Hybrid density functional theory study of Cu(In1−xGax)Se2 band structure for solar cell

application
Xu-Dong Chen, Lin Chen, Qing-Qing Sun, Peng Zhou, and David Wei Zhang

Citation: AIP Advances 4, 087118 (2014); doi: 10.1063/1.4893238

View online: http://dx.doi.org/10.1063/1.4893238
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 AIP ADVANCES 4, 087118 (2014)

Hybrid density functional theory study of Cu(In1−x Gax )Se2

band structure for solar cell application
Xu-Dong Chen, Lin Chen,a Qing-Qing Sun, Peng Zhou,
and David Wei Zhang
State Key Laboratory of ASIC and System, School of Microelectronics,
Department of Materials Science, Fudan University, Shanghai 200433, China
(Received 25 June 2014; accepted 25 July 2014; published online 13 August 2014)

Cu(In1−x Gax )Se2 (CIGS) alloy based thin film photovoltaic solar cells have attracted
more and more attention due to its large optical absorption coefficient, long term
stability, low cost and high efficiency. However, the previous theoretical investiga-
tion of this material with first principle calculation cannot fulfill the requirement of
experimental development, especially the accurate description of band structure and
density of states. In this work, we use first principle calculation based on hybrid
density functional theory to investigate the feature of CIGS, with B3LYP applied
in the CuIn1−x Gax Se2 stimulation of the band structure and density of states. We
report the simulation of the lattice parameter, band gap and chemical composition.
The band gaps of CuGaSe2 , CuIn0.25 Ga0.75 Se2 , CuIn0.5 Ga0.5 Se2 , CuIn0.75 Ga0.25 Se2
and CuInSe2 are obtained as 1.568 eV, 1.445 eV, 1.416 eV, 1.275 eV and 1.205 eV
according to our calculation, which agree well with the available experimental values.
The band structure of CIGS is also in accordance with the current theory.  C 2014 Au-

thor(s). All article content, except where otherwise noted, is licensed under a Creative
Commons Attribution 3.0 Unported License. [http://dx.doi.org/10.1063/1.4893238]

I. INTRODUCTION
Solar cells are regarded as one of the most important alternative energy sources recently. Among
all the types of solar cells, solar cells based on single crystalline silicon have been widely used all
around the world. However, this kind of single crystalline solar cells has many problems such as
high financial cost, high manufacture temperature (which means high energy cost) and so on. As an
alternative of single crystalline silicon based solar cells, thin film photovoltaic solar cells based on
Cu(In1−x Gax )Se2 (CIGS) alloys are showing more and more importance with up to 20% conversion
efficiencies were obtained.1 Moreover, this material is also a suitable candidate for both single and
multi-junction cells.2 Compared to single crystalline silicon, CIGS has many advantages, such as
large optical absorption coefficient, long term stability, low cost and high efficiency etc.,3, 4 which
makes CIGS a very promising material in the field of thin film solar cells. However, the performance
of CIGS solar cell is affected by the band structure of CIGS with different amount of indium
and gallium. The band gap of CIGS varies from 1.0 eV (CuInSe2 ) to 1.7 eV (CuGaSe2 ) with the
increasing of the gallium proportion in the film. It is reported that device performance degrades
when there are more than ∼30–50% gallium element in the absorption layer.5 The main reason of
the degradation is the well-known open-circuit voltage (VOC ) deficiency, where the VOC does not
increase along with the increasing of the band gap.6 Obviously, it is important for us to predict the
band gap and the Ga/(In + Ga) content ratio which can help us find the relationship between high
efficiency and the Gallium amount.

a Corresponding author: linchen@fudan.edu.cn

2158-3226/2014/4(8)/087118/8 4, 087118-1 
C Author(s) 2014

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 087118-2 Chen et al. AIP Advances 4, 087118 (2014)

The gap variation of CIGS is roughly described by the following equation7

Eg(x) = (1 − x)Eg(CIS) + xEg(CIS) − bx × (1 − x) (eV) (1)
where b varies from 0.15 to 0.24 eV. It has been theoretically shown and reported by Wei and Zunger8
that a variation of the Ga/(In + Ga) ratio will mainly affect the level of the conduction band minima.
In this work, we introduce a new theoretical method compared to standard DFT exchange-
correlation (XC) functionals to predict the band gaps of CIGS films with much improved accuracy
compared to traditional DFT method. The lattice structure, density of states (DOS) and band gaps of
Cu(In1−x Gax )Se2 , where x was selected from 0 to 1 (step 0.25), were discussed in details. Through
the results, we can build the relationship between band gaps and the Ga/(In + Ga) content ratio.

