RESEARCH ARTICLE | APRIL 28 2021

The mechanism of alkali doping in CsPbBr3: A first-

principles perspective 
Xuyang Zhang; Qingwei Ma; Ruiping Li; Changqing Lin; Dan Huang  ; Yingchun Cheng 

Journal of Applied Physics 129, 165110 (2021)

https://doi.org/10.1063/5.0048067

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The mechanism of alkali doping in CsPbBr3:

A first-principles perspective
Cite as: J. Appl. Phys. 129, 165110 (2021); doi: 10.1063/5.0048067
Submitted: 18 February 2021 · Accepted: 6 April 2021 · View Online Export Citation CrossMark
Published Online: 28 April 2021

Xuyang Zhang,1 Qingwei Ma,1 Ruiping Li,1 Changqing Lin,2 Dan Huang,2,a) and Yingchun Cheng1,a)

AFFILIATIONS
1
Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation
Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, China
2
Guangxi Key Laboratory for Relativistic Astrophysics, Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials
and Related Technology, Guangxi Novel Battery Materials Research Center of Engineering Technology, School of Physical
Science and Technology, Guangxi University, Nanning 530004, China

a)
Authors to whom correspondence should be addressed: [email protected] and [email protected]

ABSTRACT
All-inorganic CsPbBr3 perovskite doped with alkali metal atoms has been attracting increasing attention due to its superior optoelectronic
properties. However, there still exists significant uncertainty regarding the doping mechanism. One view of the mechanism is that alkali

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metal atoms tend to substitute Cs in CsPbBr3 crystals. Another view is that Li and Na tend to intercalate into interstitial sites because their
radii are much smaller than that of Cs. To elucidate the doping mechanism, it is necessary to investigate the point defects physics of alkali
metal elements in CsPbBr3. In this work, by using first-principles calculations we find that alkali metal atoms energetically prefer to substi-
tute for Cs or Pb atoms in CsPbBr3 crystals under different chemical potential conditions. To determine the alkali metal atoms doping site,
one should consider the chemical potential of synthesis conditions, the dopant valence states, and atomic radii. Notably, alkali metal atoms
doping mainly introduces shallow levels, which is helpful for improving the p-type conductivity of CsPbBr3.

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INTRODUCTION claimed that Li and Na are doped to replace Cs based on a

All-inorganic CsPbBr3 perovskite has emerged as a promis- decrease in lattice constants contraction after doping. Because of
ing semiconductor for light-emitting diodes1–3 and photovoltaic the controversial results of different groups, it is necessary to sys-
devices.4–6 Doping is considered a significant way to improve the tematically investigate the mechanism of alkali metal atoms
photoelectric properties of CsPbBr3,7–20 and among the various doping in CsPbBr3.
metal doping candidates available, alkali metal atoms have We investigate the mechanism of alkali metal atoms doping in
attracted increasing attention.20–29 Li and Na atoms tend to inter- CsPbBr3 using first-principles calculations. By comparing the for-
calate into interstitial sites because of their much smaller radii mation energies of various point defects, it is found that alkali
compared with Cs atom, and these atoms consequently improve metal atoms prefer to replace Cs or Pb sites in CsPbBr3. Alkali sub-
n-type conductivity.21 K or Rb atoms tend to replace Cs sites in stituting Cs is a type of isoelectronic doping and alkali substituting
the CsPbBr3 lattice because K or Rb have similar atom radius to Pb is a type of p-type doping. Alkali metal atoms doping introduces
Cs and have little influence on electrical conductivity.23–27,29 shallow levels, conducive to improving the p-type conductivity of
However, recent experiments and calculations show that alkali CsPbBr3. Moreover, two precursor groups, as well as an optimal
metal atoms doping in CsPbBr3 is complicated. For example, chemical potential range for growing high-quality CsPbBr3 crystals
density functional theory calculations demonstrate that substitu- are provided. We systematically investigate the alkali metal atoms
tion NaPb defect is energetically preferred by the doping of Na doping mechanism in CsPbBr3, which will pave the way for
atoms.28 Li et al. studied the compositional engineering of improving the performance of CsPbBr3-based optoelectronic
CsPbBr3 by doping with various alkali metal cations24 and devices.

