Journal of Materials Science

, Volume 52, Issue 16, pp 9709–9727 | Cite as

Deposition, characterizations and photoelectrochemical performance of nanocrystalline Cu–In–Cd–S–Se thin films by hybrid chemical process

  • Kishorkumar V. Khot
  • Tukaram D. Dongale
  • Sawanta S. Mali
  • Chang Kook Hong
  • Rajanish K. Kamat
  • Popatrao N. Bhosale
Energy materials


Nanocrystalline, uniform, pentanary mixed metal chalcogenide (PMMC) thin films of copper indium cadmium sulfoselenide (CuInCd(SSe)3) were successfully synthesized using simple, self-organized, arrested precipitation technique in an aqueous alkaline medium. The optical, structural, morphological, compositional and electrical properties of synthesized thin films were investigated as a function indium (In3+) concentration. An optical absorption study revealed that direct allowed transition and band gap energy decreases typically from 1.46 to 1.25 eV. The X-ray diffraction studies revealed that the PMMC thin films have a nanocrystalline nature and crystallite size increases with the increase in the In3+ concentration. Tuning of surface morphology from nanospheres to peas-like morphology with uniform, well-adhered distributed throughout the substrate surface were observed by field emission scanning electron microscopy micrographs. The high-resolution transmission electron microscopy images and selected area electron diffraction pattern were illustrated that compactly interconnected particles with nanocrystalline nature. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy results confirmed that synthesized thin films had an appropriate chemical purity. The electrical conductivity and thermoelectric power measurement indicates that, the films have n-type conductivity. A photoelectrochemical conversion efficiency of 2.40% was achieved with a current density of 2.87 mA/cm2. The developed route may provide an alternative approach to synthesize multinary metal chalcogenide thin-film solar cell. Furthermore, we have developed a predictive model of a CICSSe thin-film solar cell using the artificial neural network. The proposed model is useful for the integrated development environment for the predictive modeling and design of high-efficient solar cells.


Solar Cell Artificial Neural Network Model Field Emission Scanning Electron Microscopy Image Artificial Neural Network Architecture Copper Indium 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



One of the authors Dr. Kishorkumar V. Khot is very much thankful to Department of Science and Technology (DST), New Delhi, for providing DST-INSPIRE fellowship for financial support (Registration No. IF130751). This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2009-0094055).


