Temperature dependence of phonon modes, dielectric functions, and interband electronic transitions in Cu ₂ZnSnS ₄ semiconductor films

The quaternary semiconductor Cu ₂ZnSnS ₄ (CZTS) has attracted a lot of attention as a possible absorber material for solar cells due to its direct bandgap and high absorption coefficient. In this study, photovoltaic CZTS nanocrystalline film with a grain size of about 10 nm has been grown on a c-plane sapphire substrate by radio-frequency magnetron sputtering. With increasing the temperature from 86 to 323 K, the A ₁ phonon mode shows a red shift of about 9 cm ^-1 due to the combined effects of thermal expansion and the anharmonic coupling to the other phonons. Optical and electronic properties of the CZTS film have been investigated by transmittance spectra in the temperature range of 8-300 K. Near-infrared-ultraviolet dielectric functions have been extracted with the Tauc-Lorentz dispersion model. The fundamental band gap E ₀, and higher-energy critical points E ₁ and E ₂ are located at 1.5, 3.6, and 4.2 eV, respectively. Owing to the influences of electron-phonon interaction and the lattice expansion, the three interband transitions present a red shift trend with increasing temperature. It was found that the absorption coefficient in the visible region increases due to the modifications of electronic band structures. The detailed study of the optical properties of CZTS film can provide an experimental basis for CZTS-based solar cell applications.