Quaternary Cu2NiSnS4 Thin Films As A Solar Material Prepared Through Electrodeposition

Materials Letters 166 (2016) 215218
Contents lists available at ScienceDirect
Materials Letters
journal homepage: www.elsevier.com/locate/matlet
Quaternary Cu2NiSnS4 thin lms as a solar material prepared through

electrodeposition
Hui-Ju Chen, Sheng-Wen Fu, Tsung-Chieh Tsai, Chuan-Feng Shih n
Department of Electrical Engineering, National Cheng Kung University, Tainan, Taiwan
art ic l e i nf o
a b s t r a c t
Article history:
Received 15 October 2015
Received in revised form
18 December 2015
Accepted 19 December 2015
Available online 21 December 2015
Quaternary chalcopyrite compounds (Cu2XSnS4, X Zn, Fe, Co, Ni) are promising candidate materials for
thin-lm solar cells because of their abundance and nontoxic compositions. Here, 1.2-m-thick
Cu2NiSnS4 (CNTS) thin lms were successfully fabricated through electrodeposition. The structural,
morphological, and optical properties of the CNTS thin lms were characterized through high-resolution
X-ray diffraction, eld emission scanning electron microscopy, and ultravioletvisiblenear-infrared
spectrophotometry. The bonding properties of CNTS was measured through Raman scattering, which
revealed two principal Raman peaks of A1 mode at approximately 280 and 350 cm 1. The morphology of
CNTS was uniform with an average grain size of 1 7 0.2 m. The valences of the thin-lm constituents
were Cu 1, Ni 2, Sn 4, and S 2. The optical band gap of CNTS was approximately 1.2 eV, which is
suitable for thin-lm photovoltaic applications.
& 2015 Elsevier B.V. All rights reserved.
Keywords:
Solar energy materials
Thin lms
1. Introduction
Much efforts have been invested in fabricating Cu(In,Ga)Se2
and CdTe solar cells because of the excellent optical properties and
high-efciency performance of their starting materials. However,
the use of toxic and rare metals limits the application and commercialization of such cells. Earth-abundant quaternary chalcogenides, such as Cu2XSnS4 (X Zn, Fe, Co, Ni), are now considered
ideal absorber materials for photovoltaics (PVs). Zhang et al. synthesized Cu2FeSnS4 (CFTS) nanocrystals through a solution-based
method [1]. CFTS showed strong absorption at visible wavelength
with a band gap of approximately 1.5 eV. Yan et al. fabricated CFTS
nanocrystals with stable photoelectrochemical response through a
hot-injection method [2]. Zhang et al. developed the colloidal
synthesis of the wurtzite phase Cu2CoSnS4 (CCTS) nanocrystals
through a solution-based method [3]. Gillorin et al. synthesized
monodisperse colloidal CCTS quantum dots [4] with a band gap of
appproximately 1.5 eV. Among them, Cu2NiSnS4 (CNTS) has been
considered one of the most promising candidates because of its
suitable direct band gap and high-absorption coefcient [5]. Several methods for synthesizing CNTS have been reported. Kamble
