Incongruent reaction of Cu–(InGa) intermetallic precursors in H2Se and H2S

Abstract

The reaction pathways to form Cu(InGa)Se2 or Cu(InGa)S2 films at 450°C from metallic precursors were evaluated by reacting Cu–In–Ga films in H2Se or H2S for 10, 30, or 90min and characterizing the phase composition of the resulting films. A starting composition comprising Cu9(In0.64Ga0.36)4 and In phases was detected by x-ray diffraction in Cu–Ga–In precursors annealed at 450°C in an Ar atmosphere. When the precursors were reacted in H2Se, a graded Cu(InGa)Se2 film was formed with a Ga-rich composition and residual Cu–Ga intermetallics at the interface with the Mo back contact. The intermetallic compounds were observed to evolve from Cu9(In0.64Ga0.36)4 to Cu9Ga4 with increasing selenization time. Reaction in H2S formed inhomogeneous Cu(InGa)S2 with Cu–In intermetallics. The results are consistent with thermochemical predictions of the preferential reaction of In with Se, and Ga with S. These reaction preferences can explain the formation of a graded Cu(InGa)Se2 film during reaction in H2Se and provide a refined understanding of the reaction sequence in two-step H2Se∕H2S processes.