Interfacial electronic structure of a hybrid organic-inorganic optical upconverter device: The role of interface states

Organic-inorganic hybrid heterojunctions are critical for the integration of organic electronics with traditional Si and III-V semiconductor microelectronics. The amorphous nature of organic semiconductors eliminates the stringent lattice-matching requirements in semiconductor monolithic growth. However, as of yet it is unclear what driving forces dictate the energy-level alignment at hybrid organic-inorganic heterojunctions. Using photoelectron spectroscopy we investigate the energy-level alignment at the hybrid organic-inorganic heterojunction formed between S-passivated InP(100) and several commonly used hole injection/transport molecules, namely, copper phthalocyanine (CuPc), N,N-'-diphenyl-N,N-'-bis-(1-naphthyl)-1-1(')-biphenyl-4,4(')-diamine (alpha-NPD), and fullerene (C-60). The energy-level alignment at the hybrid organic-inorganic heterojunction is found to be consistent with traditional interface dipole theory, originally developed to describe Schottky contacts. Contrary to conventional wisdom, hole injection from S-passivated InP(100) into an organic semiconductor is found to originate from interface states at or near the Fermi level, rather than from the valance band maximum of the semiconductor. As a result the barrier height for hole injection is defined by the offset between the surface Fermi level of the S-passivated InP(100) and the highest occupied molecular orbital of the organic. This finding sheds new light on the unusual trend in device performance reported in literature for such hybrid organic-inorganic heterojunction devices.