et al. prepared wurtzite CNTS nanoparticles through the hot-injection method [6]. Wang et al. solvothermally synthesized CNTS
nanoparticles with ower-like structure [7]. Sarkar et al. hydrothermally synthesized CNTS nanoparticles that yielded a favorable
photoresponse [8]. These reports focused on CNTS nanoparticles.
n
Corresponding author.
E-mail address: cfshih@mail.ncku.edu.tw (C.-F. Shih).
http://dx.doi.org/10.1016/j.matlet.2015.12.082
0167-577X/& 2015 Elsevier B.V. All rights reserved.
However, for practical PVs applications, a thin-lm process is required. To the best of our knowledge, no study has reported on
CNTS thin lms. Moreover, reports on the synthesis and fundamental properties of CNTS thin lms are lacking.
We fabricated uniform CNTS thin lms with an average grain
size of 1 70.2 m through electrodeposition. Moreover, the absorption coefcient of the CNTS thin lms was high, and the optimal band gap was approximately 1.2 eV. These ndings highlighted the potential of CNTS-based thin lms in PVs.
2. Experimental details
CNTS precursors were electrodeposited on a molybdenum
substrate by depositing Cu, Sn, and Ni sequentially by using a
three-electrode potentiostat (Autolab PGSTAT128N, The Netherlands). The Cu aqueous solution consisted of 0.02 M CuSO4 5H2O
(Showa) and 0.085 M C6H5Na3O7 2H2O (Showa). The Sn aqueous
solution consisted of 0.022 M SnSO4 (Acros) and 0.12 M
C6H5Na3O7 2H2O. The Ni aqueous solution consisted of 0.022 M
NiSO4 6H2O (Showa), 0.12 M C6H5Na3O7 2H2O, and 0.022 M
Na2O4S (Sigma-Aldrich). The CNTS thin lms were fabricated by
sulfurization in a tube furnace (590 C, 2 h). The crystallinity of the
samples were examined through high-resolution X-ray diffraction
(HR-XRD; BRUKER D8 SSS) at a resolution of 0.01 by using Cu-K
radiation ( 1.5418 ). The CNTS microstructure was characterized by eld emission scanning electron microscopy (FE-SEM;
HITACHI SU8000). Chemical composition and mapping were
analyzed by energy dispersive spectroscopy (EDX) coupled with
216
H.-J. Chen et al. / Materials Letters 166 (2016) 215218
FE-SEM. High-resolution X-ray photoelectron spectroscopy (HRXPS, ULVAC-PHI, PHI Quantera SXM, Japan) was employed to
conrm the elemental oxidation states for CNTS. HR-XPS was
performed in an ultrahigh vacuum chamber at a background
pressure of o5 10 10 Torr, a monochromatic Al K excitation
source (1486.6 eV) at an emission angle of 45, and a capacitor
analyzer with 26 eV pass energy that provided an energy resolution of 0.5 eV. The binding energy was calibrated using the C 1 s
core level peak (285.0 eV). The optical characterization of CNTS
was measured through ultravioletvisiblenear-infrared spectrophotometry (UVvisNIR, Hitachi, U4100, Japan). Micro-Raman
and PL measurements were collected at room temperature (Horiba
Jobin Yvon Labram spectrometer, 532-nm lasers).
3. Results and discussion

