The influence of sequence of precursor films on CZTSe thin films prepared by ion-beam sputtering deposition

Jun Zhao; Guangxing Liang; Yang Zeng; Ping Fan; Juguang Hu; Jingting Luo; Dongping Zhang

doi:10.1088/1674-4926/38/2/023002

J. Semicond. > 2017, Volume 38 > Issue 2 > 023002

SEMICONDUCTOR MATERIALS

The influence of sequence of precursor films on CZTSe thin films prepared by ion-beam sputtering deposition

Jun Zhao¹, Guangxing Liang^{1, 2,}, Yang Zeng¹, Ping Fan¹, Juguang Hu¹, Jingting Luo¹ and Dongping Zhang¹

+ Author Affiliations

Corresponding author: Guangxing Liang,Email:lgx@szu.edu.cn

DOI: 10.1088/1674-4926/38/2/023002

Abstract: The CuZnSn(CZT) precursor thin films are grown by ion-beam sputtering Cu, Zn, Sn targets with different orders and then sputtering Se target to fabricate Cu₂ZnSnSe₄(CZTSe) absorber thin films on molybdenum substrates. They are annealed in the same vacuum chamber at 400℃. The characterization methods of CZTSe thin films include X-ray diffraction(XRD), energy dispersive spectroscopy(EDS), scanning electron microscopy(SEM), and X-ray photoelectron spectra(XPS) in order to study the crystallographic properties, composition, surface morphology, electrical properties and so on. The results display that the CZTSe thin films got the strongest diffraction peak intensity and were with good crystalline quality and its morphology appeared smooth and compact with a sequence of Cu/Zn/Sn/Se, which reveals that the expected states for CZTSe are Cu¹⁺, Zn²⁺, Sn⁴⁺, Se²⁺. With the good crystalline quality and close to ideal stoichiometric ratio the resistivity of the CZTSe film with the sequence of Cu/Zn/Sn/Se is lower, whose optical band gap is about 1.50 eV.