J. Appl. Phys. 129, 165110 (2021); doi: 10.1063/5.0048067 129, 165110-1

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CALCULATION METHOD where εα(q/q0 ) is the charge transition energy level of defect α
All calculations are carried out by using the Vienna between charge states q and q0 . Ef(α,q) is the formation energy of
ab initio simulation package (VASP).30 The core-valence inter- defect α in charge state q.
action is described by a projector-augmented-wave (PAW)31
method, and the exchange-correction interactions are described RESULTS AND DISCUSSION
by the Perdew–Burke–Ernzerhof (PBE)32 functional. The van
Orthorhombic CsPbBr3 in the Pmnb space group34
der Waals interactions are described by the Grimme DFT-D3
(ICSD-28312) is used for defect calculations. The crystal structure
approach.33 A cutoff energy of 500 eV is used. A 4 × 2 × 1
is shown in Fig. 1(a). The optimized lattice constants are
supercell containing 160 atoms is used for the defect calcula-
a = 4.61 Å, b = 9.90 Å, and c = 17.14 Å, which are consistent with
tions. All structures are optimized until the residual force is
experimental results (a = 4.60 Å, b = 9.72 Å, c = 16.81 Å).35 Various
below 0.01 eV/Å, and the convergence threshold of electronic
point defects are simulated within a 4 × 2 × 1 CsPbBr3 supercell,
energy is set to 10−5 eV.
which is large enough to prevent defect interactions. Taking Li
The formation energy Ef(α,q) of a defect α ionized to a charge
doping as an example, a series of Li-related impurity point defects
state q is determined as
are created, including LiCs (Cs substituted by Li), LiPb (Pb substi-
X tuted by Li), LiBr (Br substituted by Li), and Lii (interstitial Li).
Ef (α, q) ¼ E(α, q)  E( perfect)  i
ni (Δμi þ μsolid
i ) To grow high-quality CsPbBr3 crystals, it is vital to control the
chemical potentials of various elements.36–38 All nine phases, con-
þ q(EF þ EVBM ): (1) sisting of Cs, Pb, and Br elements, are investigated, with the results
shown in Table S1 in the supplementary material. The chemical
Ef(α,q) is a function of both the electron Fermi energy EF potential range in the purple area of Fig. 1(b) indicates the thermo-
and relative chemical potential Δμi. E(α,q) is the total energy of dynamic stability of CsPbBr3. In other words, the point (ΔμCs,
the supercell, including that of α. E(perfect) is the total energy of ΔμPb, ΔμBr) in the purple area is the optimum chemical potential
pristine supercell. ni is the number of atoms of type i added condition for growing CsPbBr3 crystals. The purple area is a
(ni > 0) or removed (ni < 0) from the perfect crystal supercell narrow quadrilateral, indicating that the chemical potentials of the
when a defect α is created. Δμi is the relative chemical potential various elements should be carefully controlled when growing
of element i, and μsolid iis the chemical potential of the elemen- CsPbBr3. The critical points of the purple area (points D, E, F, and
tal solids consisting of element i. EF is the Fermi energy and G), as well as their corresponding chemical potential values, are

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EVBM is the energy of the valence band maximum. The defect listed in Table S2 in the supplementary material. The purple area is
charge transition energy level εα(q/q0 ) is defined as the Fermi surrounded by a green line (PbBr2), blue line (CsBr3), and red line
energy when the formation energy of defect α in charge state q (Cs4PbBr6). This shows that these three compounds can be used as
equals that in charge state q0 : precursors for growing CsPbBr3. The purple area is also located
between the green line—PbBr2—and the brown line—CsBr—indi-
  cating these two compounds can be used for synthesizing CsPbBr3
εα ðq=q0 Þ ¼ Ef ðα; qÞ  Ef ðα; q0 Þ =ðq0  qÞ, (2) crystals, as in previous experiments.39–43

FIG. 1. (a) Crystal structure of CsPbBr3 in the space group Pmnb. (b) Chemical potential range for growing CsPbBr3 crystals.

