Photogenerated Carrier Dynamics Regulated by Doping in All-Inorganic Perovskites

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

Abstract

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

CLC Number:

O469

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.

Figures/Tables 9

Fig.1 Crystal structure diagrams at 0 and 300 K

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

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

Fig.2 Band structure of the pristine and doped systems

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

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

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

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

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

References 34

[1]	GONG S K， QU G P， QIAO Y， et al. A hot carrier perovskite solar cell with efficiency exceeding 27% enabled by ultrafast hot hole transfer with phthalocyanine derivatives［J］. Energy & Environmental Science， 2024， 17（14）： 5080-5090.
[2]	ALMORA O， CABRERA C I， ERTEN-ELA S， et al. Device performance of emerging photovoltaic materials （version 4）［J］. Advanced Energy Materials， 2024， 14（4）： 2303173. DOI URL
[3]	KOJIMA A， TESHIMA K， SHIRAI Y， et al. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells［J］. Journal of the American Chemical Society， 2009， 131（17）： 6050-6051. DOI PMID
[4]	HANDA T， YAMADA T， KUBOTA H， et al. Photocarrier recombination and injection dynamics in long-term stable lead-free CH₃NH₃SnI₃ perovskite thin films and solar cells［J］. The Journal of Physical Chemistry C， 2017， 121（30）： 16158-16165. DOI URL
[5]	CAO F R， BIAN L K， LI L. Perovskite solar cells with high-efficiency exceeding 25%： a review［J］. Energy Materials and Devices， 2024， 2（1）： 9370018. DOI URL
[6]	ASGHAR M I， ZHANG J， WANG H， et al. Device stability of perovskite solar cells： a review［J］. Renewable and Sustainable Energy Reviews， 2017， 77： 131-146. DOI URL
[7]	AZMI R， UGUR E， SEITKHAN A， et al. Damp heat-stable perovskite solar cells with tailored-dimensionality 2D/3D heterojunctions［J］. Science， 2022， 376（6588）： 73-77. DOI URL
[8]	TAN Y S， LI R Y， XU H， et al. Ultrastable and reversible fluorescent perovskite films used for flexible instantaneous display［J］. Advanced Functional Materials， 2019， 29（23）： 1900730. DOI URL
[9]	SALADO M， KAZIM S， AHMAD S. The role of Cs⁺ inclusion in formamidinium lead triiodide-based perovskite solar cell［J］. Chemical Papers， 2018， 72（7）： 1645-1650. DOI
[10]	DUAN J L， ZHAO Y Y， HE B L， et al. High-purity inorganic perovskite films for solar cells with 9.72% efficiency［J］. Angewandte Chemie International Edition， 2018， 57（14）： 3787-3791. DOI URL
[11]	WANG Q， JIN Z W， CHEN D， et al. µ-graphene crosslinked CsPbI₃ quantum dots for high efficiency solar cells with much improved stability［J］. Advanced Energy Materials， 2018， 8（22）： 1800007. DOI URL
[12]	BABEKER H， YANG Y， QIU J B， et al. Preparation and photoluminescence properties of perovskite Cs₄PbBr₆/CsPbBr₃ quantum dots integrated into lithium-borosilicate glass［J］. Ceramics International， 2023， 49（15）： 24824-24830. DOI URL
[13]	ZHU W D， ZHANG Z Y， CHAI W M， et al. Band alignment engineering towards high efficiency carbon-based inorganic planar CsPbIBr₂ perovskite solar cells［J］. ChemSusChem， 2019， 12（10）： 2318-2325. DOI URL
[14]	LIU H G， JI H H， ZHU J F， et al. Photocatalytic properties of CsPbI₃/MoSSe van der Waals heterostructure under biaxial strain［J］. Chemical Physics Letters， 2025， 876： 142180. DOI URL
