Gallium Vacancies in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e Crystals

The gallium vacancy, an intrinsic acceptor, is identified in β-Ga2O3 using electron paramagnetic resonance (EPR). Spectra from doubly ionized (V2−Ga) and singly ionized (V−Ga) gallium vacancies are observed at room temperature, without photoexcitation, after an irradiation with high-energy neutrons. The V2−Ga centers (with S = 1/2) have a slight angular variation due to a small anisotropy in the g matrix (principal values are 2.0034, 2.0097, and 2.0322). The V2−Ga centers also exhibit a resolved hyperfine structure due to equal and nearly isotropic interactions with the 69,71Ga nuclei at two Ga sites (the hyperfine parameters are 1.28 and 1.63 mT for the 69Ga and 71Ga nuclei, respectively, when the field is along the a direction). Based on these g-matrix and hyperfine results, the model for the ground state of the doubly ionized vacancy (V2−Ga) has a hole localized on one threefold-coordinated oxygen ion. The vacancy is located at one of the three neighboring gallium sites, and the remaining two gallium neighbors are responsible for the equal hyperfine interactions. The singly ionized (V−Ga) gallium vacancies are also paramagnetic. In this latter acceptor, the two holes are localized on separate oxygen ions adjacent to one gallium vacancy. Their spins align parallel to give a triplet S = 1 EPR spectrum with resolved hyperfine structure from interactions with gallium neighbors

Self-trapped Holes in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e Crystals

We have experimentally observed self-trapped holes (STHs) in a β-Ga2O3 crystal using electron paramagnetic resonance (EPR). These STHs are an intrinsic defect in this wide-band-gap semiconductor and may serve as a significant deterrent to producing usable p-type material. In our study, an as-grown undoped n-type β-Ga2O3 crystal was initially irradiated near room temperature with high-energy neutrons. This produced gallium vacancies (acceptors) and lowered the Fermi level. The STHs (i.e., small polarons) were then formed during a subsequent irradiation at 77 K with x rays. Warming the crystal above 90 K destroyed the STHs. This low thermal stability is a strong indicator that the STH is the correct assignment for these new defects. The S = 1/2 EPR spectrum from the STHs is easily observed near 30 K. A holelike angular dependence of the g matrix (the principal values are 2.0026, 2.0072, and 2.0461) suggests that the defect\u27s unpaired spin is localized on one oxygen ion in a nonbonding p orbital aligned near the a direction in the crystal. The EPR spectrum also has resolved hyperfine structure due to equal and nearly isotropic interactions with 69,71Ga nuclei at two neighboring Ga sites. With the magnetic field along the a direction, the hyperfine parameters are 0.92 mT for the 69Ga nuclei and 1.16 mT for the 71Ga nuclei

Electron Paramagnetic Resonance Study of Neutral Mg Acceptors in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e Crystals

Electron paramagnetic resonance (EPR) is used to directly observe and characterize neutral Mg acceptors (Mg0Ga) in a β-Ga2O3 crystal. These acceptors, best considered as small polarons, are produced when the Mg-doped crystal is irradiated at or near 77 K with x rays. During the irradiation, neutral acceptors are formed when holes are trapped at singly ionized Mg acceptors (Mg−Ga). Unintentionally present Fe3+ (3d5) and Cr3+ (3d3) transition-metal ions serve as the corresponding electron traps. The hole is localized in a nonbonding p orbital on a threefold-coordinated oxygen ion adjacent to an Mg ion at a sixfold-coordinated Ga site. These Mg0Ga acceptors (S = 1/2) have a slightly anisotropic g matrix (principal values are 2.0038, 2.0153, and 2.0371). There is also partially resolved 69Ga and 71Ga hyperfine structure resulting from unequal interactions with the two Ga ions adjacent to the hole. With the magnetic field along the a direction, hyperfine parameters are 2.61 and 1.18 mT for the 69Ga nuclei at the two inequivalent neighboring Ga sites. TheMg0Ga acceptors thermally convert back to their nonparamagnetic Mg−Ga charge state when the temperature of the crystal is raised above approximately 250 K

Ir \u3csup\u3e4+\u3c/sup\u3e Ions in β-Ga\u3csub\u3e2\u3c/sub\u3eO\u3csub\u3e3\u3c/sub\u3e Crystals: An Unintentional Deep Donor

Electron paramagnetic resonance (EPR) and infrared absorption are used to detect Ir4+ ions in β-Ga2O3 crystals. Mg and Fe doped crystals are investigated, and concentrations of Ir4+ ions greater than 1 × 1018 cm−3 are observed. The source of the unintentional deep iridium donors is the crucible used to grow the crystal. In the Mg-doped crystals, the Ir4+ ions provide compensation for the singly ionized Mg acceptors and thus contribute to the difficulties in producing p-type behavior. The Ir4+ ions replace Ga3+ ions at the Ga(2) sites, with the six oxygen neighbors forming a distorted octahedron. A large spin-orbit coupling causes these Ir4+ ions to have a low-spin (5d5, S = 1/2) ground state. The EPR spectrum consists of one broad line with a significant angular dependence. Principal values of the g matrix are 2.662, 1.815, and 0.541 (with principal axes near the crystal a, b, and c directions, respectively). Ionizing radiation at 77 K decreases the Ir4+ EPR signal in Mg-doped crystals and increases the signal in Fe-doped crystals. In addition to the EPR spectrum, the Ir4+ ions have an infrared absorption band representing a d-d transition within the t2g orbitals. At room temperature, this band peaks near 5153 cm−1 (1.94 μm) and has a width of 17 cm−1. The band is highly polarized: its intensity is maximum when the electric field E is parallel to the b direction in the crystal and is nearly zero when E is along the c direction