ARTICLE

https://doi.org/10.1038/s41467-019-10890-x OPEN

Flexible Cu2ZnSn(S,Se)4 solar cells with over 10%

efficiency and methods of enlarging the cell area
Kee-Jeong Yang 1, Sammi Kim1, Se-Yun Kim1, Kwangseok Ahn1, Dae-Ho Son1, Seung-Hyun Kim1, Sang-Ju Lee1,
Young-Ill Kim1, Si-Nae Park1, Shi-Joon Sung1, Dae-Hwan Kim1, Temujin Enkhbat2, JunHo Kim 2,
Chan-Wook Jeon3 & Jin-Kyu Kang1
1234567890():,;

For kesterite copper zinc tin sulfide/selenide (CZTSSe) solar cells to enter the market, in
addition to efficiency improvements, the technological capability to produce flexible and
large-area modules with homogeneous properties is necessary. Here, we report a greater
than 10% efficiency for a cell area of approximately 0.5 cm2 and a greater than 8% efficiency
for a cell area larger than 2 cm2 of certified flexible CZTSSe solar cells. By designing a thin
and multi-layered precursor structure, the formation of defects and defect clusters, parti-
cularly tin-related donor defects, is controlled, and the open circuit voltage value is enhanced.
Using statistical analysis, we verify that the cell-to-cell and within-cell uniformity char-
acteristics are improved. This study reports the highest efficiency so far for flexible CZTSSe
solar cells with small and large areas. These results also present methods for improving the
efficiency and enlarging the cell area.

1 Convergence Research Center for Solar Energy, DGIST, Daegu 42988, Korea. 2 Department of Physics, Incheon National University, Incheon 22012, Korea.
3 School of Chemical Engineering, Yeungnam University, Gyeongsangbuk-do 38541, Korea. Correspondence and requests for materials should be addressed
to K.-J.Y. (email: kjyang@dgist.ac.kr) or to J.-K.K. (email: apollon@dgist.ac.kr)

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ARTICLE
C
onsiderable value has been attributed to renewable energy
technology for preventing climate change, and solar
photovoltaic (PV) devices are required to play a note-
worthy role in carbon dioxide reduction1,2. To expand and dis-
seminate PV technology, various applications, and low costs
should be possible. Flexible solar cell technology enables appli-
cations such as building-integrated PV (BIPV) and mobile
applications to be extended. In addition, low-cost flexible sub-
strates can be used to lower manufacturing costs, which can
contribute to the expansion of the renewable energy market by
shortening the energy payback time. In addition to low-cost
flexible substrates, the application of low-cost materials is
required to realize low manufacturing costs. Kesterite materials
(e.g., Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 (CZTSe), and Cu2ZnSn(S,
Se)4 (CZTSSe)) are more beneficial for low-cost implementation
than CdTe and Cu(In,Ga)Se2 (CIGS) solar cells3. However, CIGS
solar cells exhibited a power conversion efficiency (η) of 22.8%4,
while CZTSSe solar cells had a relatively low efficiency of
12.6%5,6. Flexible CIGS solar cell efficiencies were 20.4% on
polyimide (PI) substrates7 and 17.7% on stainless steel (SS) foil
substrates8. In contrast, flexible kesterite solar cell efficiencies
were 7.04% on Mo foil substrates9 and 6.29% on SS foil sub-
strates10. In addition, the CZTS submodule efficiency of a soda
lime glass (SLG) substrate with a cell area larger than 1 cm2 was
11.3%6. For flexible kesterite solar cells, a low efficiency of 7.04%
was observed only with a small cell area of ~0.53 cm11. High solar
cell efficiencies are currently achievable with kesterite thin-film
solar cells, as the phase instability of their quaternary and sec-
ondary phases and related defects can lead to electron-hole
recombination and decrease the open circuit voltage (VOC) and
current density (JSC) characteristics2. In CIGS thin-film solar cells,
fewer secondary phases and defects form because of their superior
phase stability, but in kesterite absorber layers, secondary phases
and defects of various types can be produced12. Thus, the gen-
eration of secondary phases and defects must be controlled to
limit the recombination loss. Moreover, to enter the market of
flexible kesterite solar cells, it is necessary to advance both high-
efficiency and large-area technology.
In this paper, we report methods of enhancing the efficiency
and enlarging the cell area of flexible CZTSSe solar cells. For high-
efficiency flexible kesterite solar cells, the control of the secondary
phase and defect generation in the CZTSSe absorber layer is
required12–25. Defect formation is related to the secondary
phase16,19, and the defect density directly affects the open circuit
voltage deficit (Eg/q − VOC, where Eg/q is the bandgap and q is the
charge of an electron) characteristics26–28. As shown in Table 1,
the VOC deficit of the 7.04% efficiency flexible CZTSSe solar cell
on a Mo foil substrate was 0.593 V9, whereas that of the 4.10%
efficiency flexible CZTS solar cell on a SS430 substrate, which
had the highest VOC value of all flexible CZTS solar cells, was
0.638 V29. Therefore, the VOC deficit improvement through defect
formation control is very important to attain a high efficiency. The
absorber layer of the flexible CZTSSe solar cell exhibited a higher
efficiency9,11 than those of flexible CZTS10,29–35 and CZTSe solar
cells36–38. In addition, cell-to-cell and within-cell uniformity
characteristics must be secured to enlarge the cell area. With this
goal, we report the device characteristics of 3- and 7-stacked
precursor structures in small- and large-area cells.
Results
Photovoltaic device properties with small cell areas. There were
two types of designed precursor structures: one had a 3-stacked
structure (Fig. 1a, CZTSSe3), and the other had a 7-stacked
structure (Fig. 1b, CZTSSe7). As shown in Fig. 1c, four cells that
were ~4.5 mm × 12.3 mm in size were included in the Mo foil
2 NATURE COMMUNICATIONS | (2019)10:2959 | https://doi.org/10.1038/s41467-019-10890-x | www.nature.com/naturecommunications
NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-019-10890-x
substrate, which was ~25 mm × 25 mm in size. Figure 1d shows
the flexed sample image. The devices were labeled CZTSSe3-S and
CZTSSe7-S. Note that the ‘S’ in each sample label denotes a small
cell area. Current-voltage characteristics were measured for
30 samples of CZTSSe3-S and CZTSSe7-S. Figure 1e–g shows the
current density-voltage (IV) and external quantum efficiency
(EQE) characteristics of the CZTSSe3-S and CZTSSe7-S samples
with the highest efficiencies (Supplementary Figs. 1 and 2). It can
be observed from Fig. 1e, g that the VOC deficit of CZTSSe3-S was
0.623 V and that of CZTSSe7-S was 0.604 V. Figure 1f–l show the
statistical current density-voltage characteristics of flexible
CZTSSe3-S and CZTSSe7-S for 30 devices of each type. The
efficiency (Fig. 1h), VOC (Fig. 1i), JSC (Fig. 1j), fill factor (FF)
(Fig. 1k), Rs (Fig. 1l), and Rsh (Fig. 1m) values of CZTSSe7-S were
better than those of CZTSSe3-S. In addition, the standard
deviation (StDev) values of CZTSSe7-S were superior to those of
CZTSSe3-S. Therefore, CZTSSe7-S devices exhibited cell-to-cell
characteristics that were more uniform than those of CZTSSe3-S
devices. In Fig. 1n, the VOC deficit is expressed in terms of the
relation between Eg and VOC, Eg/q − VOC ∝ A ln N, where q
denotes the elementary charge, A is the diode ideality factor, and
N is the concentration of recombination centers in the bulk
CZTSSe absorber layer26–28. Defects in the absorber layer acted as
electron-hole recombination centers9. From the VOC deficit value
(Fig. 1n), it was deduced that the defect-related VOC loss was
lower in the CZTSSe7-S absorber layer than that in the CZTSSe3-
S absorber layer. Admittance spectroscopy (AS) was conducted to
investigate the defect characteristics of the two types of precursor
structures.
Defect analysis in CZTSSe absorber layers. AS measurements
were used to analyze the energy levels of the defects inside the
bandgaps of the CZTSSe absorber layer following previously
reported procedures16,17,19,20,26,27. Figure 2a and e shows the AS
measurement results of flexible CZTSSe solar cells with two types
of precursor structures. To determine the defect activation energy,
we constructed Arrhenius plots of the AS curve inflection points.
Each Arrhenius plot was calculated via ω0 = 2πν0T2 exp(−Ea/kT),
where ω0 is the inflection point of the capacitance function, Ea is
the energy level of the defect relative to the valence band max-
imum (Ev), and ν0 is the pre-exponential factor26. The defects
included vacancies (VA), interstitials (Ai), AB antisites (A repla-
cing B), and defect clusters compensating for and attracting each
other12. For CZTSSe3-S, as shown in Fig. 2b, the shallower main
defect energy level was 60 meV (Ea1,CZTSSe3-S), corresponding to
the VCu defect, and the deeper main defect energy level was 93
meV (Ea2,CZTSSe3-S), corresponding to CuZn and ZnSn defects12.
Furthermore, as shown in Fig. 2c, the range of energy levels was
between 22 and 117 meV for the shallower defects and between
36 and 165 meV for the deeper defects. In the range of the
shallower defect energy levels between 22 and 117 meV, the main
defects, VCu, and various other defects, including VZn, CuZn, and
ZnSn can be formed with defect densities of 6.05 × 1015 cm−3 (N1,
CZTSSe3-S). Additionally, in the range of the deeper defect energy
levels between 36 and 165 meV, the main defects, CuZn and ZnSn,
and various other defects, including VCu, VZn, VSn, and CuSn, can
be formed with defect densities of 7.23 × 1015 cm−3 (N2,CZTSSe3-S).
For CZTSSe7-S, as shown in Fig. 2f, the shallower main defect
energy level was 21 meV (Ea1,CZTSSe7-S), corresponding to the VCu
defect, and the deeper main defect energy level was 82 meV (Ea2,
12
CZTSSe7-S), which corresponded to CuZn and ZnSn defects . Fur-
thermore, as shown in Fig. 2g, the range of energy levels was
between Ev and 49 meV for the shallower defects and between 47
and 130 meV for the deeper defects. In the range of the shallower
defect energy levels between Ev and 49 meV, the main defects,
NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-019-10890-x ARTICLE

