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

[1]	STRANKS S D, EPERON G E, GRANCINI G, et al. Electron- hole diffusion lengths exceeding trihalide perovskite absorber. Science, 2013, 342(6156): 341-344. DOI URL
[2]	HEO J H, IM S H, NOH J H, et al. Efficient inorganic-organic hybrid heterojunction solar cells containing perovskite compound and polymeric hole conductors. Nature Photonics, 2013, 7: 486-491. DOI URL
[3]	SHAO Y, XIAO Z, BI C, et al. Origin and elimination of photocurrent hysteresis by fullerene passivation in CH₃NH₃PbI₃ planar heterojunction solar cells. Nature Communications, 2014, 5: 5784. DOI URL
[4]	XING G, MATHEWS N, LIM S S, et al. Long-range balanced electron- and hole-transport lengths in organic-inorganic CH₃NH₃PbI₃. Science, 2013, 342(6156): 344-347. DOI URL
[5]	TAN Z K, MOGHADDAM R S, LAI M L, et al. Bright light- emitting diodes based on organometal halide perovskite. Nature Nanotechnology, 2014, 9: 687-692. DOI URL
[6]	GAO L, ZENG K, GUO J, et al. Passivated single-crystalline CH₃NH₃PbI₃ nanowire photodetector with high detectivity and polarization sensitivity. Nano Letters, 2016, 16(12): 7446-7454. DOI URL
[7]	HAO F, STOUMPOS C C, CAO D H, et al. Lead-free solid-state organic-inorganic halide perovskite solar cells. Nature Photonics, 2014, 8: 489-494. DOI URL
[8]	STOUMPOS C C, MALLIAKAS C D, KANATZIDIS M G. Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. Inorganic Chemistry, 2013, 52(15): 9019-9038. DOI URL
[9]	NOEL N K, STRANKS S D, ABATE A, et al. Lead-free organic- inorganic tin halide perovskites for photovoltaic applications. Energy and Environmental Science, 2014, 7(9): 3061-3068. DOI URL
[10]	CHUNG I, LEE B, HE J, et al. All-solid-state dye-sensitized solar cells with high efficiency. Nature, 2012, 485: 486-489. DOI URL
[11]	KUMAR M H, DHARANI S, LEONG W L, et al. Lead-free halide perovskite solar cells with high photocurrents realized through vacancy modulation. Advanced Materials, 2014, 26(41): 7122-7127. DOI URL
[12]	MARSHALL K P, WALKER M, WALTON R I, et al. Enhanced stability and efficiency in hole-transport-layer-free CsSnI₃ perovskite photovoltaics. Nature Energy, 2016, 1: 16178. DOI URL
[13]	CHUNG I, SONG J H, IM J, et al. CsSnI₃: semiconductor or metal? high electrical conductivity and strong near-infrared photoluminescence from a single material. high hole mobility and phase-transitions. Journal of the American Chemical Society, 2012, 134(20): 8579-8587. DOI URL
[14]	LEE B, STOUMPOS C C, ZHOU N, et al. Air-stable molecular semiconducting iodosalts for solar cell applications: Cs₂SnI₆ as a hole conductor. Journal of the American Chemical Society, 2014, 136(43): 15379-15385. DOI URL
[15]	SAPAROV B, SUN J P, MENG W, et al. Thin-film deposition and characterization of a Sn-deficient perovskite derivative Cs₂SnI₆. Chemistry of Materials, 2016, 28(7): 2315-2322. DOI URL
[16]	QIU X, CAO B, YUAN S, et al. From unstable CsSnI₃ to air-stable Cs₂SnI₆: a lead-free perovskite solar cell light absorber with bandgap of 1.48 eV and high absorption coefficient. Solar Energy Materials and Solar Cells, 2017, 159: 227-234. DOI URL
[17]	WANG X D, HUANG Y H, LIAO J F, et al. In situ construction of a Cs₂SnI₆ perovskite nanocrystal/SnS₂ nanosheet heterojunction with boosted interfacial charge transfer. Journal of the American Chemical Society, 2019, 141(34): 13434-13441. DOI URL
[18]	LIU F, DING C, ZHANG Y, et al. Colloidal synthesis of air-stable alloyed CsSn_1-_xPbxI₃ perovskite nanocrystals for use in solar cells. Journal of the American Chemical Society, 2017, 139(46): 16708-16719. DOI URL
