Effects of potassium doping on solution processed kesterite Cu2ZnSnS4 thin film solar

cells
Zhengfu Tong, Chang Yan, Zhenghua Su, Fangqin Zeng, Jia Yang, Yi Li, Liangxing Jiang, Yanqing Lai, and
Fangyang Liu

Citation: Applied Physics Letters 105, 223903 (2014); doi: 10.1063/1.4903500

View online: http://dx.doi.org/10.1063/1.4903500
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 APPLIED PHYSICS LETTERS 105, 223903 (2014)

Effects of potassium doping on solution processed kesterite Cu2ZnSnS4 thin

film solar cells
Zhengfu Tong,1 Chang Yan,2 Zhenghua Su,1 Fangqin Zeng,1 Jia Yang,1 Yi Li,1
Liangxing Jiang,1 Yanqing Lai,1 and Fangyang Liu1,2,a)
1
School of Metallurgy and Environment, Central South University, Changsha 410083, China
2
Australian Centre for Advanced Photovoltaics, School of Photovoltaic and Renewable Energy Engineering,
University of New South Wales, Sydney, New South Wales 2052, Australia

(Received 11 September 2014; accepted 24 November 2014; published online 4 December 2014)
Alkaline metals doping is one of the approaches for achieving high efficiency Cu(In,Ga)Se2
(CIGS) solar cell. Recently, potassium doping helps to break the record efficiency of CIGS solar
cell doped with sodium. In this paper, we have investigated how incorporation of potassium can
influence the properties of Cu2ZnSnS4 (CZTS) thin film and the performance of resulting solar cell.
Our results showed that K doping can enhance the (112) preferred orientation, increase the grain
size and reduce the second phase ZnS of the CZTS thin films. After K doping, despite of some drop
of Voc for CZTS thin film solar cells, the Rs is decreased and the Jsc is improved markedly, and the
C 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4903500]
solar cell efficiency is boosted. V

Among the thin film solar cells, the new emerging kes-
terite semiconductor Cu2ZnSnS4 (CZTS) has inspired a huge
amount of research activities, because it exhibits an optimal
direct band gap of 1.4 eV for single-junction solar cells
according to the Shockley-Queisser model, high optical
absorption coefficients of 104 cm1 and consists of earth-
abundant and non-toxic constituents. Today, the best lab-
scale CZTS solar cell has achieved a power conversion
efficiency of 12.7%,1 which is indeed promising but still rather
far from the level needed for commercialization. One impor-
tant reason is that the structure of four component elements
make CZTS containing more possible defects and impurities
than those of binary and ternary semiconductors.2 And these
defects (such as intrinsic and grain boundary defects) and
impurities (such as second phases ZnS), are crucial to the
application of semiconductors in solar cells, since they directly
influence the generation, separation, and recombination of
electron-hole pairs.3 So, making pure phase and large grains
CZTS absorber with fewer defects is important for producing
solar cells with high power conversion efficiency.
Incorporating alkalis, especially Na and K, into CIGS
absorber layers are widely known to exert significantly bene-
ficial effects on CIGS solar cells. The positive influence of
Na on polycrystalline CIGS has been claimed for various
reasons: (i) Na reduces or passivates detrimental lattice
defects such as VSe, InCu, and grain boundary defects.4,5 (ii)
Na replacing Cu site results in the formation of other stable
compounds, such as Na(In, Ga)Se2 and NaInSe2 which have
a larger band gap energy and in turn leads to a larger Voc.6
(iii) Na doping alters electronic properties of the CIGS thin
film, especially increases the free hole carrier concentration.,
i.e., p-type conductivity.6 (iv) Na doping enlarges the grain
size and improves the morphology of the CIGS film.7
Recently, potassium doping was found favorable for CIGS
thin film solar cell device. Chirila et al. have reported that
post-deposition treatment of the CIGS layer with potassium
a)
Electronic addresses: liufangyang@csu.edu.cn and fangyang.liu@unsw.
edu.au.
fluoride led to the depletion of Cu and Ga at the CdS/CIGS
interface, enabling more Cd diffusion into CIGS. Finally, the
optical loss in the CdS buffer layer was mitigated and con-
version efficiency was improved.8 Later on, Jackson et al. at
Zentrum f€ ur Sonnenenergie- und Wasserstoff-Forschung
Baden-W€ urttemberg (ZSW) confirmed this beneficial effect
again, and they also found that K doping at CIGS/CdS inter-
face enable higher Ga content, further boosting the Voc and
resulted efficiency to the record (20.8%).9 Despite great suc-
cess of K-doping in CIGS, however, for CZTS with high
similarity to CIGS, there are very few previous reports10 on
K doping into CZTS. Herein, we synthesize CZTS thin films
with different K doping concentrations and fabricate the cor-
responding solar cells. The influences of K incorporation on
the structural properties of CZTS thin films and performance
of solar cells are discussed.
CZTS thin films were prepared by the solution method.
For preparation of the CZTS precursor solutions, copper (II)
acetate monohydrate, zinc (II) acetate dihydrate, tin (II) chlo-
ride dihydrate and thiourea were added into the solvent of
methanol and ethylenediamine. The metal ion ratio of the
precursor solution was not stoichiometric but Cu-poor and
Zn-rich (Cu/(Zn þ Sn) ¼ 0.81 and Zn/Sn ¼ 1.22). And the
potassium carbonate as the K-doping source was dropped into
the precursor solutions. Four types of precursor solutions with
K/Cu ¼ 0, 0.5%, 1%, and 1.5% (atomic percentage) were
employed. To prepare the CZTS films, the prepared precursor
solutions were spin-coated onto substrates followed by
solvent-drying on a hot plate to form precursor films. Finally,
the prepared precursor films were annealed for 40 min at
600  C in sulfur atmosphere. The chemical composition of
CZTS thin films with different K-doping concentrations were
determined by X-ray Fluorescence (XRF, K-Alpha 1063).
Table I shows the atomic ratios of Cu/(Zn þ Sn), Zn/Sn, and
K/Cu tested by XRF for the CZTS thin films. It can be
observed that the Zn/Sn ratios of the K-doped samples are
lower than that of undoped sample which implies that K incor-
poration suppresses the Sn loss during the preparation of the
CZTS thin films. For preparation of the solar cell, CdS buffer

