Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber

Wan-Jian Yin, Tingting Shi, and Yanfa Yan

Citation: Applied Physics Letters 104, 063903 (2014); doi: 10.1063/1.4864778

View online: http://dx.doi.org/10.1063/1.4864778
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 APPLIED PHYSICS LETTERS 104, 063903 (2014)

Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber

Wan-Jian Yin,a) Tingting Shi, and Yanfa Yanb)
Department of Physics and Astronomy and Center for Photovoltaics Innovation and Commercialization,
The University of Toledo, Toledo, Ohio 43606, USA

(Received 25 November 2013; accepted 28 January 2014; published online 10 February 2014)
Thin-film solar cells based on Methylammonium triiodideplumbate (CH3NH3PbI3) halide
perovskites have recently shown remarkable performance. First-principle calculations show that
CH3NH3PbI3 has unusual defect physics: (i) Different from common p-type thin-film solar cell
absorbers, it exhibits flexible conductivity from good p-type, intrinsic to good n-type depending on
the growth conditions; (ii) Dominant intrinsic defects create only shallow levels, which partially
explain the long electron-hole diffusion length and high open-circuit voltage in solar cell. The
unusual defect properties can be attributed to the strong Pb lone-pair s orbital and I p orbital
antibonding coupling and the high ionicity of CH3NH3PbI3. V C 2014 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4864778]

Methylammonium triiodideplumbate (CH3NH3PbI3)-based
organometal halide perovskite has recently emerged as a
promising solar photovoltaic absorber.1–9 Recent reports have
shown electron-hole diffusion lengths8,9 as long as 1 micro-
meter in low-temperature solution processed halide perov-
skites. A planar heterojunction solar cell with a about 330 nm
thick CH3NH3PbI3xClx absorber layer has exhibited an
energy conversion efficiency of over 15%.5 More interest-
ingly, the cell, which has the same configuration as other thin
film solar cells, has shown a very high open circuit voltage
(Voc), more than 1.0 V. Considering a bandgap (Eg) of
1.5 eV, the Voc/Eg ratio is comparable to that of the best
single-crystal GaAs thin film solar cell and outperforms that
of the high efficiency polycrystalline thin-film solar cells
such as Cu(In,Ga)Se2 and CdTe.
The properties of defects, especially point defects, in
absorbers play a critical role on determining the electron-hole
diffusion length and Voc of a solar cell. Defects that create
deep levels usually act as Shockley-Read-Hall nonradiative
recombination centers and are responsible for short minority
carrier lifetime and thus low Voc. The long electron-hole dif-
fusion length and high ratio of Voc/Eg indicate the unusual
defect properties in CH3NH3PbI3. On the other hand, the
Shockley-Queisser limit10 for single-junction solar cell based
on an absorber with Eg of 1.5 eV should be close to 30%. To
further improve the efficiency of halide perovskite-based
thin-film solar cells, it is crucial to investigate thermody-
namic stability of CH3NH3PbI3 and the formation mecha-
nisms of the dominant intrinsic defects.
In this Letter, we show by first-principles density-func-
tional theory (DFT) calculation that the electrical conductivity
of CH3NH3PbI3 can be tuned from good p-type to good
n-type by controlling growth conditions, i.e., the chemical
potential of CH3NH3I and Pb sources. Such excellent dupabil-
ity is not seen in CdTe, CuInSe2 (CISe), and Cu2ZnSnS4
(CZTS), which are intrinsically p-type. The defects in
CH3NH3PbI3 with low formation energies create only shallow
a)
Author to whom correspondence should be addressed. Electronic mail:
wanjian.yin@utoledo.edu
b)
Email: yanfa.yan@utoledo.edu
levels, whereas defects with deep levels have high formation
energies, which explains well the long electron-hole diffusion
length and high Voc. Such unusual defect properties can be
attributed to the strong Pb lone-pair s orbital and I p orbital
antibonding coupling and the high ionicity of CH3NH3PbI3.
The narrow chemical potential region in thermodynamic sta-
bility indicates that the growth conditions must be carefully
controlled to avoid the formation of secondary phases.
CH3NH3PbI3 have a cubic perovskite ABX3 structure
(space group Pm3m) at high temperature. Since the methyl-
ammonium ion, CH3NH3þ (MA) is noncentrosymmetric, the
orientation of MA should be disordered to satisfy the high Oh
symmetry. We find that the electronic structure and total
energy of CH3NH3PbI3 have very weak dependence on the
orientation of MA ion due to van der Waals interactions
between MA ion and three dimensional (3D) Pb-I framework.
In this Letter, we have performed electronic structure calcula-
tions (band structure, density of states, and partial charge den-
sity) based on the perovskite unit cell containing 12 atoms
with the orientation of MA lying along [111] direction. The
defect calculations are based on a (3  3  3) supercell with
the C point. The first-principles calculations are performed
using VASP code11 with the standard frozen-core projector
augmented-wave (PAW) method. The cut-off energy for basis
functions was 400 eV. The generalized gradient approxima-
tion (GGA) was used for exchange-correlation. Atomic posi-
tions are relaxed since all the forces on atoms are below
0.05 eV/Å. The effect of spin-orbital coupling (SOC) was pre-
viously reported in CH3NH3PbI312 due to strong relativistic
effect of Pb. However, the band gap errors of using GGA and
non-SOC are cancelled with each other in occurrence.13
Therefore, the GGA gives the experimental band gap without
any underestimation and thus SOC was not considered in our
calculations.
In perovskite CH3NH3PbI3, CH3NH3 and Pb donate one
and two electrons, respectively, to three I ions, forming a band
gap of 1.5 eV between unoccupied Pb p orbital and occupied I
p orbital [see Figures 1(e)–1(h)]. The CH3NH3 molecule do
not have any significant contribution around the band edge
[Fig. 1(f)] but donate one electron to Pb-I framework. It is
noted that for a stable perovskite ABX3, the ion radius ratio