Table 1 Summary of reported kesterite solar cells on flexible substrates and the highest efficiency CZTS-based solar cells on SLG
substrates with small and large areas

Substrate Absorber Precursor deposition Solar cell structure η (%) VOC (V) JSC (mA FF(%) Cell area Ref.
cm−2) (cm2)
SLG CZTSSe Sputtering SLG/Mo/CZTSSe/CdS/ 12.6 0.541 35.39 65.90 0.480 6
ZnO/ZnO:Al/MgF2
SLG CZTSSe Sputtering SLG/Mo/CZTSSe/CdS/ 11.3 0.533 33.57 63.0 1.176 6
ZnO/ZnO:Al/MgF2
Mo foil CZTSSe Sputtering Mo foil/CZTSSe/CdS/ 7.04 0.498 30.06 47.02 0.530 9
ZnO/ZnO:Al
Corning CZTSSe CZTS nanoparticles ink Willow Glas/Mo/ 6.90 0.370 31.70 58.40 – 29
Willow glass CZTSSe/CdS/ZnO/ITO/
Al-Ni grid
SS430 CZTS Sputtering SS430/Mo/CZTS/CdS/ 6.29 0.628 17.40 57.51 0.24 10
ZnO/ITO
SS430 CZTSe Sputtering SS430/Cr/Mo/i-ZnO/ 6.10 0.360 27.90 56.80 – 36
Mo:Na/Mo/CZTSe/
CdS/ZnO/ZnO:Al
PI foil CZTSe Sputtering PI/Mo/CZTSe/CdS/ 4.90 0.337 27.20 53.20 – 37
ZnO/ITO
SS430 CZTS Sputtering SS430/Mo/CZTS/CdS/ 4.10 0.638 13.38 48.01 0.3–0.4 28
ZnO/ITO
Mo foil CZTS Electro-deposition Mo foil/Mo/CZTS/CdS/ 3.82 0.473 18.80 42.90 0.35 30
ZnO/ZnO:Al
SS CZTSe Sputtering SS/Cr barrier/Mo/i- 3.50 0.302 24.70 47.10 0.09 38
ZnO/CZTSe/CdS/ZnO/
ZnO:Al
Corning CZTS Sputtering Willow Glass/Mo/CZTS/ 3.08 0.491 10.60 59.20 – 31
Willow Glass CdS/ZnO/ITO
Mo foil CZTS Successive ionic layer Mo foil/CZTS/CdS/i- 2.42 0.477 11.29 45.00 0.12 32
adsorption and reaction ZnO/AZO/Ag
Mo foil CZTS Spin coating Mo foil/CZTS/CdS/ 2.25 0.370 13.52 45.00 0.25 33
ZnO/AZO/Al
Al foil CZTS CZTS ink Al foil/Mo/CZTS/ZnS/i- 1.94 0.484 8.90 45.10 – 34
ZnO/ITO
Polyimide CZTS Screen printing PI/Mo/CZTS/CdS/ZnO: 0.49 0.386 4.76 27.00 0.15 35
Al

