Molecular Precursor Approach to Sulfur-Free CuInSe: Replacing Thiol Coordination in Soluble Metal Complexes.

Solution-processed CuInSe films have generally relied on sulfide or sulfoselenide precursor films that, during the grain growth process, hamper the growth of thicker films and lead to the formation of a fine-grain layer. However, recent research has indicated that sulfur reduction in the precursor film modifies the grain growth mechanism and may enable the fabrication of thicker absorbers that are free of any fine-grain layer. In this work, we pursue direct solution deposition of sulfur-free CuInSe films from the molecular precursor approach. To this end, we tune the amine-thiol reactive solvent system and study the changes to the resulting soluble complexes through a combination of analytical techniques. We show that by reactively dissolving indium(III) selenide and selenium in solutions of -butylamine and 1,2-ethanedithiol, a metal thiolate species is formed, and that this metal thiolate can be modified by isolation from the thiol-containing solvent via precipitation. As the quantity of selenium in the ink increases, the thiol content in the complex decreases, eventually producing soluble [InSe] species. Extending this method to be used with copper selenide as a copper source, molecular precursor inks can be made for solution-processed, sulfur-free CuInSe films. We then show that these CuInSe precursor films can be fully coarsened without a fine-grain layer formation, even at the desired thicknesses of 2 μm and greater.