Rational design of monolayer transition metal dichalcogenide@fullerene van der Waals photovoltaic heterojunctions...

van der Waals heterojunctions formed by transition metal dichalcogenides (TMDs) and fullerenes are promising candidates for novel photovoltaic devices due to the excellent optoelectronic properties of both TMDs and fullerenes. However, relevant experimental and theoretical investigations remain scarce to the best of our knowledge. Herein, we have first employed static density functional theory (DFT) calculations in combination with time-domain density functional theory (TDDFT) based nonadiabatic dynamics simulations to rationally evaluate the photovoltaic performances of four TMD@fullerene heterostructures, i.e. WSe₂@C₆₀, WSe₂@C₇₀, MoTe₂@C₆₀ and MoTe₂@C₇₀, respectively. Our simulation results indicate that the C₇₀-based heterostructures overall have better photoinduced electron transfer efficiencies than their C₆₀-based counterparts, among which the performance of the WSe₂@C₇₀ heterostructure is the best and the electron transfer from WSe₂ to C₇₀ almost accomplishes within 1 ps. In addition, the large build-in potential of about 0.75 eV of WSe₂@C₇₀ is beneficial for the charge separation processes. Our present work not only selects the van der Waals TMD@fullerene heterojunctions that might have excellent photovoltaic properties, but also paves the way for the rational design of novel heterojunctions with better optoelectronic performances with DFT and TDDFT simulations in the future.