Mn、Sn掺杂无机钙钛矿CsPbI3非辐射复合的第一性原理计算

doi:10.19596/j.cnki.1001-246x.8738

摘要/Abstract

摘要：

采用密度泛函理论的第一性原理计算, 研究了Mn、Sn掺杂α-CsPbI₃体系的缺陷形成能、转变能级和载流子非辐射复合系数。研究发现: Mn掺入CsPbI₃会使体系的晶格常数明显减小, Sn掺杂体系晶格常数略有减小, 提高了材料的稳定性。两种体系的深能级缺陷均靠近导带, 主要从导带中俘获电子。Mn、Sn元素的掺杂改善了完美体系声子能量分布情况, 增强了材料的热输运能力。Sn掺杂体系空穴的非辐射复合系数远高于Mn掺杂体系, 且两种掺杂体系非辐射复合系数均高于含本征缺陷I_i和I_Cs的CsPbI₃, 因此杂质可能引入了非辐射复合中心。这些研究结果为Mn、Sn掺杂CsPbI₃体系在实验上提供了数据支持, 为CsPbI₃钙钛矿的掺杂改性提供了理论指导。

关键词: CsPbI₃钙钛矿, 第一性原理, 转变能级, 非辐射复合

Abstract:

The defect forming energy, transition level and carrier nonradiative recombination coefficient of Mn and Sn doped α-CsPbI₃ system are investigated by first-principles based on density functional theory. It is found that the lattice constant of Mn doped CsPbI₃ decreases obviously, while the lattice constant of Sn doped system decreases slightly, which improves the stability of the material. The deep level defects of both systems are close to conduction band and mainly capture electrons from conduction band. The doping of Mn and Sn elements improves the phonon energy distribution of the perfect system and enhances the heat transport capacity of the material. The nonradiative recombination coefficient of the holes in Sn doping system is much higher than that in Mn doping system and the nonradiative recombination coefficient of the two doping systems is higher than that of CsPbI₃ containing intrinsic defects I_i and I_Cs, so the impurity may introduce the nonradiative recombination center. These results provide data support for the experiment of Mn and Sn doped CsPbI₃ system, and provide a theoretical basis for the CsPbI₃ doping perovskite in experiments.

Key words: CsPbI₃ perovskite, first-principles, transition level, nonradiative recombination

中图分类号:

O469

张仁杰, 陶红帅. Mn、Sn掺杂无机钙钛矿CsPbI₃非辐射复合的第一性原理计算[J]. 计算物理, 2024, 41(4): 480-486.

Renjie ZHANG, Hongshuai TAO. Nonradiative Recombination for Mn and Sn Doped in Inorganic Perovskite CsPbI₃ by First-principles[J]. Chinese Journal of Computational Physics, 2024, 41(4): 480-486.

图/表 7

图1 α-CsPbI3 2×2×2超胞掺杂结构

Fig.1 α-CsPbI3 2×2×2 supercell doping structure

表1 PBE泛函优化后CsPbI3体系的晶格常数(nm)

Table 1 Lattice constants of CsPbI3 system after PBE functional optimization (nm)

Perovskite materials	Cs₈Pb₈I₂₄	Cs₈MnPb₇I₂₄	Cs₈SnPb₇I₂₄
GGA-PBE	1.276	1.263	1.273
Other Work	0.632^[38]	0.644^[40]	0.627^[41]
	0.640^[39]
Exp.	0.629^[37]

图2 采用HSE泛函方法计算CsPbI3的能带结构

Fig.2 Energy band structure of CsPbI3 calculated by HSE functional method

图3 CsPbI3掺杂体系的缺陷形成能(a)Cs8MnPb7I24; (b) Cs8SnPb7I24

Fig.3 Formation energy and transition level of CsPbI3 doping system (a) Cs8MnPb7I24; (b) Cs8SnPb7I24

图4 CsPbI3掺杂体系的转变能级

Fig.4 Transition level of CsPbI3 doping system

图5 掺杂前后CsPbI3体系的声子态密度图

Fig.5 Phonon state density of CsPbI3 system without and with doping

图6 CsPbI3掺杂体系中载流子非辐射复合系数随温度变化

Fig.6 Carrier capture coefficients as a function of temperature in CsPbI3 doping system

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Mn、Sn掺杂无机钙钛矿CsPbI₃非辐射复合的第一性原理计算

Nonradiative Recombination for Mn and Sn Doped in Inorganic Perovskite CsPbI₃ by First-principles

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