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A series of samples in the system Al2S3–In2S3 in the In-rich region have been synthesized and studied by X-ray diffraction. At the lowest values of the Al/In (molar) ratio, r, the existing phase, β, is isostructural with the room-temperature, ordered, tetragonal phase of In2S3. As the Al content increases a progressive disorder of cations takes place. For r≳l/10 this disorder is completed and β is replaced with a phase, denoted as α, which is isostructural with the first high-temperature, cubic, phase of In2S3. The unit-cell parameters of the ternary β and α alloys, (AlxIn1 − x)2S3, decrease linearly as the Al content increases. From r≳1/3 to r~ 2/3 there is a two-phase region, α + γ1. The hexagonal phase γ1 is isostructural with AlInS3, appearing at r = 1, and with the second high-temperature, γ, modification of In2Se3. The phase γ1 also exists in the systems Ga2Se3–In2Se3 and Al2Se3–In2Se3 in the In-rich region for the (Ga, Al)/In (molar) ratio greater than ~ 1/50.

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