VCu, can be formed with defect densities of 1.32 × 1015 cm−3 (N1,
CZTSSe7-S). Additionally, in the range of the deeper defect energy
levels between 47 and 130 meV, the main defects, CuZn and ZnSn,
and various other defects, including VCu and VZn, can be formed
with defect densities of 2.62 × 1015 cm−3 (N2,CZTSSe7-S). Regarding
these results, the deeper defects within the CZTSSe3-S and
CZTSSe7-S absorber layers were similar, but the defect density
was lower and the defect distribution narrower in CZTSSe7-S
than in CZTSSe3-S. These defect characteristics within the
CZTSSe7-S absorber layer reflect improvements in the VOC and
VOC deficit values (Fig. 1i, n). The defect energy level was shal-
lower, the defect density was lower, and the defect distribution was
narrower for the shallower defects of CZTSSe7-S (Fig. 2f, g) than
for CZTSSe3-S (Fig. 2b, c). As shown in Fig. 2d, h, the activation
energy (EA) for interfacial recombination in the depletion region
could be assessed by calculating the temperature dependence
of VOC. The correlation between VOC and T can be expressed as
VOC = EA/q − AkT/q × ln (J00/JL), where A is the diode ideality
factor, kT/q is the thermal voltage, J00 is the reverse saturation
current prefactor, and JL is the photocurrent39–43. When data in
the range of VOC measurement temperatures (90 K < T < 300 K)
were linearly extrapolated, it was observed that EA was the value at
T = 0 K. If EA is close to Eg, the principal recombination
mechanism is the Shockley–Read-Hall (SRH) process in the
absorber depletion region39,44, whereas if recombination occurs
in that region, the difference Eg − EA increases. The differences in
Eg − EA for CZTSSe3-S (Fig. 2d) and CZTSSe7-S (Fig. 2h) were
0.17 and 0.077 eV, respectively. These results indicate that the
density of recombination centers in the depletion region was lower
for CZTSSe7-S than for CZTSSe3-S. Within the absorber layer, the
types of main defects were similar, but the defect density of
CZTSSe7-S was lower than that of CZTSe3-S. Additionally,
recombination occurs more often in the absorber depletion region
of CZTSSe-3S than in that of CZTSSe7-S. These characteristics
resulted in improvements in the VOC and VOC deficit values
(Fig. 1i, n). The reason that the defect characteristics differed
between samples was that chalcogenization reaction mechanisms
differed according to the stacked precursor structures9,45–53. As a
result, the elemental ratio in the absorber layer was different, as
summarized in Table 2. In the case of CZTSSe3, the variation in
the Cu, Zn, and Sn content after the chalcogenization process was
larger than that in the case of CZTSSe7. The more stable chal-
cogenization process was possible with the stacked precursor
structure of CZTSSe7.
Photovoltaic device properties with large cell areas. As shown
in Fig. 3a, applying the precursor structure depicted in Fig. 1a, b,
a 15 mm × 15 mm cell was fabricated on a 25 mm × 25 mm sized
Mo foil substrate. The devices were labeled CZTSSe3-L and
CZTSSe7-L. Note that the ‘L’ in each sample label denotes a large
cell area. Figure 3b shows the flexed sample image. The current
density-voltage characteristics were determined and certified for
9 samples each of CZTSSe3-L and CZTSSe7-L (Supplementary
Figs. 7 and 8). Figure 3c–e shows the IV and EQE characteristics
of the CZTSSe3-L and CZTSSe7-L samples with the highest

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a b c d
4.5 mm

Sn 137 nm
Sn 274 nm Cu 41 nm
Zn 144 nm
Cu 164 nm Cu 41 nm
Sn 137 nm

12.3 mm
25 mm
Zn 217 nm Cu 82 nm
Zn 73 nm
NaF 10 nm NaF 10 nm

il il
fo fo
o CZTSSe3 o CZTSSe7
M M 25 mm

e 40 f 100 g 1.2 h CZTSSe3-S CZTSSe7-S

CZTSSe3-S 12
35 CZTSSe3-S CZTSSe7-S
Eg = 1.120 eV
80 1.0
Current density (mA cm )

Avg. 7.85 9.43

–2

30 CZTSSe7-S 10
Min. 6.67 8.63

Number of events
2
Eg = 1.117 eV

(h × In[1–EQE])
25 0.8 Max. 9.80 10.34
60 8
EQE (%)

Median. 7.72 9.33

20 CZTSSe3-S CZTSSe7-S
0.6 6 StDev. 0.69 0.48
VOC (V) 0.497 0.513
15 40
JSC (mA cm–2)34.78 35.23
0.4 4
FF (%) 56.69 57.22
10
 (%) 9.80 10.34 20
0.2 2
5 Active area 0.544 0.512
2
(cm )
0 0 0.0 0
0.0 0.1 0.2 0.3 0.4 0.5 400 600 800 1000 1200 1400 1.06 1.08 1.10 1.12 1.14 1.16 1.18 1.20 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0
Voltage (V) Wavelength (nm) Energy (eV) Efficiency (%)

i 12
CZTSSe3-S CZTSSe7-S
j 12
CZTSSe3-S CZTSSe7-S
k 12
CZTSSe3-S CZTSSe7-S
l 12
CZTSSe7-S CZTSSe3-S
Avg. 0.460 0.517 Avg. 31.74 33.73 Avg. 53.68 54.08 1.8 2.3 Avg.
10 10 10 10
Min. 0.427 0.505 Min. 28.85 31.74 Min. 42.32 50.26 1.2 1.5 Min.
Max. 39.45
Number of events

