全无机钙钛矿掺杂调控的光生载流子动力学研究

doi:10.16553/j.cnki.issn1000-985x.2026.0019

摘要/Abstract

摘要： 全无机钙钛矿相较于杂化有机-无机钙钛矿具有更高的稳定性，然而电子-空穴非辐射复合现象在全无机钙钛矿中较为显著，会导致大量能量损失，成为制约光电转换效率提升的关键因素。本文采用第一性原理与非绝热分子动力学，系统研究了在全无机钙钛矿CsPbBr₃中A位、CsSnBr₃中B位分别进行Rb、Zn掺杂对非辐射电子-空穴复合的影响。结果表明通过元素掺杂能引起周边临近晶格畸变，使材料的带隙改变，同时改变非绝热耦合与退相干时间，CsPbBr₃中A位掺杂Rb使载流子的复合时间由71.45 ps延长至124.82 ps，CsSnBr₃中B位掺杂Zn使载流子的复合时间由20.72 ps大幅延长至224.39 ps，从而有效抑制电子-空穴非辐射复合。为突破全无机钙钛矿太阳能电池光电转换效率瓶颈提供了理论指导与依据。

关键词: 全无机钙钛矿; 掺杂; 第一性原理; 非绝热分子动力学; 光生载流子; 电子-空穴非辐射复合

Abstract: All-inorganic perovskites exhibit superior stability compared with hybrid organic-inorganic perovskites. Nevertheless， the non-radiative electron-hole recombination is prominent in all-inorganic perovskites， which causes substantial energy loss and acts as a critical factor restricting the improvement of their photoelectric conversion efficiency. In this work， first-principles calculations combined with nonadiabatic molecular dynamics were adopted to systematically investigate the effects of Rb doping at the A-site of CsPbBr₃ and Zn doping at the B-site of CsSnBr₃ on non-radiative electron-hole recombination in all-inorganic perovskites.The results reveal that elemental doping induces lattice distortion in adjacent regions， modulates the band gap of the material， and alters the nonadiabatic coupling strength and decoherence time. Specifically， A-site Rb doping in CsPbBr₃ prolongs the carrier recombination time from 71.45 ps to 124.82 ps， while B-site Zn doping in CsSnBr₃ dramatically extends the carrier recombination time from 20.72 ps to 224.39 ps， thereby effectively suppressing non-radiative electron-hole recombination. This study provides theoretical guidance and fundamental basis for breaking through the bottleneck of photoelectric conversion efficiency of all-inorganic perovskite solar cells.

Key words: all-inorganic perovskite; doping; first-principle; nonadiabatic molecular dynamics; photogenerated carrier; electron-hole nonradiative recombination

中图分类号:

O469

杨振清, 王森, 刘畅, 冯子涵, 邵长金, 林春丹. 全无机钙钛矿掺杂调控的光生载流子动力学研究[J]. 人工晶体学报, 2026, 55(8): 1282-1289.

YANG Zhenqing, WANG Sen, LIU Chang, FENG Zihan, SHAO Changjin, LIN Chundan. Photogenerated Carrier Dynamics Regulated by Doping in All-Inorganic Perovskites[J]. Journal of Synthetic Crystals, 2026, 55(8): 1282-1289.

图/表 9

图1 0和300 K下的晶体结构图

Fig.1 Crystal structure diagrams at 0 and 300 K

表1 0和300 K下原始体系和掺杂体系中的平均键长

Table 1 Average bond lengths in the pristine and doped systems at 0 and 300 K

Parameter	Average bond length/Å
Parameter	CsPbBr₃	Cs_0.9375Rb_0.0625PbBr₃	CsSnBr₃	CsSn_0.963Zn_0.037Br₃
0 K	3.028	3.030	2.92	2.93
300 K	3.033	3.030	2.94	2.96
Change/increase	0.005	0.000	0.02	0.03

表2 0和300 K下原始体系和掺杂体系中的平均键角

Table 2 Average bond angle in the pristine and doped systems at 0 and 300 K

Parameter	Average bond angle/（°）
Parameter	CsPbBr₃	Cs_0.9375Rb_0.0625PbBr₃	CsSnBr₃	CsSn_0.963Zn_0.037Br₃
0 K	180.00	179.31	180.00	179.70
300 K	170.43	169.72	167.65	166.56
Change/decrease	9.57	9.59	12.35	13.14

图2 原始体系及掺杂体系的能带结构

Fig.2 Band structure of the pristine and doped systems

图3 原始体系及掺杂体系的投影态密度

Fig.3 Projected density of states of the pristine and doped systems

图4 原始体系及掺杂体系的CBM及VBM上的电荷密度图

Fig.4 Charge density maps on CBM and VBM of the pristine and doped systems

图5 CsPbBr3、Cs0.9375Rb0.0625PbBr3、CsSnBr3和CsSn0.963Zn0.037Br3体系的VBM和CBM电荷密度的逆参与比（IPR）随MD轨迹的时间演化图

Fig.5 Time evolution of the inverse participation ratio （IPR） of the charge density for the VBM and CBM in the CsPbBr3， Cs0.9375Rb0.0625PbBr3， CsSnBr3 and CsSn0.963Zn0.037Br3 systems during the MD trajectory

表3 原始体系和掺杂体系的能带、NA耦合、退相干时间和非辐射复合时间

Table 3 Band gap， NA coupling， decoherence time， and recombination time for the pristine and doped systems

System	Band gap/eV	NA coupling/meV	Decoherence time/fs	Recombination time/ps
CsPbBr₃	2.10	1.50	8.23	71.45
Cs_0.9375Rb_0.0625PbBr₃	2.11	1.30	11.30	124.82
CsSnBr₃	0.51	0.60	10.33	20.72
CsSn_0.963Zn_0.037Br₃	0.27	1.10	4.45	224.39

图6 CsPbBr3和Cs0.9375Rb0.0625PbBr3体系（a），以及CsSnBr3和CsSn0.963Zn0.037Br3体系（b）载流子随时间的布居数演化

Fig.6 Evolution of carriers population with time in the CsPbBr3 and Cs0.9375Rb0.0625PbBr3 （a）， CsSnBr3 and CsSn0.963Zn0.037Br3 （b） systems

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