THE EFFECT OF DEPOSITION TEMPERATURE ON Cu2ZnSnS4 (CZTS) THIN FILMS GROWN BY DC MAGNETRON SPUTTERING
DOI:
10.29303/ipr.v9i2.616Downloads
Abstract
Cu₂ZnSnS₄ thin films were successfully deposited on soda lime glass substrates using the DC Magnetron Sputtering method at a plasma power of 42 W, an argon gas pressure of 500 mTorr, and deposition temperatures ranging from 27 °C to 400 °C for 7 hours, using a Cu₂ZnSnS₄ target with 99% purity. The effect of varying temperatures was characterized by using X-ray Diffraction (XRD) to determine the film structure, Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDX) to analyze morphology and composition, and UV-Vis-NIR spectrophotometry to evaluate optical properties. Film composition showed non-stoichiometric characteristics, with elemental ranges of Cu (20.66–32.81) %, Zn (14.08–25.67) %, Sn (21.87–37.05) %, and S (25.42–31.22) %. All samples exhibited a Cu/(Zn+Sn) ratio of less than 1, indicating Cu-poor compositions typical of p-type semiconductors. XRD analysis revealed that the formation of the Cu₂ZnSnS₄ phase began at a deposition temperature of 100 °C, while stable kesterite Cu₂ZnSnS₄ crystals were obtained at 400 °C, corresponding to the (112) crystal plane. The absorption coefficients and band gap energies ranged from 10⁴ to 10⁵ cm ¹ and from 1.34 to 2.175 eV, respectively, confirming the suitability of the films for solar cell applications. SEM observations indicated that higher deposition temperature promoted more successful grain growth. Overall, higher deposition temperatures yield better Cu₂ZnSnS₄ thin films.
Keywords:
thin films Cu2ZnSnS4 DC Magnetron Sputtering temperatureReferences
[1] M. P. Suryawanshi et al., “CZTS-based thin film solar cells: A status review,” Mar. 2013.
[2] A. M. P. Abdul, K. Adhi, G. I. Aldhiantoro, D. R. Dewi, M. H. A. Baarik, and C. V. Anghel, “Cadmium telluride (CdTe) thin-film photovoltaics: A sustainable energy solution to support national energy resilience,” International Journal of Applied Mathematics, Sciences, and Technology for National Defense, vol. 3, no. 2, pp. 77–88, 2025.
[3] A. Ravilla, E. Gullickson, A. Tomes, and I. Celik, “Economic and environmental sustainability of copper indium gallium selenide (CIGS) solar panels recycling,” Science of the Total Environment, vol. 951, Nov. 2024.
[4] J. Keller et al., “High-concentration silver alloying and steep back-contact gallium grading enabling copper indium gallium selenide solar cell with 23.6% efficiency,” Nat. Energy, vol. 9, no. 4, pp. 467–478, Apr. 2024.
[5] NREL, “Best Research-Cell Efficiencies Chart,” 2025. Accessed: Mar. 10, 2025. [Online]. Available: NREL. https ://www.nrel.gov/pv/cell-efficiency.html
[6] J. Ramanujam and U. P. Singh, “Copper indium gallium selenide-based solar cells – a review,” Energy Environ. Sci., vol. 10, no. 6, pp. 1306–1319, 2017.
[7] L. Wen, T. Zhu, T. Zhang, L. Li, and M. Ren, “Multi-omics and physiological traits analysis revealed the regulatory mechanism of selenium reducing cadmium toxicity in Desmodesmus abundans,” Ecotoxicol. Environ. Saf., vol. 303, Sep.
[8] M. A. Medinsky, R. G. Cuddihy, W. C. Griffith, S. H. Weissman, and R. O. McClellan, “Projected uptake and toxicity of selenium compounds from the environment,” Environ. Res., vol. 36, no. 1, pp. 181–192, 1985.
[9] R. Loomba et al., “Exposure to a high selenium environment in Punjab, India: Effects on blood chemistry,” Science of the Total Environment, vol. 716, May 2020.
[10] M. Banerjee, D. Chakravarty, P. Kalwani, and A. Ballal, “Voyage of selenium from environment to life: Beneficial or toxic?” J. Biochem. Mol. Toxicol., vol. 36, no. 11, Nov. 2022.
