Investigation of the CIGS Thin Film Solar Cells with Post-
Selenized Absorbers Deposited by Sputtering From a Single
Quaternary Target Using Electrical Characterization Methods
Yue-Shun Su, Chia-Hao Hsu, Chuan Chang, and Chih-Huang Lai*
Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 300, Taiwan
Abstract --- The goal of this study is to understand the role of
selenium on the quaternary-sputtered CIGS films. Based on the
CIGS thin films deposited by sputtering from a single quaternary
target, we performed a post-selenization treatments in order to
improve electrical properties of the CIGS devices. After the
devices were completed, we first conducted current-voltage
measurements to collect basic device output parameters, followed
by capacitance-voltage measurement, and admittance
measurements to gather defect-related information. With the
help of the above methods, we suggest that selenium
incorporation can possibly play the role of neutralizing selenium
vacancies and selenium-related defects near the junction
interface.
Index Terms --- admittance measurement, charge carrier
density, photovoltaic cells, sputtering, defect
I. Introduction
The advantage of low material consumption makes
Cu(In,Ga)Se2 (CIGS) thin film solar cells a promising type of
photovoltaic devices. Its efficiency over 20% has been
reported on the laboratory-scale cell by a 3-stage co-
evaporation process [1][2]. In view of industry scale,
sputtering processes for CIGS absorbers are of great interests
for large-scale production. In our previous work, we presented
a promising one-step sputtering process, which can make the
fabrication much more straightforward [3]. However, CIGS
devices prepared by sputtering techniques cannot yet reach as
high efficiency as evaporated ones. There should be some
dominating factors limiting the efficiencies, with high
possibility related to defects. Therefore, in order to improve
device properties of one-step sputtering CIGS solar cells, we
have to better understand the behaviors of defects in the CIGS
absorbers.
In this work, we made efforts to understand the role of
selenium on one-step quaternary-sputtered CIGS films. The
post-selenization was conducted on as-deposited CIGS films.
Effects of selenium on electrical properties of the sputtered
films were investigated.
II. Experimental Detail
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To understand the selenization effects in our system, we
deposited 2-µm CIGS thin films on Mo-coated soda lime glass
(SLG) by pulse-dc sputtering from a copper-poor quaternary
CIGS target, with the base pressure lower than 4×10-6 Torr and
the temperatures held at 500℃. Two samples were prepared
with conditions summarized in Table1.
TABLE I CONDITIONS OF THE DEVICES.
Sample Process Temperature Post-Selenization
A CIGS deposited at 500℃ Unselenized
B CIGS deposited at 500℃ Selenized at 300℃,
30min
Devices were completed by chemical bath deposited (CBD)
n-type CdS at 60℃, followed by rf-sputtered intrinsic ZnO,
aluminum-doped ZnO (AZO) window layer, and evaporated
Al electrodes.
After the device fabrication, current-voltage measurements
(IV), capacitance-voltage measurements (CV), and admittance
spectroscopy (AS) were carried out using Keithley 4200SCS
system. The conversion efficiency was obtained with an
AM1.5 solar simulator.
III. Results and Discussion
Photovoltaic characteristic of the samples was investigated
by I-V measurement, as shown in Figure 1. The unselenized
sample shows a distinct roll-over I-V characteristic, which
disappears when additional selenium was diffused into CIGS.
Voc, Rsh, Rs, and FF are considerably improved, leading to
2.34% efficiency enhancement, as summarized in Table 2. In
respect of eliminating roll-over phenomenon, the post-
selenization treatment seems to play the same role as Na
incorporation, as reported in the previous literature [4].
To further understand the electronic effects of selenium,
capacitance techniques were applied. Figure 2 shows the
2039
capacitance-voltage results of the two samples. After extra Se ranged from 1 kHz to 1 MHz. We held the samples at the
was diffused into CIGS, the charge density is slightly reduced. lowest temperature for 1 hour (around 90K) to ensure
The unselenized sample exhibits an extra charge distribution complete cool down.
near the interface region, which is regarded as the main cause
of the roll-over phenomenon. As explained in reference [5] , when the temperature
40 decreases, the emission rate of a defect would be lower than a
A (Unselenized)
B (Selenized) certain applied ac-frequency, so the defect fails to response,
30
resulting in an obvious step-like characteristic feature.
20
Current (mA)

