{"title":"吲哚二噻吩-4,9-二酮基D-A-D型无掺杂空穴传输材料用于环境稳健的30%高效室内钙钛矿太阳能电池","authors":"Sibu Manna, Prasun Kumar, Rahul Tiwari, Buddhadeb Mondal, Chitrak Ghosh, Ranbir Singh* and Suman Kalyan Samanta*, ","doi":"10.1021/acs.energyfuels.5c0094610.1021/acs.energyfuels.5c00946","DOIUrl":null,"url":null,"abstract":"<p >To develop low-light responsive materials for perovskite solar cells (PSCs), for the first time, we synthesized <i>s</i>-indaceno[1,2-<i>b</i>:5,6-<i>b</i>’]-dithiophene-4,9-dione core acceptor linked 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline and N,N-diphenylaniline end-cap donors based on symmetrical donor–acceptor–donor (D-A-D) type two hole-transporting materials (HTMs), <b>TPA-IDT-OMe</b> and <b>TPA-IDT-H</b>. The relative synthetic costs of the two HTMs, <b>TPA-IDT-OMe</b> and <b>TPA-IDT-H,</b> are about one-seventh and one-fifth times cheaper, respectively, compared to the commercially available spiro-OMeTAD. Both the symmetrical D-A-D type HTMs presented good thermal stability, remarkable photophysical and electrochemical properties, along with down-shifted HOMO energy levels, extended π-conjugation, and enhanced π-π stacking in the film state. Moreover, the methoxy group-bearing <b>TPA-IDT-OMe</b> exhibited superior hole extraction and hole mobilities with negligible bimolecular recombination at the perovskite/HTM interfaces due to the suitable band alignment with the perovskite energy levels, a more planar conjugated backbone, and improved intermolecular π-π stacking in the film state, which led to better interaction with the perovskite layer. As a result, the PSCs from dopant-free <b>TPA-IDT-OMe</b> yielded an impressive power conversion efficiency (PCE) value of 30.19%, with high open-circuit voltage (<i>V</i><sub>oc</sub>), short-circuit current density (<i>J</i><sub>sc</sub>) and fill factor (FF) values of 0.89 V, 157.30 μA/cm<sup>2</sup>, and 70.30%, respectively, under indoor light illumination (1000 lx, 321.6 μW/cm<sup>2</sup>) which is comparable to the PCE value of the doped spiro-OMeTAD-based devices. Moreover, <b>TPA-IDT-OMe</b> showed remarkable UV stability after 240 h of aging and admissible moisture stability with relative humidity (RH) of (40% ± 5%) at room temperature due to its greater hydrophobicity compared to <b>TPA-IDT-H</b> and the reference spiro-OMeTAD. The poor solubility of <b>TPA-IDT-H</b> illustrates its poor film formation ability, which results in greater bimolecular and trap-assisted recombination and lower hole mobility, leading to a lower PCE value of 27.08% for the undoped <b>TPA-IDT-H</b>-based PSCs. This finding opens a new path to design low-light responsive D-A-D architecture-based small molecular HTMs for efficient and stable indoor perovskite solar cells.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 21","pages":"10021–10030 10021–10030"},"PeriodicalIF":5.3000,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Indacenodithiophene-4,9-dione-Based D-A-D Type Dopant-Free Hole Transporting Materials for Environmentally Robust 30% Efficient Indoor Perovskite Solar Cells\",\"authors\":\"Sibu Manna, Prasun Kumar, Rahul Tiwari, Buddhadeb Mondal, Chitrak Ghosh, Ranbir Singh* and Suman Kalyan Samanta*, \",\"doi\":\"10.1021/acs.energyfuels.5c0094610.1021/acs.energyfuels.5c00946\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >To develop low-light responsive materials for perovskite solar cells (PSCs), for the first time, we synthesized <i>s</i>-indaceno[1,2-<i>b</i>:5,6-<i>b</i>’]-dithiophene-4,9-dione core acceptor linked 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline and N,N-diphenylaniline end-cap donors based on symmetrical donor–acceptor–donor (D-A-D) type two hole-transporting materials (HTMs), <b>TPA-IDT-OMe</b> and <b>TPA-IDT-H</b>. The relative synthetic costs of the two HTMs, <b>TPA-IDT-OMe</b> and <b>TPA-IDT-H,</b> are about one-seventh and one-fifth times cheaper, respectively, compared to the commercially available spiro-OMeTAD. Both the symmetrical D-A-D type HTMs presented good thermal stability, remarkable photophysical and electrochemical properties, along with down-shifted HOMO energy levels, extended π-conjugation, and enhanced π-π stacking in the film state. Moreover, the methoxy group-bearing <b>TPA-IDT-OMe</b> exhibited superior hole extraction and hole mobilities with negligible bimolecular recombination at the perovskite/HTM interfaces due to the suitable band alignment with the perovskite energy levels, a more planar conjugated backbone, and improved intermolecular π-π stacking in the film state, which led to better interaction with the perovskite layer. As a result, the PSCs from dopant-free <b>TPA-IDT-OMe</b> yielded an impressive power conversion efficiency (PCE) value of 30.19%, with