Vol. 38, No.

1 Journal of Semiconductors January 2017

Calculation studies on point defects in perovskite solar cells

Dan Han1; 2 , Chenmin Dai2 , and Shiyou Chen2; Ž
1 Department of Physics, East China Normal University, Shanghai 200241, China
2 Key Laboratory of Polar Materials and Devices (MOE), East China Normal University, Shanghai 200241, China

Abstract: The close-to-optimal band gap, large absorption coefficient, low manufacturing cost and rapid increase
in power conversion efficiency make the organic–inorganic hybrid halide (CH3 NH3 PbI3 ) and related perovskite
solar cells very promising for commercialization. The properties of point defects in the absorber layer semicon-
ductors have important influence on the photovoltaic performance of solar cells, so the investigation on the defect
properties in the perovskite semiconductors is necessary for the optimization of their photovoltaic performance. In
this work, we give a brief review to the first-principles calculation studies on the defect properties in a series of
perovskite semiconductors, including the organic–inorganic hybrid perovskites and inorganic halide perovskites.
Experimental identification of these point defects and characterization of their properties are called for.

Key words: point defects; perovskite solar cells; non-radiative recombination

DOI: 10.1088/1674-4926/38/1/011006 EEACC: 8420

ers significantly. Despite the remarkable progress in the first-

1. Introduction
After the solar cells based on the p–n junctions were in-
vented, the studies on the points defects in the light-absorber
semiconductors drew intensive attention, because they may act
as effective recombination centers of the photo-generated elec-
trons and holesŒ1 5 . In the conventional light-absorber semi-
conductors such as crystalline siliconŒ1 4 , and binary com-
pounds GaAsŒ2; 6 8 and CdTeŒ9; 10 , there are a limited number
of possible point defects with high concentration, mainly va-
cancies and interstitials, while the anti-site defects have low
concentration. Nevertheless, the defect properties influence
their photovoltaic performance significantly and determine
even the optimal growth conditions for high-efficiency solar
cells, which is still under intensive investigation recentlyŒ9 .
In novel light-absorber semiconductors with more component
elements, the number of possible point defects increases dra-
matically, and their influence on the photovoltaic performance
is more significant, e.g., in the chalcopyrite Cu(In,Ga)Se2 and
kesterite Cu2 ZnSnS4 Œ2; 11 20 .
Recently the perovskite-structured organic-inorganic hy-
brid halides such as CH3 NH3 PbI3 (MAPbI3 ) emerge as new
light-absorber semiconductors with superior performance, as
they have a series of superior properties including the opti-
mal band gap, large absorption coefficient, abundant compo-
nent elements, high Voc and low manufacturing costŒ5; 21 25 .
Their power conversion efficiency has increased rapidly to
over 22%Œ26; 27 , making the perovskite solar cells very promis-
ing for the future commercializationŒ28 35 . This superior per-
formance was also found to be closely related to the benign
defect properties in the organic–inorganic hybrid halides, i.e.,
the point defects that have high concentration do not produce
deep levels in the band gap and thus are not effective recombi-
nation centers, which increases the lifetime of minority carri-
principles calculation study on the point defects in these per-
ovskite semiconductors, there are still open questions, includ-
ing whether there are deep-level recombination-center defects
that may have high concentration under different growth con-
ditions, and why the defect properties are so different in the
organic–inorganic hybrid versus fully inorganic halides, and
Sn-based versus Pb-based perovskites? Furthermore, the ex-
perimental identification of these point defects that the first-
principles calculations predicted and the characterization of
their properties are still very limited.
Here we will briefly review the recent progress in the
first-principles calculation study on the point defects in these
perovskite semiconductors, reported by different theoretical
groups. Different material systems including the organic-
inorganic hybrid halide perovskites such as MAPbI3 (with dif-
ferent crystal structures), MAPbI2 Cl, MAPbBr3 and MASnI3 ,
and inorganic halide perovskites will be discussed.
2. Organic–inorganic hybrid halide perovskites
2.1. Methylammonium lead halides
2.1.1. Cubic MAPbI3
Theoretical calculation studies on the point defects in
the high-temperature pseudo-cubic phase ˛-CH3 NH3 PbI3
(CH3 NH3 denoted MA hereafter) was firstly reported by Yin
et al., which had drawn wide attention in this field. They con-
sidered all possible point defects including three vacancies
(VMA , VPb , VI ), three interstitias (MAi , Pbi , Ii ) and six anti-
sites (MAPb , PbMA , MAI , PbI , IMA , IPb ), and studied their defect
properties under three representative chemical potential condi-
tions, I-rich/Pb-poor, moderate, I-poor/Pb-rich. Formation en-
ergy of each defect as a function of the chemical potential un-

