Abstract

A technique is proposed for introducing microdoses (10−5–10−10 g) of germanium and indium metals into semiconductor compounds by coulometric titration in a solid electrolyte cell. The solid electrolytes that are reversible with respect to germanium cations (the GeSe-GeI2 system containing 5 mol % GeI2) and indium cations (the InCl3-MgCl2 system containing 15 mol % MgCl2, the InCl3-CdCl2 system containing 1.5 mol % CdCl2, and the In2S3-InCl3 system containing 5 mol % InCl3) are chosen, and their electric transport properties are characterized. The optimum conditions for electrochemical doping (temperature, current density), under which the current efficiency reaches 90–100%, are determined. The doping with germanium and indium is performed for nonstoichiometric compounds, such as lead monotelluride, indium sulfide, and ternary chalcogenide spinel Cd1 ± δCr2Se4. The doping efficiency is controlled by measuring the electromotive force of the corresponding electrochemical cells and the Hall effect, as well as using the electrical conductivity method. The solid electrolytes that are reversible with respect to indium are used to determine the standard Gibbs energies of formation of a number of indium-containing semiconductors.

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