Issue 6, 2014

Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films

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.

Graphical abstract: Alkali-metal-enhanced grain growth in Cu2ZnSnS4 thin films

Supplementary files

Article information

Article type
Paper
Submitted
19 Dec 2013
Accepted
27 Mar 2014
First published
27 Mar 2014

Energy Environ. Sci., 2014,7, 1931-1938

Author version available

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 and E. S. Aydil, Energy Environ. Sci., 2014, 7, 1931 DOI: 10.1039/C3EE44130J

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