* Project supported by the National Natural Science Foundation of China (No. 61574059), the Shanghai Rising-Star Program (No.
14QA1401500), the Shu-Guang Program (15SG20), and the CC of ECNU.
† Corresponding author. Email: chensy@ee.ecnu.edu.cn
Received 23 August 2016, revised manuscript received 26 October 2016 © 2017 Chinese Institute of Electronics

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J. Semicond. 2017, 38(1) Dan Han et al.

Fig. 1. (Color online) The calculated formation energy of intrinsic defects in ˛-MAPbI3 under three representative chemical conditions. (a)
I-rich and Pb-poor. (b) moderate. (c) I-poor and Pb-rich. Reprinted with permission from Ref. [38].

Fig. 2. The transition energy levels of 12 intrinsic defects: (a) acceptor defects and (b) donor defects. Reprinted with permission from Ref. [38].

der I-rich/Pb-poor, moderate, I-poor/Pb-rich conditions were
calculated as shown in Fig. 1.
Under the I-rich/Pb-poor condition, acceptor defect VPb
has the lowest formation energy while all the donor defects
have high formation energy, leading to the Fermi level pinned
close to VBM (valence band maximum) and making the sam-
ple show p-type conductivity. Under the moderate condition,
donor defect MAi decreased its formation energies, while the
acceptor defect VPb slightly increased the formation energies,
thus pinning the Fermi level at the mid-gap and showing neu-
tral conductivity. Under the I-poor/Pb-rich condition, donor
defects (MAi , MAI ) further decrease their formation energies,
becoming the lowest-energy defects, while acceptor defects
(VPb , MAPb and Ii ) further increase their formation energies,
making the Fermi level pinned close to the CBM (conduc-
tion band minimum) and showing intrinsic n-type conductiv-
ity. These results showed that the conductivity of the high-
temperature phase MAPbI3 may be tuned from good intrinsic
p-type, to moderate and then to good intrinsic n-type under I-
rich/Pb-poor, moderate or I-poor/Pb-rich chemical conditions
respectively, which is consistent with the fact that both intrin-
sic n-type and p-type conductivity samples could be synthe-
sized in experimentŒ36 . This interesting bipolar conductivity
may result from the dominant donor MAi and dominant ac-
ceptor VPb having comparable formation energies, which is
quite different from the conventional thin-film solar cell ab-
sorber Cu(In,Ga)Se2 Œ13 and Cu2 ZnSnS4 Œ37 where donor de-
fects generally have much higher formation energies than ac-
ceptors.
Transition energy levels of these point defects were also
calculated, as shown in Fig. 2. Combining Fig. 1 and Fig. 2,
we can see that the low formation energy (high concentra-
tion) defects such as VPb , MAPb , MAi and VI have shallow
or resonant transition energy levels, while the defects with
deep transition energy levels have high formation energies (low
concentration) under different chemical conditions. This indi-
cates that MAPbI3 has very low non-radiative recombination
rate, which explains partially the long electron–hole diffusion
lengthsŒ29; 39 . Yin et al. analyzed the origin of the shallow
transition energy levels of dominant acceptor defects VPb and
MAPb according to the anti-bonding state nature of VBM, i.e.,
the coupling of Pb s state and I p state pushes the VBM up to
a high level. For the donor defects MAi and VI , the shallow
levels result from the high ionicity of MA and Pb ions.
It is noteworthy that there are many low-energy donor and
acceptor intrinsic point defects in MAPbI3 , thus they are likely

