Replacing lead iodide(PbI_(2))with suitable non-halides lead source has been found to be an effective method to control crystallization and fabricate high-performance perovskite solar cells(PSCs).However,the solubilit...Replacing lead iodide(PbI_(2))with suitable non-halides lead source has been found to be an effective method to control crystallization and fabricate high-performance perovskite solar cells(PSCs).However,the solubility of non-halide lead sources is highly limited by traditional solvents due to the chemical interaction limitation.Here,we report a series of non-halide lead sources(e.g.,lead acetate(PbAc_(2)),lead sulfate(PbSO_(4)),lead carbonate(PbCO_(3)),lead nitrate(Pb(NO_(3))_(2)),lead formate(Pb(HCOO)_(2))and lead oxalate(PbC_(2)O_(4)))can be well dissolved in an ionic liquid solvent methylammonium acetate(MAAc).We found that the universal strong coordination of C=O with lead ion(Pb^(2+))and the formation of hydrogen bonds were observed in perovskite precursor solution.This allows the dissolution of non-halide lead salts and is able to produce perovskite film with smooth,compact,and full coverage crystal grain.The power conversion efficiency(PCE)of 14.48%,19.21%,and 20.13%in PSCs based on PbSO_(4),PbAc_(2),and PbCO_(3) was achieved,respectively,in the absence of any additives and passivation agents.This study demonstrates the universality of ionic liquid for the preparation of PSCs based on nonhalides lead sources.展开更多
Constructing low-dimensional/three-dimensional(LD/3D)perovskite heterostructures through post-treatment of 3D perovskites is an effective strategy for passivating surface defects in perovskite solar cells.Organic ammo...Constructing low-dimensional/three-dimensional(LD/3D)perovskite heterostructures through post-treatment of 3D perovskites is an effective strategy for passivating surface defects in perovskite solar cells.Organic ammonium halide salts are among the most widely used materials for converting the surface layer of 3D perovskite to LD perovskite via cation exchange.However,the formed LD perovskites typically adopt an in-plane orientation and exhibit high exciton binding energy,which can adversely impact interfacial charge transport and reduce the effectiveness of molecular defect passivation.Herein,we design and synthesize a non-halide ammonium salt of 1-naphthylmethylammonium tetrafluoroborate(NMABF4)to inhibit the transformation reaction,enabling surface termination of perovskite films with functional molecules.The use of a relatively large cation enhances the barrier of cation exchange between ammonium salt and 3D perovskite.Moreover,the non-halide anion with a strong interaction with Pb2+is introduced to prevent the formation of Pb-I octahedra,thereby preventing the formation of 2D perovskite.Therefore,NMABF4 effectively terminates the perovskite surface.This approach not only simultaneously passivates defects with opposing charges on the perovskite surface but also prevents potential drawbacks associated with heterostructure-induced intercalation.As a result,a champion device efficiency of 25.38%can be achieved using NMABF4-terminated perovskite,compared to 23.52%for the control device.Moreover,the unencapsulated device demonstrates excellent operational stability,retaining 80%of its initial efficiency after 2001 h of aging at the maximum power point under continuous one-sun illumination.展开更多
Organic–inorganic metal halide perovskites have attained extensive attention owing to their outstanding photovoltaic performances,but the existence of numerous defects in crystalline perovskites is still a serious co...Organic–inorganic metal halide perovskites have attained extensive attention owing to their outstanding photovoltaic performances,but the existence of numerous defects in crystalline perovskites is still a serious constraint for the further development of perovskite solar cells(PSCs).In particular,the rapid crystallization guided by anti-solvents leads to plenty of surficial and interfacial defects in perovskite films.Herein,we report the adoption of a pseudo-halide anion based ionic liquid additive,1-butyl-3-methylimidazolium thiocyanate(BMIMSCN)for growing ternary cation(CsFAMA,where FA=formamidinium and MA=methylammonium)perovskites with large-scale crystal grains and strong preferential orientation via the enhanced Ostwald ripening.Meanwhile,a novel halide-free passivator,benzylammonium formate(BAFa),was employed as a buffering layer on the perovskite films to suppress surface-dominated charge recombination.As a result,the cooperative effects of BMIMSCN additive and BAFa passivator lead to significant enhancements on fluorescence lifetime(from 79.41 to 201.01 ns),open-circuit voltage(from 1.13 to 1.19 V),photoelectric conversion efficiency(from 18.90%to 22.33%).Moreover,the BMIMSCN/BAFa-CsFAMA PSCs demonstrated greatly improved stability against moisture and heat.This work suggests a promising strategy to improve the quality of perovskite materials via reducing the surficial and interfacial defects by the synergistic effects of lattice doping and interface engineering.展开更多
基金the Natural Science Foundation of China(51972172,91833304,91733302)the Natural Science Foundation of Jiangsu Province for Distinguished Young Scholars,China(BK20200034)+3 种基金the Natural Science Basic Research Plan in Shaanxi Province of China(2021JLM-43)the Joint Research Funds of Department of Science&Technology of Shaanxi Province and Northwestern Polytechnical University(2020GXLH-Z-007,2020GXLH-Z-014)the Projects of International Cooperation and Exchanges NSFC(51811530018)the Young 1000 Talents Global Recruitment Program of China。
文摘Replacing lead iodide(PbI_(2))with suitable non-halides lead source has been found to be an effective method to control crystallization and fabricate high-performance perovskite solar cells(PSCs).However,the solubility of non-halide lead sources is highly limited by traditional solvents due to the chemical interaction limitation.Here,we report a series of non-halide lead sources(e.g.,lead acetate(PbAc_(2)),lead sulfate(PbSO_(4)),lead carbonate(PbCO_(3)),lead nitrate(Pb(NO_(3))_(2)),lead formate(Pb(HCOO)_(2))and lead oxalate(PbC_(2)O_(4)))can be well dissolved in an ionic liquid solvent methylammonium acetate(MAAc).We found that the universal strong coordination of C=O with lead ion(Pb^(2+))and the formation of hydrogen bonds were observed in perovskite precursor solution.This allows the dissolution of non-halide lead salts and is able to produce perovskite film with smooth,compact,and full coverage crystal grain.The power conversion efficiency(PCE)of 14.48%,19.21%,and 20.13%in PSCs based on PbSO_(4),PbAc_(2),and PbCO_(3) was achieved,respectively,in the absence of any additives and passivation agents.This study demonstrates the universality of ionic liquid for the preparation of PSCs based on nonhalides lead sources.