J. Appl. Phys. 129, 165110 (2021); doi: 10.1063/5.0048067 129, 165110-2

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As the Li doping of CsPbBr3 has been widely experimentally defects are very high, indicating difficulty of formation. Under
investigated,21,22,24 we too examine this type of doping. In order to point C conditions, the formation energies of LiCs and LiPb are rela-
find out which lattice site Li prefers, we calculated the formation tively low, thus these two point defects form relatively easily.
energy of Li-related point defects according to Eq. (1). Three chem- Figures 2(a)–2(c) show that the slope of Lii or LiBr is positive
ical potential points (points A, B, and C) in Fig. 1(b) are selected. within the band gap, indicating that Lii and LiBr behave as donors
The chemical potential values of these points are listed in Table S2 and induce n-type conductivity. Similarly, LiPb behaves as an accep-
in the supplementary material, and the chemical potential of Li is tor and induces p-type conductivity. LiCs is an isoelectronic doping
shown in Table S3 in the supplementary material. Figures 2(a)–2(c) which will not introduce excess carriers. If Lii and LiPb simultane-
show the formation energies of Li-related point defects under point ously form in CsPbBr3, there will be a compensation effect between
A, B, and C chemical potential conditions, respectively. Under the two point defects, leading to reduced doping efficiency. To
point A and B conditions, the formation energies of all four point improve the p-type conductivity of CsPbBr3, we expect that more

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FIG. 2. (a)–(c) Formation energies of various point defects in Li-doped CsPbBr3 under different chemical potential conditions. (a), (b), and (c) correspond to the chemical
potential conditions of A, B, and C points in Fig. 1(b) respectively. (d) Defect charge transition energy levels in Li-doped CsPbBr3.

J. Appl. Phys. 129, 165110 (2021); doi: 10.1063/5.0048067 129, 165110-3

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efforts should be made to dope Li into Pb sites. Figures 2(a)–2(c) acceptor level at 0.31 eV above the valence band maximum,
show a comparison of the formation energies of LiPb under three which is a relatively shallow level; and Lii introduces a donor
different chemical potential positions; point C is the best chemical level at 0.08 eV below the conduction band minimum, which is
potential condition for the p-type doping of CsPbBr3. also a shallow level. The formation energy of LiBr is so high that
A defect transition between different charge states plays an LiBr forms with great difficulty. Therefore, Li doping mainly
important role in the electrical properties of a host material.44–50 introduces shallow levels within the band gap, conducive to
The defect charge transition levels of Li-related point defects are improving the electrical conductivity of CsPbBr3. Because the
shown in Fig. 2(d). The lines represent impurity transition levels, radius of Na is similar to that of Li, the scenario of Na doping in
and the solid/hollow points represent donor/acceptor defects. (0/−) CsPbBr3 is similar to that of Li doping, as shown in Fig. S1 in the
represents εα(0/−1), that is, the transition level between charge supplementary material.
states 0 and −1. LiCs is an isoelectronic doping, which does not The radii of K and Rb are much larger than those of Li and
change its charge states with Fermi energy. LiPb introduces an Na, and similar to that of Cs. Here, we take K as an example to

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FIG. 3. (a)–(c) Formation energies of various point defects in K-doped CsPbBr3 under different chemical potential conditions. (a), (b), and (c) correspond to the chemical
potential conditions of A, B, and C points in Fig. 1(b) respectively. (d) Defect charge transition energy levels in K-doped CsPbBr3.

