Performance Regulation of Thieno[3,2-b]benzothiophene π-Spacer-Based D-π-A Organic Dyes for Dye-Sensitized Solar Cell Applications: Insights From Computational Study
Dye-sensitized solar cells (DSSCs) have been widely investigated; however, the development of promising dye sensitizers is still appealing. In this work, we perform a detailed theoretical search for high-efficiency D-π-A organic dyes using density functional theory and time-dependent density functio...
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Frontiers Media S.A.
2019-01-01
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| Series: | Frontiers in Chemistry |
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| Online Access: | https://www.frontiersin.org/article/10.3389/fchem.2018.00676/full |
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| author | Xiaoyin Xie Xiaoyin Xie Zhi-Hai Liu Fu-Quan Bai Hong-Xing Zhang |
| author_facet | Xiaoyin Xie Xiaoyin Xie Zhi-Hai Liu Fu-Quan Bai Hong-Xing Zhang |
| author_sort | Xiaoyin Xie |
| collection | DOAJ |
| description | Dye-sensitized solar cells (DSSCs) have been widely investigated; however, the development of promising dye sensitizers is still appealing. In this work, we perform a detailed theoretical search for high-efficiency D-π-A organic dyes using density functional theory and time-dependent density functional theory calculations. Specifically, we perform geometric optimization, and electronic structure and absorption spectra calculations for isolated dyes for two thieno[3,2-b]benzothiophene π-spacer-based D-π-A organic dyes SGT129 and SGT130, which show significant efficiency difference, before and after binding to a TiO2 semiconductor. The calculation results reveal that the coplanar configuration between the electron donor and the π-spacer can enhance electronic communication efficiently, thus facilitating intra-molecular charge transfer from the electron donor to the acceptor groups in SGT130. The absorption spectrum of SGT130 broadens and is red-shifted owing to the decreased bandgap. The higher light-harvesting efficiency, favorable intra-molecular charge transfer, larger shift of the conduction band edge in the TiO2 semiconductor, and slower charge recombination between the injected electrons in the TiO2 conduction band and the electrolyte explain the superior efficiency of SGT130 over that of SGT129. Using SGT130 as the reference dye, we further design four novel dyes 1–4 by modifying the π-spacer with electron-rich and electron-withdrawing moieties. Judging from the theoretical parameters influencing the short-circuit current and open-circuit voltage, we found that all dyes would perform better than SGT130 in terms of the favorable interfacial charge transfer (ICT) and light-harvesting efficiency, as well as the larger shift of the TiO2 conduction band edge. Our theoretical research is expected to provide valuable insights into the molecular modification of TBT-based D-π-A organic dyes for DSSC applications. |
| first_indexed | 2024-12-16T09:03:04Z |
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| language | English |
| last_indexed | 2024-12-16T09:03:04Z |
| publishDate | 2019-01-01 |
| publisher | Frontiers Media S.A. |
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| series | Frontiers in Chemistry |
| spelling | doaj.art-e73072d54a814313ab6f265e9b0da9642022-12-21T22:37:08ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462019-01-01610.3389/fchem.2018.00676438760Performance Regulation of Thieno[3,2-b]benzothiophene π-Spacer-Based D-π-A Organic Dyes for Dye-Sensitized Solar Cell Applications: Insights From Computational StudyXiaoyin Xie0Xiaoyin Xie1Zhi-Hai Liu2Fu-Quan Bai3Hong-Xing Zhang4International Joint Research Laboratory of Nano-Micro Architecture Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, ChinaDepartment of Chemical Technology, Jilin Institute of Chemical Technology, Jilin, ChinaSchool of Opto-Electronic Information Science and Technology, Yantai University, Shandong, ChinaInternational Joint Research Laboratory of Nano-Micro Architecture Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, ChinaInternational Joint Research Laboratory of Nano-Micro Architecture Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, ChinaDye-sensitized solar cells (DSSCs) have been widely investigated; however, the development of promising dye sensitizers is still appealing. In this work, we perform a detailed theoretical search for high-efficiency D-π-A organic dyes using density functional theory and time-dependent density functional theory calculations. Specifically, we perform geometric optimization, and electronic structure and absorption spectra calculations for isolated dyes for two thieno[3,2-b]benzothiophene π-spacer-based D-π-A organic dyes SGT129 and SGT130, which show significant efficiency difference, before and after binding to a TiO2 semiconductor. The calculation results reveal that the coplanar configuration between the electron donor and the π-spacer can enhance electronic communication efficiently, thus facilitating intra-molecular charge transfer from the electron donor to the acceptor groups in SGT130. The absorption spectrum of SGT130 broadens and is red-shifted owing to the decreased bandgap. The higher light-harvesting efficiency, favorable intra-molecular charge transfer, larger shift of the conduction band edge in the TiO2 semiconductor, and slower charge recombination between the injected electrons in the TiO2 conduction band and the electrolyte explain the superior efficiency of SGT130 over that of SGT129. Using SGT130 as the reference dye, we further design four novel dyes 1–4 by modifying the π-spacer with electron-rich and electron-withdrawing moieties. Judging from the theoretical parameters influencing the short-circuit current and open-circuit voltage, we found that all dyes would perform better than SGT130 in terms of the favorable interfacial charge transfer (ICT) and light-harvesting efficiency, as well as the larger shift of the TiO2 conduction band edge. Our theoretical research is expected to provide valuable insights into the molecular modification of TBT-based D-π-A organic dyes for DSSC applications.https://www.frontiersin.org/article/10.3389/fchem.2018.00676/fullorganic dyefused heterocyclic π-spacerDSSCDFTcharge transfer |
| spellingShingle | Xiaoyin Xie Xiaoyin Xie Zhi-Hai Liu Fu-Quan Bai Hong-Xing Zhang Performance Regulation of Thieno[3,2-b]benzothiophene π-Spacer-Based D-π-A Organic Dyes for Dye-Sensitized Solar Cell Applications: Insights From Computational Study Frontiers in Chemistry organic dye fused heterocyclic π-spacer DSSC DFT charge transfer |
| title | Performance Regulation of Thieno[3,2-b]benzothiophene π-Spacer-Based D-π-A Organic Dyes for Dye-Sensitized Solar Cell Applications: Insights From Computational Study |
| title_full | Performance Regulation of Thieno[3,2-b]benzothiophene π-Spacer-Based D-π-A Organic Dyes for Dye-Sensitized Solar Cell Applications: Insights From Computational Study |
| title_fullStr | Performance Regulation of Thieno[3,2-b]benzothiophene π-Spacer-Based D-π-A Organic Dyes for Dye-Sensitized Solar Cell Applications: Insights From Computational Study |
| title_full_unstemmed | Performance Regulation of Thieno[3,2-b]benzothiophene π-Spacer-Based D-π-A Organic Dyes for Dye-Sensitized Solar Cell Applications: Insights From Computational Study |
| title_short | Performance Regulation of Thieno[3,2-b]benzothiophene π-Spacer-Based D-π-A Organic Dyes for Dye-Sensitized Solar Cell Applications: Insights From Computational Study |
| title_sort | performance regulation of thieno 3 2 b benzothiophene π spacer based d π a organic dyes for dye sensitized solar cell applications insights from computational study |
| topic | organic dye fused heterocyclic π-spacer DSSC DFT charge transfer |
| url | https://www.frontiersin.org/article/10.3389/fchem.2018.00676/full |
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