基金supported by the National Natural Science Foundation of China(Nos.22479054,22179042,and U21A2078)the Natural Science Foundation of Fujian Province(No.2023J06034)the FuXiaQuan Self-created Zone Collaborative Project(No.3502ZCQXT2023006).
文摘Constructing low-dimensional/three-dimensional(LD/3D)perovskite heterostructures through post-treatment of 3D perovskites is an effective strategy for passivating surface defects in perovskite solar cells.Organic ammonium halide salts are among the most widely used materials for converting the surface layer of 3D perovskite to LD perovskite via cation exchange.However,the formed LD perovskites typically adopt an in-plane orientation and exhibit high exciton binding energy,which can adversely impact interfacial charge transport and reduce the effectiveness of molecular defect passivation.Herein,we design and synthesize a non-halide ammonium salt of 1-naphthylmethylammonium tetrafluoroborate(NMABF4)to inhibit the transformation reaction,enabling surface termination of perovskite films with functional molecules.The use of a relatively large cation enhances the barrier of cation exchange between ammonium salt and 3D perovskite.Moreover,the non-halide anion with a strong interaction with Pb2+is introduced to prevent the formation of Pb-I octahedra,thereby preventing the formation of 2D perovskite.Therefore,NMABF4 effectively terminates the perovskite surface.This approach not only simultaneously passivates defects with opposing charges on the perovskite surface but also prevents potential drawbacks associated with heterostructure-induced intercalation.As a result,a champion device efficiency of 25.38%can be achieved using NMABF4-terminated perovskite,compared to 23.52%for the control device.Moreover,the unencapsulated device demonstrates excellent operational stability,retaining 80%of its initial efficiency after 2001 h of aging at the maximum power point under continuous one-sun illumination.
基金the National Key R&D Program of China(No.2017YFA0208200)the National Natural Science Foundation of China(Nos.22022505,21872069,and 22109069)+3 种基金the Fundamental Research Funds for the Central Universities of China(Nos.020514380266,020514380272,and 020514380274)the Scientific and Technological Innovation Special Fund for Carbon Peak and Carbon Neutrality of Jiangsu Province(BK20220008)the Nanjing International Collaboration Research Program(Nos.202201007 and 2022SX00000955)the Suzhou Gusu Leading Talent Program of Science and Technology Innovation and Entrepreneurship in Wujiang District(No.ZXL2021273).
文摘Organic–inorganic metal halide perovskites have attained extensive attention owing to their outstanding photovoltaic performances,but the existence of numerous defects in crystalline perovskites is still a serious constraint for the further development of perovskite solar cells(PSCs).In particular,the rapid crystallization guided by anti-solvents leads to plenty of surficial and interfacial defects in perovskite films.Herein,we report the adoption of a pseudo-halide anion based ionic liquid additive,1-butyl-3-methylimidazolium thiocyanate(BMIMSCN)for growing ternary cation(CsFAMA,where FA=formamidinium and MA=methylammonium)perovskites with large-scale crystal grains and strong preferential orientation via the enhanced Ostwald ripening.Meanwhile,a novel halide-free passivator,benzylammonium formate(BAFa),was employed as a buffering layer on the perovskite films to suppress surface-dominated charge recombination.As a result,the cooperative effects of BMIMSCN additive and BAFa passivator lead to significant enhancements on fluorescence lifetime(from 79.41 to 201.01 ns),open-circuit voltage(from 1.13 to 1.19 V),photoelectric conversion efficiency(from 18.90%to 22.33%).Moreover,the BMIMSCN/BAFa-CsFAMA PSCs demonstrated greatly improved stability against moisture and heat.This work suggests a promising strategy to improve the quality of perovskite materials via reducing the surficial and interfacial defects by the synergistic effects of lattice doping and interface engineering.