J. Appl. Phys. 129, 165110 (2021); doi: 10.1063/5.0048067 129, 165110-4

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investigate doping effects in CsPbBr3. Figures 3(a)–3(c) show the radius on the doping site. Therefore, to determine the alkali doping
formation energies of K-related point defects under point A, B, and site, one should consider the chemical potential of the synthesis
C chemical potential conditions, respectively. The chemical poten- conditions, dopant valence state, and the atomic radius.
tial of K is shown in Table S5 in the supplementary material.
Because of its large atomic radius, it is difficult for the K atom to CONCLUSIONS
perform interstitial doping in CsPbBr3. Under point A conditions,
In summary, we investigate the mechanism of alkali metal
the formation energies of all three point defects are very high, indi-
atoms doping in CsPbBr3 using first-principles calculations. By
cating difficulty in formation of the defects. Under point B condi-
evaluating the chemical potential range for CsPbBr3 crystal growth,
tions, the formation energy of KCs is relatively low, so K tend to
we find two precursor groups for growing CsPbBr3 (PbBr2 and
replace Cs in CsPbBr3. Under point C conditions, the formation
Cs4PbBr6; PbBr2 and CsBr). Alkali metal atoms energetically prefer
energies of KCs and KPb are relatively low, thus both KCs and KPb
to replace Cs or Pb atoms in CsPbBr3 crystals. Cs replaced by alkali
can form.
is isoelectronic doping, and Pb substituted by alkali is p-type
The slopes of the formation energies of various point defects
doping. For Li (or Na) doping, Lii is n-type doping, which will
shown in Figs. 3(a)–3(c) indicate that KBr behaves as a donor and
compensate holes induced by LiPb. For K (or Rb) doping, there are
KPb as an acceptor. KCs is an isoelectronic doping which will not
no n-type point defects compensating holes induced by KPb.
introduce excess carriers. In contrast with the Li doping shown in
Therefore, K doping and Rb doping are efficient ways to improve
Fig. 2, it is difficult to produce K interstitial doping. Because no
the p-type conductivity of CsPbBr3 than Li doping or Na doping.
n-type point defects can compensate with KPb, K doping is a more
Moreover, by comparing the formation energies of various point
efficient way than Li doping to improve the p-type conductivity of
defects under different chemical potential conditions, point C in
CsPbBr3. To obtain this improvement, more efforts should be
Fig. 1(b) proves to be the best condition for the p-type doping of
made to dope K into Pb sites. Figures 3(a)–3(c) show that the for-
CsPbBr3. Alkali metal atoms doping mainly introduce shallow
mation energy of KPb decreases, so point C is the best chemical
levels within the band gap, conducive to improving the p-type con-
potential condition for the p-type doping of CsPbBr3. Figure 3(d)
ductivity of CsPbBr3.
shows the defect charge transition levels of K-related point defects.
KCs is an isoelectronic doping and will not change its charge states
SUPPLEMENTARY MATERIAL
with Fermi energy variation. KPb introduces an acceptor level at
0.31 eV above valence band maximum, indicating the KPb defect See supplementary material for impure phases that may form
state comprises a relatively shallow doping. KBr forms with great during CsPbBr3 growth as well as corresponding chemical potential

