Applied Physics Express 6 (2013) 061201

http://dx.doi.org/10.7567/APEX.6.061201

Theoretical Photovoltaic Conversion Efficiencies

of ZnSnP2 , CdSnP2 , and Zn1 x Cdx SnP2 Alloys
Tomoyasu Yokoyama1 , Fumiyasu Oba1
, Atsuto Seko1 , Hiroyuki Hayashi2 , Yoshitaro Nose1 , and Isao Tanaka1;3
1
Department of Materials Science and Engineering, Kyoto University, Kyoto 606-8501, Japan
2
Research Center for Low Temperature and Materials Science, Kyoto University, Kyoto 606-8501, Japan
3
Nanostructures Research Laboratory, Japan Fine Ceramics Center, Nagoya 456-8587, Japan
E-mail: oba@cms.mtl.kyoto-u.ac.jp
Received March 17, 2013; accepted April 23, 2013; published online May 14, 2013

The performances of ZnSnP2 , CdSnP2 , and Zn1 x Cdx SnP2 alloys as solar cell photoabsorbers are assessed using photovoltaic conversion
efficiency simulations in conjunction with first-principles calculations based on hybrid density functional theory. The band gap of Zn1 x Cdx SnP2
decreases with increasing Cd content x and shows a small bowing. The electronic structure and optical absorption spectrum depend weakly on
the composition, aside from the band gap and spectral threshold. The conversion efficiency is almost converged to the Shockley–Queisser limit at
a photoabsorber thickness of a few micrometers for any composition of Zn1 x Cdx SnP2 , similarly to the cases of GaAs, CdTe, CuInSe2 , and
CuGaSe2 . # 2013 The Japan Society of Applied Physics

he need for highly efficient and low-cost thin-film Table I. Lattice constants (a and c), internal parameters for the P atom

T solar cells has stimulated an extensive search for

semiconductors that can replace the existing photo-
absorbers in the last decades. ZnSnP2 with the chalcopyrite
coordinates (u), and band gaps (Eg ) of ZnSnP2 and CdSnP2 .