II. COMPUTATIONAL METHOD

The calculations were performed within the framework of the density functional theory (DFT).9
The band structure and density of states (DOS) calculations were performed with the CASTEP code
using Becke, three-parameter, Lee-Yang-Parr (B3LYP)10–12 exchange-correlation functional norm-
conserving pseudopotentials with an energy cutoff of 800 eV. All the geometries of the unit cell
of these materials were relaxed using the PW-91 version of the generalized gradient approximation
(GGA)13, 14 with ultrasoft pseudopotentials. The cut-off energy of the crystal was set to 350 eV,
and the atomic positions and lattice parameters were relaxed until atomic forces were converged
to a value smaller than 0.01 eV/Å. Monkhorst-Pack type k point sampling was chosen during the
geometry relaxation and 3 × 3 × 1 MP meshes were used in the irreducible wedge of the Brillouin
zone.
It is well-known within the framework of LDA15 and GGA method, the predicted band gaps
is much smaller than that obtained from experiment.16 In Chandramohana’s theoretical work,17
the calculated band gaps of CuIn0.25 Ga0.75 Se2 , CuIn0.5 Ga0.5 Se2 , and CuIn0.75 Ga0.25 Se2 are 0.8 eV,
0.8 eV, 0.7 eV for GGA method and 1.2 eV, 0.9 eV, 0.8 eV for LDA method, which vary to the
values obtained in experimental work, from 1.7 eV to 1.04 eV, cannot be used as a reference for the
realistic applications.
As we know, the chalcopyrite crystal structure of CGS has a P65 space group, which displays
only identity and inversions operations. There are four CGS groups (31 atoms) per unit cell. After that,
we set up CuIn0.25 Ga0.75 Se2 , CuIn0.5 Ga0.5 Se2 , CuIn0.75 Ga0.25 Se2 and CuInSe2 models by substituting
the Ga atom by In atom one by one until Ga atoms are completed substituted by In atoms.
When substituting Ga atoms with In atoms, there will be 2 types of substitution in the structure
of CuIn0.5 Ga0.5 Se2 by changing adjacent layers or separated layers of Ga atom. The calculation
of CuIn0.5 Ga0.5 Se2 is the chalcopyrite structure with In atoms in separated layers which has high
symmetry and the effect of the other type will be discussed.

III. RESULTS AND DISCUSSIONS

A. Structural Optimization
The chalcopyrite structure of CGS is shown in Figure 1. The relaxed structure parameters of five
configurations and the corresponding experimental values cited from ICSD and other works18–20 are
shown in Table I. From the table, it is clear that the calculated results and the experimental values are
in good agreement. The relaxed lattice constant of CuGaSe2 is a = 5.63 Å and c = 11.15 Å which
is reasonable to CGS, which is 0.35% and 1.17% larger than the experimental value a = 5.61 Å
and c = 11.02 Å. For the case of CuIn0.25 Ga0.75 Se2 , the calculated lattice parameter is a = 5.69 Å
and c = 11.31 Å, which is only slightly smaller than the experimental value by 0.5% and 2.75%.
For the case of CuIn0.5 Ga0.5 Se2 , the lattice parameter is estimated to be 5.75 Å (0.34% larger
than the experiment value) and 11.43 Å (2% smaller than the experiment value). Moreover, the
simulated CuIn0.75 Ga0.25 Se2 has a lattice parameter of 5.76 Å and 11.70 Å which has an error of
+0.2% and +0.1% compared to experimental value a = 5.75 Å and c = 11.69 Å. For the case of
CuInSe2 , the lattice parameters obtained (a = 5.82 Å and c = 11.76 Å) is 0.7% and 1.03% larger

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 087118-3 Chen et al. AIP Advances 4, 087118 (2014)

FIG. 1. Chalcopyrite structure of CuGaSe2 .

TABLE I. The simulated and experimental lattice parameter of CIGS chalcopyrite unit cell by GGA.

a&b (Å) c (Å)

Lattice parameter Calculated Experimented Calculated Experimented

CuGaSe2 21 5.63 5.61 11.15 11.02

CuIn0.25 Ga0.75 Se2 17 5.69 5.72 11.31 11.63
CuIn0.5 Ga0.5 Se2 17 5.75 5.73 11.43 11.66
CuIn0.75 Ga0.25 Se2 17 5.76 5.75 11.70 11.69
CuInSe2 22 5.82 5.78 11.76 11.64

TABLE II. the Final Enthalpy and Lattice Parameter using different k-point mesh for CuInSe2 structure.

Lattice Parameter
k-point mesh Final Enthalpy (eV) a&b (Å) c (Å)

3×3×1 −6864.241 5.82 11.76

8×8×8 −6864.255 5.84 11.71

than the experiment value (a = 5.78 Å and c = 11.64 Å). It should be noticed that the mismatch
between all the calculated lattice parameters and its corresponding experimental values are less than
3%, and the accuracy of in-plane parameter is much better than that of out-plane parameter.
To confirm the results are well converged with the 3 × 3 × 1 MP k-point meshes, the geometry of
CuInSe2 structure was also relaxed using 8 × 8 × 8 MP k-point meshes according to the reference.23
The results are shown in Table II.

