Seeding atomic layer deposition of high-k dielectrics on epitaxial graphene with organic self-assembled monolayers

The development of high-performance graphene-based nanoelectronics requires the integration of ultrathin and pinhole-free high-k dielectric films with graphene at the wafer scale. Here, we demonstrate that self-assembled monolayers of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) act as effective organic seeding layers for atomic layer deposition (ALD) of HfO₂ and Al₂O₃ on epitaxial graphene on SiC(0001). The PTCDA is deposited via sublimation in ultrahigh vacuum and shown to be highly ordered with low defect density by molecular-resolution scanning tunneling microscopy. Whereas identical ALD conditions lead to incomplete and rough dielectric deposition on bare graphene, the chemical functionality provided by the PTCDA seeding layer yields highly uniform and conformal films. The morphology and chemistry of the dielectric films are characterized by atomic force microscopy, ellipsometry, cross-sectional scanning electron microscopy, and X-ray photoelectron spectroscopy, while high-resolution X-ray reflectivity measurements indicate that the underlying graphene remains intact following ALD. Using the PTCDA seeding layer, metal-oxide-graphene capacitors fabricated with a 3 nm Al₂O₃ and 10 nm HfO₂ dielectric stack show high capacitance values of ∼700 nF/cm² and low leakage currents of ∼5 - 10^-9 A/cm² at 1 V applied bias. These results demonstrate the viability of sublimated organic self-assembled monolayers as seeding layers for high-k dielectric films in graphene-based nanoelectronics.