO2)38 systems and analyze the redistribution of electron density of their excited states upon photo-excitation. Our study shows the SQ dyes with their LUMO energies higher than the edge of (TiO2)38 conduction band follow direct electron injection mechanism upon excitation; on the other hand, the electron injection of SQ dyes upon excitation follow indirect electron injection mechanism when their LUMO energies are lower than the edge of (TiO2)38 conduction band or their directions of electron transfer is away from the anchoring side. SQ dyes owning two intense absorption bands (e.g. JD10 and YR6) follow both direct and indirect electron injection mechanisms. Interestingly, The JD10 and YR6 follow indirect electron injection mechanism when their most intense and low-energy bands [(SQ) →*(SQ) transition] are excited; on the other hand, JD10 and YR6 follow direct electron injection mechanism when less intense and high-energy bands are excited. Finally, we rationalize and correlate our calculated quantities of electron transfer of SQ-derived dyes with their experimental observed short-circuit currents. Our calculations provide a better understanding on the electron transfer mechanisms of SQ-derived dyes adsorbed on TiO2 upon photo-excitation.

關鍵字(中)

★ 染料敏化太陽能電池
★ 電荷轉移
★ 電子注入
★ 二氧化鈦

關鍵字(英)

★ Dye-Sensitized Solar Cell
★ Charge transfer
★ Electron injection
★ TiO2

論文目次

摘要 i
Abstract ii
Contents iii
List of Figures iv
List of Tables v
Chapter 1. Introduction 1
Chapter 2. Computational Methods 7
Chapter 3. Result and Discussion 10
3.1 Studied Systems 10
3.2 Molecular Geometries 10
3.3 Optical Properties of Dyes in Solution 17
3.4 Optical Properties of Dyes Adsorbed on TiO2 Cluster 19
3.5 Charge Transfer of Dyes upon Photo-Excitation 23
Chapter 4. Conclusions 38
Acknowledgements 40
References 40

