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The green hydrothermal synthesis of nanostructured Cu2ZnSnSe4 as solar cell material and study of their structural, optical and morphological properties

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Abstract

Cu2ZnSnSe4 (CZTSe) has attracted intensive attention as an absorber material for the thin-film solar cells due to its high absorption coefficient, direct band gap, low toxicity, and abundance of its constituent elements. In this study nanostructured CZTSe nanoparticles are prepared via green hydrothermal synthesis without using toxic solvents, organic amines, catalysts or noxious chemicals. The structural, optical, and morphological properties of CZTSe nanostructured powder were studied using X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), UV–vis absorption spectroscopy, and transmission electron microscope (TEM) techniques. Raman peaks at 170, 195, and 232 cm−1 confirm the formation of pure phase CZTSe nanostructured particles. In addition, the EDS and XPS results confirm the appropriate chemical purity of the annealed CZTSe nanoparticles. Meanwhile, the TEM analysis showed the presence of phase pure oval like CZTSe particle with size of about 80–140 nm. The UV–Vis-NIR absorption spectra analysis showed that the optical band gap of CZTSe nanostructured particles is about 1.14 eV. This band gap energy is close to the optimum value of a photovoltaic solar cell absorber material.

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References

  1. C. Jin, P. Ramasamya, J. Kim, Facile hot-injection synthesis of stoichiometric Cu2ZnSnSe4 nanocrystals using bis(triethylsilyl) selenide. Dalton Trans 43, 9481–9485 (2014)

    Article  Google Scholar 

  2. J. Britt, C. Ferekides, Thin-film CdS/CdTe solar cell with 15.8% efficiency. Appl. Phys. Lett. 62, 2851–2856 (2016)

    Article  ADS  Google Scholar 

  3. M.A. Green, K. Emery, Y. Hishikawa, W. Warta, E.D. Dunlop, D.H. Levi, A.W.Y.H. Baillie, Solar cell efficiency tables (version 49). Prog. Photovoltaic 25, 3–13 (2017)

    Article  Google Scholar 

  4. S.A. Vanalakar, G.L. Agawane, S.W. Shin, M.P. Suryawanshi, K.V. Gurav, K.S. Jeon, P.S. Patil, C.W. Jeong, J.Y. Kim, J.H. Kim, A review on pulsed laser deposited CZTS thin films for solar cell applications. J. Alloy Compd 619, 109–121 (2015)

    Article  Google Scholar 

  5. K. Ramasamy, M.A. Malik, N. Revaprasadu, P. O’Brien, Routes to nanostructured inorganic materials with potential for solar energy applications. Chem. Mater 25, 3551–3569 (2013)

    Article  Google Scholar 

  6. S.W. Shin, K.V. Gurav, C.W. Hong, J. Gwak, H.R. Choi, S.A. Vanalakar, J.H. Yun, J.Y. Lee, J.H. Moon, J.H. Kim, Phase segregations and thickness of the Mo(S,Se)2 layer in Cu2ZnSn(S,Se)4 solar cells at different sulfurization temperatures. Sol. Energ. Mat. Sol. Cells 143, 480–487 (2015)

    Article  Google Scholar 

  7. Z.H. Zhou, Y.Y. Wang, D. Xu, Y.F. Zhang, Fabrication of Cu2ZnSnS4 screen printed layers for solar cells. Sol. Energy Mater. Sol. Cells 94, 2042–2045 (2010)

    Article  Google Scholar 

  8. K.V. Gurav, Y.K. Kim, S.W. Shin, M.P. Suryawanshi, N.L. Tarwal, U.V. Ghorpade, S.M. Pawar, S.A. Vanalakar, I.Y. Kim, J.H. Yun, P.S. Patil, J.H. Kim, Pulsed electrodeposition of Cu2ZnSnS4 thin films: Effect of pulse potentials. Appl. Surf. Sci 334, 192–196 (2015)

    Article  ADS  Google Scholar 

  9. S. Chen, A. Walsh, X.G. Gong, S.H. Wei, Classification of lattice defects in the kesterite Cu2ZnSnS4 and Cu2ZnSnSe4 earth-abundant solar cell absorbers. Adv. Mater 25, 1522–1539 (2013)

    Article  Google Scholar 

  10. G.L. Agawane, A.S. Kamble, S.A. Vanalakar, S.W. Shin, M.G. Gang, J.H. Yun, J. Gwak, A.V. Moholkar, J.H. Kim, Fabrication of 3.01% power conversion efficient high-quality CZTS thin film solar cells by a green and simple sol–gel technique. Mater. Lett 158, 58–61 (2015)

