Electronic and Structural Properties of AAl2Se4(A = Ag, Cu, Cd, Zn) Chalcopyrite Semiconductors

TL;DR

This study uses DFT and TB-LMTO methods to analyze the structural and electronic properties of AAl2Se4 chalcopyrite semiconductors, revealing their direct band gaps and the effects of p-d hybridization and structural distortion.

Contribution

First-principles calculations of structural and electronic properties of AAl2Se4 chalcopyrites, including effects of hybridization and distortion, providing detailed insights into their band structure and bonding.

Findings

All compounds are direct band gap semiconductors.

p-d hybridization reduces band gaps significantly.

Structural distortion increases band gaps in these materials.

Abstract

We have studied the structural and electronic properties of defect chalcopyrite semiconductors AAl2Se4 (A = Ag, Cu, Cd, Zn) using Density Functional Theory (DFT) based first principle technique within Tight binding Linear Muffin Tin orbital (TB-LMTO) method. Our calculated structural parameters such as lattice constants, anion displacement parameter (u), tetragonal distortion ({\eta} = c/2a), bond lengths and bulk modulus are in good agreement with other work. Our band structure calculation suggests that these compounds are direct band gap semiconductors having band gaps 2.40, 2.50, 2.46 and 2.82 eV for AAl2 Se4 (A = Ag, Cu, Cd, Zn) respectively. Calculated band gaps are in good agreement with other experimental and theoretical works within LDA limitation. We have made a quantitative estimation of the effect of p-d hybridization and structural distortion on the electronic properties. The reduction in band gap due to p-d hybridization are 19.47%, 21.29%, 0% and 0.7% for AAl2 Se4 (A = Ag, Cu, Cd, Zn) respectively. Increment of the band gap due to structural distortion is 11.62%, 2.45%, 2.92% and 9.30% in case of AgAl2 Se4, CuAl2 Se4, CdAl2 Se4 and ZnAl2 Se4 respectively . We have also discussed the bond nature of all four compounds.