Dynamics of Charge Transfer and Multiple Exciton Generation in the Doped Silicon Quantum Dot–Carbon Nanotube System: Density Functional Theory-Based Computation

摘要

We use the Boltzmann transport equation (BE) to study time evolution of a photoexcited state, including phonon-mediated exciton relaxation, multiple exciton generation (MEG), and energy-transfer processes. BE collision integrals are derived using Kadanoff–Baym–Keldysh many-body perturbation theory (MBPT) based on density functional theory (DFT) simulations, including exciton effects. We apply the method to a nanostructured p –n junction composed of a 1 nm hydrogen-terminated Si quantum dot (QD) doped with two phosphorus atoms (Si_(36)P_(2)H_(42)) adjacent to the (6, 2) single-wall carbon nanotube (CNT) with two chlorine atoms per two unit cells adsorbed to the surface. We find that an initial excitation localized on either the QD or CNT evolves into a transient charge-transfer (CT) state where either electron or hole transfer has taken place. The CT state lifetime is about 40 fs. Also, we study MEG in this system by computing internal quantum efficiency (QE), which is the number of excitons generated from an absorbed photon during relaxation. We predict efficient MEG starting at 3E _(g) ? 1.5 eV and with QE reaching QE = 1.65 at about 5E _(g), where E _(g) ? 0.5 eV is the lowest exciton energy, i.e., the gap. However, we find that including energy transfer and MEG effects suppresses CT state generation.