Effect of p–d hybridization and structural distortion on the electronic properties of AgAlM2(M=S,Se,Te) chalcopyrite semiconductors

We report an ab initio calculation and study of the structural and electronic properties of AgAlM2(M=S,Se,Te) chalcopyrite semiconductors using the density functional theory (DFT)-based self-consistent tight-binding linear muffin tin orbital (TB-LMTO) method. The calculated equilibrium values of the lattice constants, anion displacement parameter (u)(u), tetragonal distortion (η=c/2a)(η=c/2a) and bond lengths are in good agreement with experimental values. Our study suggests these semiconductors to be direct band gap semiconductors with band gaps 1.98 eV, 1.59 eV and 1.36 eV, respectively. These values are in good agreement with experimental values, within the limitation of the local density approximation (LDA). Our explicit study of the effects of anion displacement and p–d hybridization show that the band gap increases by 9.8%, 8.2% and 5.1%, respectively, for AgAlM2(M=S,Se,Te) due to former effect and decreases by 51%, 47% and 42%, respectively, due to latter effect.

Research highlightsAgAlM2(M=S,Se,Te) are direct band gap semiconductors with band gap 1.98, 1.59 and 1.36 eV, respectively.
► The reduction in band gaps due to p–d hybridization are 51%, 47% and 42% for AgAlM2(M=S,Se,Te), respectively.
► There is significant enhancement in the band gap due to structural distortion in all the compounds studied.