Fig. 3 shows the admittance measurement results of the two

10 samples. The free carrier densities of the two samples stay
0 nearly at the same value. The unselenized sample contains two
obvious step features, resulting in the defect activation
-10 energies of 122meV and 474meV respectively. The latter one
-20
locates deep in the band gap, harmfully influencing Voc and
-0.6 -0.3 0.0 0.3 0.6 0.9 FF. Considering the Se-poor CIGS film composition (Se loss
Voltage (Volt) always happens during our sputtering deposition process), we
Fig. 1. The I-V characteristics of the two samples. The unselenized may refer such deep donors to selenium vacancies (VSe) or
sample (black) shows a roll-over phenomenon while the selenized VSe-related complex. The shallow one may provide free
one presents a normal curve.
carriers at room temperature. After the post- selenization,
although the C-f sweep from 200K to 300K still reflects a
TABLE II PARAMETERS OBTAINED FROM I-V broad defect states energetic distribution, the deep defect is
MEASUREMENT, THE DEVICE PERFORMANCES ARE annihilated. It suggests that in the unselenized sample, large
IMPROVED COMPREHENSIVELY. amount of selenium vacancies may exist, and these defects are
Voc Jsc Rs Rsh Efficiency compensated by additional Se doping, resulting in better Voc,
Sample FF
(Volt) (mA/cm2) (Ω-cm2) (Ω -cm2) (%) FF, and efficiency. Furthermore, the capacitance is obviously
compressed, meaning the overall defect densities are lowered,
A 0.39 27.68 8.56 57.84 0.41 4.39
which may also improve device properties.
B 0.48 25.43 4.39 124.51 0.55 6.73 40
A (Unselenized) Ea1=122meV 100
110
35 Ea2=474meV 120
130
A (Unselenized) 140
10 30 150
B (Selenized) 160
Capacitance (nF)
Charge Density (10 cm )

170
-3

25 180
190
200
17

20 210
220
230
1 15 240
250
260
10 270
280
290
5 300

0.1
10 100 1000
Frequency (kHz)
0.10 0.15 0.20 0.25 0.30 0.35
40 B(Selenized) 100
Averaged Distance from Junction <x> (um) Ea= 80 meV 110
120
35 130
140
150
30 160
Capacitance (nF)

170
Fig. 2. Charge density derived from CV measurement results. 25 180
190
There is an unique extra charge distribution near the PN interface for 200
210
20
the unselenized sample. 220
230
15 240
250
Admittance measurements were performed as a function of 10
260
270
frequency at a series of temperatures and carried out in our 280
290
5 300
home-made probe-station with the temperature ranging from
95K to 300K using Keithley 4200SCS electrical measurement 10 100 1000

system and Lakeshore temperature controller with temperature Frequency (kHz)

fluctuation within 0.05K at steady state. All data were Fig. 3. The admittance spectroscopy (C-f sweeps at various
temperatures) for the unselenized sample and the selenized sample.
obtained in dark with zero bias. The amplitude of the AC
signal was fixed at 100 mV and the sweeping frequency

978-1-4799-3299-3/13/$31.00 ©2013 IEEE 2040

 IV. Conclusion 5. J.T. Heath, J.D. Cohen, W.N. Shafarman Thin Solid
We have investigated the selenization effect on the electronic Films 2003 431 –432 p. 426–430.
properties of CIGS films from a single quaternary target. We
found significant difference between the two samples from IV,
CV, and admittance measurement. The change in IV
characteristics lies in with and without roll-over phenomenon.
CV measurement reveals a slight decrease in charge density
and increase in depletion region. Particularly, we observe an
unique extra charge distribution near the interface region,
which with high possibility can be correlated to a large amount
of defect accumulation. Furthermore, we conducted
admittance measurements to derive activation energies of the
main defects in both samples. We then attribute the deep
defect in the unselenized sample to selenium vacancies (VSe)
or VSe-related defects because the CIGS film is selenium
deficient. What is more, we may locate the above possible
defects near the interface, leading to the unique charge
distribution in the CV profile. Regarding the selenized sample,
the above defects are neutralized by the incorporation of Se
atoms, giving rise to the disappearance of roll-over
phenomenon, and therefore better Voc and FF. After the post
selenization, the capacitance difference in Admittance
spectrum is obviously compressed, meaning the overall defect
densities are lowered, contributing to the improved device
properties.

ACKNOWLEDGEMENT

This work is supported by NSC 98-3114-E-007-002-CC2 and

NSC 100-3113-E-007-009-CC2.

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