A process for producing a slightly Cu-poor thin film of Cu(In,Ga)(Se,S).sub.2 comprises depositing a first layer of (In,Ga).sub.x (Se,S).sub.y followed by depositing just enough Cu+(Se,S) or Cu.sub.x (Se,S) to produce the desired slightly Cu-poor material. In a variation, most, but not all, (about 9
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