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V

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 063903-2 Yin, Shi, and Yan
FIG. 1. (a) The schematic perovskite structure of CH3NH3PbI3. (b) and (c)
Are the partial charge density at CBM and VBM, respectively, in (d) the
band structure of CH3NH3PbI3. (e) and (f) Are total DOS and CH3NH3þ,
Pb, I partial DOS, respectively. The zero in DOS is referred to VBM. The
Pb partial DOS has enlarged by five times for clear indication of s orbital
contribution.
pffiffiffi
(rA þ rX)/ 2(rB þ rX) is required to be close to 1 and thus the
size of A atom is much larger than that of atom B.14 For
CH3NH3PbI3, Pb is already a large atom and it is difficult to
find single element A that is large enough to stabilize APbI3.
Large-size organic ion CH3NH3þ can effectively stabilize this
perovskite structures but do not make considerable contribu-
tion to the electronic structure of CH3NH3PbI3 around the
band edge. The conduction band minimum (CBM) of
CH3NH3PbI3 is mainly Pb p orbital with negligible coupling
with I, indicating the ionicity of CH3NH3PbI3 [Fig. 1(b)]. The
fully-occupied s orbital of Pb2þ has strong antibonding cou-
pling [Figs. 1(c) and 1(g)] with I p, making upper valence
bands (VBs) dispersive [Fig. 1(d)]. The band edge characters
are also consistent with recent investigation.15,16 The strong
s-p antibonding coupling results in the small hole effective
mass which is comparable with electron effective mass, mak-
ing CH3NH3PbI3-based perovskite an ideal candidate for
thin-film solar cells with a p-i-n configuration.
In thermodynamic equilibrium growth conditions, the
existence of CH3NH3PbI3 should satisfy17
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Appl. Phys. Lett. 104, 063903 (2014)
FIG. 2. Thermodynamic stable range for equilibrium growth of CH3NH3PbI3
is a narrow but long region marked as red color. Outside this region, the com-
pound will decompose into PbI2 and CH3NH3I. We choose representative
points A(lMA ¼ 2.87 eV, lPb ¼ 2.39 eV, lI ¼ 0 eV), B(lMA ¼ 2.41 eV,
lPb ¼ 1.06 eV, lI ¼ 0.60 eV), and C(lMA ¼ 1.68 eV, lPb ¼ 0 eV,
lI ¼ 1.19 eV) for the formation energy study.
lCH3 NH3 þ lPb þ 3lI ¼ DHðCH3 NH3 PbI3 Þ ¼ 5:26eV;
(1)
where li is the chemical potential of constitute element
referred to its most stable phase and DHðCH3 NH3 PbI3 Þ is
the formation enthalpy of CH3NH3PbI3. For lCH3 NH3 , we
choose body-centered-cubic phase of CH3NH3 following Cs.
To exclude the possible secondary phases PbI2 and
CH3NH3I (rock-salt phase), the following constraints must
also be satisfied:
lCH3 NH3 þ lI < DHðCH3 NH3 IÞ ¼ 2:87 eV; (2)
lPb þ 2lI < DHðPbI2 Þ ¼ 2:11 eV: (3)
The chemical potential of Pb and I satisfying Eqs.
(1)–(3) are shown as the red region in Figure 2. This narrow
and long chemical range indicate the growth conditions for
synthesizing CH3NH3PbI3 phase in the equilibrium condi-
tions. The narrow shape is in consistent with the low calcu-
lated dissociation energy (0.27 eV) of CH3NH3PbI3 to
CH3NH3I and PbI2, defined as E(CH3NH3I) þ E(PbI2) 
E(CH3NH3PbI3), which indicates that the growth conditions
FIG. 3. The formation energies of
intrinsic point defects in CH3NH3PbI3
at chemical potentials A, B, and C
shown in Figure 2. Defects with much
high formation energies have displayed
as dashed lines.
 063903-3 Yin, Shi, and Yan
should be carefully controlled to form the stoichiometric
CH3NH3PbI3 perovskite phase. On the other hand, the long
shape of chemical potential region provides the possible flexi-
bility to tune the n-type/p-type properties during growth by
controlling growth conditions, i.e., the chemical potential of
CH3NH3I and Pb sources.
We have considered all the possible point defects includ-
ing three vacancies (VMA, VPb, VI), three interstitial (MAi,
Pbi, Ii), two cation substitutions (MAPb, PbMA), and four anti-
site substitutions (MAI, PbI, IMA, IPb). As the formation ener-
gies of point defects depend on the chemical potentials of the
constituent element, we have chosen three representative
points, A (I-rich/Pb-poor), B (moderate), C (I-poor/Pb-rich),
in the chemical range shown in Figure 2 to study the defect
properties. The formation energies of the considered point
defects as a function of Fermi level position at chemical
potentials A, B, and C are shown in Figs. 3(a)–3(c), respec-
tively. It is interesting to find that the conductivity of
