The interaction of transparent oxide semiconductors with light is critically important for a range of applications. Persistent effects could be exploited for holographic memory or optically defined circuits. Conversely, they may also be detrimental to device operation. Large, room-temperature persistent photoconductivity (PPC) was discovered in strontium titanate (SrTiO3, STO) after annealing in a hydrogen-containing atmosphere. Barium titanate (BaTiO3, BTO), a ferroelectric material, was recently found to also exhibit PPC. Room-temperature photodarkening was observed in Cu-doped gallium oxide (β-Ga2O3) after exposure to sub-bandgap light. Hydrogen is believed to play a central role in these persistent phenomena. In the proposed model, a photon excites substitutional hydrogen (a proton inside an oxygen vacancy), making the defect unstable. The proton leaves and binds to a host oxygen atom, forming an O-H bond that is observed with infrared spectroscopy. An oxygen vacancy is left behind. Because oxygen vacancies in STO and BTO are shallow donors, this process results in PPC. In β-Ga2O3:Cu, however, the oxygen vacancy neighbors a Cu acceptor. In that case, photoexcitation results in the rare Cu3+ state, which absorbs visible light. The effect can be “erased” by annealing at 300-400°C.
Much excitement has surrounded the accelerating development of β-Ga2O3 for electronics due to its ultrawide band gap, high breakdown voltage, compatibility with many dopants, and comparative ease of producing large substrates via meltgrowth techniques. Our research has focused on growth and characterization of Czochralski (CZ) and vertical gradient freeze (VGF) single crystals of β-Ga2O3 with various dopants, including donors (Zr, Hf, Cr), acceptors (Mg, Zn, Fe, Ni, Cu), and alloying elements (Al). We find in general that doping in CZ and VGF materials can be different and sometimes non-uniform due to the interaction with crucible material (Ir), selective evaporation, and thermal profile. We have also explored the creation and identification of gallium vacancies (VGa) through annealing, by using positron annihilation spectroscopy (PAS), hydrogenated Fourier Transform Infrared (FTIR) spectroscopy, and electrical measurements. Different analysis techniques probe different spatial and depth averages, and thus careful consideration must be given to correctly interpret results and significance of defect concentrations determined. Insights from our work to date are offered, in terms of their applicability to devices.
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