Optical properties of pseudobinary GeTe, Ge2Sb2Te5, GeSb2Te4, GeSb4Te7, and Sb2Te3 from ellipsometry and density functional theory

We study the optical properties and the band structures of (GeTe, Sb2Te3) pseudobinary compounds experimentally and theoretically by using spectroscopic ellipsometry and density functional calculations. We measure the dielectric functions of (GeTe, Sb2Te3) pseudobinary thin films-GeTe, Ge2Sb2Te5, Ge1Sb2Te4, Ge1Sb4Te7, and Sb2Te3-by using spectroscopic ellipsometry. We anneal the thin films at various temperatures. According to x-ray diffraction, the as-grown thin films are amorphous and the annealed films have metastable and stable crystalline phases. By using standard critical-point model, we obtain the accurate values of the energy gap of the amorphous phase as well as the critical-point energies of the metastable and stable crystalline thin films. The optical gap (indirect band gap) energy of the amorphous (crystalline) thin films is estimated by the equation, (alpha E)(1/2)= A(E-E-opt(ind)). As the Sb-to-Ge atomic ratio increases, the optical (band) gap energy of amorphous) crystalline) phase decreases. Standard critical-point model analysis shows several higher band gaps. The electronic band structures, the dielectric functions, and the absorption coefficients of the thin films are calculated by using density functional theory (DFT) and are compared to the measured ones. The bandstructure calculations show in stable phase that GeTe, Ge2Sb2Te5, and Ge1Sb2Te4 have indirect gap whereas Ge1Sb4Te7 and Sb2Te3 have direct gap. The band gaps of metastable phase have similar behavior. The measured indirect band-gap energies are compared to those of the electronic band-structure calculations. The experimental critical-point energies of the pseudobinary compounds, especially GeTe, match well to those of theoretical calculation. The DFT calculations show that the stable and metastable phases have similar dielectric functions and absorption properties, etc., because of the similarity between the lowest-energy crystal structures for both the stable and metastable phases. However, experimental results show that there exist important differences between those of the stable and metastable phases. We discuss the discrepancy in terms of insufficient ordering of vacancies in the real materials of metastable phase.