An interrogation of the zinc oxide–gallium oxide phase space by plasma enhanced chemical vapor deposition

Abstract

Polycrystalline metal oxide thin films were deposited by mixing combinations of diethylzinc and trimethylgallium into an oxygen plasma. Plasma-enhanced chemical vapor deposition was shown to be a flexible tool for materials exploration, as the entire zinc–gallium-oxide phase space was explored by simply altering precursor flow rates. Film identification was performed using measurements of intrinsic optical properties as well as X-ray diffraction. The compounds synthesized included zinc oxide, gallium-doped zinc oxide (ZnO:Ga), the spinel ZnGa2O4, and amorphous gallium oxide. A phase diagram was established for PECVD synthesis as a function of the organometallic precursor composition. It was found that gallium addition had a profound impact on both the deposition rate and resistivity of the films. Small levels the gallium addition produced an order of magnitude improvement in both deposition rate and electrical properties. When the gallium fraction was >50% the deposition rate saturated and the films were insulating. Optical emission spectroscopy was used to probe the plasma chemistry of the system. It was shown to be quite complex, typified by the example that decreasing the diethylzinc fraction in the feedstream dramatically increased the density of atomic zinc in the plasma.