Manipulation of metavalent bonding to stabilize metastable phase:A strategy for enhancing zT in GeSe

Exploration of metastable phases holds profound implications for functional materials.Herein,we engineer the metastable phase to enhance the thermo-electric performance of germanium selenide(GeSe)through tailoring the chemical bonding mechanism.Initially,AgInTe2 alloying fosters a transition from stable orthorhombic to metastable rhombohedral phase in GeSe by substantially promoting p-state electron bonding to form metavalent bonding(MVB).Besides,extra Pb is employed to prevent a transition into a stable hexagonal phase at elevated temperatures by moderately enhancing the degree of MVB.The stabilization of the metastable rhombohedral phase generates an optimized bandgap,sharpened valence band edge,and stimulative band convergence compared to stable phases.This leads to decent carrier concentra-tion,improved carrier mobility,and enhanced density-of-state effective mass,culminating in a superior power factor.Moreover,lattice thermal conductivity is suppressed by pronounced lattice anharmonicity,low sound velocity,and strong phonon scattering induced by multiple defects.Consequently,a maximum zT of 1.0 at 773 K is achieved in(Ge_(0.98)Pb_(0.02)Se)_(0.875)(AgInTe_(2))_(0.125),resulting in a maximum energy conversion efficiency of 4.90%under the temperature difference of 500 K.This work underscores the significance of regulating MVB to stabilize metastable phases in chalcogenides.

Metavalent bonding impacts charge carrier transport across grain boundaries

Understanding the mechanisms underpinning the charge carrier scattering at grain boundaries is crucial to design thermoelectrics and other electronic materials.Yet,this is a very challenging task due to the complex characteristics of grain boundaries and the resulting difficulties in correlating grain boundary structures to local properties.Recent advances in characterizing charge transport across grain boundaries are reviewed,demonstrating how the microstructure,composition,chemical bonding and electrical properties of the same individual grain boundary can be correlated.A much higher potential barrier height is observed in high-angle grain boundaries.This can be ascribed to the larger number density of deep trapping states caused by the local collapse of metavalent bonding.A novel approach to study the influence of the local chemical bonding mechanism around defects on the resulting local properties is thus developed.The results provide insights into the tailoring of electronic properties of metavalently bonded compounds by engineering the characteristics of grain boundaries.

In situ characterization of vacancy ordering in Ge-Sb-Te phase-change memory alloys

Tailoring the degree of structural disorder in Ge-Sb-Te alloys is important for the development of non-volatile phase-change memory and neuro-inspired computing.Upon crystallization from the amorphous phase,these alloys form a cubic rocksalt-like structure with a high content of intrinsic vacancies.Further thermal annealing results in a gradual structural transition towards a layered structure and an insulator-to-metal transition.In this work,we elucidate the atomic-level details of the structural transition in crystalline GeSb_(2)Te_(4) by in situ high-resolution transmission electron microscopy experiments and ab initio density functional theory calculations,providing a comprehensive real-time and real-space view of the vacancy ordering process.We also discuss the impact of vacancy ordering on altering the electronic and optical properties of GeSb_(2)Te_(4),which is relevant to multilevel storage applications.The phase evolution paths in Ge-Sb-Te alloys and Sb_(2)Te_(3)are illustrated using a summary diagram,which serves as a guide for designing phase-change memory devices.