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Effects of Growth Conditions on Secondary Phases in CZTSe Thin Films Deposited by Co-evaporation

Published online by Cambridge University Press:  28 August 2013

Douglas M. Bishop ,
Brian E. McCandless ,
Thomas C. Mangan ,
Kevin Dobson  and
Robert Birkmire
Douglas M. Bishop
Affiliation:
Institute of Energy Conversion, University of Delaware, 451 Wyoming Rd, Newark, DE 19711, U.S.A.
Brian E. McCandless
Affiliation:
Institute of Energy Conversion, University of Delaware, 451 Wyoming Rd, Newark, DE 19711, U.S.A.
Thomas C. Mangan
Affiliation:
Institute of Energy Conversion, University of Delaware, 451 Wyoming Rd, Newark, DE 19711, U.S.A.
Kevin Dobson
Affiliation:
Institute of Energy Conversion, University of Delaware, 451 Wyoming Rd, Newark, DE 19711, U.S.A.
Robert Birkmire
Affiliation:
Institute of Energy Conversion, University of Delaware, 451 Wyoming Rd, Newark, DE 19711, U.S.A.
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Abstract

High temperature multi-source co-evaporation has been the most successful approach to fabricate record efficiency Cu(InGa)Se2 devices, yet many groups have been unable to replicate this success when transferring these methods to the Cu2ZnSnSe4 system. The difficulties stem from the dramatic differences in the thermochemical properties which result in decomposition and loss of volatile species, such as Zn and SnSe, at temperatures needed for growth. In co-evaporation, decomposition and element loss must be managed throughout the entire growth process, from the back contact interface to the final terminating surface of the film. The beginning and ending phases of deposition encompass different kinetic regimes suggesting a phased approach to growth may be helpful. A series of depositions with different effusion profiles were used to demonstrate the effects of decomposition during different stages of growth. Secondary phase detection can be challenging in CZTSe, but a combination of SEM imaging and thin cross-section depth profile by EDS were found to best identify and locate the secondary phases that occur during different phases of growth for co-evaporated Cu2ZnSnSe4 films.

Deposition with a uniform incident flux followed by shuttered vacuum cool-down yielded films with a ZnSe phase at the absorber/Mo interface and Cu-rich composition at the surface of the exposed film. Devices from these absorber layers never exceeded conversion efficiencies of 1%. Decomposition at the surface could be prevented by continuing effusion of Se and Sn during the cool-down of the substrate. Resulting films demonstrated more faceted grains as well as significantly improved device performance. Secondary phases that traditionally form at the back contact during the beginning of growth were minimized by decreasing the substrate temperature to 300°C during the initial stages of deposition which reduced the ZnSe formed at the Mo interface. The thermochemical origin of the secondary phases will be discussed and the performance of representative devices will be presented.

Keywords

photovoltaicthin filmphysical vapor deposition (PVD)
Type
Articles
Information
MRS Online Proceedings Library (OPL) , Volume 1538: Symposium C – Compound Semiconductors: Thin-Film Photovoltaics, LEDs and Smart Energy Controls , 2013 , pp. 75 - 82
Copyright
Copyright © Materials Research Society 2013 

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References

REFERENCES

Schubert, B.-A., Marsen, B., Cinque, S., Unold, T., Klenk, R., Schorr, S., and Schock, H.-W., “Cu2ZnSnS4 thin film solar cells by fast coevaporation,” Progress in Photovoltaics: Research and Applications, vol. 19, no. May 2010, pp. 93–96, 2011.CrossRefGoogle Scholar
Redinger, A. and Siebentritt, S., “Coevaporation of Cu2ZnSnSe4 thin films,” Applied Physics Letters, vol. 97, no. 9, p. 092111, 2010.CrossRefGoogle Scholar
Todorov, T. K., Tang, J., Bag, S., Gunawan, O., Gokmen, T., Zhu, Y., and Mitzi, D. B., “Beyond 11% Efficiency: Characteristics of State-of-the-Art Cu2ZnSn(S, Se)4 Solar Cells,” Advanced Energy Materials, p. n/a–n/a, Aug. 2012.Google Scholar
Repins, I. L., Beall, C., Vora, N., DeHart, C., Kuciauskas, D., Dippo, P., To, B., Mann, J., Hsu, W.-C., Goodrich, A., and Noufi, R., “Co-evaporated Cu2ZnSnSe4 films and devices, ” Solar Energy Materials and Solar Cells, pp. 1–6, Feb. 2012.Google Scholar
Ahn, S., Jung, S., Gwak, J., Cho, A., Shin, K., Yoon, K., Park, D., Cheong, H. H., and Yun, J. H., “Determination of band gap energy Eg of Cu2ZnSnSe4 thin films: On the discrepancies of reported band gap values,” Applied Physics Letters, vol. 97, no. 2, p. 021905, 2010.CrossRefGoogle Scholar
Redinger, A., Hönes, K., Fontané, X., Izquierdo-Roca, V., Saucedo, E., Valle, N., Pérez-Rodriguez, A., and Siebentritt, S., “Detection of a ZnSe secondary phase in coevaporated Cu2ZnSnSe4 thin films,” Applied Physics Letters, vol. 98, no. 10, p. 101907, 2011.CrossRefGoogle Scholar
Vora, N., Blackburn, J., Repins, I. L., Beall, C., To, B., Pankow, J., Teeter, G., Young, M., and Noufi, R., “Phase identification and control of thin films deposited by co-evaporation of elemental Cu, Zn, Sn, and Se,” Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol. 30, no. 5, p. 051201, 2012.CrossRefGoogle Scholar
Scragg, J. J., Dale, P. J., Colombara, D., and Peter, L. M., “Thermodynamic Aspects of the Synthesis of Thin-Film Materials for Solar Cells,” Chemphyschem: a European journal of chemical physics and physical chemistry, pp. 3035–3046, Apr. 2012.CrossRefGoogle ScholarPubMed
Redinger, A., Berg, D. M., Dale, P. J., and Siebentritt, S., “The consequences of kesterite equilibria for efficient solar cells,” Journal of the American Chemical Society, vol. 133, no. 10, pp. 3320–3, Mar. 2011.CrossRefGoogle ScholarPubMed
Scragg, J. J., Ericson, T., Kubart, T., Edoff, M., and Platzer-Björkman, C., “Chemical Insights into the Instability of Cu 2 ZnSnS 4 Films during Annealing,” Chemistry of Materials, vol. 23, no. 20, pp. 4625–4633, Oct. 2011.CrossRefGoogle Scholar
Snyder, R. C. and Doherty, M. F., “Faceted crystal shape evolution during dissolution or growth,” AIChE Journal, vol. 53, no. 5, pp. 1337–1348, May 2007.CrossRefGoogle Scholar
Hsu, W.-C., Repins, I. L., Beall, C., DeHart, C., Teeter, G., To, B., Yang, Y., and Noufi, R., “The effect of Zn excess on kesterite solar cells,” Solar Energy Materials and Solar Cells, vol. 113, pp. 160–164, Jun. 2013.CrossRefGoogle Scholar
Griffin, B. J., “A comparison of conventional Everhart-Thornley style and in-lens secondary electron detectors: a further variable in scanning electron microscopy.,” Scanning, vol. 33, no. 3, pp. 162–73.CrossRefGoogle Scholar
Berg, D. M., “KESTERITE EQUILIBRIUM REACTION and THE DISCRIMINATION OF SECONDARY PHASES FROM CU2ZNSNS4, ” University of Luxembourg, 2012.Google Scholar