[11] F. A. Jhuma, M. Z. Shaily, and M. J. Rashid, “Towards high-efficiency CZTS solar cell through buffer layer optimization,” Mater. Renew. Sustain. Energy, vol. 8, no. 1, Mar. 2019.
[12] A. Benami, “Effect of CZTS Parameters on Photovoltaic Solar Cell from Numerical Simulation,” Journal of Energy and Power Engineering, vol. 13, no. 1, pp. 32–36, Jan. 2019.
[13] L. Chen and C. Park, “Effects of annealing temperature on Cu₂ZnSnS₄ (CZTS) films formed by electrospray technique,” Korean Journal of Chemical Engineering, vol. 34, no. 4, pp. 1187–1191, Apr. 2017.
[14] M. Haghighi, M. Minbashi, N. Taghavinia, D. H. Kim, S. M. Mahdavi, and A. A. Kordbacheh, “A modeling study on utilizing SnS₂ as the buffer layer of CZT (S, Se) solar cells,” Solar Energy, vol. 167, pp. 165–171, Jun. 2018.
[15] S. Zhuk, A. Kushwaha, T. K. S. Wong, S. Masudy-Panah, A. Smirnov, and G. K. Dalapati, “Critical review on sputter-deposited Cu₂ZnSnS₄ (CZTS) based thin film photovoltaic technology focusing on device architecture and absorber quality on the solar cells performance,” Solar Energy Materials and Solar Cells, vol. 171, pp. 239–252, Nov. 2017.
[16] S. Yazici et al., “Growth of Cu₂ZnSnS₄ absorber layer on flexible metallic substrates for thin film solar cell applications,” Thin Solid Films, vol. 589, pp. 563–573, Aug. 2015.
[17] M. Nishiwaki et al., “Tail state formation in solar cell materials: First principles analyses of zincblende, chalcopyrite, kesterite, and hybrid perovskite crystals,” Phys. Rev. Mater., vol. 2, no. 8, pp. 1–28, Aug. 2018.
[18] J. H. Kim, “Developing Inorganic Thin Film Solar Cells using Earth-Abundant Cu₂ZnSn (S, Se)₄ Absorber Materials based on Sputtering Process,” 2018.
[19] M. Yang, Z. Jiang, Z. Li, S. Liu, Y. Lu, and S. Wang, “Effects of different precursors on Cu₂ZnSnS₄ thin film solar cells prepared by sputtering method,” Mater. Sci. Semicond. Process, vol. 56, pp. 238–242, Dec. 2016.
[20] Q. Zhao et al., “Fabrication and characterization of Cu₂ZnSnS₄ thin films by sputtering a single target at different temperatures,” Physica B Condens. Matter, vol. 523, pp. 62–66, Oct. 2017.
[21] H. Cui, X. Liu, L. Sun, F. Liu, C. Yan, and X. Hao, “Fabrication of efficient Cu₂ZnSnS₄ solar cells by sputtering single stoichiometric target,” Coatings, vol. 7, no. 2, Feb. 2017.
[22] A. Sharmin, M. S. Bashar, M. Sultana, and S. M. M. Al Mamun, “Sputtered single-phase kesterite Cu₂ZnSnS₄ (CZTS) thin film for photovoltaic applications: Post annealing parameter optimization and property analysis,” AIP Adv., vol. 10, no. 1, Jan. 2020.
[23] Y. P. Varshni, “Temperature dependence of the energy gap in semiconductors,” Physica, vol. 34, no. 1, pp. 149–154, 1967.
[24] Y. Zhang, Z. Wang, J. Xi, and J. Yang, “Temperature-dependent band gaps in several semiconductors: from the role of electron–phonon renormalization,” Journal of Physics: Condensed Matter, vol. 32, no. 47, p. 475503, 2020.
[25] B. Mbaluka John, S. W. Mugo, and J. M. Ngaruiya, “Dependence of Optical Band Gap on Crystallite Size of TiO2 Thin Films Prepared using Sol Gel Process,” European Journal of Material Science, vol. 8, no. 1, pp. 1–12, 2021.
[26] S. Benramache, O. Belahssen, A. Guettaf, and A. Arif, “Correlation between crystallite size–optical gap energy and precursor molarities of ZnO thin films,” Journal of Semiconductors, vol. 35, no. 4, Apr. 2014.
[27] K. Deng et al., “Temperature Dependence on Microstructure, Crystallization Orientation, and Piezoelectric Properties of ZnO Films,” Sensors, vol. 25, no. 1, 2025.
