On the origin of band-tails in kesterite

Kesterite Cu2ZnSn(SxSe1-x)(4) is an attractive earth-abundant material for low-cost thin film photovoltaics with the capability to achieve power production in the terawatt range and therefore to supply a significant part of the global electricity needs. Despite its advantageous optical and electrical properties for photovoltaic applications, the large band tailing causes voltage losses that limit the efficiency of kesterite-based devices. Here we show that the band-tailing originates mainly from band-gap fluctuations attributable to chemical composition variations at nanoscale; while electrostatic fluctuations play a lesser role. Absorption measurement reveal that the Cu-Zn disorder, always present in kesterite Cu2ZnSn(SxSe1-x)(4), is not the main source of the large band tailing. Instead defect clusters having a significant impact on the band-edge energies, e.g. [2Cu(Zn)(-)+Sn-Zn(2+)], are proposed as the main origin for the kesterite band tail.