Fabrication of Cu₂ZnSnS₄ Films by Rapid Thermal Annealing of Cu/ZnSn/Cu Precursor Layer and Their Application to Solar Cells

$Cu_2ZnSnS_4$ thin film have been fabricated by rapid thermal annealing of dc-sputtered metal precursor with Cu/ZnSn/Cu stack in sulfur ambient. A CZTS film with a good uniformity was formed at $560^{\circ}C$ in 6 min. $Cu_2SnS_3$ and $Cu_3SnS_4$ secondary phases were present at $540^{\circ}C$ and a trace amount of $Cu_2SnS_3$ secondary phase was present at $560^{\circ}C$. Single-phase large-grained CZTS film with rough surface was formed at $560^{\circ}C$. Solar cell with best efficiency of 4.7% ($V_{oc}=632mV$, $j_{sc}=15.8mA/cm^2$, FF = 47.13%) for an area of $0.44cm^2$ was obtained for the CZTS absorber grown at $560^{\circ}C$ for 6 min. The existence of second phase at lower-temperature annealing and rough surface at higher-temperature annealing caused the degradation of cell performance. Also poor back contact by void formation deteriorated cell performance. The fill factor was below 0.5; it should be increased by minimizing voids at the CZTS/Mo interface. Our results suggest that CZTS absorbers can be grown by rapid thermal annealing of metallic precursors in sulfur ambient for short process times ranging in minutes.