Fig. 1(a) shows the XRD pattern of the CNTS thin lms. The major
XRD diffraction peaks were observed at 28.47, 32.99, 47.35,
and 56.18, corresponding to the (111), (200), (220), (311) planes of
CNTS, respectively. The patterns matched well with the standard
Joint Committee on Powder Diffraction Standards database card no.
(a)
(b)
Experimental
JCPDS: 01-071-4306
30
40
2 Theta (degree)
Intensity (a.u.)
nm
(311)
(200)
(220)
(111)
Intensity (a.u.)
20
01-071-4306, indicating that CNTS possessed a cubic zinc-blende

structure (space group: F-43m, lattice parameters a 5.425 ). To examine the presence of impure phases in the CNTS lms, micro-Raman
spectroscopy was performed, as shown in Fig. 1(b). Two dominant
peaks were detected at approximately 280 and 350 cm 1, which were
ascribed to the A1 phonon mode of CNTS [9]. No other phases were
detected, indicating that the CNTS was high-grade and single-phased.
The FE-SEM images of the annealed CNTS thin lms are shown
in Fig. 2(a) and (b). The surface morphology of CNTS was uniform
[Fig. 2(a)]. Fig. 2(b) shows a cross-sectional FE-SEM image of the
CdS-deposited CNTS thin lm. Notably, the grain size was approximately 1 70.2 m, the typical size for a high-performance
solar cell. The interface of CNTS and the CdS heterojunction was
coherent, which is a desired characteristic in thin-lm PVs. The
chemical composition of the CNTS thin lms was determined
through EDX, which revealed that the Cu/Ni/Sn/S ratio was 2.2/1.0/
0.9/4.2, thus conrming the XRD result. To determine the elemental distribution in the CNTS thin lm, EDX elementary mapping was performed, and the signals from Cu-K, Ni-K, Sn-L, and
S-K lines were collected [Fig. 2(c)]. Cu, Ni, Sn, and S were found to
be homogeneously distributed over the entire lms, and no substantial segregation was observed.
50
60
P2
P1
200
250
300
350
400
Raman Shift (cm-1)
Fig. 1. (a) HR-XRD pattern and (b) Micro-Raman spectra for the CNTS thin lms.
Cu
Sn
Ni
Fig. 2. (a) Surface and (b) cross-sectional SEM images. (c) Elemental mapping of CNTS thin lms derived using Cu-K, Ni-K, Sn-L, and S-K.
Cu 2p1/2
960
(b)
Cu 2p3/2
Intensity (a. u.)
Intensity (a.u.)
(a)
950
940
217
930
Ni 2p3/2
Ni 2p1/2
880
Binding energy (eV)
870
860
850
Binding Energy (eV)
(c)
(d)
S 2p3/2
Sn 3d5/2
Sn 3d3/2
Intensity (a. u.)
Intensity (a. u.)
S 2p1/2
500
495
490
485
166
Binding energy (eV)
164
162
160
Binding energy (eV)
Fig. 3. HR-XPS analysis of CNTS thin lms: (a) Cu 2p, (b) Ni 2p, (c) Sn 3d, and (d) S 2p.
HR-XPS measurement was used to identify the electronic

structures of CNTS. Fig. 3(a) shows the binding energies of Cu 2p3/2
and Cu 2p1/2 at 932.4 and 952.4 eV, respectively. A 20-eV binding
energy splitting was discovered, which was in good agreement
with the binding energy value of Cu [10]. Fig. 3(b) shows the
binding energies of Ni 2p3/2 and Ni 2p1/2 peaks located at 854.8
and 872.3 eV, respectively. The binding energy of Ni 2p3/2
(854.8 eV) was close to that of Ni 2 (855 eV), which is larger than
that of the elementary Ni (852.6 eV) and smaller than that of Ni 3
(856.1 eV), meaning that the valence of Ni in CNTS was 2.
Moreover, the binding energy difference between Ni 2p3/2
(854.8 eV) and Ni 2p1/2 (872.3 eV) was 17.50 eV, which is close to
that of Ni 2 in NiO (17.49 eV), thus afrming that the valence of Ni
in CNTS was 2 [11]. Fig. 3(c) shows that the binding energies of
Sn 3d5/2 and Sn 3d3/2 were 486.2 and 494.5 eV, respectively. The
Sn 3d peak splitting of 8.3 eV indicated that the valence of Sn was
4 [10]. The S 2p core level spectrum showed two peaks at 161.6
and 162.8 eV [Fig. 3(d)] [10]. In summary, the valences of the
constituents of CNTS were Cu 1, Ni 2, Sn 4, and S 2.
UVvisNIR optical absorption spectra were recorded in the
wavelength range of 3001100 nm [Fig. 4(a)]. The absorbance of
the CNTS thin lms was determined by subtracting the reectance
and transmittance from the intensity of the incident light. The
samples were placed in an integrating sphere to measure the reectance and transmittance. Thereafter, the absorption coefcient
was calculated using Beer's law [12]. The absorption coefcient
corresponding to the photon energy h was used to evaluate the

