In Situ Microgravimetric Study of Ion Exchanges in the Ternary Cu-In-S System Prepared by Atomic Layer Deposition

摘要

Reaction mechanisms during the growth of multinary compounds by atomic layer deposition can be complex, especially for sulfide materials. For instance, the deposition of copper indium disulfide (CuInS ) shows a non-direct correlation between the cycle ratio, the growth per cycle of each binary growth cycles, i.e., Cu S and In S , and the film composition. This evidences side reactions that compete with the direct Atomic Layer Deposition (ALD) growth reactions and makes the deposition of large films very challenging. To develop a robust upscalable recipe, it is essential to understand the chemical surface reactions. In this study, reaction mechanisms in the Cu-In-S ternary system were investigated in-situ by using a quartz crystal microbalance system to monitor mass variations. Pure binary indium sulfide (In S ) and copper sulfide (Cu S) thin film depositions on Al O substrate were first studied. Then, precursors were transported to react on Cu S and In S substrates. In this paper, gas-phase ion exchanges are discussed based on the recorded mass variations. A cation exchange between the copper precursor and the In S is highlighted, and a solution to reduce it by controlling the thickness deposited for each stack of binary materials during the CuInS deposition is finally proposed.