Number of events

Number of events

Number of events
Max. 0.497 0.529 35.23 Max. 58.53 58.21 3.0 3.5 Max.
8 8 8 8
Median. 0.461 0.517 Median. 31.42 33.67 Median. 53.58 54.25 1.7 2.4 Median.
StDev. 0.010 0.005 StDev. 2.07 0.83 StDev. 3.49 2.28 0.4 0.5 StDev.
6 6 6 6

4 4 4 4

2 2 2 2

0 0 0 0
0.42 0.44 0.46 0.48 0.50 0.52 0.54 26 28 30 32 34 36 38 40 42 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
VOC (V) JSC (mA cm–2) FF (%) 2
Rs (Ω cm )

m 12 n 12
CZTSSe3-S
CZTSSe3-S CZTSSe7-S CZTSSe7-S
Avg. 548.9 662.3 Avg. 0.600 0.660
10 10
Min. 40.6 234.2 Min. 0.588 0.623
Number of events

Number of events

Max. 1147.4 1312.2 Max. 0.612 0.693

8 8
Median. 461.9 647.7 Median. 0.600 0.659
StDev. 291.3 276.0 StDev. 0.005 0.010
6 6

4 4

2 2

0 0
0 200 400 600 800 1000 1200 1400 1600 1800 0.56 0.58 0.60 0.62 0.64 0.66 0.68 0.70
2
Rsh (Ω cm ) Eg /q - VOC (V)

Fig. 1 Photovoltaic device properties of flexible CZTSSe3-S and CZTSSe7-S. a 3-Stacked and b 7-stacked precursor structures. c Four cells ~4.5 mm × 12.3
mm in size are included in the Mo foil substrate, which is ~25 mm × 25 mm in size and d flexed sample image. All samples are with a small cell area of ~0.5
m2 for 30 devices of each type. e Current density-voltage curves, f EQE curves at a bias of 0 V, and g calculated bandgaps of CZTSSe3-S and CZTSSe7-S
samples with the highest efficiencies (from KIER certificate, Supplementary Fig.1 and 2). h The average efficiency values are 7.85% with a StDev of 0.69 for
CZTSSe3-S and 9.43% with a StDev of 0.48 for CZTSSe7-S. i The average VOC values are 0.460 V with a StDev of 0.010 for CZTSSe3-S and 0.517 V with a
StDev of 0.005 for CZTSSe7-S. j The average JSC values are 31.74 mA cm−2 with a StDev of 2.07 for CZTSSe3-S and 33.73 mA cm−2 with a StDev of 0.83
for CZTSSe7-S. k The average FF values are 53.68% with a StDev of 3.49 for CZTSSe3-S and 54.08% with a StDev of 2.28 for CZTSSe7-S. l The average Rs
values are 2.3 Ω cm2 with a StDev of 0.5 for CZTSSe3-S and 1.8 Ω cm2 with a StDev of 0.4 for CZTSSe7-S. m The average Rsh values are 548.9 Ω cm2 with
a StDev of 291.3 for CZTSSe3-S and 662.3 Ω cm2 with a StDev of 276.0 for CZTSSe7-S. n The average VOC deficit (Eg/q − VOC) values are 0.660 V with a
StDev of 0.010 for CZTSSe3-S and 0.600 V with a StDev of 0.005 for CZTSSe7-S

efficiency values (Supplementary Figs. 7g and h, 8m and n). From To obtain large-area solar cells, it is important to improve not
Fig. 3c and e, it can be observed that the VOC deficit of CZTSSe3- only the cell-to-cell uniformity but also the within-cell uni-
L was 0.512 V and that of CZTSSe7-L was 0.538 V. Figure 3f–l formity. To verify the degree of within-cell uniformity with two
shows the statistical current density-voltage characteristics of precursor structure types, micro current-voltage (MIV) analysis
CZTSSe3-L and CZTSSe7-L for 9 devices of each type. Similar to was performed. As shown in Fig. 4, the within-cell uniformity of
the small area samples in Fig. 1, the efficiency (Fig. 3f), VOC CZTSSe7-L (Fig. 4e–h, Supplementary Fig. 8m) was better than
(Fig. 3g), JSC (Fig. 3h), FF (Fig. 3i), Rs (Fig. 3j), Rsh (Fig. 3k), and that of CZTSSe3-L (Fig. 4a–d, Supplementary Fig. 7m). As shown
Eg/q − VOC (Fig. 3l) values of CZTSSe7-L were better than those for CZTSSe3-L in Fig. 4a–d, the characteristics at point A
of CZTSSe3-L. Additionally, the StDev values of CZTSSe7-L, included a higher efficiency (Fig. 4a), VOC (Fig. 4b), ISC (Fig. 4c),
except for those of Rsh (Fig. 3k), were superior to those of and FF (Fig. 4d) than those at point B.
CZTSSe3-L. Therefore, in solar cells with areas larger than 2 cm2, To investigate the differences between points A and B of the
CZTSSe7-L devices exhibited cell-to-cell characteristics that had a CZTSSe3-L device (Fig. 4a–d) in more detail, we performed
higher degree of uniformity than those of CZTSSe3-L devices. scanning transmission electron microscopy-energy dispersive

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a 8 × 10
–8
CZTSSe3-S b 4
CZTSSe3-S c 2.0 × 10 17
CZTSSe3-S d 1.2 CZTSSe3-S

7 × 10–8 N1,CZTSSe3-S = 6.05 × 1015 cm–3 EA,CZTSSe3-S = 0.95 eV

Ea2,CZTSSe3-S = 93 meV 1.0
6 × 10–8 1.5 × 1017
Capacitance (F cm–2)

2 N2,CZTSSe3-S =
7.3 × 1015 cm–3 0.8

NT (cm eV )
–1
5 × 10–8

In (/T )
2

VOC (V)
–3
4 × 10–8 0 1.0 × 1017 0.6

3 × 10–8 Eg,CZTSSe3-S - EA,CZTSSe3-S

0.4
2 × 10–8 –2 5. × 1016 = 1.120 - 0.95

Ea1,CZTSSe3-S = 60 meV 0.2 = 0.17 eV

1 × 10–8

0 –4 0.0 0.0
2 3 4 5 6
10 10 10 10 10 4 6 8 10 12 0.00 0.05 0.10 0.15 0.20 0 50 100 150 200 250 300
Frequency (Hz) 1000/T (K–1) E – Ev (eV) Temperature (K)

e CZTSSe7-S f CZTSSe7-S g CZTSSe7-S

h 1.2 CZTSSe7-S
8 × 10–8 4 2.0 × 1017
7 × 10–8 EA,CZTSSe7-S = 1.04 eV
1.0
–8
Capacitance (F cm–2)

