Growth Kinetics and Atomistic Mechanisms of Native Oxidation of ZrSxSe2-x and MoS2 Crystals.

A thorough understanding of native oxides is essential for designing semiconductor devices. Here, we report a study of the rate and mechanisms of spontaneous oxidation of bulk single crystals of ZrSxSe2-x alloys and MoS2. ZrSxSe2-x alloys oxidize rapidly, and the oxidation rate increases with Se content. Oxidation of basal surfaces is initiated by favorable O2 adsorption and proceeds by a mechanism of Zr-O bond switching, that collapses the van der Waals gaps, and is facilitated by progressive redox transitions of the chalcogen. The rate-limiting process is the formation and out-diffusion of SO2. In contrast, MoS2 basal surfaces are stable due to unfavorable oxygen adsorption. Our results provide insight and quantitative guidance for designing and processing semiconductor devices based on ZrSxSe2-x and MoS2 and identify the atomistic-scale mechanisms of bonding and phase transformations in layered materials with competing anions.

Enhanced transport and transistor performance with oxide seeded high-κ gate dielectrics on wafer-scale epitaxial graphene.

We explore the effect of high-κ dielectric seed layer and overlayer on carrier transport in epitaxial graphene. We introduce a novel seeding technique for depositing dielectrics by atomic layer deposition that utilizes direct deposition of high-κ seed layers and can lead to an increase in Hall mobility up to 70% from as-grown. Additionally, high-κ seeded dielectrics are shown to produce superior transistor performance relative to low-κ seeded dielectrics and the presence of heterogeneous seed/overlayer structures is found to be detrimental to transistor performance, reducing effective mobility by 30-40%. The direct deposition of high-purity oxide seed represents the first robust method for the deposition of uniform atomic layer deposited dielectrics on epitaxial graphene that improves carrier transport.

Integration of hexagonal boron nitride with quasi-freestanding epitaxial graphene: toward wafer-scale, high-performance devices.

Hexagonal boron nitride (h-BN) is a promising dielectric material for graphene-based electronic devices. Here we investigate the potential of h-BN gate dielectrics, grown by chemical vapor deposition (CVD), for integration with quasi-freestanding epitaxial graphene (QFEG). We discuss the large scale growth of h-BN on copper foil via a catalytic thermal CVD process and the subsequent transfer of h-BN to a 75 mm QFEG wafer. X-ray photoelectron spectroscopy (XPS) measurements confirm the absence of h-BN/graphitic domains and indicate that the film is chemically stable throughout the transfer process, while Raman spectroscopy indicates a 42% relaxation of compressive stress following removal of the copper substrate and subsequent transfer of h-BN to QFEG. Despite stress-induced wrinkling observed in the films, Hall effect measurements show little degradation (<10%) in carrier mobility for h-BN coated QFEG. Temperature dependent Hall measurements indicate little contribution from remote surface optical phonon scattering and suggest that, compared to HfO(2) based dielectrics, h-BN can be an excellent material for preserving electrical transport properties. Graphene transistors utilizing h-BN gates exhibit peak intrinsic cutoff frequencies >30 GHz (2.4× that of HfO(2)-based devices).