參考文獻

(1) O′Regan Brian, G. M. Nature 1991, 353, 737.
(2) Mishra, A.; Fischer, M. K.; Bauerle, P. Angew Chem Int Ed Engl 2009, 48, 2474.
(3) Kim, B. G.; Chung, K.; Kim, J. Chemistry 2013, 19, 5220.
(4) Yum, J. H.; Baranoff, E.; Wenger, S.; Nazeeruddin, M. K.; Gratzel, M. Energy & Environmental Science 2011, 4, 842.
(5) Hagfeldt, A.; Boschloo, G.; Sun, L.; Kloo, L.; Pettersson, H. Chem. Rev. 2010, 110, 6595.
(6) Dualeh, A.; Delcamp, J. H.; Nazeeruddin, M. K.; Gratzel, M. Applied Physics Letters 2012, 100.
(7) Jones, D. R.; Troisi, A. Physical chemistry chemical physics : PCCP 2010, 12, 4625.
(8) Asbury, J. B.; Anderson, N. A.; Hao, E.; Ai, X.; Lian, T. The Journal of Physical Chemistry B 2003, 107, 7376.
(9) Goh, G. K. L.; Le, H. Q.; Huang, T. J.; Hui, B. T. T. Journal of Solid State Chemistry 2014, 214, 17.
(10) Chen, C.-Y.; Wang, M.; Li, J.-Y.; Pootrakulchote, N.; Alibabaei, L.; Ngoc-le, C.-h.; Decoppet, J.-D.; Tsai, J.-H.; Grätzel, C.; Wu, C.-G.; Zakeeruddin, S. M.; Grätzel, M. ACS Nano 2009, 3, 3103.
(11) Paek, S.; Choi, H.; Kim, C.; Cho, N.; So, S.; Song, K.; Nazeeruddin, M. K.; Ko, J. Chem Commun (Camb) 2011, 47, 2874.
(12) Kimura, M.; Masuo, J.; Tohata, Y.; Obuchi, K.; Masaki, N.; Murakami, T. N.; Koumura, N.; Hara, K.; Fukui, A.; Yamanaka, R.; Mori, S. Chemistry 2013, 19, 1028.
(13) Yella, A.; Lee, H.-W.; Tsao, H. N.; Yi, C.; Chandiran, A. K.; Nazeeruddin, M. K.; Diau, E. W.-G.; Yeh, C.-Y.; Zakeeruddin, S. M.; Grätzel, M. Science 2011, 334, 629.
(14) Yang, J.; Ganesan, P.; Teuscher, J.; Moehl, T.; Kim, Y. J.; Yi, C.; Comte, P.; Pei, K.; Holcombe, T. W.; Nazeeruddin, M. K.; Hua, J.; Zakeeruddin, S. M.; Tian, H.; Gratzel, M. Journal of the American Chemical Society 2014, 136, 5722.
(15) Alex, S.; Santhosh, U.; Das, S. J Photoch Photobio A 2005, 172, 63.
(16) Burke, A.; Schmidt-Mende, L.; Ito, S.; Gratzel, M. Chem Commun (Camb) 2007, 234.
(17) Choi, H.; Kim, J.-J.; Song, K.; Ko, J.; Nazeeruddin, M. K.; Grätzel, M. Journal of Materials Chemistry 2010, 20, 3280.
(18) Yum, J. H.; Walter, P.; Huber, S.; Rentsch, D.; Geiger, T.; Nuesch, F.; De Angelis, F.; Gratzel, M.; Nazeeruddin, M. K. Journal of the American Chemical Society 2007, 129, 10320.
(19) Hara, K.; Sato, T.; Katoh, R.; Furube, A.; Ohga, Y.; Shinpo, A.; Suga, S.; Sayama, K.; Sugihara, H.; Arakawa, H. The Journal of Physical Chemistry B 2003, 107, 597.
(20) Nazeeruddin, M. K.; Humphry-Baker, R.; Gratzel, M.; Wohrle, D.; Schnurpfeil, G.; Schneider, G.; Hirth, A.; Trombach, N. Journal of Porphyrins and Phthalocyanines 1999, 3, 230.
(21) Shi, Y.; Hill, R. B.; Yum, J. H.; Dualeh, A.; Barlow, S.; Gratzel, M.; Marder, S. R.; Nazeeruddin, M. K. Angew Chem Int Ed Engl 2011, 50, 6619.
(22) Geiger, T.; Kuster, S.; Yum, J. H.; Moon, S. J.; Nazeeruddin, M. K.; Gratzel, M.; Nuesch, F. Advanced Functional Materials 2009, 19, 2720.
(23) Li, J.-Y.; Chen, C.-Y.; Lee, C.-P.; Chen, S.-C.; Lin, T.-H.; Tsai, H.-H.; Ho, K.-C.; Wu, C.-G. Org. Lett. 2010, 12, 5454.
(24) Li, J. Y.; Lin, T. H.; Chen, S. C.; Wu, C. G. Journal of the Chinese Chemical Society 2012, 59, 1337.
(25) Pandey, S. S.; Watanabe, R.; Fujikawa, N.; Shivashimpi, G. M.; Ogomi, Y.; Yamaguchi, Y.; Hayase, S. Tetrahedron 2013, 69, 2633.
