Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains
We carry out a computational study of optical properties of two novel 5,6-difluorobenzo{[}c{]}{[}1,2,5{]}-thiadiazole-based polymers, PFBT-T12TT and PFBT-T20TT, aimed at elucidating the remarkably higher potential for applications in polymer solar cells exhibited by the latter as compared to former....
| Main Authors: | , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
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2015
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| Online Access: | https://hdl.handle.net/10356/79417 http://hdl.handle.net/10220/25129 |
| _version_ | 1826115530628530176 |
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| author | Lu, Jing Yao, Yao Shenai, Prathamesh Mahesh Chen, Lipeng Zhao, Yang |
| author2 | School of Materials Science & Engineering |
| author_facet | School of Materials Science & Engineering Lu, Jing Yao, Yao Shenai, Prathamesh Mahesh Chen, Lipeng Zhao, Yang |
| author_sort | Lu, Jing |
| collection | NTU |
| description | We carry out a computational study of optical properties of two novel 5,6-difluorobenzo{[}c{]}{[}1,2,5{]}-thiadiazole-based polymers, PFBT-T12TT and PFBT-T20TT, aimed at elucidating the remarkably higher potential for applications in polymer solar cells exhibited by the latter as compared to former. While the two molecules differ only in terms of the long alkyl side-chains, their geometries optimized via Density Functional Theory (DFT) based calculations at B3LYP/6-31G(d) level reveal differences in internal coordinates (dihedral angles), which are important in tuning the electronic structure and optical properties. By employing molecular dynamics (MD) simulations in combination with DFT techniques, electronic structure is obtained at room temperature. The subsequently calculated energies of the highest occupied molecular orbitals (HOMOs) are found to be in reasonable agreement with the available experimental data. More importantly, on one hand, the calculated HOMO-LUMO (lowest unoccupied MO) gap is found to be nearly similar for both the molecules accounting for nearly identical short-circuit current observed in polymer solar cell devices based on them. On the other hand, PFBT-T20TT is found to exhibit appreciably more delocalization of electronic density corresponding to the HOMO level than that in PFBT-T12TT arising from conformational distortions and pointing towards improved charge carrier mobility in the former. To take into account the influence of phonons, we have also adopted the multi-mode Brownian Oscillator (MBO) model to calculate the absorption spectra, which yields excellent fitting of the experimental measurements in both the solution and the thin-film states. The parameters of the MBO model extracted from the fitting procedure indicate a strong exciton-phonon coupling in PFBT-T12TT as compared to PFBT-T20TT, consistent with the trends revealed via the DFT-MD results. |
| first_indexed | 2024-10-01T03:56:40Z |
| format | Journal Article |
| id | ntu-10356/79417 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:56:40Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | ntu-10356/794172023-07-14T15:50:12Z Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains Lu, Jing Yao, Yao Shenai, Prathamesh Mahesh Chen, Lipeng Zhao, Yang School of Materials Science & Engineering DRNTU::Science::Physics::Optics and light We carry out a computational study of optical properties of two novel 5,6-difluorobenzo{[}c{]}{[}1,2,5{]}-thiadiazole-based polymers, PFBT-T12TT and PFBT-T20TT, aimed at elucidating the remarkably higher potential for applications in polymer solar cells exhibited by the latter as compared to former. While the two molecules differ only in terms of the long alkyl side-chains, their geometries optimized via Density Functional Theory (DFT) based calculations at B3LYP/6-31G(d) level reveal differences in internal coordinates (dihedral angles), which are important in tuning the electronic structure and optical properties. By employing molecular dynamics (MD) simulations in combination with DFT techniques, electronic structure is obtained at room temperature. The subsequently calculated energies of the highest occupied molecular orbitals (HOMOs) are found to be in reasonable agreement with the available experimental data. More importantly, on one hand, the calculated HOMO-LUMO (lowest unoccupied MO) gap is found to be nearly similar for both the molecules accounting for nearly identical short-circuit current observed in polymer solar cell devices based on them. On the other hand, PFBT-T20TT is found to exhibit appreciably more delocalization of electronic density corresponding to the HOMO level than that in PFBT-T12TT arising from conformational distortions and pointing towards improved charge carrier mobility in the former. To take into account the influence of phonons, we have also adopted the multi-mode Brownian Oscillator (MBO) model to calculate the absorption spectra, which yields excellent fitting of the experimental measurements in both the solution and the thin-film states. The parameters of the MBO model extracted from the fitting procedure indicate a strong exciton-phonon coupling in PFBT-T12TT as compared to PFBT-T20TT, consistent with the trends revealed via the DFT-MD results. Accepted version 2015-02-27T01:34:58Z 2019-12-06T13:24:46Z 2015-02-27T01:34:58Z 2019-12-06T13:24:46Z 2015 2015 Journal Article Lu, J., Yao, Y., Shenai, P. M., Chen, L., & Zhao, Y. (2015). Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains. Physical chemistry chemical physics, 17(14), 9541-9551. https://hdl.handle.net/10356/79417 http://hdl.handle.net/10220/25129 10.1039/C4CP05657D en Physical chemistry chemical physics © 2015 The Authors. This is the author created version of a work that has been peer reviewed and accepted for publication in Physical Chemistry Chemical Physics, published by Royal Society of Chemistry on behalf of The Authors. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [Article URL/DOI: http://dx.doi.org/10.1039/C4CP05657D]. application/pdf |
| spellingShingle | DRNTU::Science::Physics::Optics and light Lu, Jing Yao, Yao Shenai, Prathamesh Mahesh Chen, Lipeng Zhao, Yang Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains |
| title | Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains |
| title_full | Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains |
| title_fullStr | Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains |
| title_full_unstemmed | Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains |
| title_short | Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains |
| title_sort | elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains |
| topic | DRNTU::Science::Physics::Optics and light |
| url | https://hdl.handle.net/10356/79417 http://hdl.handle.net/10220/25129 |
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