6 × 10 2 1.5 × 1017
Ea2,CZTSSe7-S = 82 meV
0.8

NT (cm–3 eV–1)
5 × 10–8 In (/T 2)

VOC (V)
4 × 10–8 0 1.0 × 1017 0.6

3 × 10–8 N1,CZTSSe7-S = N2,CZTSSe7-S = Eg,CZTSSe7-S - EA,CZTSSe7-S

1.32 × 10 cm
15 –3
2.62 × 10 cm
15 –3 0.4
2 × 10–8 –2 5.0 × 10
16
= 1.117 - 1.04
Ea1,CZTSSe7-S = 21 meV 0.2
1 × 10
–8 = 0.077 eV

0 –4 0.0 0.0
102 10 3
104
10 5
10 6 4 6 8 10 12 0.00 0.05 0.10 0.15 0.20 0 50 100 150 200 250 300
Frequency (Hz) –1
1000/T (K ) E – Ev (eV) Temperature (K)

Fig. 2 Defect activation energies of flexible CZTSSe3-S and CZTSe7-S. (Supplementary Figs. 3–6) a, e Admittance spectra measured in the temperature
range of 90–300 K using probe frequencies from 20 Hz to 2 MHz. b, f Arrhenius plots of the inflection points of the capacitance function calculated from
derivatives of the AS measurements. Ea denotes the main defect energy level within the absorber layer. c, g Concentrations of recombination centers
(defect densities, N) derived from a and e. d, h Temperature dependence of VOC. The values of EA for CZTSSe3-S and CZTSSe7-S are 0.95 and 1.04 eV,
respectively. The values of Eg − EA for CZTSSe3-S and CZTSSe7-S are 0.17 and 0.077 eV, respectively

Table 2 Element ratios in the CZTSSe absorber layers for flexible CZTSSe3 and CZTSSe7 solar cells determined using an
inductively coupled plasma (ICP) emission spectrometer

Sample ICP data (mg kg−1) Atomic ratios

Cu Zn Sn S Se Cu/(Zn + Sn) Zn/Sn (S + S/(S
Se)/ + Se)
(Cu +
Zn;+
Sn)
CZTSSe3 Precursor 1432 1300 1625 – – 0.672 1.453 – –
Absorber 1172 1083 1371 978 34679 0.656 1.434 10.088 0.065
absorber–precursor −260 −217 −253 – – −0.015 −0.019 – –
(absorber–precursor) % −18.17% −16.70% −15.59% – – −2.29% −1.32% – –
CZTSSe7 Precursor 1421 1356 1723 – – 0.635 1.429 – –
Absorber 1329 1271 1622 982 36971 0.632 1.423 9.234 0.061
absorber–precursor −92 −85 −101 – – −0.003 −0.006 – –
(absorber–precursor) % −6.50% −6.28% −5.86% – – −0.42% −0.45% – –

spectrometry (STEM-EDS) mapping. Figures 5 and 6 show the secondary phase, various defects and defect clusters could be
STEM-EDS mapping images of points A (Fig. 5a, b) and B generated, which was a major factor in the deterioration of the
(Fig. 6a, b) of CZTSSe3-L (Fig. 4a, d). As shown in Figs. 5c and CZTSSe solar cell efficiency2,16. Moreover, at point B of the
6c, voids were observed between CZTSSe and the Mo back CZTSSe3-L device (Fig. 6a, b), Cu- (Fig. 6e) and Sn-rich regions
contact by the Kirkendall effect9,54. The CdS buffer layers were (Fig. 6g) were observed. The elemental distribution was uniform
well formed at points A and B of CZTSSe3-L (Figs. 5j and 6j). As in the EDS line scan of ①→② at point B (Fig. 6c, k). However, the
shown in Figs. 5c, d, h, i, and 6c, d, h, i, the thickness of the Mo EDS line scan of ③→④ at point B (Fig. 6c, l) indicated that the
(S, Se)x layer was very large because there was a very thick Mo foil elemental distribution fluctuated significantly in the Cu- and Sn-
substrate (0.1 mm). For point A of the CZTSSe3-L device (Fig. 5a, rich regions. In these regions, the Cu and Sn contents increased,
b), Cu (Fig. 5e) and Sn (Fig. 5g) were distributed uniformly. and Zn and S contents decreased. Therefore, the Cu- and Sn-rich
Therefore, the elemental distribution was uniform in the EDS line regions come out at similar positions, and copper-tin-selenide,
scan of ①→② (Fig. 5c and k). However, the EDS line scan of copper-sulfide/selenide, and Sn-related secondary phases may
③→④ (Fig. 5c, l) indicated that the elemental distribution also have been present9. Additionally, in these regions, Sn-related
fluctuated significantly in the Zn-rich region. In the Zn-rich donor defects, such as SnZn and SnCu, and defect clusters, such as
region, the S content increased, and Cu, Sn, and Se contents 2CuZn + SnZn, 2VCu + SnZn, and CuSn + SnCu could be formed in
decreased. Thus, zinc-sulfide/selenide secondary phase could have the CZTSSe absorber layer. These defects had a very notable
formed in this region. A zinc-sulfide/selenide secondary phase in defect energy level relative to the conduction band minimum (EC)
the Zn-rich region was also observed at point B of the CZTSSe3-L and defect clusters caused the valence and conduction band shift.
device (Fig. 6f) and in the CZTSSe absorber layer according to our These defects and defect clusters resulted in a high characteristic
previously reported results9,16,19,20. As a result of the Zn-related loss, particularly with respect to VOC. Therefore, at point A of the

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ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-019-10890-x

a 25 mm
b c 40
CZTSSe3-L
d 100
CZTSSe3-L
35
CZTSSe7-L CZTSSe7-L
80

Current density (mA cm–2)