011006-2
J. Semicond. 2017, 38(1)
Fig. 3. (Color online) The structures around two IC
i sites (a,b) and one Ii site (c). Only one Pb-I layer (parallel to the ab plane) is shown, with
the red and blue balls representing Pb and I atoms, respectively. Reprinted with permission from Ref. [42].
Fig. 4. The calculated transition energy levels of VI , Ii , IMA , Pbi , and
PbMA in ˇ-MAPbI3 calculated using different levels of exchange-
correlation functional approximations and spin-orbit coupling, includ-
ing GGA-non-SOC, GGA-SOC, and HSE-SOC (˛ D 0.43). Reprinted
with permission from Ref. [42].
to form compensated charge-neutral clusters. Walsh et al.Œ40
investigated three types of Schottky defects (vacancy clusters)
including MAPbI3 vacancy (a cluster of an MA vacancy, a Pb
vacancy and three I vacancies), MAI vacancy (a cluster of an
MA vacancy and an I vacancy) and PbI2 vacancy (a cluster of
a Pb vacancy and two I vacancies). They found that all of them
have low formation energy and high concentration in MAPbI3 ,
which means that it is energetically quite easy to remove the
MAI, PbI2 and even MAPbI3 molecules from the halide per-
ovskite lattice. This behavior may result from the reduced elec-
trostatic potential of the halide perovskite lattice, i.e., the C1
and C2 cations and –1 anions in the halide perovskites have
much weaker electrostatic Coulomb attraction compared to the
oxide perovskites in which the C2 and C4 charged cations and
–2 charged anions attracted each other tightly. The high con-
centration of Schottky defects (vacancy clusters) makes 0.4%
of the lattice sites unoccupied by any ions and explains why
the synthesized samples have lower density than expectedŒ40 .
011006-3
Dan Han et al.
2.1.2. Tetragonal MAPbI3
The defect properties of ˇ-MAPbI3 (the tetragonal room-
temperature phase) were first reported by DuŒ41 43 , which is
very important for understanding the superior performance of
the working perovskite solar cells. One low formation energy
defect, the iodine interstitial Ii , was found to create deep levels
in the band gap and may act as an effective non-radiative re-
combination center. Ii is a negative-U defect and its thermody-
namic transition energy level (C/–) is located between (C/0)
and (0/–) levels, so Ii prefers the negatively charged state Ii
when the Fermi level is low (closer to VBM) and the posi-
tively charged state IC i when the Fermi level is high (closer
to CBM), with the neutral state always metastable. The local
structures around the I interstitial in different charge states are
shown in Fig. 3. The (C/0) and (0/–) levels inside the band
gap result from large structural relaxation when the charge state
changes. However, the single-particle defect levels for IC i and Ii
are absent in the band gap, suggesting that although the electron
or hole trapping around Ii is energetically favorable, it needs
to overcome kinetic barriers thus limiting the capture cross-
section. Therefore despite the existence of low-energy Ii with
deep levels, electron and hole diffusion lengths can still be long
in MAPbI3 .
Interestingly, DuŒ42 also showed that although the band
gaps of MAPbI3 predicted by the generalized gradient approx-
imation (GGA) without spin-orbit coupling (SOC) and the hy-
brid functional HSE with SOC are both in good agreement
with the experimental value, the VBM and the CBM obtained
by these two calculations are drastically different. This differ-
ence influences the calculated transition energy levels and also
the formation energies (concentration) of point defects signif-
icantly. The disregard of SOC (which raises the CBM) causes
many deep defect levels near the CBM, and the large self-
interaction error (which raises the VBM) causes the failure to
predict the deep acceptor levels near the VBM in GGA-non-
SOC calculations. The calculated transition energy levels us-
ing HSE-SOC and GGA-non-SOC are shown in Fig. 4, from
which we can see that the results are influenced by the specific
approximations obviously.
Buin et al.Œ44 calculated the defect properties (the forma-
tion energies and transition energy levels) of ˇ-MAPbI3 using
GGA (PBE). Their results are shown in Fig. 5. Compared to
the defects in ˛-MAPbI3 , defects in ˇ-MAPbI3 have similar
J. Semicond. 2017, 38(1) Dan Han et al.

