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Introduction
Cu(In,Ga)Se2 (CIGS) thin lm solar cells are expected to play a
leading role in the photovoltaic market due to their high
eciency of around 20%.1 The conventional structure of a CIGS
solar cell is ZnO/CdS/CIGS, where CdS deposited by chemical
bath deposition (CBD) has been regarded as the best buer
material for high eciency thus far. However, Cd is a toxic metal
element, and the CBD process produces much chemical waste.
Thus, for the ecologically sustainable development of the energy
system, a Cd-free material which can be deposited by a non-CBD
process should be developed for environmental safety.
Over the last decade, the Zn1xMgxO lm has attracted an
increasing interest as an alternative Cd-free buer material for
a
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Experimental
Zn1xMgxO/CIGS heterointerfaces were fabricated by the ALD
deposition of Zn1xMgxO layers on CIGS absorbers at 120 1C
using a vertical hot-wall type ALD reactor. For the Zn1xMgxO
lm growth, diethylzinc [Zn(C2H5)2, DEZ] and bis-ethylcyclopentadienyl magnesium [Mg(C5H4C2H5)2, Mg(CpEt)2] were used
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for the CIGS absorber from the set of spectra from L31 to
L39. Therefore, valence band discontinuities of 2.70 and
2.69 eV were deduced from the bulk Zn1xMgxO (x = 0.1
and x = 0.2) region and the bulk CIGS region, respectively,
when the band bending is ignored. It is found that the VBO
values for both samples are almost same within an experimental uncertainty of 0.1 eV (which is a commonly accepted
level for XPS and UPS). The results indicate that the change in
the chemical composition of Zn1xMgxO in the range of x
from 0.10 to 0.20 does not aect the electronic structure of the
valence band.
Note that the VBMs are determined with respect to EF.
Given that the composition of the CIGS absorber was adjusted
to Cu(In0.7,Ga0.3)Se2, which corresponds to a bulk bandgap
energy of 1.12 eV, the estimated VBM of 0.48 eV places the
EF in the CIGS at 0.08 eV below the middle of the bandgap of the
CIGS. Similar values of VBM in bulk CIGS with a conventional
composition were reported in other XPS (0.40 eV) and UPS
(0.47 eV) photoemission experiments.15,17
It can be seen from Fig. 2 that we did not nd any change in
the spectral weight distribution of the emission intensity in
both sets of spectra taken at nine etch levels from L1 to L9
(bulk Zn1xMgxO) and the set of spectra taken at nine etch
levels from L31 to L39 (bulk CIGS). Furthermore, the XPS
peak positions and FWHM values for Zn 2p, Cu2p, and In 3d
core levels from the bulk Zn1xMgxO region and bulk CIGS
region also were not changed with sputter etching as shown in
Fig S1 (ESIw). These results indicate that the valence band
structures are not aected by Ar+ ion sputter damage. In
Fig. 2, a VBO value of approximately 2.69 eV was determined
between the bulk Zn1xMgxO (x = 0.1 and x = 0.2) region
and the bulk CIGS region due to the nearly identical VBM
position of the Zn0.9Mg0.1O and Zn0.8Mg0.2O lms. These
results can be supported by a UPS analysis as well. Fig. 3
shows the UPS spectra taken from L6 to L10 for both
Zn0.9Mg0.1O and Zn0.8Mg0.2O lms, and the spectra from
the CIGS absorber. As shown in Fig. 3, the VBM position
of CIGS is 0.57 eV; moreover, the same VBM position of
3.17 eV was observed for both the Zn0.9Mg0.1O and Zn0.8Mg0.2O
lms. The resulting VBO value of 2.60 eV, which is comparable
Fig. 3 The UPS spectra taken from L6 to L10 for both the
Zn0.9Mg0.1O and Zn0.8Mg0.2O lms, and taken from L6 to L10 for
the CIGS absorber. Both Zn1xMgxO lms show nearly the same
VBM position of 3.17 eV.
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Fig. 4 Evolution of the VBM energy level with the Ar+ ion beam
etch level near and at the Zn0.8Mg0.2O/CIGS interface.
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Table 1 VBO values derived based on the shifts in the Cu 2p, In 3d,
Cu2p
Zn 3d, Zn 2p, and Mg 1s subshell emissions. EIn3d
VBM and EVBM are the
binding energies of the In 3d and Cu 2p core levels with respect to
Mg1s
Zn3d
the VBM energy of the CIGS absorber. EZn2p
VBM, EVBM and EVBM are the
binding energies of the Zn 2p, Mg 1s, and Zn 3d core levels with
respect to the VBM energy of the Zn0.8Mg0.2O lm. DECL denotes the
binding energy dierence between the core levels at the interface
CIGS
(L39, eV)
ECu2p
VBM
EIn3d
VBM
932.21
444.52
Zn0.8Mg0.2O
(L10, eV)
DECL
(L17, eV)
EZn2p
VBM
EMg1s
VBM
EZn3d
VBM
EZn2p
VBM
EMg1s
VBM
EZn3d
VBM
EZn2p
Cu2p
EMg1s
Cu2p
EZn3d
Cu2p
EZn2p
In3d
EMg1s
In3d
EZn3d
In3d
1018.84
1300.48
7.58
1018.84
1300.48
7.58
VBO/
eV
89.22
370.91
922.08
576.92
858.61
434.38
2.59
2.64
2.55
2.60
2.65
2.56
the interface (Table 1). Given that the two VBO values derived
from two dierent methods show a high degree of similarity,
we can conclude that a cli alignment of 2.55 eV is a good
approximation of the valence band discontinuity at the
Zn1xMgxO/CIGS interface.
