Orbital Topology Controlling Charge Injection in Quantum-Dot-Sensitized Solar Cells

Quantum-dot-sensitized solar cells are emerging as a promising development of dye-sensitized solar cells, where photostable semiconductor quantum dots replace molecular dyes. Upon photoexcitation of a quantum dot, an electron is transferred to a high-band-gap metal oxide. Swift electron transfer is crucial to ensure a high overall efficiency of the solar cell. Using femtosecond time-resolved spectroscopy, we find the rate of electron transfer to be surprisingly sensitive to the chemical structure of the linker molecules that attach the quantum dots to the metal oxide. A rectangular barrier model is unable to capture the observed variation. Applying bridge-mediated electron-transfer theory, we find that the electron-transfer rates depend on the topology of the frontier orbital of the molecular linker. This promises the capability of fine tuning the electron-transfer rates by rational design of the linker molecules.