Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films

M. Johnson, S. V. Baryshev, E. Thimsen, M. Manno, X. Zhang, I. V. Veryovkin, C. Leighton, Eray Aydil

Research output: Contribution to journalArticle

Abstract

The highest efficiency solar cells based on copper zinc tin sulfide (CZTS), a promising photovoltaic material comprised of earth abundant elements, are built on soda lime glass (SLG), a substrate which contains many impurities, including Na and K. These impurities may diffuse into CZTS films during processing and affect film structure and properties. We have investigated the effects of these impurities on the microstructure of CZTS films synthesized by ex situ sulfidation of Cu-Zn-Sn alloy films co-sputtered on SLG, Pyrex, and quartz. CZTS films synthesized on SLG were found to have significantly larger grains than films grown on the other substrates. Furthermore, we show that by including a bare additional piece of SLG in the sulfidation ampoule, the grain size of films grown on nominally impurity-free quartz increases from 100's of nm to greater than 1 μm. This demonstrates conclusively that impurities in SLG volatilize in S-containing atmospheres and incorporate into nearby CZTS films synthesized on other substrates. Impurity concentrations in these CZTS films were examined using depth profiling with time-of-flight secondary ion mass spectrometry (TOF-SIMS). Of all the impurities present in SLG, the TOF-SIMS experiments implicated Na, K, and Ca as possible elements responsible for the enhanced grain growth. To investigate the effects of these impurities individually, we introduced very small and controllable amounts of Na, K, or Ca into the sulfidation ampoule during CZTS synthesis. Impurity amounts as low as 10-6 moles of Na or 10-7 moles of K resulted in a dramatic increase in grain size, from 100's of nm to several microns, for films deposited on quartz, while Ca loading had no visible effect on the final microstructure. Based on this vapor transport mechanism, we thus demonstrate an approach for delivering precisely controlled amounts of specific impurities into CZTS films on arbitrary substrates to facilitate large-grain growth. This journal is

Original languageEnglish (US)
Pages (from-to)1931-1938
Number of pages8
JournalEnergy and Environmental Science
Volume7
Issue number6
DOIs
StatePublished - Jan 1 2014

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Alkali Metals
alkali metal
Alkali metals
Grain growth
tin
Tin
Impurities
Thin films
Zinc
Copper
zinc
sulfide
Lime
copper
lime
glass
Glass
Quartz
substrate
Substrates

ASJC Scopus subject areas

  • Environmental Chemistry
  • Renewable Energy, Sustainability and the Environment
  • Nuclear Energy and Engineering
  • Pollution

Cite this

Johnson, M., Baryshev, S. V., Thimsen, E., Manno, M., Zhang, X., Veryovkin, I. V., ... Aydil, E. (2014). Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films. Energy and Environmental Science, 7(6), 1931-1938. https://doi.org/10.1039/c3ee44130j

Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films. / Johnson, M.; Baryshev, S. V.; Thimsen, E.; Manno, M.; Zhang, X.; Veryovkin, I. V.; Leighton, C.; Aydil, Eray.

In: Energy and Environmental Science, Vol. 7, No. 6, 01.01.2014, p. 1931-1938.

Research output: Contribution to journalArticle

Johnson, M, Baryshev, SV, Thimsen, E, Manno, M, Zhang, X, Veryovkin, IV, Leighton, C & Aydil, E 2014, 'Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films', Energy and Environmental Science, vol. 7, no. 6, pp. 1931-1938. https://doi.org/10.1039/c3ee44130j
Johnson M, Baryshev SV, Thimsen E, Manno M, Zhang X, Veryovkin IV et al. Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films. Energy and Environmental Science. 2014 Jan 1;7(6):1931-1938. https://doi.org/10.1039/c3ee44130j
Johnson, M. ; Baryshev, S. V. ; Thimsen, E. ; Manno, M. ; Zhang, X. ; Veryovkin, I. V. ; Leighton, C. ; Aydil, Eray. / Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films. In: Energy and Environmental Science. 2014 ; Vol. 7, No. 6. pp. 1931-1938.
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