Cu2ZnSn(S, Se)4 solar cell absorbers from diffusion of selenium into annealed Cu2ZnSnS4 absorbers

Small grain compound-sputtered Copper Zinc Tin Sulfide (CZTS) precursors and large grain recrystallized CZTS solar cell absorbers are annealed at sub-recrystallization temperatures in selenium atmosphere to promote selenium diffusion into the CZTS films. Grazing incidence x-ray diffraction and Raman spectroscopy show the presence of two distinct sulfide and mixed sulfide/selenide phases, with the selenide-like phase more prominent at the front surface of the absorber. Only a narrow range of sulfur-to-selenium ratios is observed in the sulfide/selenide phase. Secondary ion mass spectrometry profiles show a compositional sulfur-selenium gradient for samples annealed at 450° C. Scanning electron microscopy with energy dispersive X-ray spectroscopy reveals that the compositional gradient is formed by a spatial distribution of sulfide/selenide grains, embedded in the remaining sulfide absorber. Sulfur-selenium gradients within single absorber grains are not observed, indicating that the mixed sulfide/selenide phase nucleates and grows in competition with the existing sulfide phase, rather than forming by replacement of anions within existing crystals. IV and EQE measurements of devices fabricated from the selenized absorbers support this conclusion.