Fig. 5. (Color online) The calculated formation energy of ˇ-MAPbI3 under (a) I-rich and Pb-poor conditions, (b) I-poor and Pb-rich conditions.
The red shading area denotes the concentration of defects with deep levels exceeding 1015 cm 3 and the green shading area denotes the con-
centration of defects with deep levels below 1015 cm 3 . Reprinted with permission from Ref. [44]. Note that the symbols of the anti-site defects
in Ref. [44] are different from those in other papersŒ38; 42; 45 47 which adopted the standard Kröger-Vink notation, with IPb representing I
replacing Pb, but here IPb representing I substituted by Pb.

Fig. 6. (Color online) Structures before the SA relaxation (shaded) and after SA relaxation (not shaded) for VI , Pbi and IMA . (a) A Pb-Pb dimer
forms near the I vacancy after relaxation. (b) A Pb–Pb dimer forms near Pb interstitial. (c) An I–I–I trimer forms when MA is replaced by I.
Reprinted with permission from Ref. [45].

formation energy dependence on the Fermi energy, except: (1)
IPb (I substituted by Pb. Note: this symbol of the anti-site defect
in Ref. [44] is different from those in other papersŒ38; 42; 45 47
which adopted the standard Kröger-Vink notation, with IPb rep-
resenting I replacing Pb) has lower formation energy in ˇ-
MAPbI3 than in ˛-MAPbI3 ; (2) PbI (Pb substituted by I) and
IPb are low-energy defects with deep transition energy levels.
As shown in Fig. 5(a), under the I-rich and Pb-poor conditions,
the deep trap defect PbI always has high concentration wher-
ever the Fermi level is located; under I-poor and Pb-rich condi-
tions, the concentration of deep trap defects decreased to lower
than 1015 cm 3 , when Fermi levels are higher than 0.9 eV.
Therefore, in order to improve performance of MAPbI3 in pho-
tovoltaic application, the sample should be synthesized under
I-poor and Pb-rich conditions.
It should be noted that Buin et al. found Ii is an acceptor
defect with shallow transition energy levels, which is different
from the Du’s results that Ii has deep transition energy levels.
This difference may result from the different calculation meth-
ods (the lower level GGA calculations versus higher level HSE
calculations), and various structural configurations around the
interstitial sites. There are several different metastable config-

011006-4
J. Semicond. 2017, 38(1) Dan Han et al.

Fig. 7. (Color online) Formation energy as a function of Fermi level of four defects with deep transition energy levels under different chemical
potential conditions. Reprinted with permission from Ref. [45].

Fig. 8. The transition energy levels of 12 intrinsic defects. Blue lines represent (0/–) transition energy levels and brown lines represent (C/0)
transition energy levels. Bold lines means they are deep levels. Reprinted with permission from Refs. [45, 47].

urations which the local structural optimization may arrive at,
with the real ground state ignored, as shown by Du using the
HSE hybrid functionalŒ42 . Furthermore, the very high concen-
tration of defects predicted by the GGA-PBE functional may
result from the underestimation of the formation energies in the
GGA-level calculations.
In all the aforementioned studies, the local structure
around the point defects is determined through local structural
optimization or intuitively. Interestingly, Michael et al. per-
formed a non-intuitive search for the low-energy defect struc-
tures in the configuration space using the simulated annealing
(SA) method (on the GGA level), and found a series of new low
energy structures for the –1 charged VI and PbMA , and neutral
IMA and Pbi in ˇ-MAPbI3 , as shown in Fig. 6.
According to the defect structure determined by the lo-
cal structural optimization, both VI and PbMA are donor de-
fects with very shallow (0/C/ transition energy levels close to
CBM, and its –1 charged state is unstable with high formation
energies (as there are two electrons occupying the high CBM
level). However, the SA search showed that the –1 charged VI
and PbMA can undergo dramatic structural distortion with the
two neighboring Pb atoms forming a Pb–Pb dimer. After that,
a deep defect level is produced in the band gap, making the
two electrons occupying the CBM before the formation of Pb
dimer drop to this gap level. Therefore the energy of the –1
charged state decreases significantly and thus the (0/–) level
drops down from the CBM level to deep in the band gap, e.g.,
0.38 eV below CBM for VI , as shown in Fig. 7 where the calcu-
lated formation energies at different charge states were plotted
as a function of the Fermi energy. Pbi in neutral charge state
also has two electrons occupying the CBM level, like VI in its
–1 charged state. After relaxation (SA search), Pbi undergoes a
structure distortion and forms a Pb–Pb dimer pulling the level
occupied by two electrons above the CMB into the gap. For
IMA , the origin of deep level is different from the above cases.
When MA is replaced by I, I tends to form a trimer structure as

