https://scholars.lib.ntu.edu.tw/handle/123456789/598254
標題: | Novel Donor-Electret-Acceptor Framework for Higher Charge Transfer and Distance of Charge Transfer through Dipole Engineering | 作者: | Vikramaditya T Lin S.-T. SHIANG-TAI LIN |
關鍵字: | Binding energy;Degrees of freedom (mechanics);Density functional theory;Electron transitions;Excitons;Ground state;Molecular orbitals;Optical properties;Organic solar cells;Proteins;Donor-acceptor pairs;Electrical energy;Electronics applications;High charges;Light energy;Long-range electron transfer;Natural process;Polar groups;Protein matrix;Substitution patterns;Charge transfer | 公開日期: | 2021 | 卷: | 125 | 期: | 37 | 起(迄)頁: | 20219-20229 | 來源出版物: | Journal of Physical Chemistry C | 摘要: | Solar cells try to mimic the natural process of photosynthesis to convert light energy into electrical energy. Long-range electron transfers occur rapidly between donor-acceptor pairs within the protein matrix. However, protein-based moieties are not suited for electronic applications. The widely employed donor-(bridge)n-acceptor (DBnA; n ? 1) framework typically fails to effectively transfer the charge over longer distances, leading to larger exciton binding energies and lower power conversion efficiencies in organic solar cells. By modifying the dipole neutral bridge into an electret, we propose a donor-electretn-acceptor (DEnA; n ? 1) model, which addresses the limitations of the conventional donor-bridge-acceptor (DBA) architecture. We design a novel electret based on an aromatic-5-membered ring (A5R) substituted with polar groups in a stereoregular fashion. Due to the peculiar symmetry offered by the A5R and the asymmetry achieved through the regioregular substitution of polar groups, a co-directional dipole is induced along the electret backbone. Exploiting this unique behavior and orienting the dipole direction of the electret opposite to the donor-acceptor duo in the donor-electret-acceptor (DEA) framework, higher magnitudes of charge transfer (qCT) and distance of charge transfer (DCT) are realized. This novel design offers the following: (1) Higher qCT and DCT are achieved, which overcomes the inherent length dependency of DBAs with increasing chain length. (2) DCT over ?12 ? and beyond is possible with the proposed DEA architecture, which can compete with the natural protein helix in efficient electron transfer and exciton dissociation. (3) The electret allows us to tune the ground-state (GS) dipole without compromising on higher qCT and DCT properties; the lower GS dipole enables the solubility of DEAs in mild solvents. (4) Higher degrees of freedom in the substitution patterns provided by the electret allow us to alter not only qCT and DCT but also other electronic and optical properties including lowest unoccupied molecular orbital-highest occupied molecular orbital gaps, optical gaps, dipoles, oscillator strengths, and so on. (5) A new window in exploiting the substitution patterns provided by the electret to design novel materials is opened, which have potential applications in diverse areas. Our density functional theory/time-dependent density functional theory studies employing optimally tuned range-separated hybrids predict accurate optical properties against the experimental results. ? 2021 American Chemical Society. |
URI: | https://www.scopus.com/inward/record.uri?eid=2-s2.0-85115999649&doi=10.1021%2facs.jpcc.1c06799&partnerID=40&md5=5f3b4b1dbf81c765da35476a86e775c6 https://scholars.lib.ntu.edu.tw/handle/123456789/598254 |
ISSN: | 19327447 | DOI: | 10.1021/acs.jpcc.1c06799 |
顯示於: | 化學工程學系 |
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