    Article  Google Scholar 

  11. S.A. Vanalakar, G.L. Agawane, S.W. Shin, H.S. Yang, P.S. Patil, J.Y. Kim, J.H. Kim, Non-vacuum mechanochemical route to the synthesis of Cu2SnS3 nano-ink for solar cell applications. Acta Mater 85, 314–321 (2015)

    Article  Google Scholar 

  12. S.A. Vanalakar, R.C. Pawar, M.P. Suryawanshi, S.S. Mali, D.S. Dalavi, A.V. Moholkar, K.U. Sim, Y.B. Kown, J.H. Kim, P.S. Patil, Low temperature aqueous chemical synthesis of CdS sensitized ZnO nanorods. Mater. Lett 65, 548–551 (2011)

    Article  Google Scholar 

  13. L. Zhu, Y.H. Qiang, Y.L. Zhao, X.Q. Gu, Double junction photoelectrochemical solar cells based on Cu2ZnSnS4/Cu2ZnSnSe4 thin film as composite photocathode. Appl. Surf. Sci 292, 55–62 (2014)

    Article  ADS  Google Scholar 

  14. M. Pal, N.R. Mathews, F.P. Delgado, X. Mathew, Phase controlled solvothermal synthesis of Cu2ZnSnS4, Cu2ZnSn(S,Se)4 and Cu2ZnSnSe4 nanocrystals: the effect of Se and S sources on phase purity. Mater. Chem. Phys 166, 201–206 (2015)

    Article  Google Scholar 

  15. M.H. Chiang, Y.S. Fu, T.F. Guo, H.L. Liu, W.T. Lin, Effects of Zn precursors on solvothermal synthesis of Cu2ZnSnSe4 nanocrystals. Mater. Lett 83, 192–194 (2012)

    Article  Google Scholar 

  16. Y.F. Du, W.H. Zhou, Y.L. Zhou, P.W. Li, J.Q. Fan, J.J. He, S.X. Wu, Solvothermal synthesis and characterization of quaternary Cu2ZnSnSe4 particles. Mater. Sci. Semicond. Process 15, 214–217 (2012)

    Article  Google Scholar 

  17. R.B.V. Chalapathy, S. Das, J.S. Ma, J.C. Sung, C.H. Lu, Characterization of Cu2ZnSnSe4 (CZTSe) nanoparticles synthesized via solvothermal method for solar cell applications. J. Mater. Sci. Mater. Electron 26, 7673–7682 (2015)

    Article  Google Scholar 

  18. O. R.Vallejo, M. Sánchez, M. Pal, R. Espinal, J. Llorca, P.J. Sebastian, Synthesis and characterization of nanoparticles of CZTSe by microwave-assisted chemical synthesis. Mater. Res. Express 3, 125017–125010 (2016)

    Article  ADS  Google Scholar 

  19. S.A. Vanalakar, A.S. Kamble, S.W. Shin, S.S. Mali, G.L. Agawane, V.L. Patil, J.Y. Kim, P.S. Patil, J.H. Kim, Simplistic toxic to non-toxic hydrothermal route to synthesize Cu2ZnSnS4 nanoparticles for solar cell applications. Sol. Energy 122, 1146–1153 (2015)

    Article  ADS  Google Scholar 

  20. M. Outokesh, M. Hosseinpour, S.J. Ahmadi, T. Mousavand, S. Sadjadi, W. Soltanian, Hydrothermal synthesis of CuO nanoparticles: study on effects of operational conditions on yield, purity, and size of the nanoparticles. Ind. Eng. Chem. Res 50, 3540–3554 (2011)

    Article  Google Scholar 

  21. S.A. Vanalakar, G.L. Agwane, M.G. Gang, P.S. Patil, J.H. Kim, J.Y. Kim, A mild hydrothermal route to synthesis of CZTS nanoparticle inks for solar cell applications. Phys. Status Solidi C 12, 500–503 (2015)

    Article  ADS  Google Scholar 

  22. P.M.P. Salomé, P.A. Fernandes, A.F. da Cunh, Morphological and structural characterization of Cu2ZnSnSe4 thin films grown by selenization of elemental precursor layers. Thin Solid Films 517, 2531–2534 (2009)

    Article  ADS  Google Scholar 

  23. Y. Yang, G. Wang, W. Zhao, Q. Tian, L. Huang, D. Pan, Solution-processed highly efficient Cu2ZnSnSe4 thin film solar cells by dissolution of elemental Cu, Zn, Sn, and Se powders., ACS Appl. Mater. Interfaces 7, 460–464 (2015)

