Materials Letters ∎ (∎∎∎∎) ∎∎∎–∎∎∎

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4 Materials Letters
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journal homepage: www.elsevier.com/locate/matlet
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Copper antimony sulfide (CuSbS2) mesocrystals: A potential counter
13 electrode material for dye-sensitized solar cells
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15 Q1 Karthik Ramasamy, Benjamin Tien 1, P.S. Archana, Arunava Gupta n
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17 Q2 Center for Materials for Information Technology, The University of Alabama, Tuscaloosa, AL 35487, United States

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20 art ic l e i nf o a b s t r a c t
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22 Article history: Dye sensitized solar cells are commonly fabricated using expensive platinum as a counter electrode
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Received 16 January 2014 material. We demonstrate for the first time the use of CuSbS2 as a replacement for platinum in dye
Accepted 8 March 2014 sensitized solar cells. The performance of solar cells using CuSbS2 is found to be comparable with that
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using platinum counter electrode.
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Keywords: & 2014 Published by Elsevier B.V.
26 CuSbS2
27 Dye-sensitized solar cells
28 Counter electrode
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1. Introduction it is also a material with layered structure [12]. Layered materials are
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known to exhibit good charge transport characteristics [13]. CuSbS2
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Dye-sensitized solar cells (DSSCs) represent a promising source of has thus far mostly been studied as an absorber material in thin film
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renewable energy because of their attractive combination of low cost, solar cells due to its optimal bandgap and high absorption coefficient
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high efficiency and use of earth-abundant materials [1,2]. One of the of 4104 cm
1 [14]. Herein, we report the use of CuSbS2 mesocrystals
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major hindrances to the commercial development of DSSCs is the use as a counter electrode for DSSCs. The photoconversion efficiency of
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of platinum as the counter electrode (CE) in these devices [3]. While Pt DSSCs using CuSbS2 counter electrode is found to be comparable to
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exhibits excellent catalytic activity, electrical conductivity and stability, platinum-based counter electrode.
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it is also a material with high cost and low abundance, which is an
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impediment to the large-scale introduction of DSSCs.[4] Thus, it is
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important to investigate alternative materials that are cheaper and 2. Experimental methods
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more earth-abundant for use as CE in DSSCs. Accordingly, a wide
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range of alternative materials have been investigated in recent years, In a typical synthesis of CuSbS2 mesocrystals, 0.5 mmol of Cu
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including metal carbides [5], nitrides [5], sulfides [6], oxides [5], (acac)2 and 0.50 mmol of SbCl3. 6H2O and 10 mL of oleylamine (OLA)
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selenides [7], carbon-based materials [8], and bimetallic nanostruc- were degassed at room temperature for 15 min and then backfilled
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tures [9]. Despite numerous investigations, only a few materials have with nitrogen for 15 min. The mixture was subsequently heated to
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shown performance better or comparable to platinum [10]. Moreover, 250 1C under N2 atmosphere. To the heated solution, a 2 mL of
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the mechanism of their catalytic activity for regeneration of the mixture of 1-dodecanethiol (0.25 mL) and t-dodecanethiol (1.75 mL)
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electrolyte is poorly understood. Recently, Wang et al. demonstrated was quickly injected and the resulting mixture was continued to be
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that semiconducting iron (III) oxide is as good as Pt CE in terms of stirred at this temperature for 30 min. After cooling down to room
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catalytic activity, and using first principle calculations they showed temperature, a mixture of hexane (15 mL) and ethanol (15 mL) was
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that the catalytic activity of a CE is directly related to the surface added to precipitate the product. The black precipitate was then
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adsorption energy of atomic iodine [11]. This demonstration encoura- isolated via centrifugation (4000 rpm for 5 min). The washing
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ges investigating the use of alternative semiconductor materials with process was repeated three times to ensure removal of the excess
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suitable bandgap as counter electrode for DSSCs. For this reason we capping agent.
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have chosen to investigate CuSbS2 since it is a direct bandgap Photoanodes were prepared by doctor blading titania paste (Ti-
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semiconductor, with a bandgap value between 1.38 and 1.52 eV, and Nanoxide HT/SP, Solaronix SA, Switzerland) on a scotch tape masked
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59 FTO coated glass to obtain an area of 0.25 cm2. The coated electrodes 97
60 n
were then annealed at 500 1C for 30 min to remove the organic 98
Corresponding author.
61 E-mail address: agupta@mint.ua.edu (A. Gupta).
binders and obtain the anatase phase. The TiO2 electrodes were 99
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Department of Chemical Engineering, Princeton University, Princeton, soaked in a 1:1 volume mixture of acetonitrile and tert-butanol of 100
63 NJ 08544, United States. N719 dye for 24 h at room temperature [15]. The dye-sensitized TiO2 101
64 http://dx.doi.org/10.1016/j.matlet.2014.03.046
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65 0167-577X/& 2014 Published by Elsevier B.V. 103
66

