Zeeshan Abid, Waqas Akram, Raymundo Marcial-Hernandez, Dilara Gunturkun, Munazza Shahid, Muhammad Altaf, Jie Min, Jafar Iqbal Khan, Javed Iqbal, Shahid Rasul*, Christian B. Nielsen* and Raja Shahid Ashraf*,
{"title":"无铅钙钛矿太阳能电池空穴传输材料的策略设计、合成和计算表征","authors":"Zeeshan Abid, Waqas Akram, Raymundo Marcial-Hernandez, Dilara Gunturkun, Munazza Shahid, Muhammad Altaf, Jie Min, Jafar Iqbal Khan, Javed Iqbal, Shahid Rasul*, Christian B. Nielsen* and Raja Shahid Ashraf*, ","doi":"10.1021/acssuschemeng.4c0741510.1021/acssuschemeng.4c07415","DOIUrl":null,"url":null,"abstract":"<p >Lead-free perovskites based on nontoxic titanium(IV) are promising candidates for photovoltaic applications due to their improved intrinsic/environmental stability compared to the lead analogues in metal halide perovskite solar cells (PSCs). However, their yet lower power conversion efficiencies (PCEs) predominantly owing to a lack of compatible charge transport layers limit their commercial viability. Here, we synthesized and characterized two series of hole-transporting materials (HTMs) based on fluorene and benzothiadiazole cores functionalized with halogen-substituted indoloquinoxaline arms. Employing experimental and first-principles density functional theory calculations, the structure–property relationships and electrochemical, optical, and charge transport characteristics of these HTMs were examined. The synthesized HTMs showed low-lying highest occupied molecular orbital (HOMO) energy levels at −5.73 to −6.04 eV having ideal band alignment with the cesium titanium(IV) bromide (Cs<sub>2</sub>TiBr<sub>6</sub>) perovskite material. The HTMs exhibited minimal absorption in the visible region (λ<sub>max</sub><sup>abs</sup> ≤ 422 nm) with negligible overlap with the photoactive perovskite absorber Cs<sub>2</sub>TiBr<sub>6</sub>. Computational analysis further revealed the HTMs’ ability to possess high charge separation and transfer potential, characterized by high charge hopping rates, robust mobility, and lower exciton binding energy compared to benchmark Spiro-OMeTAD. Photovoltaic device simulations using SCAPS-1D software projected promising performance for PSCs incorporating these HTMs, with open-circuit voltage (<i>V</i><sub>OC</sub>) ranging between 1.29 and 1.32 V and predicted PCE surpassing 18%. The study introduces a new class of HTM candidates with low-lying HOMOs and tailored electronic properties, presenting a compelling alternative to Spiro-OMeTAD for lead-free PSCs.</p><p >This study presents new hole transport materials to enhance the performance and stability of lead-free perovskite solar cells for sustainable energy.</p>","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 2","pages":"867–880 867–880"},"PeriodicalIF":7.3000,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acssuschemeng.4c07415","citationCount":"0","resultStr":"{\"title\":\"Strategic Design, Synthesis, and Computational Characterization of Hole Transport Materials for Lead-Free Perovskite Solar Cells\",\"authors\":\"Zeeshan Abid, Waqas Akram, Raymundo Marcial-Hernandez, Dilara Gunturkun, Munazza Shahid, Muhammad Altaf, Jie Min, Jafar Iqbal Khan, Javed Iqbal, Shahid Rasul*, Christian B. Nielsen* and Raja Shahid Ashraf*, \",\"doi\":\"10.1021/acssuschemeng.4c0741510.1021/acssuschemeng.4c07415\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Lead-free perovskites based on nontoxic titanium(IV) are promising candidates for photovoltaic applications due to their improved intrinsic/environmental stability compared to the lead analogues in metal halide perovskite solar cells (PSCs). However, their yet lower power conversion efficiencies (PCEs) predominantly owing to a lack of compatible charge transport layers limit their commercial viability. Here, we synthesized and characterized two series of hole-transporting materials (HTMs) based on fluorene and benzothiadiazole cores functionalized with halogen-substituted indoloquinoxaline arms. Employing experimental and first-principles density functional theory calculations, the structure–property relationships and electrochemical, optical, and charge transport characteristics of these