Orbital hybridization induced band offset phenomena in NixCd1-xO thin films

TL;DR

This study investigates how Ni doping in NixCd1-xO thin films influences band offset phenomena through orbital hybridization modification, revealing changes in lattice structure, electronic properties, and band gap renormalization.

Contribution

It provides a comprehensive analysis of cationic impurity effects on band offsets and orbital hybridization in NixCd1-xO thin films, combining experimental and simulation approaches.

Findings

Ni doping causes a monotonic shift in diffraction peaks.

Orbital hybridization decreases with increasing Ni concentration.

Band gap renormalization and reduced effective mass are observed.

Abstract

We present the cationic impurity assisted band offset phenomena in NixCd1-xO (x= 0, 0.02, 0.05, 0.1, 0.2, 0.4, 0.8, 1) thin films and further discussed in the light of orbital hybridization modification. Compositional and structural studies revealed that cationic substitution of Cd2+ by Ni2+ ions leads to a monotonic shift in (220) diffraction peak, indicating the suppression of lattice distortion while evolution of local strain with increasing Ni concentration mainly associated to the mismatch in electro-negativity of Cd2+ and Ni2+ ion. In fact, Fermi level pinning towards conduction band minima takes place with increasing Ni concentration at the cost of electronically compensated oxygen vacancies, resulting modification in the distribution of carrier concentration which eventually affects the band edge effective mass of conduction band electrons and further endorses band gap renormalization. Besides that, the appearance of longitudinal optical (LO) mode at 477 cm-1 as manifested by Raman spectroscopy also indicate the active involvement of electron-phonon scattering whereas modification in local coordination environment particularly anti-crossing interaction in conjunction with presence of satellite features and shake-up states with Ni doping is confirmed by X-ray absorption near-edge and X-ray photoelectron spectroscopy studies. These results manifest the gradual reduction of orbital hybridization with Ni incorporation, leading to decrement in the band edge effective mass of electron. Finally, molecular dynamics simulation reflects 13% reduction in lattice parameter for NiO thin film as compared to undoped one while projected density of states calculation further supports the experimental observation of reduced orbital hybridization with increasing Ni concentration.