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difficulty because of its high formation energy; therefore, K doping constraints. The situation of Na-doping and Rb-doping is similar
mainly introduces shallow levels within the band gap, conducive to that of Li-doping and K-doping, respectively, which is also
for improving the p-type conductivity of CsPbBr3. The scenario of presented.
Rb doping in CsPbBr3 is similar to that of K doping, as shown in
Fig. S2 in the supplementary material. ACKNOWLEDGMENTS
Because the orthorhombic phase is the most stable CsPbBr3 This work was financially supported by the National Natural
phase,39 we only consider the defect physics in orthorhombic Science Foundation of China (No. 91833302). We are grateful to
CsPbBr3. Figures 2(a)–2(c) show that the formation energy of Lii is the High Performance Computing Center of Nanjing Tech
relatively high, suggesting a non-equilibrium doping method is University for supporting the computational resources.
required. Moreover, Lii introduces a shallow donor transition level,
suggesting an n-type conductivity improvement. This is consistent DATA AVAILABILITY
with Jiang’s work,21 in which Li is electrochemically intercalated
into an orthorhombic CsPbBr3 lattice, and n-type conductivity is The data that support the findings of this study are available
enhanced. Na is relatively easy to replace Cs and Pb sites, which is within this article and its supplementary material.
proved, respectively, in Refs. 24 and 28. All reports regarding K and
Rb doping claim that the substitution site is Cs, rather than Pb, in REFERENCES
CsPbBr3.23–27,29 1
J. Song, J. Li, X. Li, L. Xu, Y. Dong, and H. Zeng, “Quantum Dot light-emitting
There are two main viewpoints regarding alkali metal atoms diodes based on inorganic perovskite cesium lead halides (CsPbX3),” Adv.
doping in CsPbBr3. One is that alkali metal atoms are considered Mater. 27(44), 7162 (2015).
to replace Cs sites in CsPbBr3 crystals23–27,29 because of the same 2
X. Li, Y. Wu, S. Zhang, B. Cai, Y. Gu, J. Song, and H. Zeng, “Cspbx3 quantum
valence state of the alkali metal atoms. However, according to our dots for lighting and displays: Room-temperature synthesis, photoluminescence
calculations, alkali metal atoms are also likely to replace Pb under superiorities, underlying origins and white light-emitting diodes,” Adv. Funct.
Pb-poor conditions (point C). The minimum ΔμPb indicates the Mater. 26(15), 2435–2445 (2016).
3
K. Lin, J. Xing, L. N. Quan, F. P. G. de Arquer, X. Gong, J. Lu, L. Xie, W. Zhao,
possibility of the substitution of Pb sites. The other viewpoint is
D. Zhang, C. Yan, W. Li, X. Liu, Y. Lu, J. Kirman, E. H. Sargent, Q. Xiong, and
that Li and Na atoms are considered to intercalate into interstitial Z. Wei, “Perovskite light-emitting diodes with external quantum efficiency
sites because of their much smaller radius compared with Cs exceeding 20 percent,” Nature 562(7726), 245 (2018).
atoms.21 However, according to our calculations, Li and Na atoms 4
R. J. Sutton, G. E. Eperon, L. Miranda, E. S. Parrott, B. A. Kamino, J. B. Patel,
tend to replace Cs or Pb in CsPbBr3, which is the same behavior as M. T. Horantner, M. B. Johnston, A. A. Haghighirad, D. T. Moore, and
K+ and Rb atoms. Valence state has a larger influence than atomic H. J. Snaith, “Bandgap-tunable cesium lead halide perovskites with high

J. Appl. Phys. 129, 165110 (2021); doi: 10.1063/5.0048067 129, 165110-5

Published under an exclusive license by AIP Publishing.
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Applied Physics

