Cho Junsang, Mathew Preethi S, DuBose Jeffrey T, Kamat Prashant V
Radiation Laboratory, University of Notre Dame, Notre Dame, IN, 46556, USA.
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN, 46556, USA.
Adv Mater. 2021 Dec;33(48):e2105585. doi: 10.1002/adma.202105585. Epub 2021 Oct 7.
2D lead halide perovskites, which exhibit bandgap tunability and increased chemical stability, have been found to be useful for designing optoelectronic devices. Reducing dimensionality with decreasing number of layers (n = 10-1) also imparts resistance to light-induced ion migration as seen from the halide ion segregation and dark recovery in mixed halide (Br:I = 50:50) perovskite films. The light-induced halide ion segregation efficiency, as determined from difference absorbance spectra, decreases from 20% to <1% as the dimensionality is decreased for 2D perovskite film from n = 10 to 1. The segregation rate constant (k ), which decreases from 5.9 × 10 s (n = 10) to 3.6 × 10 s (n = 1), correlates well with nearly an order of magnitude decrease observed in charge-carrier lifetime (τ = 233 ps for n = 10 vs τ = 27 ps for n = 1). The tightly bound excitons in 2D perovskites make charge separation less probable, which in turn decreases the halide mobility and resulting phase segregation. The importance of controlling the dimensionality of the 2D architecture in suppressing halide ion mobility is discussed.
二维卤化铅钙钛矿具有带隙可调性和更高的化学稳定性,已被发现可用于设计光电器件。随着层数减少(n = 10 - 1)降低维度,从混合卤化物(Br:I = 50:50)钙钛矿薄膜中的卤离子偏析和暗恢复情况来看,还赋予了对光致离子迁移的抗性。根据差分吸收光谱确定的光致卤离子偏析效率,随着二维钙钛矿薄膜维度从n = 10降低到1,从20%降至<1%。偏析速率常数(k)从5.9×10⁻⁴ s⁻¹(n = 10)降至3.6×10⁻⁵ s⁻¹(n = 1),与载流子寿命中观察到的近一个数量级的降低密切相关(n = 10时τ = 233 ps,n = 1时τ = 27 ps)。二维钙钛矿中紧密束缚的激子使电荷分离的可能性降低,这反过来又降低了卤离子迁移率和由此产生的相偏析。本文讨论了控制二维结构维度在抑制卤离子迁移率方面的重要性。