Please cite this article as: Ramasamy K, et al. Copper antimony sulfide (CuSbS2) mesocrystals: A potential counter electrode material for
dye-sensitized solar cells. Mater Lett (2014), http://dx.doi.org/10.1016/j.matlet.2014.03.046i
 2 K. Ramasamy et al. / Materials Letters ∎ (∎∎∎∎) ∎∎∎–∎∎∎

1 electrodes were then washed using ethanol and dried in air. The covalently bonded quadruple layers bound together by van der Waals 67
2 devices were assembled by sealing the photoanode and the counter interaction, which connect Sb and S with a distance  3.115 Å. 68
3 electrode using a parafilm spacer with acetonitrile containing 0.1 M The morphology of the as-synthesized mesocrystals has been ana- 69
4 lithium iodide, 0.03 M iodine, 0.5 M 4-tert-butylpyrideine, and 0.6 M lyzed using a scanning electron microscope (SEM). The image in Fig. 1 70
5 1-propyl-2,3-dimethyl imidazolium iodide as the electrolyte. Spray- (b) shows nearly uniform mesobelt-like morphology over the entire 71
6 coated CuSbS2 or sputtered Pt films on FTO glass were used as the sample. The length of the mesobelts ranges between 4 and 6 mm, and 72
7 counter electrode. width of about 1 mm. The average elemental composition of the 73
8 mesobelts, as determined using energy dispersive X-ray spectroscopy 74
9 (EDX), provides a ratio of 1:1:1.95 (copper: antimony: sulfur). These 75
10 quantitative EDX values are obtained from different locations contain- 76
3. Results and discussion
11 ing a large number of mesocrystals (inset in Fig. 1(b)). 77
12 To fabricate the counter electrode, we first prepared a spray ink by 78
Mesocrystals of CuSbS2 with belt-like morphology are synthesized
13 dispersing CuSbS2 mesocrystals in hexane with a few drops of 79
at 250 1C using Cu(acac)2 and SbCl3 in oleylamine and using mixture
14 oleylamine using a sonicator. The mesocrystal ink is then air-sprayed 80
of 1-dodecanethiol and t-dodecanethiol as sulfur sources. The phase
15 on fluorine doped tin oxide (FTO) glass substrates to produce large 81
purity and crystallinity of CuSbS2 mesocrystals have been confirmed
16 area continuous films. The as-prepared films are annealed at 400 1C 82
using powder X-ray diffraction. The X-ray powder diffraction mea-
17 for 30 min under N2 atmosphere. It is noteworthy that unlike previous 83
surements show that the synthesized mesocrystals have an orthor-
18 reports we did not add any adhesive or conducting agent (e.g., 84
hombic structure and are free of impurities. XRD pattern of CuSbS2
19 graphite) in the mesocrystals ink for the preparation of electrode [6]. 85
nanoplates synthesized at 250 1C is shown in Fig. 1(a). The major
20 The films are subsequently analyzed using XRD and SEM to ensure 86
diffraction peaks are indexed as (111), (410, (020), (301), (501), (321),
21 that the original phase purity and morphology are retained. XRD 87
(521), (131) and (212) planes of orthorhombic CuSbS2 with Pmna
22 pattern of the electrode exhibit diffraction peaks similar to that obser- 88
space group (ICDD: 044-1417). The crystal structure of orthorhombic
23 ved for the starting mesocrystal sample, confirming the purity of 89
CuSbS2 is shown as an inset in Fig. 1(a). CuSbS2 exhibits a set of
24 the films. Moreover, top-view SEM image in Fig. 2(a) shows meso- 90
25 crystal morphology similar to that observed for the powder sample, 91
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(111) (410)
(301)(020)

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(501)
Intensity (a.u)

(131) (212)

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(321)

(521)

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(221)

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(120)

(122) (022)
(800)

(810) (621)
(002)

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(311) (510)

(130) (421)
(021)

(911)
(322)(040)
(320)

(711)

(412)

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(820)
(220)

(600)

(230)
(520)

(612)
(620)

(331)

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(901)

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64 Fig. 1. (a) XRD pattern of as-synthesized CuSbS2 mesocrystals (inset shows
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65 corresponding crystal structure) and (b) SEM image of CuSbS2 mesocrystals (inset: Fig. 2. (a) Top and (b) side views of SEM images of CuSbS2 counter electrode on 131
66 corresponding EDX spectra). FTO coated glass substrate. 132

Please cite this article as: Ramasamy K, et al. Copper antimony sulfide (CuSbS2) mesocrystals: A potential counter electrode material for
dye-sensitized solar cells. Mater Lett (2014), http://dx.doi.org/10.1016/j.matlet.2014.03.046i
 K. Ramasamy et al. / Materials Letters ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 3