a

(A)
c

(A)
u
Eg
(eV)
structure is a promising candidate, given that its direct ZnSnP2 Calc. 5.666 11.339 0.232 1.69
band gap of 1.68 eV1) yields a high theoretical photovoltaic Exp.1,3,4) 5.651 11.302 0.239 1.68
conversion efficiency close to 30% in AM1.5G sunlight at CdSnP2 Calc. 5.931 11.567 0.260 1.18
the Shockley–Queisser limit.2) Undoped ZnSnP2 typically Exp.7,23) 5.901 11.513 0.265 1.17
shows p-type conductivity.3,4) Band gap reduction toward
a higher efficiency can be attained by controlling cation
ordering1,5,6) or alloying it with a narrower-gap semicon-
ductor. Alloys with CdSnP2 , which is isostructural to (SQSs).19) SQSs with 16 Zn or Cd sites were constructed
ZnSnP2 and has a direct band gap of 1.17 eV,7) have been for x ¼ 0:25, 0.5, and 0.75 by optimizing correlation
considered for the latter approach.8) The chalcopyrite functions of eleven kinds of independent pairs using the
structures of ZnSnP2 and Zn1x Cdx SnP2 alloys carry an CLUPAN code.20,21) The resultant pair correlation functions
advantage in utilizing cell fabrication technologies devel- were equal to those of the perfectly random structures up to
oped for analogous systems such as chalcopyrite CuIn1x - the eleventh nearest pairs for x ¼ 0:5 and up to the fifth
Gax Se2 (CIGS) and sphalerite CdTe. The properties relevant nearest pairs for x ¼ 0:25 and 0.75; the root-mean square
to solar cell applications, however, have not been well difference from the perfectly random structures was 0.103
established for ZnSnP2 and Zn1x Cdx SnP2 alloys partly for the latter. k-point meshes with nearly the same density as
because of the difficulty in the preparation of high-quality those for the ZnSnP2 and CdSnP2 unit cells were employed
specimens. In this Letter, we report a theoretical assessment for the SQS cells.
of the performance of ZnSnP2 , CdSnP2 , and Zn1x Cdx SnP2 The calculated structural parameters and band gaps of
alloys as solar cell absorbers via photovoltaic conversion ZnSnP2 and CdSnP2 are listed in Table I, along with experi-
efficiency simulations in conjunction with first-principles mental values. The lattice constants, internal parameters, and
calculations of their electronic structures and optical band gaps are well reproduced for both ZnSnP2 and CdSnP2 .
absorption spectra. Note that standard approximations to density functional
The first-principles calculations were performed on theory, i.e., the local density approximation and the gen-
the basis of hybrid density functional theory using the pro- eralized gradient approximation (GGA), significantly under-
jector augmented-wave method9) and the Heyd–Scuseria– estimate the band gaps of ZnSnP2 and CdSnP2 : for instance,
Ernzerhof (HSE06) hybrid functional10) as implemented in the Perdew-Burke-Ernzerhof GGA22) yields band gaps of
the VASP code.11,12) The HSE06 hybrid functional has 0.69 and 0.26 eV, respectively.
been applied to a variety of semiconductors and shown to Figure 1 shows the calculated properties of Zn1x -
describe their atomic and electronic structures much better Cdx SnP2 . The band gap decreases with increasing Cd
than local and semilocal functionals.6,10,13–17) A plane-wave content x [Fig. 1(a)]. The band gaps of the alloys are
cutoff energy of 400 eV and 8  8  4 k-point mesh were slightly smaller than the linear combination of those of
employed in the total-energy evaluation and geometry ZnSnP2 and CdSnP2 . Such nonlinear behavior is often
optimization for the chalcopyrite unit cells of ZnSnP2 and observed for multicomponent semiconductors and referred
CdSnP2 . Electronic density of states and complex dielectric to as band bowing. The band gap of an A–B binary or
functions neglecting excitonic effects were calculated using pseudobinary alloy A1x Bx , Eg ðxÞ, is expressed as
a denser 16  16  8 k-point mesh.18) Optical absorption
Eg ðxÞ ¼ ð1  xÞEA
g þ xEg  bxð1  xÞ;
B
ð1Þ
spectra were obtained from the dielectric functions.
Ideally disordered Zn1x Cdx SnP2 pseudobinary alloys where b denotes the bowing parameter, and EA g and Eg are
B

were modeled using special quasi-random structures the band gaps of alloy components A and B, respectively. By
061201-1 # 2013 The Japan Society of Applied Physics
Appl. Phys. Express 6 (2013) 061201 T. Yokoyama et al.

(a) VBM CBM

2.5 6
Zn x=0
4
P Sn
2
2 Cd
0

Density of states (1/(eV f.u.))

P Sn x = 0.25
4
Band gap (eV)

1.5 2
0
x = 0.5
4
1 2
0
x = 0.75
4
0.5
2
0
0 x=1
4
0 0.2 0.4 0.6 0.8 1
x in Zn1-xCdx SnP2
.
.
2
0
(b) 110 -15 -10 -5 0 5
Volume (Å3/f.u.)

Energy (eV)
100

90 Fig. 2. Electronic density of states of Zn1x Cdx SnP2 with x ¼ 0, 0.25, 0.5,
0.75, and 1. The valence band maximum (VBM) and conduction band
80 minimum (CBM) are indicated by dotted lines. Note that the density of
0 0.2 0.4 0.6 0.8 1
x in Zn1-xCdx SnP2
. ..
states near the CBM is small and almost invisible for any composition.
(c) 50
Formation energy

40
(meV/f.u.)