15 mm 30

25 60

EQE (%)
20 CZTSSe3-L CZTSSe7-L
15 mm VOC (V) 0.512 0.538 40
25 mm

15 –2
JSC (mA cm ) 32.27 32.29
10 FF (%) 50.90 49.59
 (%) 8.40 8.61 20
5 Active area 2.227 2.214
2
(cm )
0 0
0.0 0.1 0.2 0.3 0.4 0.5 400 600 800 1000 1200 1400
Voltage (V) Wavelength (nm)

e 1.2 f g h
CZTSSe3-L CZTSSe7-L
6 6 6
1.0 CZTSSe3-L CZTSSe7-L CZTSSe3-L CZTSSe7-L CZTSSe3-L CZTSSe7-L
CZTSSe3-L
Avg. 6.77 8.07 Avg. 0.485 0.524 Avg. 31.44 32.57
Eg = 1.142 eV 5 5 5
Min. 30.00 32.03
Number of events

Number of events

Number of events
(h × In[1–EQE])2

0.8 Min. 5.23 7.42 Min. 0.427 0.507

4 Max. 8.40 8.61 4 Max. 0.525 0.538 4 Max. 32.54 33.54
CZTSSe7-L Median. 31.52 32.53
Median. 7.65 8.19 Median. 0.504 0.526
0.6 Eg = 1.147 eV
3 StDev. 1.34 0.48 3 StDev. 0.038 0.011 3 StDev. 0.91 0.44

0.4
2 2 2

0.2 1 1 1

0.0 0 0 0
1.00 1.05 1.10 1.15 1.20 1.25 1.30 4 5 6 7 8 9 10 0.40 0.42 0.44 0.46 0.48 0.50 0.52 0.54 29 30 31 32 33 34 35
Energy (eV) Efficiency (%) VOC (V) JSC (mA cm–2)

i j k l
6 6 6 6
CZTSSe3-L CZTSSe7-L CZTSSe7-L CZTSSe3-L CZTSSe3-L CZTSSe7-L CZTSSe7-LCZTSSe3-L
Avg. 44.01 47.23 Avg. 2.7 3.0 Avg. 93.5 200.7 Avg. 0.615 0.669
5 5 5 5
Min. 38.31 42.73 Min. 2.4 2.3 Min. 42.8 132.5 Min. 0.601 0.628
Number of events

Number of events

Number of events

Number of events
Max. 50.90 49.59 Max. 3.2 3.5 Max. 196.1 317.5 Max. 0.638 0.723
4 4 4 4
Median. 46.25 47.56 Median. 2.6 3.1 Median. 90.1 168.1 Median. 0.612 0.633
3 StDev. 4.60 2.51 3 StDev. 0.3 0.5 3 StDev. 55.0 60.0 3 StDev. 0.012 0.045

2 2 2 2

1 1 1 1

0 0 0 0
36 38 40 42 44 46 48 50 52 54 1.5 2.0 2.5 3.0 3.5 4.0 0 50 100 150 200 250 300 350 400 0.58 0.60 0.62 0.64 0.66 0.68 0.70 0.72 0.74
FF (%) 2
Rs (Ω cm ) Rsh (Ω cm2) Eg /q - VOC (V)

Fig. 3 Photovoltaic device properties of flexible CZTSSe3-L and CZTSSe7-L. a 1 cell with a size of ~15 mm × 15 mm is included in the Mo foil substrate with a
size of ~25 mm × 25 mm and b flexed sample image. All samples are with cell areas larger than 2 cm2 for 9 devices of each type. c Current density-voltage
curves, d EQE curves at a bias of 0 V, and e calculated bandgaps of CZTSSe3-L and CZTSSe7-L samples with the highest efficiencies (from KIER certificate,
Supplementary Figs. 7g, h, and 8m, n). f The average efficiency values are 6.77% with a StDev of 1.34 for CZTSSe3-L and 8.07% with a StDev of 0.48 for
CZTSSe7-L. g The average VOC values are 0.485 V with a StDev of 0.038 for CZTSSe3-L and 0.524 V with a StDev of 0.011 for CZTSSe7-L. h The average
JSC values are 31.44 mA cm−2 with a StDev of 0.91 for CZTSSe3-L and 32.57 mA cm−2 with a StDev of 0.44 for CZTSSe7-L. i The average FF values are
44.01% with a StDev of 4.60 for CZTSSe3-L and 47.23% with a StDev of 2.51 for CZTSSe7-L. j The average Rs values are 3.0 Ω cm2 with a StDev of 0.5 for
CZTSSe3-L and 2.7 Ω cm2 with a StDev of 0.3 for CZTSSe7-L. k The average Rsh values are 93.5 Ω cm2 with a StDev of 55.0 for CZTSSe3-L and 200.7 Ω
cm2 with a StDev of 60.0 for CZTSSe7-L. l The average VOC deficit (Eg/q − VOC) values are 0.669 V with a StDev of 0.045 for CZTSSe3-L and 0.615 V
with a StDev of 0.012 for CZTSSe7-L

a CZTSSe3-L b CZTSSe3-L c CZTSSe3-L d CZTSSe3-L

A A A
A
53.00

B
5.000
B 0.4000 B 0.6200

4.700
0.3930 0.5930 B 51.20

49.40
4.400
0.5660
0.3860
55 47.60
4.100
5.0 0.3790 0.5390
.60
45.80
4.5 3.800 0 0 50
0.4 0.3720 5
0.5 0
0.5120 44.00
4.0 45
Eff

3.5
3.500
.36 0.3650 0.5 5 0.4850
FF

0 42.20
icie

3.0 0.4 0
V OC

3.200 2 40
I SC

0.4 5
(%

0.3580 0.4580
0.3
ncy

2.5 0.3 0
40.40
)
(V)

(m

2.0 2.900
8 35
0.3510
0.3.25 0.4310 38.60
(%

1.5 0.2
A)

1.0
2.600 0 .20 30
)

0.3440 0.4040
0 36.80
2.300
0.3370 0.3770 35.00
2.000
0.3300 0.3500

e CZTSSe7-L f CZTSSe7-L g CZTSSe7-L h CZTSSe7-L

5.000 0.6200
53.00
0.4000
4.700 0.5930
51.20
0.3930
4.400 0.5660
49.40
0.3880
4.100 0.5390
47.60
5.0 3.800
0.3790
0.5120
55
.60
45.80
4.5 0 0.3720
0
3.500 0.4 5 0.4850 50
4.0 0.5 0 44.00
Effic

0.3650
3.5 3.200
0 .36 0.5 5 0.4580 45 42.20
FF

3.0 0.4 0
0.3580
V OC
ienc

2.900 2 0.4310 40
I SC

2.5 0.3 0.4 5 40.40

(%

0.3510
y (%

(V)

