Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time

Mehmet Ali Olğar; Ayşe Seyhan

doi:10.17776/csj.527260

EN TR

Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time

Abstract

In this study CZTS thin films were fabricated by a two-stage process that sputter deposition of metallic Cu, Zn, and Sn on Mo coated glass substrates and annealing process at 500 °C using various short dwell times (4, 8, and 12 min) using Rapid Thermal Processing (RTP) approach. The X-ray diffraction (XRD), Raman spectroscopy, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), and photoluminescence were employed to characterize the CZTS samples synthesized employing different sulfurization times. It was observed that all CZTS thin films showed Cu-poor and Zn-rich composition according to EDX results. XRD patterns displayed formation of kesterite CZTS and CuS secondary phases. Raman spectra of the films justified formation of kesterite CZTS phase for all CZTS thin films and formation of CTS phase, which is difficult to distinguish by XRD pattern of the films for CZTS-8 and CZTS-12 samples. SEM images of the films displayed dense, void-free, and inhomogeneous surface structure regardless of the sulfurization time. The optical band gap of the films as determined by photoluminescence was found to be about 1.36-1.37 eV.

Keywords

Cu2ZnSnS4,sputtering,annealing time,annealing temperature,RTP

References

[1] Kato T., Wu J.L., Hirai Y., Sugimoto H., Bermudez V., Record Efficiency for Thin-Film Polycrystalline Solar Cells Up to 22.9% Achieved by Cs-Treated Cu(In,Ga)(Se,S)(2), Ieee J. Photovolt., 9 (2019) 325-330.
[2] Katagiri H., Sasaguchi N., Hando S., Hoshino S., Ohashi J. and Yokota T., Preparation and evaluation of Cu2ZnSnS4 thin films by sulfurization of E-B evaporated precursors, Sol. Energ. Mat. Sol. C., 49 (1997) 407-414.
[3] Shockley W. and Queisser H.J., Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells, JPN J. Appl. Phys., 32 (1961) 510-519.
[4] Wang W., Winkler M.T., Gunawan O., Gokmen T., Todorov T.K., Zhu Y. and Mitzi D.B., Device Characteristics of CZTSSe Thin-Film Solar Cells with 12.6% Efficiency, Adv. Energy Mater., 4 (2014) 1301465.
[5] Wang K., Gunawan O., Todorov T., Shin B., Chey S.J., Bojarczuk N.A., Mitzi D. and Guha S., Thermally evaporated Cu2ZnSnS4 solar cells, Appl. Phys. Lett., 97 (2010) 143508.
[6] Mkawi E.M., Al-Hadeethi Y., Shalaan E. and Bekyarova E., Substrate temperature effect during the deposition of (Cu/Sn/Cu/Zn) stacked precursor CZTS thin film deposited by electron-beam evaporation, J. Mater. Sci-Mater. El., 29 (2018) 20476-20484.
[7] Olgar M.A., Optimization of sulfurization time and temperature for fabrication of Cu2ZnSnS4 (CZTS) thin films, Superlattice Microst., 126 (2019) 32-41.
[8] Vanalakar S.A., Agawane G.L., Shin S.W., Suryawanshi M.P., Gurav K.V., Jeon K.S., Patil P.S., Jeong C.W., Kim J.Y. and Kim J.H., A review on pulsed laser deposited CZTS thin films for solar cell applications, J. Alloy. Compd., 619 (2015) 109-121.
[9] Tanaka K., Fukui Y., Moritake N. and Uchiki H., Chemical composition dependence of morphological and optical properties of Cu2ZnSnS4 thin films deposited by sol-gel sulfurization and Cu2ZnSnS4 thin film solar cell efficiency, Sol. Energ. Mat. Sol. C., 95 (2011) 838-842.
[10] Hamada T., Fukuyama A., Jiang F., Ikeda S. and Ikari T., Effect of preheating time on uniformity of electrodeposited Cu2ZnSnS4 thin films studied by carrier lifetime and photoluminescence measurements, Phys. Status Solidi C., 12 (2015) 725-728.