[28] E. S. Hassan, A. N. Abd, and M. O. Dawood, “The Sputter Time Duration Effect on the Structural and Optical Properties of Zinc Oxide by RF Magnetron Sputtering,” Silicon, vol. 10, no. 6, pp. 2901–2906, Nov. 2018.
[29] S. Rahman, “Rancangan Eksperimen Analisis Struktur Mikro Sampel dengan Prinsip XRD Menggunakan Metode Kristal Berputar,” Jurnal Riset dan Kajian Pendidikan Fisika, vol. 3, no. 1, pp. 5–9, 2016.
[30] S. K. Swami, N. Chaturvedi, A. Kumar, and V. Dutta, “Effect of deposition temperature on the structural and electrical properties of spray deposited kesterite (Cu₂ZnSnS₄) films,” Solar Energy, vol. 122, pp. 508–516, Dec. 2015.
[31] R. Digraskar, K. Gattu, B. Sathe, A. Ghule, and R. Sharma, “Temperature-dependent fabrication of cost-effective and nontoxic Cu₂ZnSnS₄ (CZTS) thin films for solar cell,” AIP Conf. Proc., vol. 1728, no. 1, p. 020326, May 2016.
[32] F. Z. Boutebakh, N. Attaf, and M. S. Aida, “Effect of growth temperature on the physical properties of kesterite Cu₂ZnSnS₄ (CZTS) thin films,” Discov. Mater., vol. 5, no. 1, Dec. 2025.
[33] M. H. Rashid et al., “Characterization of single-step electrodeposited Cu₂ZnSnS₄ thin films,” Journal of Optics (India), vol. 47, no. 3, pp. 256–262, Sep. 2018.
[34] S. A. Khalate, R. S. Kate, J. H. Kim, S. M. Pawar, and R. J. Deokate, “Effect of deposition temperature on the properties of Cu₂ZnSnS₄ (CZTS) thin films,” Superlattices Microstruct., vol. 103, pp. 335–342, Mar. 2017.
[35] M. Xie, D. Zhuang, M. Zhao, B. Li, M. Cao, and J. Song, “Fabrication of Cu₂ZnSnS₄ thin films using a ceramic quaternary target,” Vacuum, vol. 101, pp. 146–150, 2014.
[36] S. A. Nadi et al., “Postdeposition annealing effect on CunSnS thin films grown at different substrate temperatures,” International Journal of Photoenergy, vol. 2014, 2014.
[37] V. Piacente, S. Foglia, and P. Scardala, “Sublimation study of the tin sulphides SnS2, Sn2S3 and SnS,” J. Alloys Compd., vol. 177, no. 1, pp. 17–30, 1991.
[38] J. Scragg, “PHD Studies of Cu₂ZnSnS₄ films prepared by sulfurisation of electrodeposited precursors,” Thesis, University of Bath, 2010.
[39] K. Yu and E. A. Carter, “Determining and Controlling the Stoichiometry of Cu₂ZnSnS₄ Photovoltaics: The Physics and Its Implications,” American Chemical Society, vol. 28, pp. 1–20, Jun. 2016.
[40] J. Jiang, L. Zhang, W. Wang, X. Huang, and R. Hong, “The role of pre-annealing in the sulfurization of Cu-Zn-Sn stacked metal layer prepared by magnetron sputtering,” Mater. Sci. Semicond. Process, vol. 83, pp. 125–132, Aug. 2018.
[41] S. Siebentritt and S. Schorr, “Kesterites-a challenging material for solar cells,” Progress in Photovoltaics: Research and Applications, vol. 20, no. 5, pp. 512–519, Aug. 2012.
[42] C. Malerba et al., “Stoichiometry effect on Cu₂ZnSnS₄ thin films morphological and optical properties,” Journal of Renewable and Sustainable Energy, vol. 6, no. 1, Jan. 2014.
[43] A. Ennaoui et al., “Cu₂ZnSnS₄ thin film solar cells from electroplated precursors: Novel low-cost perspective,” Thin Solid Films, vol. 517, no. 7, pp. 2511–2514, Feb. 2009.
[44] Q. Guo et al., “Fabrication of 7.2% efficient CZTSSe solar cells using CZTS nanocrystals,” J. Am. Chem. Soc., vol. 132, no. 49, pp. 17384–17386, Dec. 2010.