011006-5
J. Semicond. 2017, 38(1)
Fig. 9. (Color online) Formation energy as a function of Fermi level
of the vacancy defects and band-edge defects under different chemical
potential conditions at T D 300 K. Reprinted with permission from
Ref. [52].
shown in Fig. 6(c). This I trimer distortion pushes up an empty
level which is originally located right above the VBM to mid-
bandgap.
The formation of Pb–Pb dimers and I–I–I trimer indicates
strong covalency in MAPbI3 that was considered to be an ionic
material exhibiting weak covalency. The calculated transition
energy levels by Michael et al. are shown in Fig. 8.
As shown in Fig. 7, the formation energy of VI , Pbi and
PbMA are calculated under I-poor and Pb-rich conditions and
IMA are calculated under I-rich and Pb-poor conditions. For VI ,
when EF is higher than 1.44 eV, the –1 charge state becomes
the most stable, and VI acts as an acceptor and also an effective
recombination center, whereas when EF is lower than 1.44 eV,
C1 charge state becomes the most stable and VI acts as a nor-
mal shallow donor. The red shading region shows the Fermi
level range in which these deep-level defects prefer undergoing
structural distortion and acting as recombination centers Thus
it is necessary to control the Fermi level beyond this range, so
that the formation of these possible recombination centers can
be suppressed.
The Schottky defects in ˇ-MAPbI3 were also studied by
Kim et al.Œ48 , who calculated the electronic structure of PbI2
and MAI vacancy and found that they could not introduce deep
trap states within the band gap.
As described above, the calculated defect properties are
sensitive to the specific approximations in the first-principles
calculations, so it is important to compare these calculated
properties to the measured values. So far, only three groups
have characterized the defect levels in MAPbI3 solar cells ex-
perimentally. Samiee et al.Œ49 revealed a deep defect state 0.65
and 0.24 eV below the conduction band and a bandgap of
1.58 eV. Jiang et al.Œ50 found a state 0.21 eV above the va-
lence band. Duan et al. employed the temperature-dependent
admittance spectroscopy and identified the defect energy distri-
bution in perovskite CH3 NH3 PbI3 solar cells, revealing a deep
defect state 0.16 eV above the valence bandŒ51 , which may be
011006-6
Dan Han et al.
ascribed to the I interstitials. Since the single-particle levels of
the I interstitials are absent in the band gap, they cannot be ex-
cited by sub-band-gap excitation and cannot be easily seen in
optical absorption experimentsŒ42 .
2.1.3. Orthorhombic MAPbI3
Yang et al.Œ52 calculated the formation energy of intrinsic
vacancy defects and band-edge “defects” as a function of Fermi
level in orthorhombic MAPbI3 . They also found that Schot-
tky defects are easy to form. Due to the compensation between
dominant donor defect VI and the dominant acceptor defects
VMA and VPb , the Fermi levels are pinned at A point, B point
and C point under three different atomic chemical potentials as
depicted in Fig. 9. Therefore MAPbI3 shows n-type conductiv-
ity under I-poor condition and p-type conductivity under I-rich
condition. This conclusion is consistent with Yin et al.’s except
that the dominant donor defect is VI rather than MAi . It should
be noted that under I-rich condition the Fermi level is deter-
mined by the competition between the acceptor defect VPb and
band-edge donor “defect” H1 . H1 is the formation energy
of free electron carrier generated through thermal excitation,
which was ignored in previous studies on the defect properties
but is important for predicting the Fermi level pinning energy.
2.1.4. MAPbI2 Cl
When mixing iodide and chloride in the form of
MAPbI3 x Clx (x  1)Œ29; 53 , the carrier diffusion length is
increased to 1 micrometer which is 10 times larger than that
in MAPbI3 Œ54 . The increased carrier diffusion in MAPbI2 Cl
may result from some factors pointed out by DuŒ41 . One is
that by alloying iodide with chloride, MAPbI2 Cl has smaller
lattice constants than MAPbI3 Œ23; 55 , which may suppress the