2.0 0.3 0 35
(m

2.600 8 0.4040 38.60

1.5 0.2 0.3 5
A)

0.3440
30
)

1.0 2.300 0.2 0 0.3770 36.80

0.3370 0.2
2.000 0.3500 35.00
0.3300

Fig. 4 Within-cell uniformity of photovoltaic device properties by micro current-voltage (MIV). a Efficiency, b VOC, c ISC, and d FF of CZTSSe3-L with a
2.242 cm2 designated cell area (Supplementary Fig. 7m). e Efficiency, f VOC, g ISC, and h FF of CZTSSe7-L with a 2.214 cm2 designated cell area
(Supplementary Fig. 8m)

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NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-019-10890-x ARTICLE

a A b c d
3 1 S
/Cd
5.000
4.700 A ZnO
4.400

5.0 4.100
4.5
4.0
3.800
3.500
CZTSSe
Eff

3.5
icie

3.0 3.200
2.5
cyn

2.0 2.900
(%

1.5
1.0 2.600
)

2.300
2.000
Mo(S,Se)x
Mo
4 1 μm 1 μm
2

e f g h
3

Cu Zn Sn S
1 μm 4 Zn rich 1 μm 1 μm 1 μm

i j k l
ZnO ZnO
CZTSSe Mo(S,Se)x CZTSSe Mo(S,Se)x
80 /CdS 80 /CdS
Cu Zn Sn S Cu Zn Sn S

Atomic percentage (%)

Atomic percentage (%)
Se Cd Mo O Se Cd Mo O
60 60

40 40

20 20
Se Cd
1 μm 1 μm
0 0
0 1 2 3 0 1 2 3
1 Position (μm) 2 3 Position (μm) 4

Fig. 5 STEM-EDS mapping images of point A of flexible CZTSSe3-L. a Efficiency mapping image using MIV measurements. b Real sample image. c Cross-
sectional STEM image. EDS mapping images of the CZTSSe3-L absorber layer showing mappings of d Mo, e Cu, f Zn, g Sn, h S, i Se, and j Cd. The
elemental variations across the vertical and lateral directions in STEM images (c) were measured using EDS line scans. k EDS line scan of ①→②. l EDS line
scan of ③→④

CZTSSe3-L device (Fig. 5a, b), the defect situation may have been
similar to CZTSSe3-S in Fig. 2. At point B of the CZTSSe3-L
device (Fig. 6a, b), the defect situation may have been similar to
CZTSSe7-S in Fig. 2, or there were many Sn-related defects and
defect clusters. Compared with CZTSSe3, improvements in the
cell-to-cell and within-cell uniformities and defect characteristics
in CZTSSe7 were due to differences in the chalcogenization
mechanism. Alloying the precursor structure as a stack of thick
layers (CZTSSe3) could lead to the lateral separation of elements
into steady-phase islands, producing a nonuniform element ratio
at small length scales. However, the introduction of thin and
multi-layered precursors (CZTSSe7) allowed uniform procedurals
across the entire absorber layer. Additionally, as shown in Table 2,
the change in composition before and after chalcogenization was
also controllable in CZTSSe7, so the precursor design was
advantageous not only for obtaining a high degree of efficiency
and process reproducibility but also for fabricating large areas.
Discussion
Through the application of a thin and multi-layered precursor
structure, the efficiency of flexible CZTSSe solar cells and the
possibility of large-area sizes were confirmed. The improvement
in the cell-to-cell and within-cell uniformity characteristics is
important for developing the efficiency and size of flexible
CZTSSe solar cells. The most significant factor of these uni-
formities is the VOC deficit loss due to the occurrence of defect
and defect clusters. In particular, the control of deep-level defects,
such as Sn-related donor defects, through control of the Sn-
related secondary phase is important. Finally, chalcogenization
processes are to be performed uniformly across the entire
absorber layer to suppress the formation of defects and defect
clusters and to minimize the VOC deficit loss. As such, high
efficiency and large-area technology by improving the cell-to-cell
and within-cell uniformity will enable obtaining a high perfor-
mance in other solar cell fields and contribute to the market
expansion by increasing the productivity and application.
Methods
Solar cell fabrication. A 10-nm-thick NaF layer was deposited on the Mo foil
substrate (0.1 mm thickness, MTI Co.) using a thermal evaporator for all samples.
Metal precursors were deposited on the NaF layer using 99.99% pure Cu, Zn, and
Sn sputtering targets with two different stacking orders. The layers were deposited
under sputtering powers of 150 W, 300 W, and 300 W for the Cu, Zn, and Sn
targets, respectively, at a working pressure of 1 mTorr in an Ar atmosphere. The
following precursor stacking orders were employed: Mo foil/NaF (10 nm)/Zn (217
nm)/Cu (164 nm)/Sn (274 nm), which was labeled CZTSSe3; and Mo foil/NaF (10
nm)/Zn (73 nm)/Cu (82 nm)/Sn (137 nm)/Cu (41 nm)/Zn (144 nm)/Cu (41 nm)/
Sn (137 nm), which labeled CZTSSe7. Note that the number in each precursor label
denoted the number of precursor layers it contained. For the sulfo-selenization
process, all samples were put in an annealing jig that consisted of a Se boat made of
quartz, a sample holder made of SiC-coated graphite, and a quartz cover plate.
Before the sulfo-selenization process was started, Se (250 mg), H2S (diluted with
250 sccm of 90 vol% Ar for 8 min) and Ar (2000 sccm, 8 min) gas were supplied to
the rapid thermal processing (RTP) chamber. When the pressure reached 700 Torr,
the supply of all gases was stopped and the heating process was performed. To
avoid the decomposition of the CZTSSe, the sulfo-selenization process was per-
formed using an RTP chamber at 700 Torr. The samples were heated from room

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a b c d
1 S
B 3 /Cd
5.000
4.700
ZnO
4.400

5.0 4.100
CZTSSe
4.5 3.800
4.0
Eff

3.500
3.5
icie

3.0 3.200
2.5 B
cyn

2.0 2.900
(%

1.5
1.0
)