Key words: CZTSe, thin films, ion-beam sputtering, chalcogenide

References

[1]	Brammertz G, Bufère M, Oueslati S, et al. Characterization of defects in 9.7% efficient Cu₂ZnSnSe₄-CdS-ZnO solar cells. Appl Phys Lett, 2013, 103(16):163904 doi: 10.1063/1.4826448
[2]	Repins I, Beall C, Vora N, et al. Co-evaporated Cu₂ZnSnSe₄ films and devices. Sol Energy Mater Sol Cells, 2012, 101(2):154
[3]	Sun D, Xu S Z. Zhang L, et al. Influence of selenium evaporation temperature on the structure of Cu₂ZnSnSe₄ thin film deposited by a co-evaporation process. J Semicond, 2015, 36(4):044009 doi: 10.1088/1674-4926/36/4/044009
[4]	Sun K W, Yan Y, Liu F Y, et al. Over 9% efficient kesterite Cu₂ZnSnS₄ solar cell fabricated by using Zn_1-xCd_xS buffer layer. Adv Energy Mater, 2016, 1600046:1
[5]	Wang W, Winkler M T, Gunawan O, et al. Device characteristics of CZTSSe thin-film solar cells with 12.6% efficiency. Adv Energy Mater, 2014, 4(7):1301465 doi: 10.1002/aenm.201301465
[6]	Mitzi D B, Gunawan O, Todorov T K, et al. Prospects and performance limitations for Cu-Zn-Sn-S-Se photovoltaic technology. Philos Trans Royal Soc A, 2013, 371(1996):20110432 doi: 10.1098/rsta.2011.0432
[7]	Fairbrother A, Neuschitzer M, Saucedoet E, et al. Zn-poor Cu₂ZnSnSe₄ thin films and solar cell devices. Phys Status Solidi Appl Mater, 2014, 212(1):109
[8]	Todorov T K, Tang J, Bag S, et al. Beyond 11% efficiency:characteristics of state-of-the-art Cu₂ZnSn(S,Se)₄ solar cells. Adv Energy Mater, 2013, 3(1):34 doi: 10.1002/aenm.201200348
[9]	Shin B, Zhu Y, Bojarczuk N A, et al. Control of an interfacial MoSe₂ layer in Cu₂ZnSnSe₄ thin film solar cells:8.9% power conversion efficiency with a TiN diffusion barrier. Appl Phys Lett, 2012, 101(5):053903 doi: 10.1063/1.4740276
[10]	Fairbrother A, Fontané X, Izquierdo-Roca V, et al. Secondary phase formation in Zn-rich Cu₂ZnSnSe₄-based solar cells annealed in low pressure and temperature conditions. Prog Photovoltaics:Res Appl, 2014, 22(4):479 doi: 10.1002/pip.v22.4
[11]	Fan P, Zhao J, Liang G X, et al. Effects of annealing treatment on the properties of CZTSe thin films deposited by RF-magnetron sputtering. J Alloys Compnd, 2014, 625(2):171 http://cn.bing.com/academic/profile?id=ef66d7ca12e55713e905f1a5b4c1e2c0&encoded=0&v=paper_preview&mkt=zh-cn
[12]	Zhao J, Fan P, Liang G X, et al. The influence of precursor films on CIGS films prepared by ion beam sputtering deposition. Proc SPIE, 2015, 90681H:1 http://cn.bing.com/academic/profile?id=97f550e5fbafc9a022b577960efb145a&encoded=0&v=paper_preview&mkt=zh-cn
[13]	Liang G X, Fan P, Chen C M, et al. A promising sputtering for in situ fabrication of CIGS thin films without post-selenization. J Alloys Compd, 2014, 610(30):337 http://cn.bing.com/academic/profile?id=21ac5dc1ce7f03ad96b64f6ee8b4ae3c&encoded=0&v=paper_preview&mkt=zh-cn
[14]	Salomé P M M, Fernandes P A, Da Cunha A F, et al. Growth pressure dependence of Cu₂ZnSnSe₄ properties. Sol Energy Mater Solar Cells, 2010, 94(12):2176 doi: 10.1016/j.solmat.2010.07.008
[15]	Zoppi G, Forbes I, Miles R W, et al. Cu₂ZnSnSe₄ thin film solar cells produced by selenisation of magnetron sputtered precursors. Prog Photovoltaics:Res Appl, 2009, 17(5):315 doi: 10.1002/pip.v17:5
[16]	Xiong Y J, Xie Y, Du G, et al. From 2D framework to quasi-1D nanomaterial:preparation, characterization, and formation mechanism of Cu₃SnS₄. Nanorods Inorg Chem, 2002, 41(11):2953 doi: 10.1021/ic0200242
[17]	Zhang S Y, Fang C Z, Tian Y P, et al. Synthesis and characterization of hexagonal CuSe nanotubes by templating against trigonal Se Nanotubes. Cryst Growth Des, 2006, 6(12):2809 doi: 10.1021/cg0604430
[18]	Murali K R, Thilakvathy K, Vasantha S, et al. Properties of ZnSe films pulse plated on high temperature substrates. Chalcogenide Lett, 2008, 5(6):111 http://cn.bing.com/academic/profile?id=a2d4fe7c593ff1210af3f2b74bf67c4a&encoded=0&v=paper_preview&mkt=zh-cn
[19]	Wagner C D, Riggs W M, Davis L E, et al. Handbook of X-ray photoelectron spectroscopy. U.S.A:Perkin-Elmer Corporation, Physical Electronics Division, 1979
[20]	Park D, Nam D, Jung S, et al. Optical characterization of Cu₂ZnSnSe₄ grown by thermal co-evaporation. Thin Solid Films, 2001, 519(21):1
[21]	Pawar S M, Moholkar A V, Kim I K, et al. Effect of laser incident energy on the structural morphological and optical properties of Cu₂ZnSnS₄(CZTS) thin films. Curr Appl Phys, 2010, 10(2):565 doi: 10.1016/j.cap.2009.07.023
[22]	Moholkar A V, Shinde S S, Babar A R, et al. Development of CZTS thin films solar cells by pulsed laser deposition:influence of pulse repetition rate. Sol Energy, 2011, 85(7):1354 doi: 10.1016/j.solener.2011.03.017
[23]	Babu G S, Kumar Y B K, Bhaskar P U, et al. Effect of Cu/(ZnCSn) ratio on the properties of co-evaporated Cu₂ZnSnSe₄ thin films. Sol Energy Mater Sol Cells, 2010, 94(2):221 doi: 10.1016/j.solmat.2009.09.005

Fig. 1. The XRD patterns of CZTSe films prepared by different sequences of sputtering.

DownLoad: Full-Size Img PowerPoint

Fig. 2. SEM images of the top surface of CZTSe films prepared by different sequences of sputtering (a) Cu/Zn/Sn/Se, (b) Cu/Sn/Zn/Se, (c) Zn/Sn/Cu/Se, (d) Sn/Zn/Cu/Se.