30
(a) 106
20
x = 0.5

Absorption coefficient (cm-1)

10
0 x = 0.75
0 0.2 0.4 0.6 0.8 1
105
x in Zn1-xCdx SnP2
. ..

x=1 x=0

Fig. 1. Properties of Zn1x Cdx SnP2 with x ¼ 0, 0.25, 0.5, 0.75, and 1. x = 0.25
104
(a) Band gap. The structures of the unit cells (x ¼ 0 and 1) and SQS cells
(x ¼ 0:25, 0.5, and 0.75) are also shown. (b) Volume. (c) Formation energy.
The dotted lines denote the linear combination of the values for ZnSnP2 and
103
CdSnP2 . The solid curves are obtained by quadratic least-squares fitting. 1 2 3 4
Energy (eV)

(b) 106
fitting the calculated band gaps to Eq. (1), we obtain a GaAs
Absorption coefficient (cm-1)

bowing parameter of 0.17 eV for Zn1x Cdx SnP2 . Calcula-

tions also conducted for CIGS using crystallographically CuInSe2
105
the same chalcopyrite SQSs for alloys yielded a bowing CdTe
parameter of 0.13 eV. This is close to the value obtained by
CuGaSe2
the cluster expansion in conjunction with first-principles 104

calculations, 0.16 eV,24) and an experimental value of

0.15 eV,25) validating the SQSs used in the present study.
The band bowing of Zn1x Cdx SnP2 is thus suggested to
be similar in magnitude to CIGS. In actual Zn1x Cdx SnP2
alloys, short-range ordering of the Zn and Cd atoms may
affect the composition dependence of the band gap.
Furthermore, disordering of the Zn or Cd and Sn atoms
can also occur and reduce the band gap, by analogy with
the cation ordering dependence of the band gap of ZnSnP2
as identified experimentally1) and theoretically.6)
The volume shows a nearly linear composition de-
pendence [Fig. 1(b)]. Positive formation energies of the
Zn1x Cdx SnP2 alloys found in Fig. 1(c) indicate their phase
separation tendency. Using a regular solution model with
an interaction parameter obtained by quadratic fitting, the
phase-separation critical temperature is estimated to be
500 K. The low critical temperature is consistent with an
experimental phase diagram showing alloy formation for the
whole composition range at 673 K.8)
The calculated electronic density of states and optical
absorption spectra of Zn1x Cdx SnP2 are shown in Figs. 2
and 3(a). The absorption spectra of GaAs, CdTe, CuInSe2 ,
and CuGaSe2 , which are direct-gap semiconductors em-
ployed for thin-film solar cells, are presented in Fig. 3(b) for
061201-2
103
1 2 3 4
Energy (eV)
Fig. 3. Optical absorption spectra of (a) Zn1x Cdx SnP2 with x ¼ 0, 0.25,
0.5, 0.75, 1, and (b) GaAs, CdTe, CuInSe2 , and CuGaSe2 .
comparison. The spectral thresholds for these compounds
are shifted by 0.17, 0.09, 0.24, and 0.31 eV, respectively,
toward the higher energy side to correct errors in the calcu-
lated band gaps. The orientation dependence of the absorp-
tion spectra of chalcopyrite ZnSnP2 , CdSnP2 , CuInSe2 , and
CuGaSe2 is found to be small, as reported in previous first-
principles studies.26,27) An orientation average is taken in
Fig. 3.
Aside from the band gap and localized Zn 3d and Cd 4d
states at 8:5 and 9 eV, respectively, the shape of the
density of states weakly depends on the composition of
Zn1x Cdx SnP2 (Fig. 2). This leads to the resemblance in the
shape of the absorption spectra [Fig. 3(a)]. The absorption
coefficients reach 104 cm1 at energies slightly above the
spectral thresholds, which correspond to the band gaps, and
become higher than 105 cm1 at 1:2 eV above the thresh-
# 2013 The Japan Society of Applied Physics
Appl. Phys. Express 6 (2013) 061201 T. Yokoyama et al.