HTMs were examined. The synthesized HTMs showed low-lying highest occupied molecular orbital (HOMO) energy levels at −5.73 to −6.04 eV having ideal band alignment with the cesium titanium(IV) bromide (Cs<sub>2</sub>TiBr<sub>6</sub>) perovskite material. The HTMs exhibited minimal absorption in the visible region (λ<sub>max</sub><sup>abs</sup> ≤ 422 nm) with negligible overlap with the photoactive perovskite absorber Cs<sub>2</sub>TiBr<sub>6</sub>. Computational analysis further revealed the HTMs’ ability to possess high charge separation and transfer potential, characterized by high charge hopping rates, robust mobility, and lower exciton binding energy compared to benchmark Spiro-OMeTAD. Photovoltaic device simulations using SCAPS-1D software projected promising performance for PSCs incorporating these HTMs, with open-circuit voltage (<i>V</i><sub>OC</sub>) ranging between 1.29 and 1.32 V and predicted PCE surpassing 18%. The study introduces a new class of HTM candidates with low-lying HOMOs and tailored electronic properties, presenting a compelling alternative to Spiro-OMeTAD for lead-free PSCs.</p><p >This study presents new hole transport materials to enhance the performance and stability of lead-free perovskite solar cells for sustainable energy.</p>\",\"PeriodicalId\":25,\"journal\":{\"name\":\"ACS Sustainable Chemistry & Engineering\",\"volume\":\"13 2\",\"pages\":\"867–880 867–880\"},\"PeriodicalIF\":7.3000,\"publicationDate\":\"2025-01-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acssuschemeng.4c07415\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Sustainable Chemistry & Engineering\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acssuschemeng.4c07415\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Sustainable Chemistry & Engineering","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acssuschemeng.4c07415","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Strategic Design, Synthesis, and Computational Characterization of Hole Transport Materials for Lead-Free Perovskite Solar Cells
Lead-free perovskites based on nontoxic titanium(IV) are promising candidates for photovoltaic applications due to their improved intrinsic/environmental stability compared to the lead analogues in metal halide perovskite solar cells (PSCs). However, their yet lower power conversion efficiencies (PCEs) predominantly owing to a lack of compatible charge transport layers limit their commercial viability. Here, we synthesized and characterized two series of hole-transporting materials (HTMs) based on fluorene and benzothiadiazole cores functionalized with halogen-substituted indoloquinoxaline arms. Employing experimental and first-principles density functional theory calculations, the structure–property relationships and electrochemical, optical, and charge transport characteristics of these HTMs were examined. The synthesized HTMs showed low-lying highest occupied molecular orbital (HOMO) energy levels at −5.73 to −6.04 eV having ideal band alignment with the cesium titanium(IV) bromide (Cs2TiBr6) perovskite material. The HTMs exhibited minimal absorption in the visible region (λmaxabs ≤ 422 nm) with negligible overlap with the photoactive perovskite absorber Cs2TiBr6. Computational analysis further revealed the HTMs’ ability to possess high charge separation and transfer potential, characterized by high charge hopping rates, robust mobility, and lower exciton binding energy compared to benchmark Spiro-OMeTAD. Photovoltaic device simulations using SCAPS-1D software projected promising performance for PSCs incorporating these HTMs, with open-circuit voltage (VOC) ranging between 1.29 and 1.32 V and predicted PCE surpassing 18%. The study introduces a new class of HTM candidates with low-lying HOMOs and tailored electronic properties, presenting a compelling alternative to Spiro-OMeTAD for lead-free PSCs.
This study presents new hole transport materials to enhance the performance and stability of lead-free perovskite solar cells for sustainable energy.
期刊介绍：
ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment.
The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