0003-6951/2014/105(22)/223903/4/$30.00 105, 223903-1 C 2014 AIP Publishing LLC

V

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 223903-2 Tong et al. Appl. Phys. Lett. 105, 223903 (2014)

TABLE I. Chemical composition ratio of different K-doping CZTS thin

films and the corresponding XRD characteristics of the (112) plane.

Compositional ratio

Sample Cu/(Zn þ Sn) Zn/Sn K/Cu (at. %) FWHM(112) (O) I(112)/I(220)

Undoped 0.82 1.31 0.239 2.808

0.5% K 0.81 1.18 0.52 0.184 3.829
1% K 0.77 1.18 1.15 0.184 9.632
1.5% K 0.80 1.15 1.52 0.182 4.699

layer was deposited on the CZTS thin film by chemical bath

method, i-ZnO and ITO layers were deposited by sputtering,
and the Ni/Al collection grid was deposited by thermal
evaporation.
The XRD patterns of CZTS thin films with different
K-doping concentrations (0, 0.5%, 1%, and 1.5%) are shown
in Fig. 1(a). The peaks of 2h ¼ 28.53 , 32.99 , 47.33 ,
56.17 , and 76.44 can be observed, which are consistent
with the diffraction of (112), (200), (220), (312), and (332)
planes of kesterite structure CZTS (JCPDS NO: 26-0575).11
Table I also exhibits the (112) reflection details of CZTS thin
films with different K-doping concentrations. The K-doped
CZTS thin films show smaller full width at half-maximum
(FWHM) of (112) plane than that of pure CZTS thin film,
which indicates improved crystallinity. Besides, it can be
observed that the I(112)/I(220) ratios ((112) peak intensity/
(220) peak intensity) of K doped CZTS thin films are larger
than that of undoped one. Previously, Ishizuka et al.7 found
that sodium can enhance (112) preferred orientation of CIGS.
Similarly, our result indicates that K doping can also facilitate
the (112) preferred orientation of CZTS thin films, which
implies the promotion of the crystal nucleation and growth.12,13
Fig. 1(b) shows Raman spectra of CZTS thin films (exci-
tation wavelength of 532 nm) with different K-doping con-
centrations (0, 0.5%, 1%, and 1.5%) deposited onto Mo glass
substrates. The peaks at 286 and 337 cm1 match with the
vibrational signals of CZTS.14 Fig. 1(c) depicts the enlarged
337 cm1 vibrational signals of CZTS films with different
K-doping concentrations. It can be found that the peak at the
337 cm1 is slightly red shifted after K doping. Like Na
replaces Cu leading to the reduction of the InCu defects in
the CIGS thin film,6 K would replaces the Cu site in Cu-poor
CZTS thin film forming the K-S instead of Cu-S. As Kþ ra-
dius (1.33 Å)15 was larger than Cuþ radius (0.96 Å),16 the
bond force constant of K-S should be smaller than that of
Cu-S. Consequently, the smaller bond force constant will
lead to the lattice vibrations red shifted.17,18 Fig. 1(d) shows
Raman spectra of CZTS thin films with different K-doping
concentrations (0, 0.5%, 1%, and 1.5%) measured with exci-
tation wavelength of 325 nm. The ZnS peaks at 345, 691,
and 1040 cm1 can be easily identified. After K doping, the
peak intensity of ZnS is decreased obviously, indicating that FIG. 1. The XRD patterns (a) of CZTS thin films with different K-doping
concentrations and the Raman spectra of corresponding films measured with
K doping helps reducing the second phase of ZnS, which can excitation wavelengths of 532 nm (b) and (c) and 325 nm (d).
be related to the inhibition of Sn loss. It has been frequently
reported that the instability of the CZTS films during the
annealing process would lead the formation of the second reported that an excess Cu rich is beneficial to the formation
phase such as ZnS and loss of Sn.19–21 Cu cannot be too poor and stability of the kesterite structure CZTS phase.22 Similar
than a certain condition as the narrow stable chemical poten- to the case of Na doped into CIGS,6 doped K atoms are
tial range of the kesterite structure CZTS phase.3 It has been believed to occupy the Cu sites and accordingly reduce the
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 223903-3 Tong et al.
ZnCu defects. It would relieve the influence of Cu-poor and
Zn-rich on the stability of kesterite structure CZTS phase
against the second phases such as ZnS, and reduce the loss
of Sn which is consistent with the drop of Zn/Sn ratio after K
doping.
Surface images of CZTS thin films with different
K-doping concentrations (0, 0.5%, %1, and 1.5%) deposited
onto Mo glass substrates are shown in Fig. 2(a). The
undoped CZTS thin film surface consists of grains on the
order of a couple of hundred nanometers. After K doping,
some large grains with size of 1–2 lm appears. It implies the
improvement of the grain size of CZTS thin film, which is
consistent with XRD result. To see the grains vertically,
the cross-sections SEM of CZTS thin film solar cells with
different K-doping concentrations are taken and shown in
FIG. 2. Surface images (a) of CZTS thin films with different K-doping. The
cross-sections (b) of CZTS thin film solar cells with different K-doping con-
centrations (Mo glass/ CZTS/CdS/ZnO/ITO).
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Appl. Phys. Lett. 105, 223903 (2014)
Fig. 2(b). The thickness of various CZTS layers is about
0.7 lm. According to Fig. 2(b), the undoped CZTS layer is
consist of many small grains. After 0.5% K doping, the quan-
tity of smaller grains at the CZTS layer is reduced and some
larger grains appear. With the 1% K doping, the sample
shows the largest grain size and the grains stand from the top
to the bottom crossing the whole CZTS layer. But when the
K doping concentration rises up to 1.5% sequentially, the
grain size looks begin to reduce.
Fig. 3(a) displays the J–V characteristics of the corre-
sponding solar cells tested under 100 mW cm2 AM 1.5G illu-
mination. Comparing the photovoltaic parameters, K doping
improves Jsc and FF, and decreases Rs, and accordingly the
conversion efficiency rises from 2.94% to 3.34% with
the 1% K-doping concentration. As is clearly observed in
Fig. 3(a), this improvement is mainly due to the enhance-
ment on short-circuit current density (Jsc). The Jsc promotion
is directly related to the improvement of grain size and less
ZnS phase of the CZTS thin film with K doping.
Undoubtedly, larger grains facilitate the current transport
and less high-resistivity ZnS can reduce cell series resistance
(Rs), consequently increasing Jsc. And the EQE data further
FIG. 3. The J–V characteristics (a) and EQE curves (b) of solar cells with
different K-doped CZTS thin films. The open-circuit voltage (Voc), short cir-
cuit current density (Jsc), efficiency (g), fill factor (FF), and series resistance
(Rs) are given.
 223903-4 Tong et al. Appl. Phys. Lett. 105, 223903 (2014)

