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Laboratory for Thin Films and Photovoltaics, EmpaSwiss Federal Laboratories for Materials Science and Technology, 8600 Dbendorf, Switzerland
Zentrum fr Sonnenenergie- und Wasserstoff-Forschung Baden-Wrttemberg (ZSW), 70565 Stuttgart, Germany
art ic l e i nf o
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This review describes a specic group of non-vacuum methods for depositing kesterite solar cell
absorbers, which we refer to as direct solution coating (DSC). These methods work by coating a layer of
precursor-containing solution on the surface of a substrate followed by appropriate thermal processing to
yield the desired kesterite Cu2ZnSn(S,Se)4 phase. General aspects, challenges and future prospects of
the DSC are discussed in detail. Two research highlights are presented in which kesterite layers are
processed from solutions of metal salts in simple non-toxic organic solvents to yield up to 7.5% efcient
solar cells.
& 2013 Elsevier B.V. All rights reserved.
Keywords:
Kesterite
Cu2ZnSn(S,Se)4
CZTS
Non-vacuum deposition
Direct solution coating
Thin lm solar cell
1. Introduction
Kesterites the family of compounds comprising Cu2ZnSnS4
(CZTS), Cu2ZnSnSe4 (CZTSe) and associated alloys are certainly
one of the most intriguing absorber materials for thin-lm solar
cells today. They may offer low-cost manufacturing starting from
abundant and non-toxic materials, provided that the optoelectronic characteristics of kesterite solar cells are better understood and can be further improved [1,2]. Kesterite thin lms can
be prepared by a variety of deposition methods resulting in
different material qualities and solar cell efciencies. The current
record efciency of 11.1% is reported for a Cu2ZnSn(S,Se)4 (CZTSSe)
absorber processed with a mixed solution-particle approach in
hydrazine solvent [3]. Other notable results include 9.3% efciency
for CZTSSe by co-sputtering with post-annealing in SnS and S [4],
9.15% for CZTSe by co-evaporation [5], 8.4% for CZTGeSSe sintered
from nanoparticle inks [6], 7.3% for CZTS by electroplating metal
precursors with post-sulfurization [7], and recently, 7.5% for
CZTSSe processed from a metal salt solution in dimethyl sulfoxide
(DMSO) followed by selenization [8]. Several recent reviews
summarize the state of the art in non-vacuum processing of
kesterites [1,9], the current understanding of the defect physics
[10], as well as general aspects of the emerging kesterite solar cell
technology [1,2,11,13].
Corresponding author. Tel.: +41 58 765 4169; fax: +41 58 765 1122.
E-mail addresses: yaroslav.romanyuk@empa.ch,
yaroslav.romanyuk@gmail.com (Y.E. Romanyuk).
0927-0248/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.solmat.2013.06.038
Y.E. Romanyuk et al. / Solar Energy Materials & Solar Cells 119 (2013) 181189
layer properties over large area and nally, potential deployment of large-scale production with low capital investment.
In contrast to the other popular solution-based techniques for
kesterites such as chemical bath deposition (CBD) [15,16],
electrodeposition (ED) [7], successive ionic layer absorption
and reaction (SILAR) [17], and spray pyrolysis [18,21] which
imply a slow growth of the kesterite phase during the actual
deposition step, the DSC techniques such as spin-, spray-, dip-,
knife-, and curtain-coating, as well as printing techniques like
ink-jet, exography, and gravure allow fast coating of the wet
layer with low wastage of the precursor solution.
As compared to nanoparticle-based inks, solutions offer the
following benets: (i) no need for pre-synthesized nanocrystals; (ii) readily available, cheap metal salts with high purity
and long storage time; and (iii) reproducible processing with a
homogeneous intermixing of constituent elements on the
molecular level.
It is important to note that the nucleation of nanoparticles can
also occur in an initially homogeneous precursor solution leading
to the formation of a colloid sol, especially if the solution
constituents favor condensation and redox reactions. This fact
blurs out the clear division between true solution and colloidal
dispersion approaches. In this paper we will focus on homogeneous precursor solutions prepared without any pre-synthesized
nanoparticles, not excluding the possibility of the in-situ formation of colloidal aggregates.
