Materials Letters ∎ (∎∎∎∎) ∎∎∎–∎∎∎

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4 Materials Letters
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journal homepage: www.elsevier.com/locate/matlet
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Cu2MSnS4 (M: Zn, Cd, MN) thin films fabricated with stacked layers by
13 CBD-annealing route
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Q1 Jianmin Li, Yaguang Wang, Guoshun Jiang, Weifeng Liu n, Changfei Zhu n
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17 CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China,
Hefei 230026, China
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21 art ic l e i nf o a b s t r a c t
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Article history: In this letter, a simple and low cost route is proposed to fabricate Cu2MSnS4 (M: Cd, Mn) thin films. As a
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Received 15 April 2015 comparison, Cu2MSnS4 (M: Zn) is also listed. The precursor films of Cu2MSnS4 (M: Zn, Cd, Mn), stacked as
24 Received in revised form SnS, Cu, and ZnS(CdS or MnS), are deposited by the CBD method, along with a subsequent sulfurization
25 15 May 2015
heat treatment. All films show good morphology, analogous crystal structure, strong optical absorption
26 Accepted 15 May 2015
characteristics and proper values of band gaps (CZTS-1.41 eV, CCTS-1.07 eV and CMTS-1.45 eV) for thin
27 film solar cells, which suggest that the high quality Cu2MSnS4 (M: Zn, Cd, Mn) thin films can be easily
28 Keywords: obtained by this CBD-annealing route. If the present technique was properly extended, it would be also
29 Cu2MSnS4 (M: Zn, Cd, Mn) thin films possible for the low cost and large-scale preparation of other multi-elements thin films with stacked
CBD
30 layers for practical application.
Stacked layer
31 & 2015 Published by Elsevier B.V.
Thin film solar cells
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34 68
35 1. Introduction SnS/Cu/ZnS. In this work, we extend this method to prepare 69
36 Cu2MSnS4 (M: Cd, Mn) thin films with stacked layer SnS/Cu/ (CdS, 70
37 Recently, earth abundant Cu2ZnSn(Sx,Se4
x)(CZTSSe) thin films MnS) and compare with Cu2MSnS4 (M: Zn) thin films on mor- 71
38 are being considered as ideal absorber materials for thin film solar phology, chemical composition, structure and band gaps. In addi- 72
39 cells (TFSC) due to its suitable properties such as large absorption tion, since the deposition of CoS, NiS and FeS2 thin films by CBD 73
40 coefficient ( 4104 cm
1), tunable direct band gap ranging from have been already demonstrated [14], not only Cu2MSnS4 (M: Zn, 74
41 1.0 to 1.5 eV, and suitable charge carrier concentrations Cd, Mn) thin films can be successfully fabricate by this method, 75
42 (5  1015–6  1016 cm
3) [1,2]. To date, the most efficient thin film Cu2MSnS4 (M: Fe, Co, Ni) thin films would also can be taken out by 76
43 solar cells currently use the Cu2ZnSnSSe4 as absorber layers give this way. 77
44 laboratory efficiencies of 12.6% for mixed sulfoselenide (CZTSSe) 78
45 absorbers [3]. 79
46 Due to the analogous structures comparing with CZTSSe, sui- 2. Experimental 80
47 table direct band gaps, and high absorption coefficients, the earth 81
48 abundant Cu2(M)(M)(S,Se)4(M ¼Cd, Mn, Fe, Co, Ni; M ¼Si, Ge) The precursor films of Cu2MSnS4 (M: Zn, Cd, Mn), stacked as 82
49 chalcogenide semiconductor materials have also received great SnS, Cu, and ZnS(CdS or MnS), are deposited by CBD method, along 83
50 attentions and been considered as the important potential solar with a subsequent sulfurization heat treatment. Three kinds of 84
51 stacked layers are marked “CZTS:Zn”, “CCTS:Cd” and “CMTS:Mn”, 85
cell materials [4–6]. According to the literature survey, CZTSSe thin
52 respectively. Same deposition of stacked layer SnS/Cu/ZnS and CdS 86
films and their devices have been prepared by various methods
53 thin films in our previous study [12] are taken out in present study. 87
including: Nanocrystal (NCs)-based fabrication method [1,3]
54 MnS thin film is deposited in an open system containing 88
Thermal evaporation [7], Sputtering [8], Pulsed laser deposition
55 Mn(CH3COOH)2 and thioacetamide(TAA) at 60 °C by CBD method 89
[9], Electrodeposition [10] and CBD method [11–13]. To our best
56 [15] with the complex agent triethanolamine(TEA).The PH of the 90
knowledge, there are many similar synthesis methods of
57 solution has been stabilized at 10.5 by adding NH3  H2O during the 91
Cu2MSnS4 (M: Zn, Cd, Mn) [4–6], but few with CBD method. In our
58 deposition process. All the coated samples mentioned above were 92
previous work [12], the CBD-annealing route was demonstrated
59 rinsed thoroughly with deionized water and then blow-dried with 93
properly for fabrication of CZTSSe thin films with stacked layer nitrogen. After the deposition of each layers, stacked precursor
60 94
61 films were anneal at 600 °C for 20 min with the S powder in a 95
62 n
Corresponding authors. Fax: þ 86 551 360195. sealed tube to form the Cu2MSnS4 (M: Zn, Cd, Mn) phase. The 96
63 E-mail addresses: liuwf@ustc.edu.cna (W. Liu), cfzhu@ustc.edu.cn (C. Zhu). temperature of S powder is maintained at 600 °C. 97
64 98
http://dx.doi.org/10.1016/j.matlet.2015.05.068
65 0167-577X/& 2015 Published by Elsevier B.V. 99
66 100