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 087118-4 Chen et al. AIP Advances 4, 087118 (2014)

FIG. 2. Band structure and DOS of CuGaSe2 .

From Table II, the difference of Final Enthalpy using different k-point mesh for CuInSe2
structure is less than 0.02 eV and the difference of lattice parameter is less than 0.5%, which indicate
that the results are well converged with the current k-point mesh setup.

B. Band structure and DOS

The band structures and DOS of the five configurations are shown from Figure 2–6. From those
figures, all the five configurations are direct band gap semiconductors with the conduction band
minima and valence band maxima at G point. The band gap is decreased along with the consistent
lacking of Gallium.
The theoretical values and experimental values of band gaps are compared in Table III. From
Table III, the Eg of CuGaSe2 is 1.568 eV which is 6% smaller than the experimental value and the
Eg of CuInSe2 is 1.205 eV which is 15% larger than experimental value. The difference between
theoretical value and experimental results may be originated from the fact that the DFT calculation
does not include the effects of phonon scattering to the band structure. In addition, the band gaps
of CuIn0.25 Ga0.75 Se2 , CuIn0.5 Ga0.5 Se2 and CuIn0.75 Ga0.25 Se2 are 1.445 eV, 1.416 eV and 1.275 eV
which has no precise experimental data for comparing. The band gaps are increasing along with the
increasing of the Gallium amount which agree well with the available experimental values. It should
be noticed that the curvature of the conduction band is much sharper than that of valence band, and
the electron mobility of CIGS is much bigger than the hole mobility. The results of the band gaps
derived from B3LYP density functional is much better compared to the conventional LDA and GGA
method.17
When substituting Ga atoms with In atoms, there will be another types of substitution in the struc-
ture of CuIn0.5 Ga0.5 Se2 by changing adjacent layers of Ga atoms. The band gap of CuIn0.5 Ga0.5 Se2
will decrease about 0.08 eV according to our calculation.

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 087118-5 Chen et al. AIP Advances 4, 087118 (2014)

FIG. 3. Band structure and DOS of CuIn0.25 Ga0.75 Se2 .

FIG. 4. Band structure and DOS of CuIn0.5 Ga0.5 Se2 .

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 087118-6 Chen et al. AIP Advances 4, 087118 (2014)

FIG. 5. Band structure and DOS of CuIn0.75 Ga0.25 Se2 .

FIG. 6. Band structure and DOS of CuInSe2 .

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TABLE III. The simulated band gap of CIGS chalcopyrite unit cell by B3LYP.

Band Gap Calculated Eg (eV) Experimented Eg (eV)

CuGaSe2 1.568 1.6721

CuIn0.25 Ga0.75 Se2 1.445 N/A
CuIn0.5 Ga0.5 Se2 1.416 N/A
CuIn0.75 Ga0.25 Se2 1.275 N/A
CuInSe2 1.205 1.0422

FIG. 7. Summary partial density of states of Cu(In1−x Gax )Se2 structure. (a) Partial density of states of CuGaSe2;
(b) Partial density of states of CuIn0.25 Ga0.75 Se2 ; (c) Partial density of states of CuIn0.5 Ga0.5 Se2; (d) Partial density of
states of CuIn0.75 Ga0.25 Se2 ; (e) Partial density of states of CuInSe2 .

C. Partial Density of States

Figures 7(a)–7(e) depict the PDOS of the five configurations. For the case of the GuGaSe2 , the
conduction band of the material is consisted by the Ga s orbital and Se s orbital while the valence
band is composed by the Cu d orbital and Se p orbital. With the introduction of In, the conduction
band minima becomes composed by In, Ga and Se s orbitals, And with the increasing of the In
amount in the film, the density of the states from In s orbital becomes stronger, and the band gaps of
the films reduce.

IV. CONCLUSION
In summary, the geometry structure, band structure and DOS of the Cu(In1−x Gax )Se2 were
investigated under the framework of B3LYP functional which gives a better description of band
structure compared to traditional LDA and GGA methods. The lattice constants obtained from our
calculation are in good agreement with the available experimental values with the mismatch less
than 3%. The band structure of CIGS is also in accordance with experiment, and the band gaps
decrease as the decrease of the Gallium amount. According to the analysis of the DOS and PDOS
of the five configuration, it was concluded that the conduction band of CIGS was consisted by the
Ga, In, and Se s orbitals and the valence bands of the CIGS was consisted by the Se p orbital and
Cu d orbital. The work can be used to the profiling of the CIGS band gaps and is also useful for the
further experimental investigations.

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ACKNOWLEDGMENT
This work was supported by NSFC (61076114, 61106108 and 51172046), Shanghai Educational
Development Foundation (10CG04), SRFDP (20100071120027), the Fundamental Research Funds
for the Central Universities, and the S&T Committee of Shanghai (10520704200).
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