Charge Injection Across Self-Assembly Monolayers in Organic Field-Effect Transistors:  Odd−Even Effects

We investigate the role of self-assembly monolayers in modulating the response of organic field-effect transistors. Alkanethiol monolayers of chain length n are self-assembled on the source and drain electrodes of pentacene field-effect transistors. The charge carrier mobility μ exhibits large fluctuations correlated with odd−even n. For n < 8, μ increases by 1 order of magnitude owing to the decrease of the hole injection barrier and the improved molecular order at the organic−metallic interface. For n ≥ 8, μ decays exponentially with an inverse decay length β = 0.6 Å-1. Our results show that (i) charge injection across the interface occurs by through-bond tunneling of holes mediated by the alkanethiol layer; (ii) in the long-chain regime, the charge injection across the alkanethiol monolayer completely governs the transistor response; (iii) the transistor is a sensitive gauge for probing charge transport across single monolayers. The odd−even effect is ascribed to the anisotropic coupling between the alkanethiol terminal σ bond and the HOMO level of ordered pentacene molecules.