DownLoad: Full-Size Img PowerPoint

Fig. 3. XPS spectra of CZTSe films with sequence of Cu/Zn/Sn/Se: (a) Cu 2p core level spectrum, (b) Zn 2p core level spectrum, (c) Sn 3d core level spectrum, (d) Se 3d core level spectrum.

DownLoad: Full-Size Img PowerPoint

Fig. 4. The optical band gap of CZTSe thin films prepared with different sequences of sputtering.

DownLoad: Full-Size Img PowerPoint

Fig. 5. The images of resistivity along with different sequences of sputtering.

DownLoad: Full-Size Img PowerPoint

Table 1. The parameters for ion-beam sputtering Cu and Zn target.

Table 2. The parameters for ion beam sputtering Sn and Se target.

Table 3. The FWHM and grain size of the CZTSe thin films along (112) diffracting plane.

Table 4. The composition of the CZTSe thin films determined by EDS analysis.

[1]	Brammertz G, Bufère M, Oueslati S, et al. Characterization of defects in 9.7% efficient Cu₂ZnSnSe₄-CdS-ZnO solar cells. Appl Phys Lett, 2013, 103(16):163904 doi: 10.1063/1.4826448
[2]	Repins I, Beall C, Vora N, et al. Co-evaporated Cu₂ZnSnSe₄ films and devices. Sol Energy Mater Sol Cells, 2012, 101(2):154
[3]	Sun D, Xu S Z. Zhang L, et al. Influence of selenium evaporation temperature on the structure of Cu₂ZnSnSe₄ thin film deposited by a co-evaporation process. J Semicond, 2015, 36(4):044009 doi: 10.1088/1674-4926/36/4/044009
[4]	Sun K W, Yan Y, Liu F Y, et al. Over 9% efficient kesterite Cu₂ZnSnS₄ solar cell fabricated by using Zn_1-xCd_xS buffer layer. Adv Energy Mater, 2016, 1600046:1
[5]	Wang W, Winkler M T, Gunawan O, et al. Device characteristics of CZTSSe thin-film solar cells with 12.6% efficiency. Adv Energy Mater, 2014, 4(7):1301465 doi: 10.1002/aenm.201301465
[6]	Mitzi D B, Gunawan O, Todorov T K, et al. Prospects and performance limitations for Cu-Zn-Sn-S-Se photovoltaic technology. Philos Trans Royal Soc A, 2013, 371(1996):20110432 doi: 10.1098/rsta.2011.0432
[7]	Fairbrother A, Neuschitzer M, Saucedoet E, et al. Zn-poor Cu₂ZnSnSe₄ thin films and solar cell devices. Phys Status Solidi Appl Mater, 2014, 212(1):109
[8]	Todorov T K, Tang J, Bag S, et al. Beyond 11% efficiency:characteristics of state-of-the-art Cu₂ZnSn(S,Se)₄ solar cells. Adv Energy Mater, 2013, 3(1):34 doi: 10.1002/aenm.201200348
[9]	Shin B, Zhu Y, Bojarczuk N A, et al. Control of an interfacial MoSe₂ layer in Cu₂ZnSnSe₄ thin film solar cells:8.9% power conversion efficiency with a TiN diffusion barrier. Appl Phys Lett, 2012, 101(5):053903 doi: 10.1063/1.4740276
[10]	Fairbrother A, Fontané X, Izquierdo-Roca V, et al. Secondary phase formation in Zn-rich Cu₂ZnSnSe₄-based solar cells annealed in low pressure and temperature conditions. Prog Photovoltaics:Res Appl, 2014, 22(4):479 doi: 10.1002/pip.v22.4