formation of iodine interstitials (Ii has a higher formation en-
ergy in MAPbI2 Cl than in MAPbI3 ). The second factor is that
ClCi has an even higher formation energy, and Cli is a rel-
atively shallow acceptor and not an effective recombination
center. Therefore, the recombination rate in MAPbCl2 I can be
much lower than that in MAPbI3 . Jiang et al.Œ50 compared the
defect level and densities between MAPbI3 and MAPbI3 x Clx
by admittance spectroscopy. They found that the defect levels
of MAPbI3-x Clx and MAPbI3 are quite similar but the defect
density of MAPbI3-x Clx is nearly half of MAPbI3 , which is
consistent with Du’s theoretical prediction.
2.2. MAPbBr3
Heo et al.Œ56 reported that planar MAPbBr3 hybrid solar
cell has power conversion efficiency of 10.4%, despite the ef-
ficiency still being lower than MAPbI3 . Shi et al.Œ57 reported
charge carrier diffusion lengths of single crystal MAPbBr3
which is over 10 times longer than that of MAPbI3 and ob-
served extremely low trap-state densities. Through density
functional theory calculations, they analyzed the origin of low
trap-state densities. They calculated the formation energy of
defects with deep trap states. In Fig. 10, the gray rectangle de-
notes the Fermi level region in which the deep trap states are
suppressed. Under Br-rich and Pb-poor conditions, there is a
wider region free of deep-level defects than that under Bi-poor
and Pb-rich conditions, which suggests that the Br-rich synthe-
sis condition leads to lower density of trap states. According to
J. Semicond. 2017, 38(1)
Fig. 10. Formation energies of intrinsic defects except vacancies (due to their shallow nature). Reprinted with permission from Ref. [56].
Fig. 11. (Color online) The stable chemical potential region of single-
phase CsSnI3: Reprinted with permission from Ref. [69].
Shi et al.’s calculations of binding energy of complex defects,
the anti-site defects PbBr and BrPb are not stable and they tend
to decompose into VBr and Pbi or VPb and Bri .
2.3. Methylammonium tin halides
MASnI3 is more environmental friendly than
MAPbI3 Œ58; 59 . However, the easy oxidation of the Sn2C
makes this lead-free hybrid halide perovskite show poorer
photovoltaic performance. Direct calculation studies on the
defect properties in MASnI3 have not been reported. However,
considering that MASnI3 and CsSnI3 differ only in the C1
charged cation, we may deduce the main characteristics of
MASnI3 defects from the following discussion about the
defect properties in CsSnI3 .
3. Inorganic halide perovskite
The poor stability of MAPbX3 has become a crucial prob-
lem when they are exposed to humidity, oxygen or heat-
ingŒ60 65 . Comparing to the organic/inorganic hybrid per-
011006-7
Dan Han et al.
ovskites, the fully inorganic perovskites exhibit slightly higher
stability. In experiments, Hodes et al.Œ66 enhanced long-term
stability of lead bromide perovskite-based solar cells through
substituting MAC with CsC while maintaining comparable
power conversion efficiency versus MAPbBr3 . Xin et al.Œ67
theoretically proposed a method for enhancing the stability
of MAPbX3 , which can be achieved when the organic cation
MAC is replaced by the inorganic CsC . Recently, Kanatzidis
et al.Œ68 fabricated CsSnI3 , which was unique in combining
a high p-type electrical conductivity and strong photolumines-
cence. Therefore, CsSnI3 has been proposed as both a light-
absorber material and a hole-transport material.
Xu et al.Œ69 have demonstrated through the first-principles
calculations that controlling the concentration of intrinsic de-
fects is crucial for optimizing the performance of CsSnI3 -based
solar cells. They found that the pure CsSnI3 can be synthe-
sized only in a very narrow chemical potential region (Fig. 11),
where CsSnI3 is more stable with respect to other competitive
phases such as Cs, Sn, I elemental phases and CsI, SnI2 , SnI4 ,
and Cs2 SnI6 compounds.
They considered all the possible intrinsic point defects in-
cluding three vacancies (VCs , VSn , VI /, three interstitial (Csi ,
Sni , Ii /, and six anti-site substitutions (CsSn , CsI , SnCs , SnI , ICs ,
