论文标题

混合壁性钙钛矿的热力学稳定相对于相隔离

Thermodynamic stabilization of mixed-halide perovskites against phase segregation

论文作者

Hutter, Eline M., Muscarella, Loreta A., Wittmann, Francesca, Versluis, Jan, McGovern, Lucie, Bakker, Huib J., Woo, Young-Won, Jung, Young-Kwang, Walsh, Aron, Ehrler, Bruno

论文摘要

在卤化物钙钛矿半导体中将碘化物和溴化物混合是调整带隙的有效策略,因此混合壁式钙钛矿对可调色的LED和串联太阳能电池具有很大的希望。然而,在(太阳)的光线下,混合壁孔孔的带隙是不稳定的,因为卤化物将隔离为不同带盖的域。使用压力依赖性的超快瞬态吸收光谱,我们表明高外部压力增加了热力学稳定的卤化物混合比的范围。化学压力通过插入较小的阳离子具有相同的作用,这意味着任何碘与溴比的比率都可以通过调整晶体体积和可压缩性来热力学地稳定。我们通过在很大程度上被忽视的pdeltav项改变了Helmholtz自由能的改变来解释这种稳定。

Mixing iodide and bromide in halide perovskite semiconductors is an effective strategy to tune their bandgap, therefore mixed-halide perovskites hold great promise for color-tunable LEDs and tandem solar cells. However, the bandgap of mixed-halide perovskites is unstable under (sun-)light, since the halides segregate into domains of different bandgaps. Using pressure-dependent ultrafast transient absorption spectroscopy, we show that high external pressure increases the range of thermodynamically stable halide mixing ratios. Chemical pressure, by inserting a smaller cation, has the same effect, which means that any iodide-to-bromide ratio can be thermodynamically stabilized by tuning the crystal volume and compressibility. We interpret this stabilization by an alteration of the Helmholtz free energy via the largely overlooked PdeltaV term.

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