[45] P. K. Sarswat, M. L. Free, and A. Tiwari, “Temperature-dependent study of the Raman A mode of Cu₂ZnSnS₄ thin films,” Phys. Status Solidi B Basic Res., vol. 248, no. 9, pp. 2170–2174, Sep. 2011.
[46] T. P. Dhakal, C. Y. Peng, R. Reid Tobias, R. Dasharathy, and C. R. Westgate, “Characterization of a CZTS thin film solar cell grown by sputtering method,” Solar Energy, vol. 100, pp. 23–30, Feb. 2014.
[47] A. Aldalbahi, E. M. Mkawi, K. Ibrahim, and M. A. Farrukh, “Effect of sulfurization time on the properties of copper zinc tin sulfide thin films grown by electrochemical deposition,” Sci. Rep., vol. 6, Sep. 2016.
[48] C. J. Hages et al., “Identifying the Real Minority Carrier Lifetime in Nonideal Semiconductors: A Case Study of Kesterite Materials,” Adv. Energy Mater., vol. 7, no. 18, Sep. 2017.
[49] L. Sun, J. He, H. Kong, F. Yue, P. Yang, and J. Chu, “Structure, composition and optical properties of Cu₂ZnSnS₄ thin films deposited by Pulsed Laser Deposition method,” Solar Energy Materials and Solar Cells, vol. 95, no. 10, pp. 2907–2913, Oct. 2011.
[50] D. Tang et al., “An alternative route towards low-cost Cu₂ZnSnS₄ thin film solar cells,” Surf. Coat. Technol., vol. 232, pp. 53–59, oct. 2013.
[51] Sugianto, P. Marwoto, B. Astuti, R. Zannah, and Yanti, “Pengaruh Temperatur Deposisi terhadap Struktur dan Sifat Optik Film Tipis ZnO: Al dengan metode DC Magnetron Sputtering,” Jurnal Fisika, vol. 5, 2015.
[52] R. Moreno, E. A. Ramirez, and G. Gordillo Guzmán, “Study of optical and structural properties of CZTS thin films grown by co-evaporation and spray pyrolysis,” in Journal of Physics: Conference Series, Institute of Physics Publishing, Feb. 2016.
[53] J. Poortmans and V. Arkhipov, “Thin Film Solar Cells Fabrication, Characterization and Applications,” in Thin Film Solar Cells, J. Poortmans and V. Arkhipov, Eds., Wiley, 2006.
[54] S. M. Pawar et al., “Single step electrosynthesis of Cu₂ZnSnS₄ (CZTS) thin films for solar cell application,” Electrochim. Acta, vol. 55, no. 12, pp. 4057–4061, Apr. 2010.
[55] R. S. Christy, J. Thampi, and T. Kumaran, “Phase Transition in CuS Nanoparticles,” Journal of Non-Oxide Glasses, vol. 6, no. 1, pp. 13–22, 2014.
[56] A. M. Abdulwahab et al., “Synthesis, characterization, and anti-cancer activity evaluation of Ba-doped CuS nanostructures synthesized by the co-precipitation method,” The Royal Society of Chemistry Advances, vol. 15, no. 6, pp. 4669–4680, Feb. 2025.
[57] E. Mkawi, K. Ibrahim, M. K. M Ali, and A. Salhin Mohamed, “Dependence of Copper Concentration on the Properties of Cu₂ZnSnS₄ Thin Films Prepared by Electrochemical Method,” Int. J. Electrochem. Sci., vol. 8, pp. 359–368, 2013.
[58] A. Khalkar, K. S. Lim, S. M. Yu, S. P. Patole, and J. B. Yoo, “Deposition of Cu₂ZnSnS₄ thin films by magnetron sputtering and subsequent sulphurization,” Electronic Materials Letters, vol. 10, no. 1, pp. 43–49, Jan. 2014.
License
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
Authors who publish with Indonesian Physical Review Journal, agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution-ShareAlike 4.0 International Licence (CC BY SA-4.0). This license allows authors to use all articles, data sets, graphics, and appendices in data mining applications, search engines, web sites, blogs, and other platforms by providing an appropriate reference. The journal allows the author(s) to hold the copyright without restrictions and will retain publishing rights without restrictions.
- Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgment of its initial publication in Indonesian Physical Review Journal.
- Authors are permitted and encouraged to post their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work (See The Effect of Open Access).