thermal stability for efficient solar cells,” Adv. Energy Mater. 6(8), 1502458 of halide perovskites with Ion intercalation,” ACS Nano 11(1), 1073–1079
(2016). (2017).
5
R. E. Beal, D. J. Slotcavage, T. Leijtens, A. R. Bowring, R. A. Belisle, 22
Q. Jiang, X. Zeng, N. Wang, Z. Xiao, Z. Guo, and J. Lu, “Electrochemical
W. H. Nguyen, G. F. Burkhard, E. T. Hoke, and M. D. McGehee, “Cesium lead lithium doping induced property changes In halide perovskite CsPbBr3 crystal,”
halide perovskites with improved stability for tandem solar cells,” J. Phys. Chem. ACS Energy Lett. 3(1), 264–269 (2018).
Lett. 7(5), 746–751 (2016). 23
G. Shao, S. Liu, L. Ding, Z. Zhang, W. Xiang, and X. Liang, “KxCs1-xPbBr3
6
C. Yi, J. Luo, S. Meloni, A. Boziki, N. Ashari-Astani, C. Gratzel, NCs glasses possessing super optical properties and stability for white light emit-
S. M. Zakeeruddin, U. Rothlisberger, and M. Gratzel, “Entropic stabilization of ting diodes,” Chem. Eng. J. 375, 122031 (2019).
mixed A-cation ABX3 metal halide perovskites for high performance perovskite 24
Y. Li, J. Duan, H. Yuan, Y. Zhao, B. He, and Q. Tang, “Lattice modulation of
solar cells,” Energy Environ. Sci. 9(2), 656–662 (2016). alkali metal cations doped Cs1-xRxPbBr3 halides for inorganic perovskite solar
7
Y. Zhao, Y. Wang, J. Duan, X. Yang, and Q. Tang, “Divalent hard Lewis acid cells,” Sol. RRL 2(10), 1800164 (2018).
25
doped CsPbBr3 films for 9.63%-efficiency and ultra-stable all-inorganic perov- R. Zhang, Y. Yuan, J. Li, Z. Qin, Q. Zhang, B. Xiong, Z. Wang, F. Chen, X. Du,
skite solar cells,” J. Mater. Chem. A 7(12), 6877–6882 (2019). and W. Yang, “Ni and K ion doped CsPbX3 NCs for the improvement of lumi-
8
R. Begum, M. R. Parida, A. L. Abdelhady, B. Murali, N. M. Alyami, nescence properties by a facile synthesis method in ambient Air,” J. Lumin. 221,
G. H. Ahmed, M. N. Hedhili, O. M. Bakr, and O. F. Mohammed, “Engineering 117044 (2020).
26
interfacial charge transfer in CsPbBr3 perovskite nanocrystals by heterovalent H. Zhang, R. Yuan, M. Jin, Z. Zhang, Y. Yu, W. Xiang, and X. Liang,
doping,” J. Am. Chem. Soc. 139(2), 731–737 (2017). “Rb+-doped CsPbBr3 quantum dots with multi-color stabilized in
9
J. Yin, G. H. Ahmed, O. M. Bakr, J. -L. Bredas, and O. F. Mohammed, borosilicate glass via crystallization,” J. Eur. Ceram. Soc. 40(1), 94–102
“Unlocking the effect of trivalent metal doping in all-inorganic CsPbBr3 perov- (2020).
skite,” ACS Energy Lett. 4(3), 789–795 (2019). 27
J. Li, X. Du, G. Niu, H. Xie, Y. Chen, Y. Yuan, Y. Gao, H. Xiao, J. Tang,
10
Z. -L. Yu, Y. -Q. Zhao, Q. Wan, B. Liu, J. -L. Yang, and M. -Q. Cai, A. Pan, and B. Yang, “Rubidium doping to enhance carrier transport in CsPbBr3
“Theoretical study on the effect of the optical properties and electronic structure single crystals for high-performance x-ray detection,” ACS Appl. Mater.
for the Bi-doped CsPbBr3,” J. Phys.: Condes. Matter 32(20), 205504 (2020). Interfaces 12(1), 989–996 (2020).
11 28
G. Huang, C. Wang, S. Xu, S. Zong, J. Lu, Z. Wang, C. Lu, and Y. Cui, S. Li, Z. Shi, F. Zhang, L. Wang, Z. Ma, D. Yang, Z. Yao, D. Wu, T. -T. Xu,
“Postsynthetic doping of MnCl2 molecules into preformed CsPbBr3 perovskite Y. Tian, Y. Zhang, C. Shan, and X. J. Li, “Sodium doping-enhanced emission
nanocrystals via a halide exchange-driven cation exchange,” Adv. Mater. 29(29), efficiency and stability of CsPbBr3 nanocrystals for white light-emitting devices,”
1700095 (2017). Chem. Mater. 31(11), 3917–3928 (2019).
12
D. Parobek, Y. Dong, T. Qiao, and D. Son, “Direct hot-injection synthesis 29
P. Todorovic, D. Ma, B. Chen, R. Quintero-Bermudez, M. I. Saidaminov,
of Mn-doped CsPbBr3 nanocrystals,” Chem. Mater. 30(9), 2939–2944 Y. Dong, Z. -H. Lu, and E. H. Sargent, “Spectrally tunable and stable electrolumi-
(2018). nescence enabled by rubidium doping of CsPbBr3 nanocrystals,” Adv. Opt.
13
F. Li, Z. Xia, Y. Gong, L. Gu, and Q. Liu, “Optical properties of Mn2+ doped Mater. 7(24), 1901440 (2019).