[15]	YAN L， XUE Q F， LIU M Y， et al. Interface engineering for all-inorganic CsPbI₂Br perovskite solar cells with efficiency over 14%［J］. Advanced Materials， 2018， 30（33）： 1802509. DOI URL
[16]	CHEN X G， PENG H R， SUN X X， et al. The mixed phases of α and γ-CsPbI₃ enable efficient and stable semitransparent solar cells［J］. Small， 2025， 21（14）： 2500710. DOI URL
[17]	PARK J H， YOON Y S， KIM J Y. Fabrication processes for all-inorganic CsPbBr₃ perovskite solar cells［J］. EcoMat， 2023， 5（11）： e12407.
[18]	JAEGER H M， FISCHER S， PREZHDO O V. Decoherence-induced surface hopping［J］. The Journal of Chemical Physics， 2012， 137（22）： 22A545. DOI URL
[19]	MONDAL N， SAMANTA A. Complete ultrafast charge carrier dynamics in photo-excited all-inorganic perovskite nanocrystals （CsPbX₃）［J］. Nanoscale， 2017， 9（5）： 1878-1885. DOI URL
[20]	KRESSE G， FURTHMÜLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set［J］. Physical Review B， 1996， 54（16）： 11169-11186. DOI URL
[21]	PERDEW J P， BURKE K， ERNZERHOF M. Generalized gradient approximation made simple［J］. Physical Review Letters， 1996， 77（18）： 3865-3868. DOI PMID
[22]	BLÖCHL P E. Projector augmented-wave method［J］. Physical Review B， 1994， 50（24）： 17953-17979. DOI PMID
[23]	MONKHORST H J， PACK J D. Special points for Brillouin-zone integrations［J］. Physical Review B， 1976， 13（12）： 5188-5192. DOI URL
[24]	BRANKA A. Nose-Hoover chain method for nonequilibrium molecular dynamics simulation［J］. Physical Review E， Statistical Physics， Plasmas， Fluids， and Related Interdisciplinary Topics， 2000， 61（5A）： 4769-4773.
[25]	ZHENG Q J， CHU W B， ZHAO C Y， et al. Ab initio nonadiabatic molecular dynamics investigations on the excited carriers in condensed matter systems［J］. WIREs Computational Molecular Science， 2019， 9（6）： e1411.
[26]	LINABURG M R， MCCLURE E T， MAJHER J D， et al. Cs_1- _x Rb _x PbCl₃ and Cs_1- _x Rb _x PbBr₃ solid solutions： understanding octahedral tilting in lead halide perovskites［J］. Chemistry of Materials， 2017， 29（8）： 3507-3514. DOI URL
[27]	ZHANG M G， XIAO Z R， CHEN L， et al. Pressure-induced phase transitions of CsSnBr₃ perovskite from first-principles calculations［J］. Physica Scripta， 2022， 97（11）： 115811. DOI
[28]	CAO S， SU Y， SONG K K， et al. Biaxial strain improving carrier mobility for inorganic perovskite： ab initio Boltzmann transport equation［J］. Journal of Physics： Condensed Matter， 2023， 35（5）： 055702.
[29]	QIAO L， FANG W H， PREZHDO O V， et al. Suppressing oxygen-induced deterioration of metal halide perovskites by alkaline earth metal doping： a quantum dynamics study［J］. Journal of the American Chemical Society， 2022， 144（12）： 5543-5551. DOI URL
[30]	JUSTO J F， DE BRITO M F， FAZZIO A. First-principles investigation of a-SiN _x ∶H［J］. Physical Review B， 2002， 65（7）： 073202.
[31]	ASHHAB S， VOZNYY O， HOOGLAND S， et al. Effect of disorder on transport properties in a tight-binding model for lead halide perovskites［J］. Scientific Reports， 2017， 7： 8902. DOI PMID
[32]	GRANUCCI G， PERSICO M. Critical appraisal of the fewest switches algorithm for surface hopping［J］. The Journal of Chemical Physics， 2007， 126（13）： 134114. DOI URL
[33]	GRANUCCI G， PERSICO M， ZOCCANTE A. Including quantum decoherence in surface hopping［J］. The Journal of Chemical Physics， 2010， 133（13）： 134111. DOI URL
[34]	AKIMOV A V， PREZHDO O V. The PYXAID program for non-adiabatic molecular dynamics in condensed matter systems［J］. Journal of Chemical Theory and Computation， 2013， 9（11）： 4959-4972. DOI PMID