optical band gap, as follows: (h)=A (h Eg)n , where A is the
optical constant, h is Planck's constant, is the frequency of light,
1
Eg is the optical band gap energy, and n = 2 for direct-band gap
semiconductors. The optical band gap of Eg was estimated from
the plots of (h)2versus (h), as shown in the inset of Fig. 4(a). The
optical band gap of CNTS was estimated to be 1.2 eV, which was
close to the optimal value for the solar spectrum. The PL analysis of
the CNTS thin lms is presented in Fig. 4(b). Although kesterite
CNTS has been reported to have an a-axis lattice constant of
5.417 and a c/a ratio of approximately 2, which would yield an
XRD diffraction pattern similar to that of cubic CNTS [5], the band
gap in our CNTS lms was larger than the theoretical prediction
(0.86 eV). Therefore, the fabricated CNTS may have a cubic and not
a kesterite structure. Additional structural and electronic investigations of the CNTS lms are necessary in the future. CNTS
thin lms were routinely fabricated, and the results could be duplicated. The properties of the fabricated CNTS render it a candidate material for PVs applications.
4. Conclusion
CNTS thin lms were successfully fabricated through electrodeposition. The chemical states of the elements in synthesized
CNTS thin lms were Cu 1, Ni 2, Sn 4 and S 2. No second phases
218
(b)
Absorbance (a.u.)
PL Intensity (a.u.)
(a)
400
600
800
1000
Wavelength (nm)
0.9
1.0
1.1
1.2
1.3
1.4
Energy (eV)
Fig. 4. (a) UVvisNIR absorption spectrum of CNTS. (Inset: optical band gap of CNTS). (b) PL spectrum of CNTS.
were observed in the CNTS, thus conrming the high quality of the
thin lms. The lms were compact and uniformly grained. Elemental mapping of the lms demonstrated that the constituents
were homogeneously distributed. Furthermore, the lms had a
coherent interface with the CdS buffer layer. The Raman spectrum
of the lms showed two dominant Raman peaks with A1 phonon
mode at approximately 280 and 350 cm 1. The band gap of CNTS
was 1.2 eV, which matched well with the solar spectrum. This
study demonstrated the feasibility of CNTS as an absorber in thinlm solar cells.
References
[1] X. Zhang, N. Bao, K. Ramasamy, Y.-H.A. Wang, Y. Wang, B. Lin, et al., Chem.
Commun. 48 (2012) 49564958.
[2] C. Yan, C. Huang, J. Yang, F. Liu, J. Liu, Y. Lai, et al., Chem. Commun. 48 (2012)
26032605.
[3] X. Zhang, N. Bao, B. Lin, A. Gupta, Nanotechnology 24 (2013) 105706.

[4] A. Gillorin, A. Balocchi, X. Marie, P. Dufour, J.Y. Chane-Ching, J. Mater. Chem. 21
(2011) 56155619.
[5] A. Ghosh, R. Thangavel, M. Rajagopalan, Energy Env. Focus 3 (2014) 142151.
[6] A. Kamble, K. Mokurala, A. Gupta, S. Mallick, P. Bhargava, Mater. Lett. 137
(2014) 440443.
[7] T.-X. Wang, Y.-G. Li, H.-R. Liu, H. Li, S.-X. Chen, Mater. Lett. 124 (2014) 148150.
[8] S. Sarkar, B. Das, P.R. Midya, G.C. Das, K.K. Chattopadhyay, Mater. Lett. 152
(2015) 155158.
[9] S. Podsiadlo, M. Bialoglowski, M. Fadaghi, W. Gebicki, C. Jastrzebski, E. Zero,
et al., Cryst. Res. Technol. (2015) 15.
[10] L. Li, X. Liu, J. Huang, M. Cao, S. Chen, Y. Shen, et al., Mater. Chem. Phys. 133
(2012) 688691.
[11] W.J. Liu, X.D. Tang, Z. Tang, W. Bai, N.Y. Tang, Adv. Cond. Matter Phys. 2013
(2013) 6.
[12] A.M. Fox, Optical Properties of Solids, Oxford University Press, 2001.

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Materials Letters 166 (2016) 215218

Contents lists available at ScienceDirect

Quaternary Cu2NiSnS4 thin lms as a solar material prepared through

H.-J. Chen et al. / Materials Letters 166 (2016) 215218

3. Results and discussion

01-071-4306, indicating that CNTS possessed a cubic zinc-blende

Raman Shift (cm-1)

H.-J. Chen et al. / Materials Letters 166 (2016) 215218

Intensity (a. u.)

Binding energy (eV)

Binding Energy (eV)

Intensity (a. u.)

Intensity (a. u.)

Binding energy (eV)

Binding energy (eV)

HR-XPS measurement was used to identify the electronic

corresponding to the photon energy h was used to evaluate the

H.-J. Chen et al. / Materials Letters 166 (2016) 215218

[3] X. Zhang, N. Bao, B. Lin, A. Gupta, Nanotechnology 24 (2013) 105706.

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