碘化物
钙钛矿(结构)
密度泛函理论
材料科学
带隙
微晶
氯化铅
卤化物
无机化学
氯化物
化学
分析化学(期刊)
结晶学
计算化学
有机化学
冶金
光电子学
作者
Subham Dastidar,David Egger,Liang Z. Tan,Samuel B. Cromer,Andrew D. Dillon,Shi Liu,Leeor Kronik,Andrew M. Rappe,Aaron T. Fafarman
出处
期刊:Nano Letters
[American Chemical Society]
日期:2016-05-13
卷期号:16 (6): 3563-3570
被引量:245
标识
DOI:10.1021/acs.nanolett.6b00635
摘要
Cesium lead iodide possesses an excellent combination of band gap and absorption coefficient for photovoltaic applications in its perovskite phase. However, this is not its equilibrium structure under ambient conditions. In air, at ambient temperature it rapidly transforms to a nonfunctional, so-called yellow phase. Here we show that chloride doping, particularly at levels near the solubility limit for chloride in a cesium lead iodide host, provides a new approach to stabilizing the functional perovskite phase. In order to achieve high doping levels, we first co-deposit colloidal nanocrystals of pure cesium lead chloride and cesium lead iodide, thereby ensuring nanometer-scale mixing even at compositions that potentially exceed the bulk miscibility of the two phases. The resulting nanocrystal solid is subsequently fused into a polycrystalline thin film by chemically induced, room-temperature sintering. Spectroscopy and X-ray diffraction indicate that the chloride is further dispersed during sintering and a polycrystalline mixed phase is formed. Using density functional theory (DFT) methods in conjunction with nudged elastic band techniques, low-energy pathways for interstitial chlorine diffusion into a majority-iodide lattice were identified, consistent with the facile diffusion and fast halide exchange reactions observed. By comparison to DFT-calculated values (with the PBE exchange-correlation functional), the relative change in band gap and the lattice contraction are shown to be consistent with a Cl/I ratio of a few percent in the mixed phase. At these incorporation levels, the half-life of the functional perovskite phase in a humid atmosphere increases by more than an order of magnitude.
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