The interfacial energy level alignment in the copper phthalocyanine/SiO2/p-Si(100) heterojunction has been studied in dark conditions and under illumination. The element-sensitivity of the time-resolved X-ray photoemission provides a real-time picture of the photoexcited carrier dynamics at the interface and within the film, enabling one to distinguish between substrate and molecular contributions. We observe a molecule-to-substrate charge transfer under photoexcitation, which is directly related to the transient modification of the band bending in the substrate due to the surface photovoltage effect. Our results show that charge generation in the heterojunction is driven by the molecular layer in contact with the substrate. The different molecular orientation at the interface creates a new channel for charge injection in the substrate under photoexcitation.