(a) 40 yields the highest efficiency is estimated to be x ¼ 0:60 at

x = 0.75 x = 0.5
x=1 x = 0.25 the Shockley–Queisser limit (Eg ¼ 1:34 eV). The conver-
Conversion efficiency (%) x=0
sion efficiency is almost converged to the Shockley–
30
Queisser limit at a photoabsorber thickness of a few m
20 for any composition. The simulated conversion efficiencies
L = 10 (µm) of GaAs, CdTe, CuInSe2 , and CuGaSe2 are presented in
L=5
10 L=1 Fig. 4(c). As in the case of Zn1x Cdx SnP2 , a convergence to
L = 0.5
L = 0.1 the Shockley–Queisser limit is found at a thickness of a few
0 m, consistent with the typical thickness in their practical
0.5 1 1.5 2 2.5
Band gap (eV) applications. The present results thus suggest a photoabsor-
(b) 35 ber thickness of a few m for Zn1x Cdx SnP2 , which is
x=1
similar to those for GaAs, CdTe, CuInSe2 , and CuGaSe2 .
Conversion efficiency (%)

30

25
In summary, the electronic structure, optical absorption,
x = 0.25
x=0 and photovoltaic conversion efficiency of ZnSnP2 , CdSnP2 ,
20 x = 0.5
x = 0.75 and Zn1x Cdx SnP2 alloys have been evaluated theoretically.
15
The band gap of Zn1x Cdx SnP2 decreases with increasing x
10
and shows a small bowing. The highest conversion effi-
5 ciency is given for x ¼ 0:60 at the Shockley–Queisser limit.
0
0 1 2 3 4 5 6 7 8 9 10
A photoabsorber thickness of a few m is suggested for any
Thickness (µm) composition of Zn1x Cdx SnP2 .
(c) 35 Acknowledgments Support by the Elements Science and Technology
GaAs
Project from MEXT and JSPS KAKENHI [Grants-in-Aid for Young Scientists
Conversion efficiency (%)

30
(A), Grant Numbers 23686089 and 23686090] is acknowledged. Computing
25 resources of ACCMS at Kyoto University were used in this work.
CuInSe2 CuGaSe2
20 CdTe
15

10 1) P. St-Jean, G. A. Seryogin, and S. Francoeur: Appl. Phys. Lett. 96 (2010)

5 231913.
0
0 1 2 3 4 5 6 7
Thickness (µm)
Fig. 4. Photovoltaic conversion efficiency of Zn1x Cdx SnP2 with x ¼ 0,
0.25, 0.5, 0.75, and 1 in AM1.5G sunlight as a function of (a) band gap and
(b) photoabsorber thickness. The curve in (a) denotes the conversion
efficiency at the Shockley–Queisser limit. (c) Conversion efficiencies of
GaAs, CdTe, CuInSe2 , and CuGaSe2 as a function of photoabsorber
thickness.
olds. Such absorption coefficients are as large as those of
GaAs, CdTe, CuInSe2 , and CuGaSe2 [Fig. 3(b)].
Using the calculated absorption coefficients, the photo-
voltaic conversion efficiency was evaluated on the basis of
the approaches reported by Shockley and Queisser2) and by
Yu and Zunger.28) The simulations were conducted under the
assumption that nonradiative recombination of photogener-
ated carriers does not occur. Reflection at the front surface
of a solar cell was neglected because it can be substantially
reduced by antireflection coating and/or surface texturing. In
addition, the perfect reflection at the rear surface or interface
was assumed; in typical cell structures, an interface with a
rear metal electrode reflects photons transmitted through a
photoabsorber layer and leads them back to the photoabsor-
ber to a large extent. The absorbance aðEÞ is then described
as aðEÞ ¼ 1  exp½2ðEÞL, where ðEÞ is the absorption
coefficient and L is the thickness of a photoabsorber layer.
The infinite thickness limit L ! 1 corresponds to aðEÞ ¼ 1
for E  Eg at the Shockley–Queisser limit.
Figures 4(a) and 4(b) show the simulated photovoltaic
conversion efficiency for Zn1x Cdx SnP2 in AM1.5G sun-
light.29) Using the theoretical band gaps of ZnSnP2 and
CdSnP2 and band bowing parameter, the composition that
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061201-3 # 2013 The Japan Society of Applied Physics