[11]	Fan P, Zhao J, Liang G X, et al. Effects of annealing treatment on the properties of CZTSe thin films deposited by RF-magnetron sputtering. J Alloys Compnd, 2014, 625(2):171 http://cn.bing.com/academic/profile?id=ef66d7ca12e55713e905f1a5b4c1e2c0&encoded=0&v=paper_preview&mkt=zh-cn
[12]	Zhao J, Fan P, Liang G X, et al. The influence of precursor films on CIGS films prepared by ion beam sputtering deposition. Proc SPIE, 2015, 90681H:1 http://cn.bing.com/academic/profile?id=97f550e5fbafc9a022b577960efb145a&encoded=0&v=paper_preview&mkt=zh-cn
[13]	Liang G X, Fan P, Chen C M, et al. A promising sputtering for in situ fabrication of CIGS thin films without post-selenization. J Alloys Compd, 2014, 610(30):337 http://cn.bing.com/academic/profile?id=21ac5dc1ce7f03ad96b64f6ee8b4ae3c&encoded=0&v=paper_preview&mkt=zh-cn
[14]	Salomé P M M, Fernandes P A, Da Cunha A F, et al. Growth pressure dependence of Cu₂ZnSnSe₄ properties. Sol Energy Mater Solar Cells, 2010, 94(12):2176 doi: 10.1016/j.solmat.2010.07.008
[15]	Zoppi G, Forbes I, Miles R W, et al. Cu₂ZnSnSe₄ thin film solar cells produced by selenisation of magnetron sputtered precursors. Prog Photovoltaics:Res Appl, 2009, 17(5):315 doi: 10.1002/pip.v17:5
[16]	Xiong Y J, Xie Y, Du G, et al. From 2D framework to quasi-1D nanomaterial:preparation, characterization, and formation mechanism of Cu₃SnS₄. Nanorods Inorg Chem, 2002, 41(11):2953 doi: 10.1021/ic0200242
[17]	Zhang S Y, Fang C Z, Tian Y P, et al. Synthesis and characterization of hexagonal CuSe nanotubes by templating against trigonal Se Nanotubes. Cryst Growth Des, 2006, 6(12):2809 doi: 10.1021/cg0604430
[18]	Murali K R, Thilakvathy K, Vasantha S, et al. Properties of ZnSe films pulse plated on high temperature substrates. Chalcogenide Lett, 2008, 5(6):111 http://cn.bing.com/academic/profile?id=a2d4fe7c593ff1210af3f2b74bf67c4a&encoded=0&v=paper_preview&mkt=zh-cn
[19]	Wagner C D, Riggs W M, Davis L E, et al. Handbook of X-ray photoelectron spectroscopy. U.S.A:Perkin-Elmer Corporation, Physical Electronics Division, 1979
[20]	Park D, Nam D, Jung S, et al. Optical characterization of Cu₂ZnSnSe₄ grown by thermal co-evaporation. Thin Solid Films, 2001, 519(21):1
[21]	Pawar S M, Moholkar A V, Kim I K, et al. Effect of laser incident energy on the structural morphological and optical properties of Cu₂ZnSnS₄(CZTS) thin films. Curr Appl Phys, 2010, 10(2):565 doi: 10.1016/j.cap.2009.07.023
[22]	Moholkar A V, Shinde S S, Babar A R, et al. Development of CZTS thin films solar cells by pulsed laser deposition:influence of pulse repetition rate. Sol Energy, 2011, 85(7):1354 doi: 10.1016/j.solener.2011.03.017
[23]	Babu G S, Kumar Y B K, Bhaskar P U, et al. Effect of Cu/(ZnCSn) ratio on the properties of co-evaporated Cu₂ZnSnSe₄ thin films. Sol Energy Mater Sol Cells, 2010, 94(2):221 doi: 10.1016/j.solmat.2009.09.005

