Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu₂SnS₃, Cu₂ZnSnS₄, and Cu₂ZnSnSe₄ Chalcogenides for Thermoelectric Applications

Copper-based chalcogenides have emerged as promising thermoelectric materials due to their high thermoelectric performance, tunable transport properties, earth abundance and low toxicity. We have presented an overview of experimental results and first-principal calculations investigating the thermoelectric properties of various polymorphs of Cu2SnS3 (CTS), Cu2ZnSnS4 (CZTS), and Cu2ZnSnSe4 (CZTSe) synthesized by high-energy reactive mechanical alloying (ball milling). Of particular interest are the disordered polymorphs of these materials, which exhibit phonon-glass–electron-crystal behavior—a decoupling of electron and phonon transport properties. The interplay of cationic disorder and nanostructuring leads to ultra-low thermal conductivities while enhancing electronic transport. These beneficial transport properties are the consequence of a plethora of features, including trap states, anharmonicity, rattling, and conductive surface states, both topologically trivial and non-trivial. Based on experimental results and computational methods, this report aims to elucidate the details of the electronic and lattice transport properties, thereby confirming that the higher thermoelectric (TE) performance of disordered polymorphs is essentially due to their complex crystallographic structures. In addition, we have presented synchrotron X-ray diffraction (SR-XRD) measurements and ab initio molecular dynamics (AIMD) simulations of the root-mean-square displacement (RMSD) in these materials, confirming anharmonicity and bond inhomogeneity for disordered polymorphs

Investigating the Electromechanical Behavior of Unconventionally Ferroelectric Hf0.5Zr0.5O2‐Based Capacitors Through Operando Nanobeam X‐Ray Diffraction

Abstract Understanding various aspects of ferroelectricity in hafnia‐based nanomaterials is of vital importance for the development of future nonvolatile memory and logic devices. Here, the unconventional and weak electromechanical response of epitaxial La0.67Sr0.33MnO3/Hf0.5Zr0.5O2/La0.67Sr0.33MnO3 ferroelectric capacitors is investigated, via the sensitivity offered by nanobeam X‐ray diffraction experiments during application of electrical bias. It is shown that the pristine rhombohedral phase exhibits a linear piezoelectric effect with piezoelectric coefficient (|d33|) ≈ 0.5–0.8 pmV−1. It is found that the piezoelectric response is suppressed above the coercive voltage. For higher voltages, and with the onset of DC conductivity throughout the capacitor, a second‐order effect is observed. The work sheds light into the electromechanical response of rhombohedral Hf0.5Zr0.5O2 and suggests its (un)correlation with ferroelectric switching