Please cite this article as: Li J, et al. Cu2MSnS4 (M: Zn, Cd, MN) thin films fabricated with stacked layers by CBD-annealing route. Mater
Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.05.068i
 2 J. Li et al. / Materials Letters ∎ (∎∎∎∎) ∎∎∎–∎∎∎

1 The morphology and composition of post-annealing thin films Table1 67

2 were characterized by field emission SEM (FE-SEM siron 200, Chemical composition of post-annealing Cu2MSnS4 (M: Zn, Cd, Mn) thin films. 68
3 equipped with energy dispersive X-ray spectroscopy (EDX)). The 69
Sample Cu (at%) M (at%) (M:Zn, Sn (at%) S (at%) Cu/(M þSn) M/Sn
4 crystallinity and preferred orientations of samples were in- Cd,Mn) 70
5 vestigated by X-ray diffraction (XRD) using a Bruker Advance D8 71
6 diffractometer equipped with graphite-monochromatized Cu K CZTS:Zn 16.85 9.98 7.93 52.89 0.94 1.25 72
7 (radiation (λ ¼ 1.5406 Å). The further identification of phase of CCTS:Cd 29.04 13.85 10.55 46.56 1.19 1.31 73
CMTS:Mn 19.09 12.95 11.47 56.50 0.78 1.13
8 Cu2MSnS4 (M: Zn, Cd, Mn) thin films was characterized by Raman 74
9 analysis at room temperature, using a LABRAM-HR micro-Raman 75
10 system in the back scatting configuration with a laser source of identification. 76
11 532 nm. The optical absorbance of the CMTS thin films was mea- Fig. 2c shows the Raman spectra of post-annealing Cu2MSnS4 77
12 sured with a UV–vis spectrophotometer (SOLID 3700) from (M: Zn, Cd, Mn) thin films. The existence of CZTS, CCTS and CMTS 78
13 300 nm to 1600 nm. are confirmed by the intense peaks at 286, 337 cm
1, 79
14 282,331 cm
1, and 244, 282, 326 cm
1, respectively, which are 80
15 characteristic Raman peaks of the analogous crystal structure 81
16 3. Results and discussion Cu2MSnS4 (M: Zn, Cd, Mn) [12,18,19]. Obviously, combing the re- 82
17 sults of XRD analyses, no other obvious Raman peaks were found 83
18 3.1. Morphologies and chemical composition in all samples, it can further infer that the films were primarily 84
19 Cu2MSnS4 (M: Zn, Cd, Mn). 85
20 Fig. 1 shows the surface and cross section morphologies of 86
21 post-annealing Cu2MSnS4 (M: Zn, Cd, Mn) thin films. As can be 3.3. Optical properties 87
22 seen from the surface images, obviously, all the three kinds of films 88
23 are composed of uniform, dense and void free particles. In addi- Fig. 3 shows the absorption spectra of the Cu2MSnS4 (M: Zn, Cd, 89
24 tion, as the results of the cross section morphologies show, some Mn) thin films that measured with the wavelength of the incident 90
25 grains are almost extending to the full thickness of the layer. It is radiation ranging from 300 to 1600 nm. It is clear that the sample 91
26 well known that large grain size is benefit to the collection of absorbs radiation spanning the whole range of the visible spec- 92
27 charge and decreasing the recombination at the grain boundaries trum and all samples show relatively high absorbance. Meanwhile, 93
28 of final devices [16]. Table 1 shows the chemical composition of calculations of band gaps are carried out from the UV–vis spectra. 94
29 three kinds of films. As the one advantage of the approach for the The calculation of the band gap of the films which is determined 95
30 stacked precursors, the compositional ratio of absorber layers can by extrapolation of the plot of (ahν)2 vs hν (shown in inset ), gives 96
31 be easily controlled by adjusting the thickness of each stacked the values of Eg of Cu2MSnS4 (M: Zn, Cd, Mn) thin films around 97