2.600
2.300
2.000

Mo(S,Se)x
Mo
4 1 μm 1 μm
2

e f g h
3 3

Cu Cu rich Zn Zn rich Sn
Sn rich
S
1 μm 1 μm 1 μm 1 μm
4 4

i j k ZnO
l ZnO
CZTSSe Mo(S,Se)x CZTSSe Mo(S,Se)x
80 /CdS 80 /CdS
Cu Zn Sn S Cu Zn Sn S
Atomic percentage (%)

Atomic percentage (%)

Se Cd Mo O Se Cd Mo O
60 60

40 40

20 20
Se Cd
1 μm 1 μm
0 0
0 1 2 3 0 1 2 3
1 Position (μm) 2 3 Position (μm) 4

Fig. 6 STEM-EDS mapping images of point B of flexible CZTSSe3-L. a Efficiency mapping image using MIV measurements. b Real sample image. c Cross-
sectional STEM image. EDS mapping images of the CZTSSe3-L absorber layer showing mappings of d Mo, e Cu, f Zn, g Sn, h S, i Se, and j Cd. The
elemental variations across vertical and lateral directions in the STEM images (c) were measured using EDS line scans. k EDS line scan of ①→②. l EDS line
scan of ③→④

temperature to 300 °C for 560 s and then maintained at 300 °C for 900 s. Subse-
quently, the sample was heated from 300 °C to 480 °C during 1800 s and then
maintained at 480 °C for 600 s. A 50-nm-thick CdS buffer layer was deposited by
CBD from a bath containing cadmium sulfate (CdSO4), ammonium hydroxide
(NH4OH), thiourea (NH2CSNH2), and DI H2O. The bath solution was composed
of 732 ml of DI H2O, 80 ml of NH4OH ammonium hydroxide, 100 ml of cadmium
sulfate (0.015 M CdSO4), and 50 ml of thiourea (1.5 M NH2CSNH2). The pH range
is commonly 11–11.5 in a thin-film deposition process. The solution is heated by
bath with continuous stirring to the required temperature of deposition, and the
temperature is controlled to within ± 1 °C at 65 °C. After being deposited for 13
min, the film was cleaned using ultrasonic in DI H2O to eliminate any adhered
particles. Next, a 50-nm-thick intrinsic ZnO layer and a 300-nm-thick Al-doped
ZnO (AZO) layer were deposited by RF sputtering. An intrinsic ZnO layer was
deposited under sputtering power of 150 W at a working pressure of 6 mTorr for
750 s. An AZO layer was deposited under a sputtering power of 200 W at a working
pressure of 2 mTorr at 200 °C for 3000 s. Finally, a 500-nm-thick Al collection grid
was deposited on the top of the device using thermal evaporation.
Solar cell characterization. The samples were characterized using a solar simu-
lator, EQE analysis, ICP emission spectrometry, AS, MIV analysis, and STEM-EDS.
The current-voltage characteristics were determined under a simulated air mass of
1.5 global (AM 1.5 G) spectrum and 100 mW cm−2 (1 sun) illumination at 25 °C
using a 94022A solar simulator (Newport Co.) at the Daegu Gyeongbuk Institute of
Science and Technology (DGIST), and a solar simulator (WACOM, WXS-155S-L2
(Class AAA)) at the Korea Institute of Energy Research (KIER) was used for
certification. A class AAA solar simulator, which was described in IEC 60904-
9, and a WPVS packaged calibrated reference solar cell as described in IEC 60904-2
were used. In addition, KIER certified the calibration of the reference solar cell. For
the voltage scan, the average of 4 IV curves was obtained from forward and reverse
voltage sweeps. Each IV parameter from the forward and reverse sweeps indicated
a StDev within ~1%. There were ~200 data points per IV sweep. Samples were
measured with a 2 ms sampling delay time for each data point measurement, i.e.,
~1–2 s for 1 IV curve sweep, and approximately 30 s of light soaking and 15 s of
dwell time between each IV curve sweep. The EQE values were obtained using a
SOMA Optics (S-9230) at KIER. ICP (Shimadzu Co., model ICPS-8100) mea-
surements were taken to analyze compositions of the absorber layers. AS mea-
surements were performed to assess the defect energy levels inside the bandgaps of
the CZTSSe absorber layer and within the temperature range of 90–300 using an
E4980A LCR meter (Agilent Co.), which utilized probe frequencies from 20 Hz to 2
MHz. The measurements were conducted using a temperature tolerance of ± 0.05 K
or less. To verify the defect activation energy, we calculated Arrhenius plots of the
AS curve inflection points. MIV values were obtained by placing a device on a
microscope stage and irradiating a red and blue laser with a 3 mW output power
through a ×50 objective lens with an optical fiber guide. The size of the laser beam
spot was ~100 μm in diameter. The measured device with dimensions of 15 mm ×
15 mm was divided into four sections, and the MIV was measured at 20 × 20 points
at intervals of 0.4 mm for each section. STEM-EDS (Bruker Co., model QUAN-
TAX-200) measurements were performed to analyze the elements of the absorber
layers and map out the elemental distribution.
Data availability
The data that support the findings of this study are available from the corresponding
author (K.J. Yang, kjyang@dgist.ac.kr) upon reasonable request.
Received: 21 February 2019 Accepted: 6 June 2019
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Acknowledgements
This work was supported by the DGIST R&D Programs of the Ministry of Science and
ICT (19-BD-05), the Korea Institute of Energy Technology Evaluation and Planning
(KETEP) and the Ministry of Trade, Industry & Energy (MOTIE) (No.
20173010012980), and the Technology Development Program to Solve Climate Changes
of the National Research Foundation (NRF) funded by the Ministry of Science and ICT
(2016M1A2A2936781).
Author contributions
K.J. Yang and J.K. Kang designed the overall experiments, devices fabrication, and
measurement methods. K.J. Yang, S. Kim, S.Y. Kim, K. Ahn, D.H. Son, S.H. Kim, S.J. Lee,
Y.I. Kim, S.N. Park, S.J. Sung, and D.H. Kim contributed to the flexible CZTSSe solar cell
fabrication, EQE, ICP, and STEM-EDS measurements. T. Enkhbat and J. Kim con-
tributed to the AS measurements and analysis. C.W. Jeon contributed to the MIV
measurements and analysis. The manuscript was mainly written and revised by K.J.
Yang. All of the authors discussed the results and commented on the manuscript.
9
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Additional information
Supplementary Information accompanies this paper at https://doi.org/10.1038/s41467-
019-10890-x.
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