The work reports a comprehensive study of the Seebeck coefficient, electrical resistivity and heat capacity of CuCrS₂ in a wide temperature range of 100–740 K. It was shown that the value of the Seebeck coefficient is significantly affected by the sample treatment procedure. The order-to-disorder (ODT) phase transition was found to cause a metal-insulator transition (MIT). It was established that the ODT diminishes the Seebeck coefficient at high temperatures (T > 700 K). The DFT calculations of the CuCrS₂ electronic structure showed that the localization of copper atoms in octahedral sites makes the band gap vanish due to the MIT. The decrease of CuCrS₂ electrical resistivity in the ODT temperature region corresponds to the MIT.

The comprehensive study of the lanthanide-doped solid solutions CuCr_0.99Ln_0.01S₂ (Ln = La…Lu) magnetic properties was carried out using static magnetochemistry and differential scanning calorimetry techniques. It was shown that magnetic properties of CuCr_0.99Ln_0.01S₂ are significantly affected by the magnetic properties of the lanthanide ion. The magnetic susceptibility and the effective magnetic moment were found to deviate from the Curie-Weiss law in the temperature 90 K below and 50 K above the order-disorder transition at 695 K. The observed behavior of the temperature dependence of the effective magnetic moment in the order-disorder transition temperature region was described as a result of copper atoms redistribution over different types of the crystallographic sites.

The atom oxidation states were determined using the binding energies of the core S2p-, Cu2p-, Cr2p-, and Ln3d-levels in CuCr_0.99Ln_0.01S₂ (Ln = Dy–Lu) solid solutions. The charge distribution on the matrix elements (Cu, Cr, and S) remained unaffected after cationic substitution. The sulfur atoms were found to be in the S²⁻ oxidation state, the copper–Cu⁺, and the chromium–Cr³⁺. The cationic substitution of the initial CuCrS₂-matrix occurred via the isovalent mechanism. The obtained results were compared with the electrophysical properties for CuCr_0.99Ln_0.01S₂. The measured carrier concentration was from 10¹⁷ to 10¹⁸ cm⁻³. The largest Seebeck coefficient value of 157 µV/K was measured for CuCr_0.99Yb_0.01S₂ at 500 K. The cationic substitution with lanthanides allowed one to enhance the Seebeck coefficient of the initial CuCrS₂-matrix.