The DSC approach obviously has its own challenges and
limitations. The most critical issues are: (i) the absolute need for
a high-temperature annealing step, preferably in a chalcogencontaining atmosphere; (ii) the adequate chemical coordination of
metal species in coated precursor layers to prevent undesirable
metal segregations and metal losses during a subsequent thermal
treatment; (iii) unwanted effects associated with the drying of a
wet lm such as increased layer porosity, cracking and delamination; (iv) possible contamination with solvent elements and
unwanted residuals of the initial precursor solution. Here we
present a critical assessment of the most important aspects of
the DSC and describe two research highlights in which kesterite
layers are processed from solutions of metal salts in simple nontoxic organic solvents to yield up to 7.5% efcient solar cells.
Precursor solution
coating
multilayer coating
182
Wet film
drying
Dry film
annealing / crystallization
Crystalline CZTS(Se) layer
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2.2.3. Drying
Even though drying can be considered as a primitive, standard step
for solvent evaporation, it is found to be decisive for the layer
morphology, uniformity, and the presence of impurity elements and
phases in the nal CZTS(Se) layer. Drying starts already when the wet
lm is being coated, but it is typically performed as a separate step.
Wet layers are often dried on a hot plate for several minutes at
temperatures from 200 1C to 350 1C. On the one hand, the drying
temperature is selected to be as high as possible to maximize the
evaporation of solvent and remove carbon and, on the other hand, it is
restricted by the oxidation of the precursor material and also the
molybdenum substrate. Inert atmosphere, e.g. N2, allows increasing
the temperature up to 580 1C [37]. Additional top heating with IR
lamps can improve the layer homogeneity [27,32].
It is important to ensure a good wetting of the substrate,
e.g. Mo-coated glass, with the precursor solution in order to obtain a
homogeneous wet layer without uncoated spots and also to avoid the
appearance of thicker, inhomogeneous areas at the edgesthe socalled coffee-ring effect [47]. For achieving controlled drying, highboiling point solvents that dry slowly, such as propylene glycol (b.p.
188.2 1C) or DMSO (b.p. 189 1C), are often preferred. This implies that a
relatively high drying temperature, e.g. 300 1C for DMSO, has to be
applied to ensure complete solvent evaporation. A small amount of
surfactants for reducing surface tension, or coating on a pre-heated
substrate could also be helpful for suppressing the coffee-ring effect.
The tensile stress generated during the removal of the solvent
and organic components can give rise to lm cracking. Microscopic
cracks in the dried layer which propagate through the whole dry
layer thickness can be fatal for the solar cell absorber because they
can short the top and back contacts. This phenomenon is very
pronounced if the lm thickness exceeds a certain critical thickness which is inversely proportional to the tensile stress and the
Young's modulus of the lm [14]. The multi-layering approach
demonstrated for spin-coating e.g. [25,32,37] and knife-blading
[8,27] is an effective way to avoid microscopic cracks, and also to
improve the layer uniformity. This is because each layer is thinner
than the critical thickness, and an intermediate drying between
coatings helps to fully evaporate/decompose solvent species. If a
dried precursor undergoes a volume expansion during the last
chalcogenation step, compressive stress can even be observed in
the nal absorber layer, resulting not in cracks but in bulges [32].
One important question rarely addressed in publications on the
DCS of kesterites is the chemical state and coordination of metal
ions in the dried lm that is often called amorphous precursor
lm. It is rather impossible to obtain an amorphous precursor lm
that consists of a molecularly homogeneous mixture of initial
metal salts without any additives. Instead, a carbon-rich matrix
with coordinated metal ions, mixed metal oxides or chalcogenides,
or ideally the CZTS(Se) phase is obtained depending on the initial
solution and drying conditions. The chemical coordination of
metal cations in the dry lm should prevent possible oxidation,
hydrolysis and segregations, and should at the same time be weak
enough to decompose cleanly during the nal annealing step.