[19]	DOLZHNIKOV D S, WANG C, XU Y, et al. Ligand-free, quantum- confined Cs₂SnI₆ perovskite nanocrystals. Chemistry of Materials, 2017, 29(18): 7901-7907. DOI URL
[20]	MAUGHAN A E, GANOSE A M, BORDELON M M, et al. Defect tolerance to intolerance in the vacancy-ordered double perovskite semiconductors Cs₂SnI₆ and Cs₂TeI₆. Journal of the American Chemical Society, 2016, 138(27): 8453-8464. DOI URL
[21]	XIAO Z, ZHOU Y, HOSONO H, et al. Intrinsic defects in a photovoltaic perovskite variant Cs₂SnI₆. Physical Chemistry Chemical Physics, 2015, 17(29): 18900-18903. DOI URL
[22]	KAPIL G, OHTA T, KOYANAGI T, et al. Investigation of interfacial charge transfer in solution processed Cs₂SnI₆ thin films. Journal of Physical Chemistry C, 2017, 121(24): 13092-13100. DOI URL
[23]	SHIN H O, KIM B M, JANG T, et al. Surface state-mediated charge transfer of Cs₂SnI₆ and its application in dye-sensitized solar cells. Advanced Energy Materials, 2019, 9(3): 1803243.
[24]	XU Y, LI S, ZHANG Z, et al. Ligand-mediated synthesis of colloidal Cs₂SnI₆ three-dimensional nanocrystals and two-dimensional nanoplatelets. Nanotechnology, 2019, 30(29): 295601.
[25]	ZHU W, SHEN J, LI M, et al. Kinetically controlled growth of sub-millimeter 2D Cs₂SnI₆ nanosheets at the liquid-liquid interface. Small, 2021, 17(4): 2006279.
[26]	LUO R, ZHANG S, ZHAO S, et al. Ultrasmall blueshift of near-infrared fluorescence in phase-stable Cs₂SnI₆ thin films. Physical Review Applied, 2020, 14(1): 014048. DOI URL
[27]	ZHOU P, CHEN H, CHAO Y, et al. Single-atom Pt-I₃ sites on all-inorganic Cs₂SnI₆ perovskite for efficient photocatalytic hydrogen production. Nature Communications, 2021, 12: 4412. DOI URL
[28]	ULLAH S, ULLAH S, WANG J, et al. Investigation of air-stable Cs₂SnI₆ films prepared by the modified two-step process for lead-free perovskite solar cells. Semiconductor Science and Technology, 2020, 35: 125027. DOI URL
[29]	KRESSE G, FURTHMÜLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B, 1996, 54(16): 11169-11186. DOI URL
[30]	KRESSE G, JOUBERT D. From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 1999, 59(3): 1758-1775. DOI URL
[31]	PENG H, YANG Z H, PERDEW J P, et al. Versatile van der Waals density functional based on a meta-generalized gradient approximation. Physical Review X, 2016, 6(4): 041005. DOI URL
[32]	XIAO Z, LEI H, ZHANG X, et al. Ligand-hole in [SnI₆] unit and origin of band gap in photovoltaic perovskite variant Cs₂SnI₆. Bulletin of the Chemical Society of Japan, 2015, 88(9): 1250-1255. DOI URL
[33]	ZHANG S B, NORTHRUP J E. Chemical potential dependence of defect formation energies in GaAs: application to Ga self-diffusion. Physical Review Letters, 1991, 67(17): 2339-2342. DOI URL
[34]	VAN DE WALLE C G, NEUGEBAUER J. First-principles calculations for defects and impurities: applications to III-nitrides. Journal of Applied Physics, 2004, 95(8): 3851-3879. DOI URL
[35]	CHEN H, DING Y H, YU H T, et al. First-principles investigation of the electronic properties and stabilities of the LaAlO₃ (001) and (110) (1 × 1) polar terminations. Journal of Physical Chemistry C, 2015, 119(17): 9364-9374. DOI URL
[36]	HUANG X, PAUDEL T R, DOWBEN P A, et al. Electronic structure and stability of the CH₃NH₃PbBr₃ (001) surface. Physical Review B, 2016, 94(19): 195309. DOI URL

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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