  1. 1.
    Gao MR, Xu YF, Jiang J, Yu SH (2013) Nanostructured metal chalcogenides: synthesis, modification, and applications in energy conversion and storage devices. Chem Soc Rev 42:2986CrossRefGoogle Scholar
  2. 2.
    Santiago FF, Belmonte GG, Sero IM, Bisquert J (2011) Characterization of nanostructured hybrid and organic solar cells by impedance spectroscopy. Phys Chem Chem Phys 13:9083CrossRefGoogle Scholar
  3. 3.
    Waldau AJ (2004) Status of thin film solar cells in research, production and the market. Sol Energy 77:667CrossRefGoogle Scholar
  4. 4.
    Afzaal M, O’Brien P (2006) Recent developments in II–VI and III–VI semiconductors and their applications in solar cells. J Mater Chem 16:1597CrossRefGoogle Scholar
  5. 5.
    Selinsky RS, Ding Q, Faber MS, Wright JC, Jin S (2013) Quantum dot nanoscale heterostructures for solar energy conversion. Chem Soc Rev 42:2963CrossRefGoogle Scholar
  6. 6.
    Lewis NS (2007) Toward cost-effective solar energy use. Science 315:798CrossRefGoogle Scholar
  7. 7.
    Lewis NS, Nocera DG (2006) Powering the planet: chemical challenges in solar energy utilization. Proc Natl Acad Sci USA 103:15729CrossRefGoogle Scholar
  8. 8.
    Balzani V, Credi A, Venturi M (2008) Photochemical conversion of solar energy. Chemsuschem 1:26CrossRefGoogle Scholar
  9. 9.
    Kamat PV, Tvrdy K, Baker DR, Radich JG (2010) Beyond photovoltaics: semiconductor nanoarchitectures for liquid-junction solar cells. Chem Rev 110:6664CrossRefGoogle Scholar
  10. 10.
    Gratzel M (2001) Photoelectrochemical cells. Nature 414:338CrossRefGoogle Scholar
  11. 11.
    Sheikh A, Yengantiwar A, Deo M, Kelkar S, Ogale S (2013) Near-field plasmonic functionalization of light harvesting oxide-oxide heterojunctions for efficient solar photoelectrochemical water splitting: the AuNP/ZnFe2O4/ZnO system. Small 9(12):2091CrossRefGoogle Scholar
  12. 12.
    Zou Y, Li D, Yang D (2012) Colloidal synthesis of monodisperse quaternary CuInSSe nanocrystals. Mater Chem Phys 132:865CrossRefGoogle Scholar
  13. 13.
    Arnou P, Cooper CS, Malkov AV, Bowers JW, Walls JM (2015) Solution-processed CuIn(S, Se)2 absorber layers for application in thin film solar cells. Thin Solid Films 582:31CrossRefGoogle Scholar
  14. 14.
    Khot KV, Mali SS, Pawar NB, Kharade RR, Mane RM, Kondalkar VV, Patil PB, Patil PS, Hong C, Kim JH, Heo J, Bhosale PN (2014) Development of nanocoral-like Cd(SSe) thin films using an arrested precipitation technique and their application. New J Chem 38:5964CrossRefGoogle Scholar
  15. 15.
    Purohit A, Chander S, Nehra SP, Dhaka MS (2015) Effect of air annealing on structural, optical, morphological and electrical properties of thermally evaporated CdSe thin films. Physica E 69:342CrossRefGoogle Scholar
  16. 16.
    Kumar V, Sharma SK, Dwivedi DK (2012) Crystallographic, optical and electrical properties of low zinc content cadmium zinc sulphide composite thin films for photovoltaic applications. J Alloys Compd 512:351CrossRefGoogle Scholar
  17. 17.
    Gruszecki T, Holmstorm B (1993) Preparation of thin films of polycrystalline CdSe for solar energy conversion I. A. literature survey. Sol Energy Mater Sol Cells 31:227CrossRefGoogle Scholar
  18. 18.
    Heo J, Ahn H, Lee R, Han Y, Kim D (2003) Influence of ITO surface modification on the growth of CdS and on the performance of CdS/CdTe solar cells. Sol Energy Mater Sol Cells 75:193CrossRefGoogle Scholar
  19. 19.
    Xiong WW, Zhang G, Zhang Q (2014) New strategies to prepare crystalline chalcogenides. Inorg Chem Front 1:292CrossRefGoogle Scholar
  20. 20.
    Aldakov D, Lefrancois A, Reiss P (2013) Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications. J Mater Chem C 1:3756CrossRefGoogle Scholar
  21. 21.
    Pawar NB, Kharade SD, Mali SS, Mane RM, Hong CK, Patil PS, Bhosale PN (2014) Effect of indium(III) content on photoelectrochemical performance of MoBi(2 − x)InxS5 thin films. Solid State Sci 35:10CrossRefGoogle Scholar
  22. 22.
    Khot KV, Mali SS, Pawar NB, Kharade RR, Mane RM, Patil PB, Patil PS, Hong CK, Kim JH, Heo J, Bhosale PN (2015) Simplistic construction of cadmium sulfoselenide thin films via a hybrid chemical process for enhanced photoelectrochemical performance. RSC Adv 5:40283CrossRefGoogle Scholar
  23. 23.
    Shen S, Zhao L, Zhou Z, Guo L (2008) Enhanced photocatalytic hydrogen evolution over Cu-doped ZnIn2S4 under visible light irradiation. J Phys Chem C 112:16148CrossRefGoogle Scholar
  24. 24.
    Kose S, Atay F, Bilgin V, Akyuz I, Ketenci E (2010) Optical characterization and determination of carrier density of ultrasonically sprayed CdS: Cu films. Appl Surf Sci 256:4299CrossRefGoogle Scholar
  25. 25.
    Cheng KW, Huang C, Yu Y, Li C, Shu C, Liu WL (2011) Photoelectrochemical performance of Cu-doped ZnIn2S4 electrodes created using chemical bath deposition. Sol Eng Mater Sol Cells 95:1940CrossRefGoogle Scholar
  26. 26.
