We used depth-resolved cathodoluminescence spectroscopy and surface photovoltage spectroscopy to measure the effects of near-surface plasma processing and neutron irradiation on native point defects in β-Ga2O3. The near-surface sensitivity and depth resolution of these optical techniques enabled us to identify spectral changes associated with removing or creating these defects, leading to identification of one oxygen vacancy-related and two gallium vacancy-related energy levels in the β-Ga2O3 bandgap. The combined near-surface detection and processing of Ga2O3 suggests an avenue for identifying the physical nature and reducing the density of native point defects in this and other semiconductors.

Gallium oxide (β-Ga2O3) is an emerging semiconductor with relevant properties for power electronics, solar-blind photodetectors, and some sensor applications due to its ultra-wide bandgap and developing technology base for high quality, melt-based substrate growth and thick, low-doped homoepitaxial layers. Of critical importance for the commercialization of this potentially important material is understanding of doping mechanisms in the monoclinic lattice, where two types of Ga sites and three types of O sites have been identified. A critical literature review of doping and defects of the monoclinic β-phase of gallium oxide is provided in this work. Theoretical fundamentals of both donor and acceptor doping in Ga2O3 are reviewed. Advances in doping of epitaxial Ga2O3 with a focus on molecular beam epitaxy and ion implantation are critically examined. As doping is fundamentally related to defects, particularly in this material, a review of defect characterization by optical and electrical spectroscopic methods is provided as well. P-type doping, one of the fundamental challenges for Ga2O3, is discussed in terms of first-principles calculations and ion implantation of known acceptors such as Mg and N.

Ga 2 O 3 has emerged as a promising material for next-generation power electronics. Beyond the most stable and studied β phase, metastable α-, ε-, and κ-Ga 2 O 3 have unique characteristics such as larger bandgaps, potential alloying for dopant and band engineering, and polarization, all of which can be leveraged in electronic device applications. Plasma-enhanced atomic layer deposition (PEALD) is a conformal, energy-enhanced synthesis method with many advantages including reduced growth temperatures, access to metastable phases, and improved crystallinity. In this study, PEALD was employed to deposit highly resistive, crystalline Ga 2 O 3 films from 265 to 475 °C on cplane sapphire substrates. Crystallinity, atypical at these low growth temperatures, was presumably due to the high flux of energetic ions to the growth surface independent of other growth parameters. Phase selectivity of β, α, ε(κ)-Ga 2 O 3 was demonstrated as a function of plasma gas composition, gas flow and pressure during the plasma pulse, as well as growth temperature. Factors such as atomic oxygen generation and the flux of energetic ions were found to have a significant impact on the ability to attain metastable phases. Optimum films of each phase were fully characterized to determine the feasibility of PEALD Ga 2 O 3 films. While both highquality, single-phase βand α-Ga 2 O 3 films were achieved, ε-Ga 2 O 3 films were not able to be completely isolated and even under the best conditions contained components of βand κ-Ga 2 O 3 as identified by transmission electron microscopy. Trends suggest that this could be a limitation of the underlying substrate or reactor configuration.

Surface states that induce depletion regions are commonly believed to control the transport of charged carriers through semiconductor nanowires. However, direct, localized optical, and electrical measurements of ZnO nanowires show that native point defects inside the nanowire bulk and created at metal–semiconductor interfaces are electrically active and play a dominant role electronically, altering the semiconductor doping, the carrier density along the wire length, and the injection of charge into the wire. We used depth-resolved cathodoluminescence spectroscopy to measure the densities of multiple point defects inside ZnO nanowires, substitutional Cu on Zn sites, zinc vacancy, and oxygen vacancy defects, showing that their densities varied strongly both radially and lengthwise for tapered wires. These defect profiles and their variation with wire diameter produce trap-assisted tunneling and acceptor trapping of free carriers, the balance of which determines the low contact resistivity (2.6 × 10–3 Ω·cm–2) ohmic, Schottky (Φ ≥ 0.35 eV) or blocking nature of Pt contacts to a single nano/microwire. We show how these defects can now be manipulated by ion beam methods and nanowire design, opening new avenues to control nanowire charge injection and transport.

This review presents recent research advances in measuring native point defects in ZnO nanostructures, establishing how these defects affect nanoscale electronic properties, and developing new techniques to manipulate these defects to control nano- and micro- wire electronic properties. From spatially-resolved cathodoluminescence spectroscopy, we now know that electrically-active native point defects are present inside, as well as at the surfaces of, ZnO and other semiconductor nanostructures. These defects within nanowires and at their metal interfaces can dominate electrical contact properties, yet they are sensitive to manipulation by chemical interactions, energy beams, as well as applied electrical fields. Non-uniform defect distributions are common among semiconductors, and their effects are magnified in semiconductor nanostructures so that their electronic effects are significant. The ability to measure native point defects directly on a nanoscale and manipulate their spatial distributions by multiple techniques presents exciting possibilities for future ZnO nanoscale electronics.