Se-loss-induced CIS Thin Films in RTA Process after Co-sputtering Using CuSe2 and InSe2 Targets

  • Kim, Nam-Hoon ;
  • Jun, Young-Kil ;
  • Cho, Geum-Bae
  • Received : 2013.12.03
  • Accepted : 2014.03.19
  • Published : 2014.05.01


Chalcopyrite $CuInSe_2$ (CIS) thin films were prepared without Se- / S-containing gas by co-sputtering using $CuSe_2$ and $InSe_2$ selenide-targets and rapid thermal annealing. The grain size increased to a maximum of 54.68 nm with a predominant (112) plane. The tetragonal distortion parameter ${\eta}$ decreased and the inter-planar spacing $d_{(112)}$ increased in the RTA-treated CIS thin films annealed at a $400^{\circ}C$, which indicates better crystal quality. The increased carrier concentration of RTA-treated p-type CIS thin films led to a decrease in resistivity due to an increase in Cu composition at annealing temperatures ${\geq}350^{\circ}C$. The optical band gap energy ($E_g$) of CIS thin films decreased to 1.127 eV in RTA-treated CIS thin films annealed at $400^{\circ}C$ due to the improved crystallinity, elevated carrier concentration and decreased In composition.


Thin Film;$CuSe_2$ and $InSe_2$ Targets;Co-sputtering;RTA


  1. I. H. Choi, "The Preparation of CIS Absorber Layers by Using MOCVD with Two Different Methods," Journal of the Korean Physical Society, Vol. 59, No. 1, July 2011, pp. 80-84.
  2. Y. C. Lin, Z. Q. Lin, C. H. Shen, L. Q. Wang, C. T. Ha and C. Peng, "Cu(In, Ga)$Se_2$ films prepared by sputtering with a chalcopyrite Cu(In,Ga)$Se_2$ quarternary alloy and In targets," Journal of Materials Science: Materials in Electronics, Vol. 23, No. 2, 2012, pp. 493-500.
  3. M. Varela, E. Bertran, M. Manchon, J. Esteve and J. L. Morenza, "Optical properties of co-evaporated CuInSe, thin films," Journal of Physics D: Applied Physics, Vol. 19, No. 1, 1986, pp. 127-136.
  4. M. A. S. Bhuiyan, A. S. Bhuiyan, A. Hossain and Z. H. Mahmood, "Studies on optical characteristics of $CuInSe_2$ thin films," Central European Journal of Engineering, June 2013, Vol. 3, No. 2, pp. 170-173.
  5. O. Schultz, S.W. Glunz and G.P. Willeke, "Multicrystalline silicon solar cells exceeding 20% efficiency," Progress in Photovoltaics: Research and Applications, Vol. 12, No. 7 , 2004, pp. 553-558.
  6. S. Karthikeyan, A. E. Hill, R. D. Pilkington, J. S. Cowpe, J. Hisek and D. M. Bagnall, "Single step deposition method for nearly stoichiometric $CuInSe_2$ thin films," Thin Solid Films Vol. 519, 2011, pp. 3107-3112.
  7. B. T. Jheng, P. T. Liu, M. C. Wu and H. P. D. Shieh, "A non-selenization technology by co-sputtering deposition for solar cell applications," Optics Letters, Vol. 37, No. 13, 2012, pp. 2760-2762.
  8. D. Chen and D. Wang, "Formation of $CuInSe_2$ from $Cu_2Se$ and $In_2Se_3$ compounds," Phys. Status Solidi A, Vol. 208, No. 10, 2011, pp. 2415-2423.
  9. K. Bouabid, A. Ihlal, A. Manar, A. Outzourhit and E. L. Ameziane, "Effect of deposition and annealing parameters on the properties of electrodeposited $CuIn_{1-x}Ga_xSe_2$ thin films," Thin Solid Films, Vol. 488, 2005, pp. 62-67.
  10. E. Ahmed, A. Zegadi, A. E. Hill, R. D. Pilkington, R. D. Tomlinson, A. A. Dost, W. Ahmed, S. Leppavuori, J. Levoska and O. Kusmartseva, "The influence of annealing processes on the structural, compositional and electro-optical properties of $CuIn_{0.75}Ga_{0.25}Se_2$ thin films," Journal of Materials Science: Materials in Electronics, Vol. 7, No. 3, 1996, pp. 213-219.
  11. X. Wang, S. S. Li, W. K. Kim, S. Yoon, V. Craciun, J. M. Howard, S. Easwaran, O. Manasreh, O. D. Crisalle and T. J. Anderson, "Investigation of rapid thermal annealing on Cu(In, Ga)$Se_2$ films and solar cells," Solar Energy Materials and Solar Cells, Vol. 90, No. 17, 2006, pp. 2855-2866.
  12. B. D. Cullity, Elements of X-Ray Diffraction, 3rd ed. Addison-Wesley, Reading, Mass., London, 1967.
  13. F. O. Adurodija, J. Song, S. D. Kim, S. H. Kwon, S. K. Kim, K. H. Yoon and B. T. Ahn, "Growth of $CuInSe_2$ thin flms by high vapour Se treatment of cosputtered Cu-In alloy in a graphite container," Thin Solid Films, Vol. 338, 1999, pp. 13-19.
  14. S. Phok, S. Rajaputra and V. P. Singh, "Copper indium diselenide nanowire arrays by electrodeposition in porous alumina templates," Nanotechnology, Vol. 18 , No. 47, 2007, p. 475601.
