Defect chemistry for extrinsic doping in ductile semiconductor α-Ag_(2)S

As a new type of inorganic ductile semiconductor,silver sulfide(α-Ag_(2)S)has garnered a plethora of interests in recent years due to its promising applications in flexible electronics.However,the lack of detailed defect calculations and chemical intuition has largely hindered the optimization of material's performance.In this study,we systematically investigate the defect chemistry of extrinsic doping inα-Ag_(2)S using first-principles calculations.We computationally examine a broad suite of 17 dopants and find that all aliovalent elements have extremely low doping limits(<0.002%)in α-Ag_(2)S,rendering them ineffective in tuning the electron concentrations.In contrast,the isovalent elements Se and Te have relatively high doping limits,being consistent with the experimental observations.While the dopant Se or Te itself does not provide additional electrons,its introduction has a significant impact on the band gap,the band-edge position,and especially the formation energy of Ag interstitials,which effectively improve the electron concentrations by 2–3 orders of magnitudes.The size effects of Se and Te doping are responsible for the more favorable Ag interstitials in Ag_(2)S_(0.875)Se_(0.125) and Ag_(2)S_(0.875)Te_(0.125) with respect to pristine Ag2S.This work serves as a theoretical foundation for the rational design of Ag_(2)S-based functional materials.

Non-layered InSe nanocrystalline bulk materials with ultra-low thermal conductivity

Exploring new prototypes for a given chemical composition is of great importance and interest to several disciplines.As a famous semiconducting binary compound,InSe usually exhibits a two-dimensional layered structure with decent physical and mechanical properties.However,it is less noticed that InSe can also adopt a monoclinic structure,denoted as mcl-InSe.The synthesis of such a phase usually re-quires high-pressure conditions,and the knowledge is quite scarce on its chemical bonding,lattice dynamics,and thermal transport.Here in this work,by developing a facile method combining me-chanical alloying and spark plasma sintering,we successfully synthesize mcl-InSe bulks with well-crystallized nanograins.The chemical bonding of mcl-InSe is understood as compared with layered InSe via charge analysis.Low cut-off frequencies of acoustic phonons and several low-lying optical modes are demonstrated.Noticeably,mcl-InSe exhibits a low room-temperature thermal conductivity of 0.6 W·m^(-1)·K^(-1),which is smaller than that of other materials in the IneSe system and many other selenides.Low-temperature thermal analyses corroborate the role of nanograin boundaries and low-frequency optical phonons in scattering acoustic phonons.This work provides new insights into the non-common prototype of the InSe binary compound with potential applications in thermoelectrics or thermal insulation.