12 July 2023 18:13:53

cesium lead halide perovskite nanocrystals via a cation-anion Co-substitution 30
G. Kresse and J. Furthmuller, “Efficient iterative schemes for ab initio total-
exchange reaction,” J. Mater. Chem. C 5(36), 9281–9287 (2017). energy calculations using a plane-wave basis Set,” Phys. Rev. B 54(16),
14
W. van der Stam, J J. Geuchies, T. Altantzis, K. H. W. van den Bos, 11169–11186 (1996).
J. D. Meeldijk, S. Van Aert, S. Bals, D. Vanmaekelbergh, and C. de Mello 31
P. E. Blöchl, “Projector augmented wave method,” Phys. Rev. B 50(24),
Donega, “Highly emissive divalent-Ion-doped colloidal CsPb1-xMxBr3 perovskite 17953–17979 (1994).
nanocrystals through cation exchange,” J. Am. Chem. Soc. 139(11), 4087–4097 32
J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approxima-
(2017). tion made simple,” Phys. Rev. Lett. 77(18), 3865–3868 (1996).
15
J. -S. Yao, J. Ge, B. -N. Han, K. -H. Wang, H. -B. Yao, H. -L. Yu, J. -H. Li, B. 33
S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, “A consistent and
-S. Zhu, J. -Z. Song, C. Chen, Q. Zhang, H. -B. Zeng, Y. Luo, and S. -H. Yu, accurate ab initio parametrization of density functional dispersion correction
“Ce3+-doping to modulate photoluminescence kinetics for efficient CsPbBr3 (DFT-D) for the 94 elements H-Pu,” J. Chem. Phys. 132(15), 154104
nanocrystals based light-emitting diodes,” J. Am. Chem. Soc. 140(10), (2010).
34
3626–3634 (2018). J. Lin, M. Lai, L. Dou, C. S. Kley, H. Chen, F. Peng, J. Sun, D. Lu, S. A. Hawks,
16
M. Liu, G. Zhong, Y. Yin, J. Miao, K. Li, C. Wang, X. Xu, C. Shen, and C. Xie, F. Cui, A. P. Alivisatos, D. T. Limmer, and P. Yang, “Thermochromic
H. Meng, “Aluminum-Doped cesium lead bromide perovskite nanocrystals with halide perovskite solar cells,” Nat. Mater. 17(3), 261 (2018).
stable blue photoluminescence used for display backlight,” Adv. Sci. 4(11), 35
A. Marstrander and C. Møller, “The structure of white cesium lead (II)
1700335 (2017). bromide, CsPbBr3,” Mat. Fys. Medd. Dan. Vid. Selsk. 35, 5 (1966).
17
C. Bi, S. Wang, Q. Li, S. Kershaw, J. Tian, and A. L. Rogach, “Thermally stable 36
X. Wu, S. Xiong, Z. Liu, J. Chen, J. Shen, T. Li, P. Wu, and P. Chu, “Green
copper(II)-doped cesium lead halide perovskite quantum dots with strong blue light stimulates terahertz emission from mesocrystal microspheres,” Nat.
emission,” J. Phys. Chem. Lett. 10(5), 943–952 (2019). Nanotechnol. 6(2), 102–105 (2011).
18
S. Zhou, Y. Ma, G. Zhou, X. Xu, M. Qin, Y. Li, Y. -J. Hsu, H. Hu, G. Li, 37
J. Wang, S. J. Xiong, X. L. Wu, T. H. Li, and P. K. Chu, “Glycerol-bonded
N. Zhao, J. Xu, and X. Lu, “Ag-doped halide perovskite nanocrystals for tunable 3C-SiC nanocrystal solid films exhibiting broad and stable violet to blue-green
band structure and efficient charge transport,” ACS Energy Lett. 4(2), 534 emission,” Nano Lett. 10(4), 1466–1471 (2010).
(2019). 38
P. Zhao, D. Hu, and X. Wu, “Quantum confinement of Si nanosphere
19
J. Duan, Y. Zhao, X. Yang, Y. Wang, B. He, and Q. Tang, “Lanthanide ions with radius smaller than 1.2nm,” Chin. Phys. Lett. 22(6), 1492–1495
doped CsPbBr3 halides for HTM-free 10.14%-efficiency inorganic perovskite (2005).
39
solar cell with an ultrahigh open-circuit voltage of 1.594 V,” Adv. Energy Mater. C. Stoumpos, C. D. Malliakas, J. Peters, Z. Liu, M. Sebastian, J. Im,
8(31), 1802346 (2018). T. C. Chasapis, A. C. Wibowo, D. Y. Chung, A. J. Freeman, B. W. Wessels, and
20
H. Wang, X. Zhao, B. Zhang, and Z. Xie, “Blue perovskite light-emitting M. G. Kanatzidis, “Crystal growth of the perovskite semiconductor CsPbBr3: A
diodes based on RbX-doped polycrystalline CsPbBr3 perovskite films,” J. Mater. New material for high-energy radiation detection,” Cryst. Growth Des. 13(7),
Chem. C 7(19), 5596–5603 (2019). 2722–2727 (2013).
21 40
Q. Jiang, M. Chen, J. Li, M. Wang, X. Zeng, T. Besara, J. Lu, Y. Xin, X. Shan, S. Yakunin, L. Protesescu, F. Krieg, M. Bodnarchuk, G. Nedelcu, M. Humer,
B. Pan, C. Wang, S. Lin, T. Siegrist, Q. Xiao, and Z. Yu, “Electrochemical doping G. De Luca, M. Fiebig, W. Heiss, and M. Kovalenko, “Low-threshold amplified