1 indicating retention of morphology (4–6 mm (l), 1–1.5 mm (w)) even It is important to investigate the stability of the solar cells con- 67
2 after annealing at 400 1C. It can also be noticed in the SEM image that structed using CuSbS2 counter electrode to determine their photo- 68
3 the mesobelts are well connected. The thickness of the film from stability in the presence of liquid (I
/I3
) electrolyte. For this purpose 69
4 cross-section SEM image (Fig. 2(b)) is determined to be 15 mm. we have measured J–V profile of the cells at different time intervals 70
5 To study the catalytic activity of CuSbS2 counter electrode against (Fig. 4). The detailed solar cell parameters at different time intervals 71
6 I
/I3
redox pair, we have carried out cyclic voltammetry (C–V) experi- are given in Table 1. Interestingly, the solar energy conversion 72
7 ments using CuSbS2 and Pt electrodes in acetonitrile solution of LiI and efficiency of the cells using CuSbS2 increases from an initial value 73
8 I2. Fig. 3(a) shows the C–V curves of CuSbS2 and Pt electrodes. C–V of 1.97–2.49% after 30 min, and further increases to 2.60% after 74
9 curves exhibit two distinct redox peaks, indicating good catalytic 90 min with notable increase in the fill factor (FF) and short-circuit 75
10 activity of these electrodes. The negative and positive redox pairs can current density (Jsc). These values are retained even after 24 h. The 76
11 be assigned to redox of I
/I3
and I2/I3
, respectively. The peak increase in current density may be attributed to the diffusion of 77
12 positions of these redox pairs are comparable to Pt, which indicate electrolyte through CuSbS2 to the FTO surface, since the as-prepared 78
13 the catalytic activity of CuSbS2 counter electrode is similar to Pt. CuSbS2 electrode is relatively thick ( 15 mm). In contrast to these 79
14 The solar energy conversion efficiency of the solar cells con- parameters, the open circuit voltage (Voc) is somewhat reduced from 80
15 structed using CuSbS2 counter electrode are derived from the current its initial value. The reduction in Voc is likely due to the formation of 81
16 density–voltage (J–V) curves. The J–V curves for the solar cells using surface states on the CuSbS2 electrode. The Voc is measured as the 82
17 CuSbS2 and Pt are shown in Fig. 3(b). At the start, the DSSC with energy difference between TiO2 conduction band minimum and 83
18 CuSbS2 counter electrode shows energy conversion efficiency of I
/I3
redox potential in DSSC constructed using Pt as the counter 84
19 around 2%, which is comparable to the DSSC constructed using Pt. electrode. While in the DSSCs using CuSbS2 counter electrode, Voc is 85
20 related to the energy difference between TiO2 conduction band and 86
21 CuSbS2 valence band maximum. In order to determine whether the 87
22 performance of CuSbS2 is a consequence of suitable bandgap, we 88
23 have carried out similar experiments using another phase Cu3SbS4, 89
24 which has a lower bandgap than CuSbS2 [16]. The resulting J–V 90
25 measurements are significantly worse than with either CuSbS2 or Pt 91
26 (Supporting Information). This suggests that the bandgap and 92
27 photostability of the semiconductor counter electrode plays an 93
28 essential role in the I
/I3
catalytic activity. 94
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Fig. 4. Performance parameters of dye sensitized solar cell fabricated using CuSbS2
50 mesocrystal counter electrode measured at different time intervals. 116
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55 Table 1 121
DSSC solar cell parameters obtained using CuSbS2 and Pt counter electrodes.
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57 Time (min) Voc (mV) Jsc (mA/cm2) FF (%) η (%) 123
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59 Initial 732 5.510 49.0 1.97 125
30 728 6.223 55.0 2.49
60 126
60 729 6.285 54.5 2.49
61 75 722 6.318 54.7 2.49 127
62 90 719 6.818 53.2 2.60 128
63 120 717 6.840 53.2 2.60 129
Fig. 3. (a) Cyclic voltammograms measured using CuSbS2 and Pt as working 150 713 6.845 53.4 2.60
64 electrodes. Pt wire is used as the counter electrode and Ag/Ag þ electrode as the
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1440 709 6.765 54.4 2.61
65 reference electrode for measurements with both working electrodes. (b) Current Pt 744 5.585 49.3 2.05
131
66 density–voltage (J–V) curves showing DSSC solar cell performance. 132

Please cite this article as: Ramasamy K, et al. Copper antimony sulfide (CuSbS2) mesocrystals: A potential counter electrode material for
dye-sensitized solar cells. Mater Lett (2014), http://dx.doi.org/10.1016/j.matlet.2014.03.046i
 4 K. Ramasamy et al. / Materials Letters ∎ (∎∎∎∎) ∎∎∎–∎∎∎

1 4. Conclusion References 25
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Supplementary data associated with this article can be found in
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the online version at http://dx.doi.org/10.1016/j.matlet.2014.03.
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046.
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Please cite this article as: Ramasamy K, et al. Copper antimony sulfide (CuSbS2) mesocrystals: A potential counter electrode material for
dye-sensitized solar cells. Mater Lett (2014), http://dx.doi.org/10.1016/j.matlet.2014.03.046i