Doping is an effective strategy for enhancing the stability and productivity of perovskite optoelectronic devices. This study presents a first-principles investigation of the structural, electronic, and optical properties of Sr-doped CsPbCl3 compared with undoped CsPbCl3. The results demonstrate that Sr-doped CsPbCl3 retains the perovskite structure with enhanced structural stability based on the tolerance factor and dopant formation energy. Sr doping leads to an expansion of the bandgap, which is attributed to the influence of the dopant’s orbitals on the original perovskite electronic structure, as well as a shift of the high-symmetry point where the direct bandgap occurs from R to Γ. Additionally, Sr doping improves carrier transport characteristics and reduces exciton binding energy. The study also reveals significant modifications in the optical properties of CsPbCl3 upon Sr doping. The calculation of vacancy formation energy shows that the Cl vacancy is preferable to formation in the undoped CsPbCl3. Overall, this work provides important insights into the potential of Sr-doped CsPbCl3 perovskites for future development in optoelectronic applications.
REFERENCES
1.
A.
Kojima
, “Organometal halide perovskites as visible-light sensitizers for photovoltaic cells
,” J. Am. Chem. Soc.
131
, 6050
(2009
). 2.
F.
Sahli
, J.
Werner
, B. A.
Kamino
, M.
Brauninger
, R.
Monnard
, B.
Paviet-Salomon
, L.
Barraud
, L.
Ding
, J. J.
Diaz Leon
, D.
Sacchetto
, G.
Cattaneo
, M.
Despeisse
, M.
Boccard
, S.
Nicolay
, Q.
Jeangros
, B.
Niesen
, and C.
Ballif
, “Fully textured monolithic perovskite/silicon tandem solar cells with 25.2% power conversion efficiency
,” Nat. Mater
. 17
, 820
(2018
). 3.
C.
Weeks
and M.
Franz
, “Topological insulators on the lieb and perovskite lattices
,” Phys. Rev. B
82
, 085310
(2010
). 4.
G.
Murtaza
, I.
Ahmad
, B.
Amin
, A.
Afaq
, M.
Maqbool
, J.
Maqsood
, I.
Khan
, and M.
Zahid
, “Investigation of structural and optoelectronic properties of BaThO3
,” Opt. Mater
. 33
, 553
(2011
). 5.
M.
Kulbak
, S.
Gupta
, N.
Kedem
, I.
Levine
, T.
Bendikov
, G.
Hodes
, and D.
Cahen
, “Cesium enhances long-term stability of lead bromide perovskite-based solar cells
,” J. Phys. Chem. Lett.
7
, 167
(2016
). 6.
A.
Voloshynovskii
, P.
Savchyn
, I.
Karbovnyk
, S.
Myagkota
, M. C.
Guidi
, M.
Piccinini
, and A. I.
Popov
, “Cspbcl3 nanocrystals dispersed in the Rb0.8Cs0.2Cl matrix studied by far-infrared spectroscopy
,” Solid State Commun
. 149
, 593
(2009
). 7.
S.
Myagkota
, A.
Gloskovskii
, R.
Gladyshevskii
, and A.
Voloshynovskii
, “Luminescent kinetic characteristics of CsPbCl3 aggregates dispersed in Rb1−xCsxCl (x = 0.05–0.2) matrices
,” Condens. Matter Phys
. 6
, 325
(2003
). 8.
S.
Zou
, Y.
Liu
, J.
Li
, C.
Liu
, R.
Feng
, F.
Jiang
, Y.
Li
, J.
Song
, H.
Zeng
, M.
Hong
, and X.
Chen
, “Stabilizing cesium lead halide perovskite lattice through Mn(II)-substitution for air-stable light-emitting diodes
,” J. Am. Chem. Soc.
139
, 11443
(2017
). 9.
E.-P.
Yao
, Z.
Yang
, L.
Meng
, P.
Sun
, S.
Dong
, Y.
Yang
, and Y.
Yang
, “High-brightness blue and white leds based on inorganic perovskite nanocrystals and their composites
,” Adv. Mater.
29
, 1606859
(2017
). 10.
L.
Lv
, Y.
Xu
, H.
Fang
, W.
Luo
, F.
Xu
, L.
Liu
, B.
Wang
, X.
Zhang
, D.
Yang
, W.
Hu
, and A.
Dong
, “Generalized colloidal synthesis of high-quality, two-dimensional cesium lead halide perovskite nanosheets and their applications in photodetectors
,” Nanoscale
8
, 13589
(2016
). 11.
D. M.
Trots
and S. V.
Myagkota
, “High-temperature structural evolution of caesium and rubidium triiodoplumbates
,” J. Phys. Chem. Solid
69
, 2520
(2008
). 12.
S.
Kachhap
, S.
Singh
, A. K.
Singh
, and S. K.
