Effects of Mn and Co Doping on the Electronic Structure and Optical Properties of Cu2ZnSnS4

The electronic structures and optical properties of Mn-doped, Co-doped, and (Mn,Co)-co-doped Cu2ZnSnS4 were calculated and analyzed using the first-principles pseudopotential plane-wave approach. The results indicate that doping with Mn or Co increases the bond population and decreases the bond length of the S-Mn and S-Co bonds, respectively, enhancing their covalent character. The undoped Cu2ZnSnS4 exhibits a bandgap of 0.16 eV, whereas doping with Mn or Co introduces impurity levels near the Fermi level, resulting in bandgap narrowing. Within the visible light spectrum, the static dielectric constant ε1(0) reaches its maximum value of 67.7 under co-doping conditions, and the absorption coefficient also attains its maximum value of 6.7 × 104 cm−1 under co-doping. Doping with Mn and Co induces a redshift (shift towards lower energy) in both the absorption peaks and dielectric function peaks, concomitantly increasing the probability of photon-induced electronic transitions. Conversely, doping shifts the reflectivity peaks towards higher energies (blue-shift), with the most pronounced blue-shift occurring under co-doping; the strongest reflectivity peaks remain below 43%. A prominent conductivity peak is observed at 1.7 eV. Doping shifts this peak position towards lower energies, with the maximum peak intensity reaching 1.6. These findings collectively suggest that Mn and Co doping effectively modulate key optical properties of Cu2ZnSnS4, such as its band gap and absorption coefficient, constituting an effective strategy for enhancing its optoelectronic transport characteristics.