32 layers. In present study, all films shows relatively proper elemental 1.41 eV, 1.07 eV and 1.45 eV, respectively, which are in good 98
33 components with two ratios (Cu/(M þ Sn), M/Sn) around 0.78–1.19 agreement with the reported values in literature [6,20]. Notably, 99
34 and 1.13–1.31. reported by Reshak et al. [21], the domain reason for Cu2ZnSnS4 100
35 possess larger band gap (0.54 eV) than Cu2ZnSnS4 (0.22 eV) is the 101
36 3.2. Phase structure Se atoms have bigger radius than S and the atomic terms of pSe lie 102
37 higher in energy the atomic terms of pS. It can infer that the en- 103
38 The XRD patterns of post-annealing Cu2MSnS4 (M: Zn, Cd, Mn) ergy gaps as well as the principal optical properties in our de- 104
39 thin films and standard PDF cards of each crystal structure are signed materials are defined by the cationic re-arrangement fol- 105
40 shown in Fig. 2a and b. All the samples are polycrystalline and lowing the DFT calculations. 106
41 exhibit three characteristic peaks of Cu2MSnS4 (M: Zn, Cd, Mn) 107
42 (CZTS-PDF#26-0575, CCTS-PDF#29-0537, CMTS-PDF#51-0757) 108
43 along (112), (220/204) and (312), respectively. As shown in stan- 4. Conclusion 109
44 dard PDF cards, with the atomic Zn instead by atomic Cd and Mn, 110
45 the XRD diffraction peaks slightly shift to the left as illustrated by In this study, Cu2MSnS4 (M: Zn, Cd, Mn) thin films have been 111
46 the magnified figure on the right, primarily owing to the partial successfully prepared by CBD-annealing route with stacked layer 112
47 substitution of the larger size Cd or Mn for the smaller size Zn ion. SnS/Cu/ZnS (CdS, MnS). The results of SEM, EDX, XRD and RAMAN 113
48 However, the XRD pattern alone is insufficient to identify the characterizations have confirmed the good morphology, proper 114
49 phase purity of the post-annealing films, arisen frequently in CZTS composition and analogous structure of the films. In addition, all 115
50 studies, since some binary(such as cubic ZnS) and ternary(such as films show strong optical absorption characteristics and proper 116
51 tetragonal Cu2SnS3) chalcogenides have very similar lattice para- values of band gap (CZTS-1.41 eV, CCTS-1.07 eV and CMTS- 117
52 meters or analogous pattern features to CZTS phase [17]. Thus, 1.45 eV), which are all within the scope of the proper Eg values 118
53 Raman analyses at room temperature are further utilized for phase (1.0–.5 eV) for high performance thin film solar cells. These results 119
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66 Fig. 1. Surface and cross section morphologies of post-annealing Cu2MSnS4 (M: Zn, Cd, Mn) thin films. 132

Please cite this article as: Li J, et al. Cu2MSnS4 (M: Zn, Cd, MN) thin films fabricated with stacked layers by CBD-annealing route. Mater
Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.05.068i
 J. Li et al. / Materials Letters ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 3

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16 Fig. 2. XRD and Raman spectra of post-annealing Cu2MSnS4 (M: Zn, Cd, Mn) thin films. 82
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Please cite this article as: Li J, et al. Cu2MSnS4 (M: Zn, Cd, MN) thin films fabricated with stacked layers by CBD-annealing route. Mater
Lett (2015), http://dx.doi.org/10.1016/j.matlet.2015.05.068i