Vol. 7, Issue 6, Part A (2025)

Organic semiconductor-MXene heterostructures have emerged as versatile materials for energy storage and optoelectronic applications because of their tunable band alignment, high surface area, and superior charge transport properties. Among these, perylene-based organic semiconductors integrated with titanium carbide MXenes (Ti₃C₂Tx, where Tx represents surface groups -O, -OH, and -F) show particular promise, owing to their stable interfaces that promote efficient charge separation and storage. This work presents a theoretical study of the electronic band alignment and charge storage capacity of perylene-Ti₃C₂Tx heterostructures using density functional theory (DFT) and electronic structure analysis. The results reveal a type-II band alignment, with the perylene conduction band minimum aligned favorably with the MXene Fermi level, enabling efficient electron transfer. Surface functionalization strongly affects band bending, interface dipole formation, and electronic coupling. Oxygen-terminated Ti₃C₂Tx provides the most favorable conditions for charge transfer, whereas fluorine terminations suppress conductivity through electron localization. Projected density of states (PDOS) analysis confirms strong hybridization between perylene π orbitals and Ti-d states, enhancing interfacial communication. Charge density difference maps further show significant redistribution, indicating improved charge storage relative to pristine perylene or Ti₃C₂Tx. Capacitance values estimated from the density of states near the Fermi level suggest that perylene-Ti₃C₂Tx heterostructures could function as high-performance electrodes for supercapacitors and hybrid storage systems. Overall, the findings emphasize the importance of surface terminations and molecular orientation in designing optimized organic semiconductor-MXene heterostructures for future technologies.