2. Optical analysis of Zn1xMgxO (x = 0.1, 0.14, 0.17, 0.2,
and 0.25) lms
To estimate the optical bandgap energies of Zn1xMgxO lms,
the extinction coecients were obtained by spectroscopic
ellipsometry. The optical absorption coecients were derived
as functions of the incident photon energy from the extinction
coecients for 45 nm-thick Zn1xMgxO lms.
Given that the Zn1xMgxO compound is a direct semiconductor, the spectral response of the absorption coecient
with the photon energy near the absorption edge for direct
allowed transitions can be expressed as follows:
ahn
B
hn Eg 1=2 ;
hn
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(hn) is tted using relation (1). The results of the tting are shown
in Fig. 6. The Eg value for the ZnO lm was determined to be
3.25 eV, which is in good agreement with the previously reported
value.21,22 The Eg value increased from 3.44 to 3.76 eV as the Mg
content increased from 10% to 25%. A widening of Eg with
increasing Mg content was also reported in earlier research.7,11
3. Estimation of the conduction band oset at Zn1xMgxO/
CIGS interfaces
The conduction band discontinuity at the Zn1xMgxO/CIGS
interface was calculated as follows: CBO = Eg (Zn1xMgxO)
Eg (CIGS) VBO. As mentioned in the experimental section, the
Ga/(Ga + In) atomic ratio in the CIGS absorbers was adjusted to
0.3. This composition results in a CIGS bandgap value of 1.12 eV.
The experimentally determined bandgap energies of Zn1xMgxO
lms from 3.44 to 3.76 eV were used for the CBO estimations.
The scheme of the energy band alignment at the
Zn0.8Mg0.2O/CIGS interfaces is presented in Fig. 7. A cli
CBO of 0.14 eV was deduced between Zn0.8Mg0.2O and
CIGS without considering the band bending in the interface
region. However, a at conduction band alignment was estimated at the Zn0.8Mg0.2O/CIGS interface due to the small
band bending which was induced by interface formation.
Zn1xMgxO (x = 0.1 and x = 0.2) lms (Fig. 2 and 3) showed
almost same VBM positions. The at VBO between ZnO and
Zn0.85Mg0.15O was estimated based on the transitivity rule by Rao
et al.23 Given these data, our experimental results, and the common
anion rule, we assumed that the Mg content does not aect the
valence band structure of the Zn1xMgxO lms. We calculated the
CBO values between the bulk Zn1xMgxO and CIGS region, and
conduction band discontinuities at the Zn1xMgxO/CIGS interfaces using determined bandgap energies of the Zn1xMgxO lms
(Fig. 6). Fig. 8 shows the calculated CBO values for the
Zn1xMgxO lms with various levels of Mg. The conduction band
alignment between the Zn1xMgxO and CIGS could be changed
from a cli to a spike by increasing the bandgap energy of the
Zn1xMgxO lm. It has been known that the CBO value should be
adjusted between 0 and 0.3 eV to ensure high eciency. Thus, the
Mg content in the Zn1xMgxO lms should be carefully
controlled between 20% and 30% to obtain a proper CBO value.
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Acknowledgements
This work was supported by the Engineering Research Center
Program (2011-0001000) and the Priority Research Center
Programs (2009-0094040 and 2010-0029714) through the National
Research Foundation of Korea (NRF) funded by the Korean
Ministry of Education, Science and Technology (MEST).
References
Fig. 8 The calculated CBO values using Zn1xMgxO lms with
various Mg content.
Conclusion
We investigated the energy band alignment at the Zn1xMgxO
(x = 0.1 and x = 0.2)/Cu(In0.7Ga0.3)Se2 interface using XPS
and UPS depth prole measurements. From the XPS measurement, the VBM positions of the bulk Zn1xMgxO (x = 0.1 and
0.2) region and the bulk CIGS region were determined at 3.18,
3.17, and 0.48 eV, respectively. Thus, the VBO value of approximately 2.69 eV was estimated between the bulk Zn1xMgxO region
and the bulk CIGS region without considering the band bending.
These results were also conrmed by UPS analysis, which indicated
the nearly same VBM position of 3.17 eV for both the Zn0.9Mg0.1O
and Zn0.8Mg0.2O lms. The same valence band discontinuity of
approximately 2.55 eV was directly determined at the Zn0.9Mg0.1O/
CIGS and Zn0.8Mg0.2O/CIGS interfaces after considering the
small band bending of 0.14 eV in the interface region. This
result suggests a nearly at valence band alignment at the
Zn0.9Mg0.1O/Zn0.8Mg0.2O interface according to the transitivity
rule for a band discontinuity.
Given that valence band discontinuity does not change with
the Mg content within an acceptable level of experimental
uncertainty, the dierence in the bandgap energy of the
Zn1xMgxO lms only contributes to the CBO at the
Zn1xMgxO/CIGS interfaces. Thus, the conduction band
alignment at the Zn1xMgxO/CIGS interfaces could be changed
from a cli to a spike according to the bandgap energy of the
Zn1xMgxO lm. In a CIGS solar cell with bandgap energy of its
buer layer of less than 3.67 eV, the cli CBO can lower the open
circuit voltage by enhancing the interface recombination. Therefore, to create a suitable conduction band alignment at the
Zn1xMgxO/CIGS interface, the Mg content in the Zn1xMgxO
lms should be carefully controlled.
This study is the rst to quantify energy band alignments at
ALD Zn1xMgxO (0.1 r x r 0.25)/CIGS interfaces. The
results can be used to adjust the electronic structure at the
Zn1xMgxO/CIGS interface so as to improve the device
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