Insights and Implications of Intricate Surface Charge Transfer and sp(3)-Defects in Graphene/Metal Oxide Interfaces

[Image: see text] Adherence of metal oxides to graphene is of fundamental significance to graphene nanoelectronic and spintronic interfaces. Titanium oxide and aluminum oxide are two widely used tunnel barriers in such devices, which offer optimum interface resistance and distinct interface conditions that govern transport parameters and device performance. Here, we reveal a fundamental difference in how these metal oxides interface with graphene through electrical transport measurements and Raman and photoelectron spectroscopies, combined with ab initio electronic structure calculations of such interfaces. While both oxide layers cause surface charge transfer induced p-type doping in graphene, in sharp contrast to TiO(x), the AlO(x)/graphene interface shows the presence of appreciable sp(3) defects. Electronic structure calculations disclose that significant p-type doping occurs due to a combination of sp(3) bonds formed between C and O atoms at the interface and possible slightly off-stoichiometric defects of the aluminum oxide layer. Furthermore, the sp(3) hybridization at the AlO(x)/graphene interface leads to distinct magnetic moments of unsaturated bonds, which not only explicates the widely observed low spin-lifetimes in AlO(x) barrier graphene spintronic devices but also suggests possibilities for new hybrid resistive switching and spin valves.