    Khallaf H, Chai G, Lupan O, Chow L, Park S, Schulte A (2009) Characterization of gallium-doped CdS thin films grown by chemical bath deposition. Appl Surf Sci 255:4129CrossRefGoogle Scholar
  27. 27.
    Herberholz R, Carter MJ (1996) Investigation of the chalcogen interdiffusion in CuIn(TeSe)2 thin films. Sol Energy Mater Sol Cells 44:357CrossRefGoogle Scholar
  28. 28.
    Cullity BD (1957) The elements of X-ray diffraction, 1st edn. Addison Wesley Publishing Company Inc., BostonGoogle Scholar
  29. 29.
    Dai P, Zhang G, Chen Y, Jiang H, Feng Z, Lin Z, Zhan J (2012) Porous copper zinc tin sulfide thin film as photocathode for double junction photoelectrochemical solar cells. Chem Commun 48:3006CrossRefGoogle Scholar
  30. 30.
    Khot KV, Ghanwat VB, Bagade CS, Mali SS, Bhosale RR, Bagali AS, Dongale TD, Bhosale PN (2016) Synthesis of SnS2 thin film via non vacuum arrested precipitation technique for solar cell application. Mater Lett 180:23–26CrossRefGoogle Scholar
  31. 31.
    Gordilloa G, Calderon C, Bartolo-Perez P (2014) XPS analysis and structural and morphological characterization of Cu2ZnSnS4 thin films grown by sequential evaporation. Appl Surf Sci 305:506CrossRefGoogle Scholar
  32. 32.
    Riha SC, Parkinson BA, Prieto AL (2009) Solution-based synthesis and characterization of Cu2ZnSnS4 nanocrystals. J Am Chem Soc 131:12054CrossRefGoogle Scholar
  33. 33.
    Li WJ, Zhou YN, Fu ZW (2011) Fabrication and lithium electrochemistry of InSe thin film. Appl Surf Sci 257:2881CrossRefGoogle Scholar
  34. 34.
    Merdes S, Steigert A, Ziem F, Lauermann I, Klenk R, Hergert F, Kaufmann CA, Schlatmann R (2015) Influence of Cu(In, Ga)(Se, S)2 surface treatments on the properties of 30 × 30 cm2 large are a modules with atomic layer deposited Zn(O, S) buffers. Thin Solid Films 574:28CrossRefGoogle Scholar
  35. 35.
    Liu T, Hua Y, Chang W (2014) Characterization of Cu2−xSe thin films synthesized from electrochemical deposition. Mater Sci Eng, B 180:33CrossRefGoogle Scholar
  36. 36.
    Salunkhe MM, Khot KV, Patil PS, Bhave TM, Bhosale PN (2015) Novel route for the synthesis of surfactant-assisted MoBi2(Se0.5Te0.5)5 thin films for solar cell applications. New J Chem 39:3405CrossRefGoogle Scholar
  37. 37.
    Ronge J, Bosserez T, Martel D, Nervi C, Boarino L, Taulelle F, Decher G, Bordiga S, Martens JA (2014) Monolithic cells for solar fuels. Chem Soc Rev 43:7963CrossRefGoogle Scholar
  38. 38.
    Bignozzi CA, Caramori S, Cristino V, Argazzi R, Meda L, Tacca A (2013) Nanostructured photoelectrodes based on WO3: applications to photooxidation of aqueous electrolytes. Chem Soc Rev 42:2228CrossRefGoogle Scholar
  39. 39.
    Jana A, Bhattacharya C, Sinha S, Datta J (2009) Study of the optimal condition for electroplating of Bi2S3 thin films and their photoelectrochemical characteristics. J Solid State Electrochem 13:1339CrossRefGoogle Scholar
  40. 40.
    Fonash SJ (2010) Solar cell device physics, 2nd edn. Elsevier, AmsterdamGoogle Scholar
  41. 41.
    Hou H, Jiang Y, Li J, Yu S, Wang C (2012) Enhanced photoelectric performance of Cu2xSe nanostructure by doping with In3+. J Mater Chem 22:1950CrossRefGoogle Scholar
  42. 42.
    Dongale TD, Patil KP, Vanjare SR, Chavan AR, Gaikwad PK, Kamat RK (2015) Modelling of nanostructured memristor device characteristics using artificial neural network. J Comput Sci 11:82CrossRefGoogle Scholar
  43. 43.
    Dongale TD, Jadhav PR, Navathe GJ, Kim JH, Karanjkar MM, Patil PS (2015) Development of nano fiber MnO2 thin film electrode and cyclic voltammetry behavior modeling using artificial neural network for supercapacitor application. Mater Sci Semicond Process 36:43CrossRefGoogle Scholar
  44. 44.
    Dongale TD, Katkar SV, Khot KV, More KV, Delekar SD, Bhosale PN, Kamat RK (2016) Simulation of randomly textured tandem silicon solar cells using quadratic complex rational function approach along with artificial neural network. J Nanoeng Nanomanuf 6:103CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2017

Authors and Affiliations

  • Kishorkumar V. Khot
    • 1
    • 2
  • Tukaram D. Dongale
    • 3
  • Sawanta S. Mali
    • 4
  • Chang Kook Hong
    • 4
  • Rajanish K. Kamat
    • 5
  • Popatrao N. Bhosale
    • 1
  1. 1.Materials Research Laboratory, Department of ChemistryShivaji UniversityKolhapurIndia
  2. 2.Department of General Engineering and SciencesSharad Institute of Technology, College of EngineeringYadrav, IchalkaranjiIndia
  3. 3.Computational Electronics and Nanoscience Research Laboratory, School of Nanoscience and BiotechnologyShivaji UniversityKolhapurIndia
  4. 4.Polymer Energy Materials Laboratory, Department of Advanced Chemical EngineeringChonnam National UniversityGwangjuSouth Korea
  5. 5.Embedded System and VLSI Research Laboratory, Department of ElectronicsShivaji UniversityKolhapurIndia

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