J. Appl. Phys. 129, 165110 (2021); doi: 10.1063/5.0048067 129, 165110-6

Published under an exclusive license by AIP Publishing.
 Journal of ARTICLE scitation.org/journal/jap
Applied Physics

46
spontaneous emission and lasing form colloidal nanocrystals of caesium lead X. L. Wu, Y. F. Mei, G, G. Siu, K. L. Wong, K. Moulding, M. J. Stokes,
halide perovskites,” Nat. Commun. 6, 8056 (2015). C. L. Fu, and X. M. Bao, “Spherical growth and surface-quasifree vibrations of Si
41
M. Kulbak, D. Cahen, and G. Hodes, “How important Is the organic part of nanocrystallites in Er-doped Si nanostructures,” Phys. Rev. Lett. 86(14),
lead halide perovskite photovoltaic cells? efficient CsPbBr3 cells,” J. Phys. Chem. 3000–3003 (2001).
Lett. 6(13), 2452–2456 (2015). 47
X. L. Wu, S. J. Xiong, G. G. Siu, G. S. Huang, Y. F. Mei, Z. Y. Zhang,
42
M. Kulbak, S. Gupta, N. Kedem, I. Levine, T. Bendikov, G. Hodes, and S. S. Deng, and C. Tan, “Optical emission from excess Si defect centers in Si
D. Cahen, “Cesium enhances long-term stability of lead bromide perovskite- nanostructures,” Phys. Rev. Lett. 91(15), 157402 (2003).
based solar cells,” J. Phys. Chem. Lett. 7(1), 167–172 (2016). 48
H. T. Chen, S. J. Xiong, X. L. Wu, J. Zhu, J. C. Shen, and P. Chu, “Tin oxide
43
A. F. Akbulatov, L. A. Frolova, N. N. Dremova, I. Zhidkov, V. M. Martynenko, nanoribbons with vacancy structures in luminescence-sensitive oxygen sensing,”
S. A. Tsarev, S. Y. Luchkin, E. Z. Kurniaev, S. M. Aldoshin, K. J. Stevenson, and Nano Lett. 9(5), 1926–1931 (2009).
P. A. Troshin, “Light or heat: What is killing lead halide perovskites under solar 49
X. L. Wu, S. J. Xiong, J. Zhu, J. Wang, J. C. Shen, and P. K. Chu,
cell operation conditions?,” J. Phys. Chem. Lett. 11(1), 333–339 (2020). “Identification of surface structures on 3C-SiC nanocrystals with hydrogen
44
C. Persson, Y. -J. Zhao, S. Lany, and A. Zunger, “N-type doping of CuInSe2 and hydroxyl bonding by photoluminescence,” Nano Lett. 9(12), 4053–4060
and CuGaSe2,” Phys. Rev. B 72(3), 035211 (2005). (2009).
45
S. -H. Wei, “Overcoming the doping bottleneck in semiconductors,” Comput. 50
J. Fan, X. Wu, and T. Qiu, “Experimental evidence for quantum confinement
Mater. Sci. 30(3), 337–348 (2004). in 3C-SiC nanoparticles,” Physics 34(8), 570–572 (2005).

12 July 2023 18:13:53

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