Singh
, “Lanthanide-doped inorganic halide perovskites (CsPbX3): Novel properties and emerging applications
,” J. Mater. Chem. C
10
, 3647
(2022
). 13.
C. M.
Guvenc
, Y.
Yalcinkaya
, S.
Ozen
, H.
Sahin
, and M. M.
Demir
, “Gd3+-doped α-CsPbI3 nanocrystals with better phase stability and optical properties
,” J. Phys. Chem. C
123
, 24865
(2019
). 14.
T. J.
Milstein
, D. M.
Kroupa
, and D. R.
Gamelin
, “Picosecond quantum cutting generates photoluminescence quantum yields over 100% in ytterbium-doped CsPbCl3 nanocrystals
,” Nano Lett
. 18
, 3792
(2018
). 15.
C.
Chen
, T.
Xuan
, W.
Bai
, T.
Zhou
, F.
Huang
, A.
Xie
, L.
Wang
, and R.
Xie
, “Highly stable CsPbI3:Sr2+ nanocrystals with near-unity quantum yield enabling perovskite light-emitting diodes with an external quantum efficiency of 17.1%
,” J. Nano Energy
85
, 106033
(2021
). 16.
M. D.
Segall
, P. J. D.
Lindan
, M. J.
Probert
, C. J.
Pickard
, P. J.
Hasnip
, S. J.
Clark
, and M. C.
Payne
, “First-principles simulation: Ideas, illustrations and the CASTEP code
,” J. Phys.: Condens. Matter
14
, 2717
(2002
). 17.
E.
Welch
, L.
Scolfaro
, and A.
Zakhidov
, “Density functional theory + U modeling of polarons in organohalide lead perovskites
,” AIP Adv.
6
, 125037
(2016
). 18.
S.
Semak
, V.
Kapustianyk
, Yu
.
Eliyashevskyy
, O.
Bovgyra
, M.
Kovalenko
, U.
Mostovoi
, B.
Doudin
, and B.
Kundys
, “On the photovoltaic effect asymmetry in ferroelectrics
,” J. Phys.: Condens. Matter
35
, 094001
(2023
). 19.
M.
Kovalenko
, O.
Bovgyra
, V.
Kolomiets
, V.
Kapustianyk
, and O.
Kozachenko
, Structural, electronic and optical properties of CsPbBr3 and CH3NH3PbBr3: First-principles modeling, IEEE 12th International Conference on Electronics and Information Technologies (ELIT) (2021), p. 232.20.
M.
Kovalenko
, O.
Bovgyra
, V.
Kapustianyk
, and O.
Kozachenko
, “The local structure, electronic and optical properties of Pb(Mg1/3Nb2/3)O3–PbTiO3: First-principles study
,” Condens. Matter Phys
. 27
, 23702
(2024
). 21.
A. A.
Abdulkareem
, S. A.
Sami
, and B. H.
Elias
, “Structural, electronic and optical properties of cubic perovskite CsPbX3 (X = Br, Cl and I)
,” Sci. J. Univ. Zakho
. 8
, 23
(2020
). 22.
C. K.
Moller
, “Crystal structure and photoconductivity of cesium plumbohalides
,” Nature
182
, 1436
(1958
). 23.
M.
Zhang
, G.
Xianga
, Y.
Wu
, J.
Liu
, J.
Leng
, C.
Cheng
, H.
Ma
, “Influence of Sr doping on the photoelectronic properties of CsPbX3 (X = Cl, Br, or I): A DFT investigation
,” Phys. Chem. Chem. Phys
. 25
, 9592
(2023
). 24.
M.
Ahmad
, G.
Rehman
, L.
Ali
, M.
Shafiq
, R.
Iqbal
, R.
Ahmad
, T.
Khan
, S.
Jalali-Asadabadi
, M.
Maqbool
, and I.
Ahmad
, “Structural, electronic and optical properties of CsPbX3 (X = Cl, Br, I) for energy storage and hybrid solar cell applications
,” J. Alloys Compd
. 705
, 828
(2017
). 25.
Y.
Ye
, X.
Run
, X. H.
Tao
, H.
Feng
, X.
Fei
, and W.
Lin-Jun
, “Nature of the bandgap of halide perovskites ABX3 (A = CH3NH3, Cs; B = Sn, Pb; X = Cl, Br, I): First-principles calculations
,” Chin. Phys. B
24
, 116302
(2015
). 26.
L.
Lang
, J. H.
Yang
, H. R.
Liu
, H. J.
Xiang
, and X. G.
Gong
, “First-principles study on the electronic and optical properties of cubic ABX3 halide perovskites
,” Phys. Lett. A
378
, 290
(2014
). 27.
G.
Murtaza
and I.
Ahmad
, “First principle study of the structural and optoelectronic properties of cubic perovskites CsPbM3 (M = Cl, Br, I)
,” Physica B
406
, 3222
(2011
). 28.