2.3. Annealing and crystallization
Annealing is the last processing step (Fig. 1) that can be
performed in either inert or reactive atmosphere. There are only
a few investigations of the DSC of kesterites which employ an inert
atmosphere, including annealing under nitrogen atmosphere [35]
or in vacuum [33,41]. These studies, however, do not prove the
quality of the obtained kesterite materials by fabricating solar
cells, but are rather focused on exploring new solution chemistries
to obtain the kesterite phase. All DSC-processed kesterite cells
reported to date were fabricated with an annealing step in sulfuror selenium-containing atmosphere, clearly indicating the necessity of the reactive atmosphere even if the initial precursor
solution already contains a chalcogen source.
The effect of the reactive chalcogen-containing atmosphere is
manifold. First, the reactive annealing can compensate the decit of
chalcogen in the dried precursor layer by increasing the S(Se)/Me ratio
to 1:1. This condition is imperative for a phase-pure material with
suitable electronic properties, since anion vacancies (VS and VSe) can
induce detrimental deep donor levels [10]. Second, the reaction with
chalcogen can lead to a volume expansion and densication during
annealing, thus eliminating the layer porosity and increasing the grain
size. Finally, the chalcogen vapor overpressure is essential for preventing a possible decomposition of the kesterite phase into binary copper
and zinc chalcogenides, and volatile SnS(Se) and S(Se) [48].
Elemental selenium [8,25,27,32,37], sulfur [34] or H2S [2931]
have been employed to date. H2S has the highest reactivity and can
be diluted with inert nitrogen down to 3% without deteriorating the
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Fig. 3. Currentvoltage (JV) characteristics in the dark (dashed lines) and under
AM1.5 illumination (solid lines) for two CZTSe absorbers with different Zn/Sn
composition ratios as determined by EDX. The solar cell with higher Zn content
(B) features a higher Voc, whereas both cells exhibit similar conversion efciency.
Fig. 5. Cross-section SEM images showing (a) a dry precursor lm processed from a
DMSO solution and (b) a nished CZTSSe solar cell. The selenized CZTSSe absorber
exhibits a three-layer morphology with a crystalline top and bottom crust, and a
porous middle part.
Fig. 6. Raman spectra of the selenized samples measured after scratching the
sample in order to remove material to the different depths as listed. The relevant
Raman modes are indicated.
Y.E. Romanyuk et al. / Solar Energy Materials & Solar Cells 119 (2013) 181189
187
Table 1
Highest reported solar efciencies for kesterite absorbers processed by the direct solution coating. The currently highest efciency for the hybrid nanoparticle-solution
approach with hydrazine solvent is also given as a reference.
Compound
CZTS
CZTSe
CZTSSe
Solvent/stabilizer
2-Methoxyethanol/monoethanolamine
Ethanol+1,2-propanediol / ethyl cellulose
2-Methoxyethanol / monoethanolamine
DMSO
DMSO
Pyridine
Hydrazine
Hydrazinea
Coating technique
Spin-coating
Knife-coating
Spin-coating
Knife-coating
Spin-coating
Spin-coating
Spin-coating
Spin-coating
Crystallization
Atmosphere
Temperature (1C)
N2+H2S (5%)
Se in N2
Se in N2
Se in N2
Se in Ar
S and Se in vacuum
Se in inert atmosphere
S
500
470
560
540
500
500
500
4 500
Refe-rence
2.23
4.28
2.76
7.5
4.1
1.44
8.08
11.1
[30]
[27]
[32]
[8]
[37]
[34]
[25]
[3]
Acknowledgements
Y.E.R. acknowledges the nancial support from the Swiss
National Science Foundation, project no. PZ00P2_126435/1 under
Ambizione program. T.S. acknowledges nancial support from a
Karlsruhe School of Optics and Photonics PhD grant. Hamamatsu
(Switzerland) is acknowledged for enabling TR-PL measurements.
188
Y.E. Romanyuk et al. / Solar Energy Materials & Solar Cells 119 (2013) 181189
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