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Received: 07 June 2016 Revised: 14 July 2016 Online: Published: 01 February 2017

Article Navigation > Journal of Semiconductors > 2017 > 38(2): 023002

Jun Zhao, Guangxing Liang, Yang Zeng, Ping Fan, Juguang Hu, Jingting Luo, Dongping Zhang. The influence of sequence of precursor films on CZTSe thin films prepared by ion-beam sputtering deposition[J]. Journal of Semiconductors, 2017, 38(2): 023002. doi: 10.1088/1674-4926/38/2/023002 ****J Zhao, G X Liang, Y Zeng, P Fan, J G Hu, J T Luo, D P Zhang. The influence of sequence of precursor films on CZTSe thin films prepared by ion-beam sputtering deposition[J]. J. Semicond., 2017, 38(2): 023002. doi: 10.1088/1674-4926/38/2/023002.

Citation:

J Zhao, G X Liang, Y Zeng, P Fan, J G Hu, J T Luo, D P Zhang. The influence of sequence of precursor films on CZTSe thin films prepared by ion-beam sputtering deposition[J]. J. Semicond., 2017, 38(2): 023002. doi: 10.1088/1674-4926/38/2/023002.

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The influence of sequence of precursor films on CZTSe thin films prepared by ion-beam sputtering deposition

DOI: 10.1088/1674-4926/38/2/023002

1.
Institute of Thin Film Physics and Applications, College of Physics and Energy, Shenzhen University, Shenzhen 518060, China
2.
Institute of Chemical Science UMR CNRS 6226, University of Rennes 1, 35042 Rennes, France

Funds:

Project supported by the National Natural Science Foundation of China 61404086

the Basical Research Program of Shenzhen JCYJ20150324140036866

the Natural Science Foundation of SZU 2014017

Project supported by the National Natural Science Foundation of China(No.61404086), the Basical Research Program of Shenzhen(Nos.JCYJ20150324140036866, JCYJ20150324141711581), and the Natural Science Foundation of SZU(No.2014017).

the Basical Research Program of Shenzhen JCYJ20150324141711581

More Information

Corresponding author: Guangxing Liang,Email:lgx@szu.edu.cn
Received Date: 2016-06-07
Revised Date: 2016-07-14
Published Date: 2017-02-01

Abstract

Abstract

The CuZnSn(CZT) precursor thin films are grown by ion-beam sputtering Cu, Zn, Sn targets with different orders and then sputtering Se target to fabricate Cu₂ZnSnSe₄(CZTSe) absorber thin films on molybdenum substrates. They are annealed in the same vacuum chamber at 400℃. The characterization methods of CZTSe thin films include X-ray diffraction(XRD), energy dispersive spectroscopy(EDS), scanning electron microscopy(SEM), and X-ray photoelectron spectra(XPS) in order to study the crystallographic properties, composition, surface morphology, electrical properties and so on. The results display that the CZTSe thin films got the strongest diffraction peak intensity and were with good crystalline quality and its morphology appeared smooth and compact with a sequence of Cu/Zn/Sn/Se, which reveals that the expected states for CZTSe are Cu¹⁺, Zn²⁺, Sn⁴⁺, Se²⁺. With the good crystalline quality and close to ideal stoichiometric ratio the resistivity of the CZTSe film with the sequence of Cu/Zn/Sn/Se is lower, whose optical band gap is about 1.50 eV.
- CZTSe,
- thin films,
- ion-beam sputtering,
- chalcogenide

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References(23)