confirm that (Fig. 3(b)) the improved current comes from
the whole spectrum, due to low Rs and better current trans-
port. Unfortunately, K doping reduces the open circuit
voltage (Voc) which might be due to two aspects. First, the
ZnS phase at the surface of the CZTS thin film plays a sim-
ilar role as CdS in establishing a higher contact potential
and hence increasing the Voc.23–25 So the reduction of ZnS
after the K doping would lead to the drop of Voc. Second,
according to the previous report, despite K exerts benefi-
cial effects at CIGS/CdS interface8 but when K comes into
the bulk CIGS, it will introduce a deep minority trap under
CB of CIGS,26 which would decrease Voc. In this scenario,
we speculate that introducing K into bulk kesterite may
lead to the formation of similar deep level minority traps
that lower the Voc. Despite of the tradeoff between Jsc and
Voc, the solar cell with 1% K-doping concentration showed
the best performance. It should be noted that, although the
reference efficiency of the undoped CZTS device is a
little bit low due to potential impurities such as C, N, O,
and Cl, which are commonly encountered when using or-
ganic solvents or metal salt precursors,27 the effects of K
doping on absorber properties and device performance
have been confirmed by several batches of repeated experi-
ments, and the further process optimization including
solvent components and metal sources (for example, using
tin (IV) disulfide to substitute tin (II) chloride) for chemi-
cally cleaner absorbers to improve the efficiency is under
investigation.
In summary, we have fabricated CZTS thin films with
different K-doping concentrations by a facile solution method.
Our experiments clearly show that K doping enhances the
(112) preferred orientation and crystallinity of the CZTS
films, and reduces the second phase ZnS. Furthermore, due to
the improvement of the quality of the CZTS films, the per-
formance of the solar cells is improved. Despite of some drop
of Voc, the Rs is decreased, FF is increased and Jsc is improved
markedly which lead to the promotion of the solar cell effi-
ciency. These results open up a very important and promising
route to preparing high conversion efficiency CZTS thin film
solar cells.
This work was supported by the National Natural
Science Foundation of China (Grant Nos. 51204214,
51272292, and 51222403).
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