TY - JOUR
T1 - Effect of Nanocrystal Size and Carbon on Grain Growth during Annealing of Copper Zinc Tin Sulfide Nanocrystal Coatings
AU - Williams, Bryce A.
AU - Smeaton, Michelle A.
AU - Trejo, Nancy D.
AU - Francis, Lorraine F.
AU - Aydil, Eray S.
N1 - Funding Information:
This work was supported primarily by the National Science Foundation through the University of Minnesota MRSEC under Award Number DMR-1420013. Part of this work was carried out in the College of Science and Engineering Characterization Facility, University of Minnesota, which has received capital equipment funding from the NSF through the UMN MRSEC program under Award Number DMR-1420013
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/28
Y1 - 2017/2/28
N2 - Polycrystalline films were prepared by annealing coatings cast from colloidal dispersions of Cu2ZnSnS4 (CZTS) nanocrystals in sulfur vapor. This nanocrystal dispersion-based route is a promising potential low-cost approach for production of low-cost thin-film solar cells. We studied the effects of nanocrystal size, sulfur pressure, and carbon concentration on the microstructure development and grain growth during annealing. Coatings prepared from dispersions of CZTS nanocrystals with an average diameter of either 5 or 35 nm were annealed for 10-60 min at 600 °C in 50 or 500 Torr of sulfur. The CZTS nanocrystal size influenced both the rate and mechanism of grain growth. When coatings composed of 5 nm nanocrystals are annealed, abnormal grain growth forms micrometer-scale CZTS grains on the surface of the coating. In contrast, when CZTS coatings composed of 35 nm nanocrystals are annealed, grains grow uniformly via normal grain growth. Grain growth rates increased with sulfur pressure regardless of the nanocrystal size. The presence of carbon, originating from ligands used to stabilize nanocrystal dispersions, enhances abnormal grain growth, but too much carbon eventually inhibits all grain growth. On the basis of these observations, we propose a mechanism for microstructure development during annealing of CZTS nanocrystal coatings in sulfur. While much research effort has been expended on the reduction of carbon from nanocrystal coatings prior to sulfidation or selenization by means of ligand exchange or preannealing treatments in the belief that reduced carbon concentration aids CZTS microstructure development and solar cell efficiencies, this work indicates that carbon plays a more complex and significant role in CZTS grain growth than previously assumed: carbon may be beneficial or even required for rapid grain growth during sulfidation.
AB - Polycrystalline films were prepared by annealing coatings cast from colloidal dispersions of Cu2ZnSnS4 (CZTS) nanocrystals in sulfur vapor. This nanocrystal dispersion-based route is a promising potential low-cost approach for production of low-cost thin-film solar cells. We studied the effects of nanocrystal size, sulfur pressure, and carbon concentration on the microstructure development and grain growth during annealing. Coatings prepared from dispersions of CZTS nanocrystals with an average diameter of either 5 or 35 nm were annealed for 10-60 min at 600 °C in 50 or 500 Torr of sulfur. The CZTS nanocrystal size influenced both the rate and mechanism of grain growth. When coatings composed of 5 nm nanocrystals are annealed, abnormal grain growth forms micrometer-scale CZTS grains on the surface of the coating. In contrast, when CZTS coatings composed of 35 nm nanocrystals are annealed, grains grow uniformly via normal grain growth. Grain growth rates increased with sulfur pressure regardless of the nanocrystal size. The presence of carbon, originating from ligands used to stabilize nanocrystal dispersions, enhances abnormal grain growth, but too much carbon eventually inhibits all grain growth. On the basis of these observations, we propose a mechanism for microstructure development during annealing of CZTS nanocrystal coatings in sulfur. While much research effort has been expended on the reduction of carbon from nanocrystal coatings prior to sulfidation or selenization by means of ligand exchange or preannealing treatments in the belief that reduced carbon concentration aids CZTS microstructure development and solar cell efficiencies, this work indicates that carbon plays a more complex and significant role in CZTS grain growth than previously assumed: carbon may be beneficial or even required for rapid grain growth during sulfidation.
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U2 - 10.1021/acs.chemmater.6b05058
DO - 10.1021/acs.chemmater.6b05058
M3 - Article
AN - SCOPUS:85014018349
SN - 0897-4756
VL - 29
SP - 1676
EP - 1683
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 4
ER -