(26) Sreejith, S.; Carol, P.; Chithra, P.; Ajayaghosh, A. Journal of Materials Chemistry 2008, 18, 264.
(27) Li, H.-B.; Zhang, J.; Wu, Y.; Jin, J.-L.; Duan, Y.-A.; Su, Z.-M.; Geng, Y. Dyes and Pigments 2014, 108, 106.
(28) Rees, T. W.; Baranoff, E. Polyhedron 2014.
(29) Velusamy, M.; Hsu, Y. C.; Lin, J. T.; Chang, C. W.; Hsu, C. P. Chemistry, an Asian journal 2010, 5, 87.
(30) Wu, C.-G.; Chung, M.-F.; Tsai, H.-H. G.; Tan, C.-J.; Chen, S.-C.; Chang, C.-H.; Shih, T.-W. ChemPlusChem 2012, 77, 832.
(31) Rocca, D.; Gebauer, R.; De Angelis, F.; Nazeeruddin, M. K.; Baroni, S. Chem. Phys. Lett. 2009, 475, 49.
(32) Wu, C. G.; Shieh, W. T.; Yang, C. S.; Tan, C. J.; Chang, C. H.; Chen, S. C.; Wu, C. Y.; Tsai, H. H. G. Dyes and Pigments 2013, 99, 1091.
(33) Maeda, T.; Shirna, N.; Tsukamoto, T.; Yagi, S.; Nakazumi, H. Synthetic Metals 2011, 161, 2481.
(34) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
(35) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
(36) Petersson, G. A.; Al-Laham, M. A. J. Chem. Phys. 1991, 94, 6081.
(37) Frisch, M. J. T., G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.; Gaussian, Inc.: Wallingford CT, 2009.
(38) Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J. Comput. Chem. 2003, 24, 669.
(39) Yakhanthip, T.; Jungsuttiwong, S.; Namuangruk, S.; Kungwan, N.; Promarak, V.; Sudyoadsuk, T.; Kochpradist, P. J. Comput. Chem. 2011, 32, 1568.
(40) Delley, B. The Journal of Chemical Physics 1990, 92, 508.
(41) Delley, B. The Journal of Chemical Physics 2000, 113, 7756.
(42) Perdew, J. P.; Burke, K.; Ernzerhof, M. Physical Review Letters 1996, 77, 3865.
(43) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Physical review. B, Condensed matter 1992, 46, 6671.
(44) O′Boyle, N. M.; Tenderholt, A. L.; Langner, K. M. J. Comput. Chem. 2008, 29, 839.
(45) Paterson, M. J.; Blancafort, L.; Wilsey, S.; Robb, M. A. J. Phys. Chem. A 2002, 106, 11431.
(46) Yesudas, K.; Chaitanya, G. K.; Prabhakar, C.; Bhanuprakash, K.; Rao, V. J. J Phys Chem A 2006, 110, 11717.
(47) Ning, Z. J.; Fu, Y.; Tian, H. Energy & Environmental Science 2010, 3, 1170.
(48) Jungsuttiwong, S.; Yakhanthip, T.; Surakhot, Y.; Khunchalee, J.; Sudyoadsuk, T.; Promarak, V.; Kungwan, N.; Namuangruk, S. Journal of computational chemistry 2012, 33, 1517.
(49) Choi, H.; Lee, J. K.; Song, K.; Kang, S. O.; Ko, J. Tetrahedron 2007, 63, 3115.
(50) Hua, Y.; Chang, S.; Huang, D. D.; Zhou, X.; Zhu, X. J.; Zhao, J. Z.; Chen, T.; Wong, W. Y.; Wong, W. K. Chemistry of Materials 2013, 25, 2146.
(51) Burdett, J. K.; Hughbanks, T.; Miller, G. J.; Richardson, J. W.; Smith, J. V. Journal of the American Chemical Society 1987, 109, 3639.
(52) Srinivas, K.; Prabhakar, C.; Devi, C. L.; Yesudas, K.; Bhanuprakash, K.; Rao, V. J. J Phys Chem A 2007, 111, 3378.
(53) Wu, C.-G.; Shieh, W.-T.; Yang, C.-S.; Tan, C.-J.; Chang, C.-H.; Chen, S.-C.; Wu, C.-Y.; Tsai, H.-H. G. Dyes and Pigments 2013, 99, 1091.
(54) Persson, P.; Bergström, R.; Lunell, S. J. Phys. Chem. B 2000, 104, 10348.
(55) Marinado, T.; Hagberg, D. P.; Hedlund, M.; Edvinsson, T.; Johansson, E. M. J.; Boschloo, G.; Rensmo, H.; Brinck, T.; Sun, L.; Hagfeldt, A. Physical Chemistry Chemical Physics 2009, 11, 133.

指導教授

蔡惠旭(Hui-hsu Tsai)

審核日期

2014-7-11

推文