CH3NH3PbI3 can be from intrinsic good p-type, moderate to
good n-type when chemical potential is at A(I-rich/Pb-poor),
B (moderate), or C (I-poor/Pb-rich). Such flexible defect prop-
erties are distinguished from conventional thin-film solar cell
absorber CISe18 and CZTS.19 Donors in CIS and CZTS gener-
ally have much higher formation energies than acceptors. For
example, the formation energies of donors Cui and InCu in
CIS are more than 2 eV higher than acceptor VCu. Thus, VCu
dominates the conductivity of CISe.18 In CH3NH3PbI3, the
dominant donor MAi and dominant acceptor VPb have compa-
rable formation energies. The low formation energy of VPb in
CH3NH3PbI3 is due to the energetically unfavorable s-p anti-
bonding coupling, which resembles the p-d antibonding cou-
pling in CISe.18 The fully occupied antibonding state between
Pb s and I p coupling does not gain electronic energy thus
tends to bond break and form a vacancy. The lower formation
energy of MAi could be explained by its weak van der Waals
interaction with Pb-I framework.
The transition level of a defect is the Fermi level posi-
tion where the defect can donate/accept electrons. Therefore,
the defect with transition level deep in the band gap will
attract electron/hole and acts as Shockley-Read-Hall nonra-
diative recombination centers. The high performance of
CIGS-based thin-film solar cell is partially attributed to its
shallow dominant defects (VCu) with transition level only
0.03 eV above VBM.18 In CZTS, the dominant defect (CuZn)
has a deeper transition level 0.10 eV above VBM,19 which is
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Appl. Phys. Lett. 104, 063903 (2014)
FIG. 4. The transition energy levels of
(a) intrinsic acceptors and (b) intrinsic
donors in CH3NH3PbI3.
considered as the possible reason for the low Voc of CZTS.20
The calculated transition levels for all considered point
defects in CH3NH3PbI3 are shown in Figure 4. It is seen that
the defects with low formation energies (Table I), such as
MAi, VPb, MAPb, Ii, VI, and VMA, have transition energies
less than 0.05 eV above (below) VBM (CBM). On the other
hand, all the defects that create deep levels, such as IPb, IMA,
Pbi, and PbI, have high formation energies. Because only the
defects with deep levels are responsible for non-radiative
recombination, these formation energies strongly indicate
that CH3NH3PbI3 should intrinsically have rather low nonra-
diative recombination rate, explaining the reported long
electron-hole diffusion length. The shallow nature of domi-
nant acceptors VPb and MAPb originates from antibonding
state at VBM. Without Pb s lone-pair orbital, the VBM
should be derived from I p orbital. The coupling between Pb
lone pair s and I p orbital push the VBM up to a high level so
that the acceptors are generally shallower than that without
the strong sp coupling. The mechanism resembles the shal-
low VCu in CISe where the VBM is antibonding state of Cu
d and Se p. The shallow nature of dominant donors MAi and
VI is due to the high ionicity of MA and Pb ions. As dis-
cussed before, the large-size MA ion helps to stabilize the
perovskite structures and donate one electron to 3D Pb-I
framework for charge balance. The MAi has no covalent
bonds to Pb-I framework and does not create additional gap
states. As shown in Fig. 1(b), the CBM of CH3NH3PbI3 is
mostly contributed from Pb p orbital exhibiting very weak
covalence. Our previous study has shown that weak cova-
lence generally leads to the shallow vacancy level.21
It should be noted that the above results are calculated
from pure CH3NH3PbI3 perovskite. In halide perovskite-based
solar cells, the absorbers may not be pure perovskite phases.
For example, secondary phases22 may form in CH3NH3PbI3-
based absorbers. The secondary phases may form defects that
have low formation energies and produce deep defect states.
TABLE I. The formation energies (unit: eV) of twelve neutral defects in
CH3NH3PbI3 at chemical potential points A, B, and C shown in Figure 2.
Ii MAPb VMA VPb IMA IPb MAi PbMA VI Pbi MAI PbI
A 0.23 0.28 0.81 0.29 1.96 1.53 1.39 2.93 1.87 4.24 3.31 5.54
B 0.83 1.15 1.28 1.62 3.01 3.45 0.93 2.51 1.27 2.91 2.25 3.62
C 1.42 1.47 2.01 2.68 4.34 5.10 0.20 1.74 0.67 1.85 0.93 1.97
 063903-4 Yin, Shi, and Yan Appl. Phys. Lett. 104, 063903 (2014)

4
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