  15. J. C. Osuwa and N. I. Chigbo, "Effects of temporal variations in deposition on the optical and solid state properties of electro-deposited cadmium telluride (CdTe) thin films on glass FTO," Chalcogenide Lett., Vol. 9, No. 12, 2012, pp. 501-508.
  16. G. Gordillo, J. M. Florez and L. C. Hernandez, "Preparation and characterization of CdTe thin films deposited by CSS," Solar Energy Materials and Solar Cells, Vol. 37, No. 3-4, 1995, pp. 273-281.
  17. N. H. Kim, C. I. Park, J. Park, "A Pilot Investigation on Laser Annealing for Thin-film Solar Cells: Crystallinity and Optical Properties of Laser-annealed CdTe Thin Films by Using an 808-nm Diode Laser," Journal of the Korean Physical Society, Vol. 62, No. 3, 2013, pp. 502-507.
  18. G. K. Williamson, R. E. Smallman, "Dislocation densities in some annealed and cold-worked metals from measurements on the x-ray Debye-Scherrer spectrum," Philosophical Magazine, Vol. 1, No. 1, 1956, pp. 34-45.
  19. M. A. Islam, Q. Huda, M. S. Hossain, M. M. Aliyu, M. R. Karim, K. Sopian, N. Amin, "High quality $1{\mu}m$ thick CdTe absorber layers grown by magnetron sputtering for solar cell application," Current Applied Physics, Vol. 13, Suppl. 2, 2013, pp. S115-S121.
  20. L. L. Kazmerski, O. Jamjoum, P. J. Ireland, S. K. Deb, R. A. Mickelsen and W. Chen, "Initial oxidation of $CuInSe_2$," Journal of Vacuum Science and Technology, Vol. 19, No. 3, 1981, pp. 467-471.
  21. M. L. Fearheiley, K. J. Bachmann, Y. H. Shing, S. A. Vasquez and C. R. Herrington, "The lattice constants of $CuInSe_2$," Journal of Electronic Materials, Vol. 14, No. 6, 1985, pp. 677-683.
  22. A. A. I. Al-Bassam and U. A. Elani, Proceeding of 2012 International Conference on Environment, Energy and Biotechnology, IPCBEE Vol. 33, IACSUT Press, Singapore, 2012, pp. 163-167.
  23. R. Chen and C. Persson, "Band-edge density-ofstates and carrier concentrations in intrinsic and ptype $CuIn_{1-x}Ga_xSe_2$," Journal of Applied Physics, Vol. 112, No. 10, 2012, p. 103708.
  24. A. Bouraiou, M. S. Aida, A. Mosbah, and N. Attaf, "Annealing time effect on the properties of $CuInSe_2$ grown by electrodeposition using two electrodes system," Brazilian Journal of Physics, Vol. 39, No. 3, 2009, pp. 543-546.
  25. H. Neumann and R.D. Tomlinson, "Relation between electrical properties and composition in $CuInSe_2$ single crystals," Solar Cells, Vol. 28, No. 4, 1990, pp. 301-313.
  26. D. Haneman, "Properties and applications of copper indium diselenide," Critical Reviews in Solid State and Materials Sciences, Vol. 14, No. 4, 1988, pp. 377-413
  27. G. A. Medvedkin and M. A. Magomedov, "Growth of polycrystalline $CuInSe_2$ thin films by effusion evaporation," Semiconductor Science and Technology, Vol. 8, No. 5, 1993, pp. 652-656.
  28. S. R. Kodigala, $Cu(In_{1-x}Ga_x)Se_2$ Based Thin Film Solar Cells, Vol. 35, Academic Press, MA, USA, 2011, p. 215.
  29. A. Knowlcs, H. Oumous. M. J. Carter and R. Hill, Conference Record of the Twentieth IEEE Photovoltaic Specialists Conference, Vol. 2, IEEE, Las Vegas, NV, USA, 1988, p. 1482.
  30. T. Datta, R. Noufi and S. K. Deb, "Electrical conductivity of p-type $CuInSe_2$ thin films," Applied Physics Letters, Vol. 47, No. 10, 1985, pp. 1102-1104.
  31. H. Khallaf, G. Chai, O. Lupan, L. Chow, S. Park and A. Schulte, "Characterization of gallium-doped CdS thin films grown by chemical bath deposition," Applied Surface Science, Vol. 255, No. 7, 2009, pp. 4129-4134.
  32. D. S. Reddy, K. N. Rao, K. R. Gunasekhar, N. K. Reddy, K. S. Kumar and P. S. Reddy, "Annealing effect on structural and electrical properties of thermally evaporated $Cd_{1-x}Mn_xS$ nanocrystalline films," Materials Research Bulletin, Vol. 43, No. 12, 2008, pp. 3245-3251.
  33. Y. Gu, X. Li, W. Yu, X. Gao, J. Zhao and C. Yang, "Microstructures, electrical and optical characteristics of ZnO thin films by oxygen plasma-assisted pulsed laser deposition," Journal of Crystal Growth, Vol. 305, No. 1, 2007, pp. 36-39.
  34. S. Wageh, A. A. Higazy and M. A. Algradee, "Optical Properties and Activation Energy of A Novel System of CdTe Nanoparticles Embedded in Phosphate Glass Matrix," Journal of Modern Physics, Vol. 2, No. 8, 2011, pp. 913-921.
  35. C. V. Ramana, R. J. Smith and O. M. Hussain, "Grain size effects on the optical characteristics of pulsedlaser deposited vanadium oxide thin films," Physica Status Solidi A, Vol. 199, No. 1, 2003, pp. R4-R6.

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