Structural Polymorphism in Kesterite Cu2ZnSnS4: Raman Spectroscopy and First-Principles Calculations Analysis

This work presents a comprehensive analysis of the structural and vibrational properties of the kesterite Cu2ZnSnS4 (CZTS, 14 space group) as well as its polymorphs with the space groups P42c and P42m, from both experimental and theoretical point of views. Multiwavelength Raman scattering measurements performed on bulk CZTS polycrystalline samples were utilized to experimentally determine properties of the most intense Raman modes expected in these crystalline structures according to group theory analysis. The experimental results compare well with the vibrational frequencies that have been computed by first-principles calculations based on density functional theory. Vibrational patterns of the most intense fully symmetric modes corresponding to the P42c structure were compared with the corresponding modes in the I4 CZTS structure. The results point to the need to look beyond the standard phases (kesterite and stannite) of CZTS while exploring and explaining the electronic and vibrational properties of these materials,as well as the possibility of using Raman spectroscopy as an effective technique for detecting the presence of different crystallographic modifications within the same material.