ABSTRACT
The solubility limit of carbon in α-Al2O3 (alumina) equilibrated at 1,600°C under He in a graphite furnace was measured by wavelength-dispersive spectroscopy. Undoped alumina and alumina containing carbon at a concentration resulting in the precipitation of a second phase were prepared and equilibrated at 1,600°C. The undoped alumina was used to quantify the amount of carbon deposited on the surface of samples because of hydrocarbon contamination in the electron microscope, and this background level was removed from the signal measured from carbon-doped samples. The solubility limit of carbon in alumina was found to be 5,300 ± 390 at. ppm, and it is believed that carbon substitutes oxygen as an anion and is charge-compensated by oxygen vacancies. Doping alumina with carbon at concentrations below the solubility limit does not impede densification and reduces grain growth. Doping above the solubility limit hinders densification during sintering.
ABSTRACT
Research efforts in large area graphene synthesis have been focused on increasing grain size. Here, it is shown that, beyond 1 µm grain size, grain boundary engineering determines the electronic properties of the monolayer. It is established by chemical vapor deposition experiments and first-principle calculations that there is a thermodynamic correlation between the vapor phase chemistry and carbon potential at grain boundaries and triple junctions. As a result, boundary formation can be controlled, and well-formed boundaries can be intentionally made defective, reversibly. In 100 µm long channels this aspect is demonstrated by reversibly changing room temperature electronic mobilities from 1000 to 20,000 cm2 V-1 s-1. Water permeation experiments show that changes are localized to grain boundaries. Electron microscopy is further used to correlate the global vapor phase conditions and the boundary defect types. Such thermodynamic control is essential to enable consistent growth and control of two-dimensional layer properties over large areas.
