Substitutional Doped GeSe: Tunable Oxidative States with Strain Engineering

TL;DR

This study uses first-principles calculations to investigate substitutional doping in GeSe, revealing how different metallic dopants and strain influence electronic states, oxidation levels, and potential applications in resistive switching and photocatalysis.

Contribution

It systematically analyzes various metallic dopants in GeSe and their effects on electronic properties and oxidation states, including strain-induced state shifts, offering insights for nanoelectronic applications.

Findings

Al doping suggests high mobility and resistive switching potential.

Localized states appear with Fe, Co, Ni doping, affecting electronic properties.

Au doping enhances photocatalytic and plasmonic features.

Abstract

Layered chalcogenide materials have a wealth of nanoelectronics applications like resistive switching and energy-harvesting such as photocatalyst owing to rich electronic, orbital, and lattice excitations. In this work, we explore monochalcogenide germanium selenide GeSe with respect to substitutional doping with 13 metallic cations by using first-principles calculations. Typical dopants including s-shell (alkali elements Li and Na), p-shell (Al, Pb and Bi), 3d (Fe, Cu, Co and Ni), 4d (Pd and Ag) and 5d (Au and Pt) elements are systematically examined. Amongst all the cationic dopants, Al with the highest oxidation states, implying a high mobility driven by electric field, and Al-doped GeSe may be a promising candidate for novel resistive switching devices. We show that there exist many localized induced states in the band gap of GeSe upon doping Fe, Co, or Ni, while for Cu, Ag, and Au cases there is no such states in the gap. The Ag and Cu are + 0.27 and + 0.35 charged respectively and the positive charges are beneficial for field-driven motion in GeSe. In contrast, Au is slightly negatively charged renders Au-doped GeSe a promising photocatalyst and enhanced surface plasmon. Moreover, we explore the coexistence of dopant and strain in GeSe and find dynamical adjustments of localized states in GeSe with levels successive shifting upward/downward with strain. This induces dynamic oxidative states of the dopants under strain which should be quite popular in composites where motion of metal adatoms causes significant deformation.