[11] Hages C.J., Levcenco S., Miskin C.K., Alsmeier J.H., Abou-Ras D., Wilks R.G., Bar M., Unold T. and Agrawal R., Improved performance of Ge-alloyed CZTGeSSe thin-film solar cells through control of elemental losses, Prog. Photovoltaics, 23 (2015) 376-384.
[12] Tanaka K., Kato M., Goto K., Nakano Y. and Uchiki H., Face-to-Face Annealing Process of Cu2ZnSnS4 Thin Films Deposited by Spray Pyrolysis Method, Jpn. J. Appl. Phys., 51 (2012) 10S.
[13] Emrani A., Vasekar P. and Westgate C.R., Effects of sulfurization temperature on CZTS thin film solar cell performances, Sol. Energy, 98 (2013) 335-340.
[14] Guan H., Shen H.L., Gao C. and He X.C., Sulfurization time effects on the growth of Cu2ZnSnS4 thin films by solution method, J. Mater. Sci-Mater. El., 24 (2013) 2667-2671.
[15] Olgar M.A., Klaer J., Mainz R., Levcenco S., Just J., Bacaksiz E. and Unold T., Effect of precursor stacking order and sulfurization temperature on compositional homogeneity of CZTS thin films, Thin Solid Films, 615 (2016) 402-408.
[16] Olgar M.A., Atasoy Y., Basol B.M., Tomakin M., Aygun G., Ozyuzer L. and Bacaksiz E., Influence of copper composition and reaction temperature on the properties of CZTSe thin films, J. Alloy. Compd., 682 (2016) 610-617.
[17] Espindola-Rodriguez M., Placidi M., Vigil-Galan O., Izquierdo-Roca V., Fontane X., Fairbrother A., Sylla D., Saucedo E. and Perez-Rodriguez A., Compositional optimization of photovoltaic grade Cu2ZnSnS4 films grown by pneumatic spray pyrolysis, Thin Solid Films, 535 (2013) 67-72.
[18] Olgar M.A., Bacaksiz E., Tomakin M., Kucukomeroglu T. and Basol B.M., CZTS layers formed under sulfur-limited conditions at above atmospheric pressure, Mat. Sci. Semicon. Proc., 90 (2019) 101-106.
[19] He J., Sun L., Chen Y., Jiang J.C., Yang P.X. and Chu J.H., Influence of sulfurization pressure on Cu2ZnSnS4 thin films and solar cells prepared by sulfurization of metallic precursors, J. Power Sources, 273 (2015) 600-607.
[20] Weber A., Mainz R. and Schock H., On the Sn loss from thin films of the material system Cu–Zn–Sn–S in high vacuum, J. Appl. Phys., 107 (2010) 013516.
[21] Olgar M.A., Basol B.M., Tomakin M., Seyhan A., Bacaksiz E., Influence of pre-annealing Cu-Sn on the structural properties of CZTSe thin films grown by a two-stage process, Mat. Sci. Semicon. Proc., 88 (2018) 234-238.
[22] Gurav S.V., Pawar S.M., Shin S.W., Suryawanshi M.P., Agawane G.L., Patil P.S., Moon J.H., Yun J.H. and Kim J.H., Electrosynthesis of CZTS films by sulfurization of CZT precursor: Effect of soft annealing treatment, Appl. Surf. Sci., 283 (2013) 74-80. [23] Lin Y.-P., Hsieh T.-E., Chen Y.-C. and Huang K.-P., Characteristics of Cu2ZnSn(SxSe1− x)4 thin-film solar cells prepared by sputtering deposition using single quaternary Cu2ZnSnS4 target followed by selenization/sulfurization treatment, Sol. Energ. Mat. Sol. C., 162 (2017) 55-61.
[24] Olgar M.A., Klaer J., Mainz R., Ozyuzer L. and Unold T., Cu2ZnSnS4-based thin films and solar cells by rapid thermal annealing processing, Thin Solid Films, 628 (2017) 1-6.
[25] Fernandes P., Salomé P. and Da Cunha A., CuxSnSx+1 (x= 2, 3) thin films grown by sulfurization of metallic precursors deposited by dc magnetron sputtering, Physica Status Solidi C, 7 (2010) 901-904.
[26] Chaudhuri T.K. and Tiwari D., Earth-abundant non-toxic Cu2ZnSnS4 thin films by direct liquid coating from metal–thiourea precursor solution, Sol. Energ. Mat. Sol. C, 101 (2012) 46-50.