References

[1]	Brammertz G, Bufère M, Oueslati S, et al. Characterization of defects in 9.7% efficient Cu₂ZnSnSe₄-CdS-ZnO solar cells. Appl Phys Lett, 2013, 103(16):163904 doi: 10.1063/1.4826448
[2]	Repins I, Beall C, Vora N, et al. Co-evaporated Cu₂ZnSnSe₄ films and devices. Sol Energy Mater Sol Cells, 2012, 101(2):154
[3]	Sun D, Xu S Z. Zhang L, et al. Influence of selenium evaporation temperature on the structure of Cu₂ZnSnSe₄ thin film deposited by a co-evaporation process. J Semicond, 2015, 36(4):044009 doi: 10.1088/1674-4926/36/4/044009
[4]	Sun K W, Yan Y, Liu F Y, et al. Over 9% efficient kesterite Cu₂ZnSnS₄ solar cell fabricated by using Zn_1-xCd_xS buffer layer. Adv Energy Mater, 2016, 1600046:1
[5]	Wang W, Winkler M T, Gunawan O, et al. Device characteristics of CZTSSe thin-film solar cells with 12.6% efficiency. Adv Energy Mater, 2014, 4(7):1301465 doi: 10.1002/aenm.201301465
[6]	Mitzi D B, Gunawan O, Todorov T K, et al. Prospects and performance limitations for Cu-Zn-Sn-S-Se photovoltaic technology. Philos Trans Royal Soc A, 2013, 371(1996):20110432 doi: 10.1098/rsta.2011.0432
[7]	Fairbrother A, Neuschitzer M, Saucedoet E, et al. Zn-poor Cu₂ZnSnSe₄ thin films and solar cell devices. Phys Status Solidi Appl Mater, 2014, 212(1):109
[8]	Todorov T K, Tang J, Bag S, et al. Beyond 11% efficiency:characteristics of state-of-the-art Cu₂ZnSn(S,Se)₄ solar cells. Adv Energy Mater, 2013, 3(1):34 doi: 10.1002/aenm.201200348
[9]	Shin B, Zhu Y, Bojarczuk N A, et al. Control of an interfacial MoSe₂ layer in Cu₂ZnSnSe₄ thin film solar cells:8.9% power conversion efficiency with a TiN diffusion barrier. Appl Phys Lett, 2012, 101(5):053903 doi: 10.1063/1.4740276
[10]	Fairbrother A, Fontané X, Izquierdo-Roca V, et al. Secondary phase formation in Zn-rich Cu₂ZnSnSe₄-based solar cells annealed in low pressure and temperature conditions. Prog Photovoltaics:Res Appl, 2014, 22(4):479 doi: 10.1002/pip.v22.4
[11]	Fan P, Zhao J, Liang G X, et al. Effects of annealing treatment on the properties of CZTSe thin films deposited by RF-magnetron sputtering. J Alloys Compnd, 2014, 625(2):171 http://cn.bing.com/academic/profile?id=ef66d7ca12e55713e905f1a5b4c1e2c0&encoded=0&v=paper_preview&mkt=zh-cn
[12]	Zhao J, Fan P, Liang G X, et al. The influence of precursor films on CIGS films prepared by ion beam sputtering deposition. Proc SPIE, 2015, 90681H:1 http://cn.bing.com/academic/profile?id=97f550e5fbafc9a022b577960efb145a&encoded=0&v=paper_preview&mkt=zh-cn
[13]	Liang G X, Fan P, Chen C M, et al. A promising sputtering for in situ fabrication of CIGS thin films without post-selenization. J Alloys Compd, 2014, 610(30):337 http://cn.bing.com/academic/profile?id=21ac5dc1ce7f03ad96b64f6ee8b4ae3c&encoded=0&v=paper_preview&mkt=zh-cn
[14]	Salomé P M M, Fernandes P A, Da Cunha A F, et al. Growth pressure dependence of Cu₂ZnSnSe₄ properties. Sol Energy Mater Solar Cells, 2010, 94(12):2176 doi: 10.1016/j.solmat.2010.07.008
[15]	Zoppi G, Forbes I, Miles R W, et al. Cu₂ZnSnSe₄ thin film solar cells produced by selenisation of magnetron sputtered precursors. Prog Photovoltaics:Res Appl, 2009, 17(5):315 doi: 10.1002/pip.v17:5
[16]	Xiong Y J, Xie Y, Du G, et al. From 2D framework to quasi-1D nanomaterial:preparation, characterization, and formation mechanism of Cu₃SnS₄. Nanorods Inorg Chem, 2002, 41(11):2953 doi: 10.1021/ic0200242
[17]	Zhang S Y, Fang C Z, Tian Y P, et al. Synthesis and characterization of hexagonal CuSe nanotubes by templating against trigonal Se Nanotubes. Cryst Growth Des, 2006, 6(12):2809 doi: 10.1021/cg0604430
[18]	Murali K R, Thilakvathy K, Vasantha S, et al. Properties of ZnSe films pulse plated on high temperature substrates. Chalcogenide Lett, 2008, 5(6):111 http://cn.bing.com/academic/profile?id=a2d4fe7c593ff1210af3f2b74bf67c4a&encoded=0&v=paper_preview&mkt=zh-cn
[19]	Wagner C D, Riggs W M, Davis L E, et al. Handbook of X-ray photoelectron spectroscopy. U.S.A:Perkin-Elmer Corporation, Physical Electronics Division, 1979
[20]	Park D, Nam D, Jung S, et al. Optical characterization of Cu₂ZnSnSe₄ grown by thermal co-evaporation. Thin Solid Films, 2001, 519(21):1
[21]	Pawar S M, Moholkar A V, Kim I K, et al. Effect of laser incident energy on the structural morphological and optical properties of Cu₂ZnSnS₄(CZTS) thin films. Curr Appl Phys, 2010, 10(2):565 doi: 10.1016/j.cap.2009.07.023
[22]	Moholkar A V, Shinde S S, Babar A R, et al. Development of CZTS thin films solar cells by pulsed laser deposition:influence of pulse repetition rate. Sol Energy, 2011, 85(7):1354 doi: 10.1016/j.solener.2011.03.017
[23]	Babu G S, Kumar Y B K, Bhaskar P U, et al. Effect of Cu/(ZnCSn) ratio on the properties of co-evaporated Cu₂ZnSnSe₄ thin films. Sol Energy Mater Sol Cells, 2010, 94(2):221 doi: 10.1016/j.solmat.2009.09.005

The influence of sequence of precursor films on CZTSe thin films prepared by ion-beam sputtering deposition

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