Cs2SnI6低指数晶面稳定性的第一性原理计算研究

doi:10.15541/jim20210491

摘要/Abstract

摘要：

Cs₂SnI₆是一种稳定且环保的卤化物钙钛矿材料, 在光伏和光电应用方面具有巨大潜力。虽然表面性质对于光电器件的制备至关重要, 但目前尚没有对该材料开展相关的理论研究。利用密度泛函理论计算结合SCAN+rVV10泛函, 本工作研究了Cs₂SnI₆的(001)、(011)和(111)表面以揭示其热力学稳定性。针对每个表面, 研究考虑了具有不同截断的模型, 包括两个沿(001)方向(分别为CsI₂和SnI₄终止的表面), 两个沿(011)方向(分别为I₄和Cs₂SnI₂ 终止的表面)和三个沿(111)方向(分别为非化学计量比的CsI₃、Sn和满足化学计量比的CsI₃终止的表面)。由于大多数表面模型是非化学计量比的, 它们的相对稳定性取决于实验制备条件, 因此需要考虑组成元素的化学势。通过确定允许的化学势区域, 研究分析了这些表面的热力学稳定性。结果表明, (001)和 (011)面的表面能会受到化学势的影响, 而满足化学计量比的CsI₃终止的(111)表面不受化学势影响, 是Cs₂SnI₆最稳定的表面。该结果说明, 近期实验普遍观察到的暴露(111)面的晶体是受热力学稳定性驱动形成的。

关键词: 钙钛矿, 表面能, Cs₂SnI₆, 光伏材料, 发光材料

Abstract:

Cs₂SnI₆ is a stable and environmentally friendly halide perovskite material with great potential for photovoltaic and optoelectronic applications. While the surface properties are of paramount importance for device fabrications, there have been no such theoretical studies on this material. Using density functional theory calculations with the SCAN+rVV10 functional, the (001), (011) and (111) surfaces of Cs₂SnI₆were studied to reveal their thermodynamic stability. We constructed seven models for these surfaces, including two along the (001) orientation (CsI₂- and SnI₄-terminated surfaces), two along the (011) orientation (I₄- and Cs₂SnI₂-terminated surfaces) and three along the (111) orientation (non-stoichiometric CsI₃-, Sn- and stoichiometric CsI₃-terminated surfaces). Because most of the surfaces are non-stoichiometric, their relative stability depends on the experimental preparation condition, which is reflected by the chemical potentials of the constituent elements in the calculation. By determining the allowed chemical potential region, the thermodynamic stability of these Cs₂SnI₆ surfaces is analyzed. The results show that the surface energies of the (001) and (011) surfaces are affected by the chemical potentials, while the stoichiometric CsI₃-terminated (111) surface is unaffected by the chemical potentials and is energetically the most stable surface of Cs₂SnI₆. Thus, the observed exposure of (111) surface of Cs₂SnI₆ crystals in several recent experiments is determined to be driven by thermodynamics.

Key words: perovskite, surface energy, Cs₂SnI₆, photovoltaic material, luminescent material

中图分类号:

TQ174

林啊鸣, 孙宜阳. Cs₂SnI₆低指数晶面稳定性的第一性原理计算研究[J]. 无机材料学报, 2022, 37(6): 691-696.

LIN Aming, SUN Yiyang. Stability of Low-index Surfaces of Cs₂SnI₆ Studied by First-principles Calculations[J]. Journal of Inorganic Materials, 2022, 37(6): 691-696.

图/表 5

Fig. 1 (a) Atomic structure and (b) band structure and projected density of states (pDOS) of Cs2SnI6 Colorful figures are available on website

Fig. 2 Seven supercell models of Cs2SnI6 surfaces (a) For (001) surface: CsI2-terminated and SnI4-terminated slabs; (b) For (011) surface: I4-terminated and Cs2SnI2-terminated slabs; (c) For (111) surface: non-stoichiometric Sn-terminated, CsI3-terminated and stoichiometric CsI3-terminated slabs

Fig. 3 Calculated total cleavage, relaxation and surface energies of two complementary non-stoichiometric terminations in (001), (011) and (111) orientations, which are compared with the cleavage, relaxation and surface energies of the stoichiometric CsI3-terminated (111) surface

Fig. 4 Illustration of the accessible chemical potential region for Cs2SnI6 Constraints imposed by the formation of competing secondary phases resulting in the allowed region shaded in green

Fig. 5 Stability of low-index surfaces of Cs2SnI6 as a function of chemical potentials (a) Analysis of stability of the two terminations of Cs2SnI6 (001) surface with respect to the allowed region for maintaining equilibrium with the primary phase Cs2SnI6. The orange and blue regions indicate the stable region for CsI2- and SnI4-terminations, respectively; (b) Similar to (a) for the Cs2SnI6 (011) surface. The orange and blue regions are for the I4- and Cs2SnI2-terminations, respectively; (c) Similar to (a) for the Cs2SnI6 (111) surface. The orange and blue regions are for the Sn- and stoichiometric CsI3-terminations, respectively; (d) Surface energies of the seven surface models of Cs2SnI6 as a function of the chemical potentials colorful figures are available on website

参考文献 36

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Cs₂SnI₆低指数晶面稳定性的第一性原理计算研究

Stability of Low-index Surfaces of Cs₂SnI₆ Studied by First-principles Calculations

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