We present the investigation of novel metal/organic monolayer/metal heterostructure diodes. Our technique provides well-defined, stable, and reproducible metallic contacts to a self-assembled monolayer of 4-thioacetylbiphenyl with nanoscale area. Electronic transport measurements show a prominent rectifying behavior arising from the asymmetry of the molecular heterostructure. Variable-temperature measurements reveal that thermal emission of electrons over a barrier of 0.22 eV dominates for electron injection from Ti into the organic layer while the transport for electron injection from Au into the organic layer satisfies the formula for hopping conduction.

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