    Google Scholar 

  24. X. Wang, D.X. Kou, W.H. Zhou, Z.J. Zhou, S.X. Wu, X. Cao, Cu2ZnSnSe4 nanocrystals capped with S2– by ligand exchange: utilizing energy level alignment for efficiently reducing carrier recombination. Nanoscale Res. Lett 9, 262–265 (2014)

    Article  ADS  Google Scholar 

  25. J. Polte, Fundamental growth principles of colloidal metal nanoparticles—a new perspective. CrystEngComm 17, 6809–6830 (2015)

    Article  Google Scholar 

  26. S.A. Vanalakar, V.L. Patil, P.S. Patil, J.H. Kim, Controllable synthesis of stiochiometric Cu2ZnSnS4 nanoparticles by solvothermal method and its properties. AIP Conf. Proc 1665, 050061–050004 (2015)

    Article  Google Scholar 

  27. A. Benedicto, T. Missana, C. Degueldre, Predictions of TiO2 driven migration of Se(IV) based on an integrated study of TiO2 colloid stability and Se(IV) surface adsorption. Sci. Total Environ 449, 214–222 (2013)

    Article  ADS  Google Scholar 

  28. B.B. Wang, X.Z. Xu, Study on effects of time and temperature on growth of nanocrystalline zinc selenide synthesized by hydrothermal method. J. Cryst. Growth 311, 4759–4762 (2009)

    Article  ADS  Google Scholar 

  29. S.A. Vanalakar, S.W. Shin, G.L. Agawane, M.P. Suryawanshi, K.V. Gurav, P.S. Patil, J.H. Kim, Effect of post-annealing atmosphere on the grain-size and surface morphological properties of pulsed laser deposited CZTS thin films. Ceram. Int 40, 15097–15103 (2014)

    Article  Google Scholar 

  30. M.P. Suryawanshi, S.W. Shin, U.V. Ghorpade, K.V. Gurav, C.W. Hong, G.L. Agawane, S.A. Vanalakar, J.H. Moon, J.H. Yun, P.S. Patil, J.H. Kim, A.V. Moholkar, Improved photoelectrochemical performance of Cu2ZnSnS4 (CZTS) thin films prepared using modified successive ionic layer adsorption and reaction (SILAR) sequence. ‎Electrochim. Acta 150, 136–145 (2014)

    Article  Google Scholar 

  31. Y.F. Du, J.Q. Fan, W.H. Zhou, Z.J. Zhou, J. Jiao, S.X. Wu, One-step synthesis of stoichiometric Cu2ZnSnSe4 as counter electrode for dye-sensitized solar cells., ACS Appl. Mater. Interfaces 4, 1796–1802 (2012)

    Google Scholar 

  32. S.J. Ahn, S. Jung, J. Gwak, A. Cho, K. Shin, K. Yoon, D. Park, H. Cheong, J.H. Yun, Determination of band gap energy (Eg) of Cu2ZnSnSe4 thin films: On the discrepancies of reported band gap values. Appl. Phys. Lett. 97, 021905–021904 (2010)

    Article  ADS  Google Scholar 

Download references

Acknowledgements

The first and one of the corresponding authors S. A. Vanalakar is thankful to University Grant Commission (UGC), New Delhi, India, for the Raman Fellowship for Post-Doc Research in USA (F. no. 5/155/2016 (IC)). This work was supported by the Human Resources Development of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government Ministry of Knowledge Economy (no. 20124010203180).

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Authors and Affiliations

  1. Department of Physics, Karmaveer Hire Arts, Science, Commerce and Education College, Gargoti, 416009, India

    S. A. Vanalakar

  2. Microelectronic Research Centre, Department of Computer and Electrical Engineering, Iowa State University, Ames, 50014, USA

    S. A. Vanalakar

  3. Department of Materials Science and Engineering, Chonnam National University, Gwangju, 500757, Republic of Korea

    S. A. Vanalakar & A. S. Kamble

  4. Advanced Optical Lens Research Center, Korea Photonics Technology Institute (KOPTI), Gwangju, 61007, Republic of Korea

    G. L. Agawane & J. H. Kim

  5. Thin Film Materials Laboratory, Department of Physics, Shivaji University, Kolhapur, 416004, India

    P. S. Patil

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  1. S. A. Vanalakar
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Correspondence to S. A. Vanalakar or J. H. Kim.

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Vanalakar, S.A., Agawane, G.L., Kamble, A.S. et al. The green hydrothermal synthesis of nanostructured Cu2ZnSnSe4 as solar cell material and study of their structural, optical and morphological properties. Appl. Phys. A 123, 782 (2017). https://doi.org/10.1007/s00339-017-1407-2

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  • DOI: https://doi.org/10.1007/s00339-017-1407-2

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