Details

Primary Language

English

Subjects

-

Journal Section

Research Article

Authors

Mehmet Ali Olğar ^*
0000-0002-6359-8316
Türkiye

Ayşe Seyhan
0000-0001-8090-1404
Türkiye

Publication Date

September 30, 2019

Submission Date

February 14, 2019

Acceptance Date

April 19, 2019

Published in Issue

Year 2019 Volume: 40 Number: 3

DOI

https://doi.org/10.17776/csj.527260

IZ

https://izlik.org/JA42DT33WS

APA

Olğar, M. A., & Seyhan, A. (2019). Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time. Cumhuriyet Science Journal, 40(3), 554-562. https://doi.org/10.17776/csj.527260

AMA

1.Olğar MA, Seyhan A. Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time. CSJ. 2019;40(3):554-562. doi:10.17776/csj.527260

Chicago

Olğar, Mehmet Ali, and Ayşe Seyhan. 2019. “Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time”. Cumhuriyet Science Journal 40 (3): 554-62. https://doi.org/10.17776/csj.527260.

EndNote

Olğar MA, Seyhan A (September 1, 2019) Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time. Cumhuriyet Science Journal 40 3 554–562.

IEEE

[1]M. A. Olğar and A. Seyhan, “Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time”, CSJ, vol. 40, no. 3, pp. 554–562, Sept. 2019, doi: 10.17776/csj.527260.

ISNAD

Olğar, Mehmet Ali - Seyhan, Ayşe. “Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time”. Cumhuriyet Science Journal 40/3 (September 1, 2019): 554-562. https://doi.org/10.17776/csj.527260.

JAMA

1.Olğar MA, Seyhan A. Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time. CSJ. 2019;40:554–562.

MLA

Olğar, Mehmet Ali, and Ayşe Seyhan. “Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time”. Cumhuriyet Science Journal, vol. 40, no. 3, Sept. 2019, pp. 554-62, doi:10.17776/csj.527260.

Vancouver

1.Mehmet Ali Olğar, Ayşe Seyhan. Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time. CSJ. 2019 Sep. 1;40(3):554-62. doi:10.17776/csj.527260

Cited By

The choice of Zn or ZnS layer in the stacked precursors for preparation of Cu2ZnSnS4 (CZTS) thin films

Superlattices and Microstructures

https://doi.org/10.1016/j.spmi.2020.106669

As of 2026, Cumhuriyet Science Journal will be published in six issues per year, released in February, April, June, August, October, and December

Growth of Cu2ZnSnS4 Thin Films Using Moderate Annealing Temperature and Short Dwell Time

Abstract

Keywords

Yüksek Olmayan Tavlama Sıcaklığı ve Kısa Bekleme Süresi Kullanılarak Cu2ZnSnS4 İnce Filmlerin Üretimi

Abstract

Keywords

References

Details

Primary Language

Subjects

Journal Section

Authors

Publication Date

Submission Date

Acceptance Date

Published in Issue

DOI

IZ

Cite

Cited By

The choice of Zn or ZnS layer in the stacked precursors for preparation of Cu2ZnSnS4 (CZTS) thin films