钴（Ⅱ/Ⅲ）共掺杂调控钙钛矿缺陷及器件稳定性

doi:10.6023/A26050166

摘要/Abstract

钙钛矿太阳电池可通过低成本溶液法制备,且光电性能优异,但薄膜成膜过程中易产生多种铅/碘基缺陷,引发深能级陷阱及离子迁移,导致非辐射复合与结构退化,严重制约器件效率和稳定性。针对现有钝化策略多集中于单一类型缺陷、难以实现铅/碘基缺陷协同钝化的问题,本研究选用FA_0.95Cs_0.05PbI₃钙钛矿体系,创新性地引入Co(acac)₂/Co(acac)₃作为体相掺杂剂,通过刮涂工艺制备薄膜与器件,系统探究了其对结晶动力学、缺陷化学、电荷传输与器件稳定性的综合影响。研究发现,Co³⁺通过氧化作用钝化Pb⁰缺陷,其乙酰丙酮配体同时与不饱和Pb²⁺配位,增强结构整合;Co²⁺则与碘空位及活性碘物种相互作用,有效抑制碘迁移与挥发。二者在体系中同步调控铅、碘相关缺陷态。在摩尔分数为0.1%的掺杂浓度下,薄膜结晶质量显著提升,晶粒尺寸增大,缺陷密度降低;相应器件效率达19.52%,Jsc为25.07 mA·cm^-2,FF为76.36%。未封装器件在AM 1.5G持续光照400 h后效率保持率达82%,并在热老化与长期储存测试中表现出优越的稳定性。本工作发展了一种钙钛矿太阳电池体相铅碘缺陷同步钝化策略,为构建高效稳定钙钛矿太阳电池提供了新途径。

关键词: 钙钛矿太阳电池, 乙酰丙酮钴（Ⅱ/Ⅲ）, 缺陷钝化, 体相掺杂, 稳定性

Perovskite solar cells (PSCs) possess the advantages of low-cost solution processing and excellent optoelectronic properties. However, various lead- and iodine-related defects are inevitably generated during film formation, which induce deep-level trap states and accelerate ion migration, thereby aggravating non-radiative recombination and structural degradation.These drawbacks severely restrict the power conversion efficiency and long-term stability of PSCs.Most existing passivation strategies focus merely on a single type of defect and cannot realize the synergistic regulation of both lead- and iodine-based defects. To tackle this issue, the FA_0.95Cs_0.05PbI₃ perovskite system was selected, and Co(acac)₂/Co(acac)₃ was introduced as a bulk dopant. Perovskite films and devices were prepared by blade coating, and the influences of the Co(II/III) acetylacetonates on crystallization kinetics, defect chemistry, charge transport behavior and device durability were systematically explored.Co³⁺passivates zero-valent lead defects through oxidation, and its acetylacetonate ligands coordinate with undercoordinated Pb²⁺ to strengthen lattice structural integrity. Meanwhile, Co²⁺ interacts with iodine vacancies and active iodine species, efficiently inhibiting iodine migration and volatilization. The Co(II/III) acetylacetonates simultaneously modulate lead- and iodine-derived defect states.At an optimal molar fraction of 0.1%, the resulting perovskite film exhibits improved crystallinity, enlarged grain size and reduced defect density. The optimized device delivers a champion efficiency of 19.52%, with a J_sc of 25.07 mA·cm^-2 and an FF of 76.36%. Benefiting from the simultaneous modulation effect, the unencapsulated device maintains 82% of the original efficiency after 400 h of continuous AM 1.5G light irradiation, and presents superior resistance to thermal aging and long-term storage.This work develops a bulk lead-iodine defect synchronous passivation strategy for perovskite solar cells, offering a promising route for constructing high-efficiency and ultra-stable perovskite solar cells.

Key words: Perovskite solar cells, Co(II)/Co(III) acetylacetonate, defect passivation, bulk doping, stability

引用此文

唐景航, 张林, 徐文军, 杨英. 钴（Ⅱ/Ⅲ）共掺杂调控钙钛矿缺陷及器件稳定性[J]. 化学学报, doi: 10.6023/A26050166.

Tang Jinghang, Zhang Lin, Xu Wenjun, Yang Ying. Regulation of Perovskite Defects and Device Stability via Co (II/III) Co-Doping[J]. Acta Chimica Sinica, doi: 10.6023/A26050166.

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