Effects of the annealing temperature on the properties of sulfur-graded Cu2ZnSn(S,Se)4 thin films grown by a modified two-step process

Byoung-Soo Ko; Dae-Hwan Kim; Dae-Kue Hwang; Seoung-Jun Lee; Jong Su Kim

Journal of Industrial and Engineering Chemistry, Vol.82, 406-412, February, 2020

DOI10.1016/j.jiec.2019.11.004 Export Citation

Effects of the annealing temperature on the properties of sulfur-graded Cu2ZnSn(S,Se)4 thin films grown by a modified two-step process

Byoung-Soo Ko^{1, 2}, Dae-Hwan Kim³, Dae-Kue Hwang^{3, †}, Seoung-Jun Lee⁴, and Jong Su Kim^{2, †}

¹Department of Radiation Oncology, Kyungpook National University Chilgok Hospital, Daegu, Republic of Korea
²Department of Physics, Yeungnam University, Gyeongsan 38541, Republic of Korea
³Daegu Gyeongbuk Institute of Science and Technology, Daegu 711-873, Republic of Korea
⁴Department of Radiation Oncology, Kyungpook National University Hospital, Daegu, Republic of Korea

E-mail:,

In this study, we investigated the electrical and structural properties of sulfur-graded Cu2ZnS (S,Se)4 (CZTSSe) thin films grown using a modified two-step process according to the annealing temperature. The sulfur content of the CZTSSe thin film was increased with annealing temperature and a Zn(S, Se) secondary phase was observed at temperatures higher than 500 °C. The Raman spectrum of the CZTSSe thin film shifted continuously toward the high frequency direction with increasing S content and the Cu2SnSe3 (CTSe) secondary phase was present below 440 °C. From the results of dimpling Raman spectroscopy and scanning transmission electron microscopy (STEM) line scanning, we confirmed that the S content increased gradually from the Mo back contact to the surface of the CZTSSe thin film. Finally, a sulfur-graded CZTSSe thin film with a photovoltaic efficiency of 7.03% was fabricated by optimizing the annealing temperature.

Keywords:CZTSSe;Co-evaporation;H2S gas;Rapid thermal process;Sulfur-graded;Zn(S Se)

[References]

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Hironiwa D, Murata M, Ashida N, Tang Z, Minemoto T, Jap. J. Appl. Phys., 53, 071201 (2014)
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[Referenced By]

[1] Kato T, Wu JL, Hirai Y, Sugimoto H, Bermudez V, IEEE J. Photovoltaics, 9(1), 325 (2018)

[2] Moriya K, Watabe J, Tanaka K, Uchiki H, Phys. Status Solidi (c) 3, 2848 (2006).

[3] Wang W, Winkler MT, Gunawan O, Gokmen T, Todorov TK, Zhu Y, Mitzi DB, Adv. Eng. Mater., 4, 130146 (2014)

[4] Green MA, Hishikawa Y, Dunlop ED, Levi DH, Hohl-Ebinger J, Yoshita M, Ho-Baillie AWY, Prog. Photovolt.: Res. Appl., 27, 3 (2019)

[5] Lundberg O, Bodegard M, Malmstrom J, Stolt L, Prog. Photovolt.: Res. Appl., 11, 77 (2003)

[6] Riedel I, Keller J, Parisi J, Dalibor T, Avellan A, Physica B, 439, 9 (2014)

[7] Nagoya Y, Kushiya K, Tachiyuki M, Yamase O, Sol. Energy Mater. Sol. Cells, 67(1-4), 247 (2001)

[8] Knecht R, Hammer MS, Parisi J, Riedel I, Phys. Status Solidi (a) 210, 1392 (2013).

[9] Hironiwa D, Murata M, Ashida N, Tang Z, Minemoto T, Jap. J. Appl. Phys., 53, 071201 (2014)

[10] Wibowo RA, Lee ES, Munir B, Kim KH, Phys. Status Solidi (a) 204, 3373 (2007).

