Growth, Characterization and Contacts to Ga2O3 Single Crystal Substrates and Epitaxial Layers
Gallium Oxide (Ga2O3) has emerged over the last decade as a new up-and-coming alternative to traditional wide bandgap semiconductors. It exists as five polymorphs (α-, β-, γ-, δ-, and ε-Ga2O3), of which β-Ga2O3 is the thermodynamically stable form, and the most extensively studied phase. β-Ga2O3 has a wide bandgap of ~4.8 eV and exhibits a superior figure-of-merit for power devices compared to other wide bandgap materials, such as SiC and GaN. These make β-Ga2O3 a promising candidate in a host of electronic and optoelectronic applications. Recent advances in β-Ga2O3 single crystals growth have also made inexpensive β-Ga2O3 single crystal grown from the melt a possibility in the near future. Despite the plethora of literature on β-Ga2O3-based devices, understanding of contacts to this material --- a device component that fundamentally determines device characteristics — remained lacking. For this research, ohmic and Schottky metal contacts to Sn-doped β-Ga2O3 (-201) single crystal substrates, unintentionally doped (UID) homoepitaxial β-Ga2O3 (010) on Sn-doped β-Ga2O3 grown by molecular beam epitaxy (MBE), and UID heteroepitaxial β-Ga2O3 (-201) epitaxial layers on c-plane sapphire by metal-organic chemical vapor deposition (MOCVD) were investigated. Each of the substrates was characterized for their structural, morphological, electrical, and optical properties, the results will be presented in the following document. Nine metals (Ti, In, Ag, Sn, W, Mo, Sc, Zn, and Zr) with low to moderate work functions were studied as possible ohmic contacts to β-Ga2O3. It was found that select metals displayed either ohmic (Ti and In) or pseudo-ohmic (Ag, Sn and Zr) behavior under certain conditions. However, the morphology was often a problem as many thin film metal contacts dewetted the substrate surface. Ti with a Au capping layer with post-metallization annealing treatment was the only consistently reliable ohmic contact to β-Ga2O3. It was concluded that metal work function is not a dominant factor in forming an ohmic contact to β-Ga2O3 and that limited interfacial reactions appear to play an important role. Prior to a systematic study of Schottky contacts to β-Ga2O3, a comparison of the effects of five different wet chemical surface treatments on the β-Ga2O3 Schottky diodes was made. It was established that a treatment with an organic solvent clean followed by HCl, H2O2 and a deionized water rinse following each step yielded the best results. Schottky diodes based on (-201) β-Ga2O3 substrates and (010) β-Ga2O3 homoepitaxial layers were formed using five different Schottky metals with moderate to high work functions: W, Cu, Ni, Ir, and Pt. Schottky barrier heights (SBHs) calculated from current-voltage (I-V) and capacitance-voltage (C-V) measurements of the five selected metals were typically in the range of 1.0 – 1.3 eV and 1.6 – 2.0 eV, respectively, and showed little dependence on the metal work function. Several diodes also displayed inhomogeneous Schottky barrier behavior at room temperature. The results indicate that bulk or near-surface defects and/or unpassivated surface states may have a more dominant effect on the electrical behavior of these diodes compared to the choice of Schottky metal and its work function. Lastly, working with collaborators at Structured Materials Industries (SMI) Inc., heteroepitaxial films of Ga2O3 were grown on c-plane sapphire (001) using a variety of vapor phase epitaxy methods, including MOVPE, and halide vapor phase epitaxy (HVPE). The stable phase β-Ga2O3 was observed when grown using MOVPE technique, regardless of precursor flow rates, at temperatures ranging between 500 – 850 °C. With HVPE growth techniques, instead of the stable β-phase, we observed the growth of the metastable α- and ε-phases, often a combination of the two. Cross-sectional transmission electron microscopy (TEM) shows the better lattice matched α-phase first growing semi-coherently on the c-plane sapphire substrate, followed by domain matched epitaxy of ε-Ga2O3 on top. Secondary ion mass spectrometry (SIMS) revealed that epilayers forming the ε-phase contain higher concentrations of chlorine, which suggests that compressive stress due to Cl- impurities may play a role in the growth of ε-Ga2O3 despite it being less than thermodynamically favorable.