ISn /, as shown in Fig. 12. Under the Sn-rich condition, VCs
is the lowest-energy acceptor defect, while SnI is the lowest-
energy donor defect. Owing to the effect of defect compen-
sation, the Fermi energy will be pinned at the middle of the
band gap (about 0.7 eV above VBM). Hence, the concentra-
tion of the hole carriers cannot be high, which indicates CsSnI3
has low p-type conductivity under the Sn-rich condition. Un-
der the Sn-poor condition, the dominant defect becomes VSn .
The acceptor VSn compensates the donor defect VI , making
the Fermi energy pinned close to VBM, so CsSnI3 becomes
a good p-type material, explaining why CsSnI3 exhibits an ob-
served high conductivity and may act as a hole-transport mate-
rialŒ68; 70 . To increase the p-type conductivity, Sn poorer con-
dition is preferred.
Fig. 13 shows the calculated transition energy levels. It is
obvious that the levels of all acceptor defects are in the va-
J. Semicond. 2017, 38(1)
Fig. 12. (Color online) Formation energies as a function of Fermi energy of intrinsic defects in CsSnI3 under two different chemical conditions,
A (Sn-rich) and D (Sn-poor). Reprinted with permission from Ref. [69].
Fig. 13. (Color online) Transition energy levels of intrinsic defects in
CsSnI3 . Reprinted with permission from Ref. [69].
lence band, indicating that the acceptor defects are ionized once
formed, thus high concentration of VCs and VSn generates a
large number of hole carriers, leading to high p-type electrical
conductivity. The transition energy levels of most of the donor
defects are in the conduction band, except SnI anti-site which
produces a deep donor level in the band gap. Due to the low
local symmetry at the I site, once Sn substitutes for I, the de-
generate levels of 5p orbitals split, producing a shallow (0/C/
level near the CBM and a deep (C1/C3) level at the middle
of the band gap. Therefore SnI can act as a recombination cen-
ter of the photogenerated electron-hole pairs under the Sn-rich
condition, which is detrimental to the solar cell. To suppress
the SnI formation and improve the photovoltaic performance of
CsSnI3 as a light absorber, a Sn-poor environment is required.
However, a very Sn-poor condition increases the hole concen-
tration to a very high level, causing the shunt resistance to be
very low and thus affecting the solar cell performance. There-
fore, the best chemical environment for synthesizing CsSnI3 as
011006-8
Dan Han et al.
a light absorber is moderately Sn-rich.
4. Conclusions
From the above theoretical analysis and discussions, we
can see that the formation of deep-level defects acting as possi-
ble non-radiative recombination centers can be suppressed ef-
ficiently by adjusting Fermi levels (carrier concentration) and
changing chemical potentials (growth conditions) especially in
MAPbI3 , so MAPbI3 and MAPbI2 Cl could possess a long car-
rier diffusion length and exhibit superior performance in photo-
voltaic devices. Even so, the formation energy of intrinsic point
defects in MAPbI3 are not high and the Schottky defects such
as the PbI2 and MAI vacancy clusters are very easy to form, in-
dicating that MAPbI3 is not stable enough with respect to the
phase separation. This may be one intrinsic bottleneck for the
application of MAPbI3 light absorber in wide-area solar cells.
In contrast, the suppression of the recombination-center
defects in Sn-based perovskites is more challenging, because
it requires a Sn-poor condition which, however, increases the
concentration of Sn-oxidized acceptor defects and hole carriers
significantly and thus decreases the shunt resistance, detrimen-
tal to the photovoltaic performance.
Systematical experimental identification of these point de-
fects predicted by the theoretical calculations has not been re-
ported. Recent fabrication of high-quality single-crystal sam-
ples of the MAPbI3 related halides may make that possible in
the near future. Then the defect control and optimization may
further improve the efficiency and stability of the perovskite
solar cells.
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