high open-circuit voltage (<i>V</i><sub>oc</sub>), short-circuit current density (<i>J</i><sub>sc</sub>) and fill factor (FF) values of 0.89 V, 157.30 μA/cm<sup>2</sup>, and 70.30%, respectively, under indoor light illumination (1000 lx, 321.6 μW/cm<sup>2</sup>) which is comparable to the PCE value of the doped spiro-OMeTAD-based devices. Moreover, <b>TPA-IDT-OMe</b> showed remarkable UV stability after 240 h of aging and admissible moisture stability with relative humidity (RH) of (40% ± 5%) at room temperature due to its greater hydrophobicity compared to <b>TPA-IDT-H</b> and the reference spiro-OMeTAD. The poor solubility of <b>TPA-IDT-H</b> illustrates its poor film formation ability, which results in greater bimolecular and trap-assisted recombination and lower hole mobility, leading to a lower PCE value of 27.08% for the undoped <b>TPA-IDT-H</b>-based PSCs. This finding opens a new path to design low-light responsive D-A-D architecture-based small molecular HTMs for efficient and stable indoor perovskite solar cells.</p>\",\"PeriodicalId\":35,\"journal\":{\"name\":\"Energy & Fuels\",\"volume\":\"39 21\",\"pages\":\"10021–10030 10021–10030\"},\"PeriodicalIF\":5.3000,\"publicationDate\":\"2025-05-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy & Fuels\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.energyfuels.5c00946\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENERGY & FUELS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy & Fuels","FirstCategoryId":"5","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.energyfuels.5c00946","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENERGY & FUELS","Score":null,"Total":0}
Indacenodithiophene-4,9-dione-Based D-A-D Type Dopant-Free Hole Transporting Materials for Environmentally Robust 30% Efficient Indoor Perovskite Solar Cells
To develop low-light responsive materials for perovskite solar cells (PSCs), for the first time, we synthesized s-indaceno[1,2-b:5,6-b’]-dithiophene-4,9-dione core acceptor linked 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline and N,N-diphenylaniline end-cap donors based on symmetrical donor–acceptor–donor (D-A-D) type two hole-transporting materials (HTMs), TPA-IDT-OMe and TPA-IDT-H. The relative synthetic costs of the two HTMs, TPA-IDT-OMe and TPA-IDT-H, are about one-seventh and one-fifth times cheaper, respectively, compared to the commercially available spiro-OMeTAD. Both the symmetrical D-A-D type HTMs presented good thermal stability, remarkable photophysical and electrochemical properties, along with down-shifted HOMO energy levels, extended π-conjugation, and enhanced π-π stacking in the film state. Moreover, the methoxy group-bearing TPA-IDT-OMe exhibited superior hole extraction and hole mobilities with negligible bimolecular recombination at the perovskite/HTM interfaces due to the suitable band alignment with the perovskite energy levels, a more planar conjugated backbone, and improved intermolecular π-π stacking in the film state, which led to better interaction with the perovskite layer. As a result, the PSCs from dopant-free TPA-IDT-OMe yielded an impressive power conversion efficiency (PCE) value of 30.19%, with high open-circuit voltage (Voc), short-circuit current density (Jsc) and fill factor (FF) values of 0.89 V, 157.30 μA/cm2, and 70.30%, respectively, under indoor light illumination (1000 lx, 321.6 μW/cm2) which is comparable to the PCE value of the doped spiro-OMeTAD-based devices. Moreover, TPA-IDT-OMe showed remarkable UV stability after 240 h of aging and admissible moisture stability with relative humidity (RH) of (40% ± 5%) at room temperature due to its greater hydrophobicity compared to TPA-IDT-H and the reference spiro-OMeTAD. The poor solubility of TPA-IDT-H illustrates its poor film formation ability, which results in greater bimolecular and trap-assisted recombination and lower hole mobility, leading to a lower PCE value of 27.08% for the undoped TPA-IDT-H-based PSCs. This finding opens a new path to design low-light responsive D-A-D architecture-based small molecular HTMs for efficient and stable indoor perovskite solar cells.
期刊介绍:
Energy & Fuels publishes reports of research in the technical area defined by the intersection of the disciplines of chemistry and chemical engineering and the application domain of non-nuclear energy and fuels. This includes research directed at the formation of, exploration for, and production of fossil fuels and biomass; the properties and structure or molecular composition of both raw fuels and refined products; the chemistry involved in the processing and utilization of fuels; fuel cells and their applications; and the analytical and instrumental techniques used in investigations of the foregoing areas.