V. M.
Goldschmidt
, “Die gesetze der krystallochemie
,” Die Naturwissenschaften
14
, 477
(1926
). 29.
M.
Zhang
, G.
Xiang
, Y.
Wu
, J.
Liu
, J.
Leng
, C.
Cheng
, and H.
Ma
, “Revealing the influence of doping elements (Ge, Sn, Ca, and Sr) on the properties of α-CsPbI3 a DFT investigation
,” Opt. Express
31
, 28624
(2023
). 30.
M.
Baranowski
, P.
Plochocka
, R.
Su
, L.
Legrand
, Th.
Barisien
, F.
Bernardot
, Q.
Xiong
, Ch.
Testelin
, and M.
Chamarro
, “Exciton binding energy and effective mass of CsPbCl3: A magneto-optical study: Publisher’s note
,” Photon. Res
. 10
, 2447
(2022
). 31.
K.
Heidrich
, W.
Schafer
, M.
Schreiber
, J.
Sochtig
, G.
Trendel
, J.
Treusch
, T.
Grandke
, and H. J.
Stolz
, “Electronic structure, photoemission spectra, and vacuum-ultraviolet optical spectra of CsPbCl3 and CsPbBr3
,” Phys. Rev. B
24
, 5642
(1981
). 32.
A.
Voloshinovskii
, Ya.
Chornodolskyy
, O.
Pidhornyi
, A.
Pushak
, M.
Kovalenko
, O.
Bovgyra
, R.
Gamernyk
, O.
Antonyak
, A.
Kotlov
, A.
Smortsova
, T.
Malyi
, and T.
Demkiv
, Luminescence of Sr2+-activated CsPbCl3 single crystals, Book of Abstracts, 12th European Conference on Luminescent Detectors and Transformers of Ionising Radiation, LUMDETR 2024, Riga, Latvia (2024), p. 80.33.
H.
Yuce
, M.
Mandal
, Y.
Yalcinkaya
, D.
Andrienko
, and M. M.
Demir
, “Improvement of photophysical properties of CsPbBr3 and Mn2+:CsPb(Br,Cl)3 perovskite nanocrystals by Sr2+ doping for white light-emitting diodes
,” J. Phys. Chem. C
126
, 11277
(2022
). 34.
Gh. H.
Ahmed
, Y.
Liu
, I.
Bravić
, X.
Ng
, I.
Heckelmann
, P.
Narayanan
, M. S.
Fernández
, B.
Monserrat
, D. N.
Congreve
, and S.
Feldmann
, “Universal mechanism of luminescence enhancement in doped perovskite nanocrystals from symmetry analysis
,” J. Am. Chem. Soc.
144
, 15862
(2022
). 35.
L.
Huang
, L.
Song
, Y.
Yang
, Y.
Xiao
, Sh.
Chen
, H.
Dong
, and F.
Wu
, “Abnormal variation in the host bandgap of Mn-doped perovskite CsPbCl3
,” Physica B: Condens. Matter
650
, 414507
(2023
). 36.
P. P.
Sun
, Q. S.
Li
, L. N.
Yang
, and Z. S.
Li
, “Theoretical insights into a potential lead-free hybrid perovskite: Substituting Pb2+ with Ge2+
,” Nanoscale
8
, 1503
(2016
). 37.
A.
Miyata
, A.
Mitioglu
, P.
Plochocka
, O.
Portugall
, J. T.-W.
Wang
, S. D.
Stranks
, H. J.
Snaith
, and R. J.
Nicholas
, “Direct measurement of the exciton binding energy and effective masses for charge carriers in organic-inorganic tri-halide perovskites
,” Nat. Phys.
11
, 582
(2015
). 38.
S.
Baroni
, S.
de Gironcoli
, A.
Dal Corso
, and P.
Giannozzi
, “Phonons and related crystal properties from density-functional perturbation theory
,” Rev. Mod. Phys.
73
, 515
(2001
). 39.
C.
Ambrosch-Draxl
and J. O.
Sofo
, “Linear optical properties of solids within the full-potential linearized augmented planewave method
,” Comput. Phys. Commun.
175
, 1
(2006
). 40.
S.
Adachi
, Properties of semiconductor alloys: Group-IV, III–V, and II–VI semiconductors
(John Wiley and Sons
, 2009
).41.
H.
Jiang
, Y.
Zhao
, F.
Liu
, Y.
Yan
, Y.
Ma
, H.
Bao
, Z.
Wu
, W.-Y.
Cong
, and Y.-B.
Lu
, “Mono- and Co-doped Mn-doped CsPbCl3 perovskites with enhanced doping efficiency and photoluminescent performance
,” Materials
16
, 5545
(2023
). © 2025 Author(s). Published under an exclusive license by AIP Publishing.
2025
Author(s)
You do not currently have access to this content.