[11] Repins I, Beall C, Vora N, DeHart C, Kuciauskas D, Dippo P, To B, Mann J, Hsu WC, Goodrich A, Noufi R, Sol. Energy Mater. Sol. Cells, 101, 154 (2012)

[12] Redinger A, Siebentritt S, Appl. Phys. Lett., 97, 092111 (2010)

[13] Park D, Nam D, Jung S, An S, Gwak J, Yoon K, Yun JH, Cheong H, Thin Solid Films, 519(21), 7386 (2011)

[14] Salome PMP, Fernandes PA, da Cunha AF, Thin Solid Films, 517(7), 2531 (2009)

[15] Zoppi G, Forbes I, Miles RW, Dale PJ, Scragg JJ, Peter LM, Progr. Photovolt.:Res. Appl., 17, 315 (2009)

[16] Yoo H, Wibowo RA, Holzing A, Lechner R, Palm J, Jost S, Gowtham M, Sorin F, Louis B, Hock R, Thin Solid Films, 535, 73 (2013)

[17] Fella CM, Uhl AR, Romanyuk YE, Tiwari AN, Phys. Status Solidi (a) 209, 1043 (2012).

[18] Zhang YZ, Liao C, Zong K, Wang H, Liu JB, Jiang T, Han JF, Liu GQ, Cui L, Ye QY, Yan H, Lau WM, Sol. Energy, 94, 1 (2013)

[19] Redinger A, Mousel M, Djemour R, Gutay L, Valle N, Siebentritt S, Progr. Photovolt.: Res. Appl., 22, 51 (2013)

[20] Fairbrother A, Fontane X, Izquierdo-Roca V, Espindola-Rodriguez M, Lopez-Marino S, Placidi M, Lopez-Garcia J, Perez-Rodriguez A, Saucedo E, Cemphyschem.: Eur. J. Chem. Phys. Phys. Chem. 14, 1836 (2013).

[21] Vora N, Blackburn J, Repins I, Beall C, To B, Pankow J, Teeter G, Young M, Noufi R, J. Vacuum Sci. Technol. A, 30, 051201 (2012)

[22] Woo K, Kim Y, Yang W, Kim K, Kim I, Oh Y, Kim JY, J. Moon, Sci. Rep., 3, 3069 (2013)

[23] Juskenas R, Kanapeckaite S, Karpavitciene V, Mockus Z, Pakstas V, Selskiene A, Giraitis R, Niaura G, Sol. Energy Mater. Sol. Cells, 101, 277 (2012)

[24] Jung HR, Shin SW, Gurav KV, Suryawanshi MP, Hong CW, Yang HS, Lee JY, Moon JH, Kim JH, Ceram. Int., 41, 13006 (2015)

[25] He J, Sun L, Chen S, Chen Y, Yang P, Chu J, J. Alloy. Compd., 511, 129 (2012)

[26] Altosaar M, Raudoja J, Timmo K, Danilson M, Grossberg M, Krustok J, Mellikov E, Phys. Status Solidi (a) 205, 167 (2008).

[27] Salome PMP, Fernandes PA, Leitao JP, Sousa MG, Teixeira JP, da Cunha AF, J. Mater. Sci., 49(21), 7425 (2014)

[28] Kim SY, Son DH, Kim YI, Kim SH, Kim S, Ahn K, Sung SJ, Hwang DK, Yang KJ, Kang JK, Kim DH, Nano Energy, 59, 399 (2019)

[29] Pierret RF, Semiconductor Device Fundamentals, MA, pp.235-300 (1996).

[30] Rudmann D, Zurich, Eidgenossische Technische Hochschule, pp.56-57 2004.

[31] Hsu WC, Repins I, Beall C, DeHart C, Teeter G, To B, Yang Y, Noufi R, Sol. Energy Mater. Sol. Cells, 113, 160 (2013)