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Ultra-wide bandgap, conductive, high mobility, and high quality melt-grown bulk ZnGa2O4 single crystals
2019, Galazka, Zbigniew, Ganschow, Steffen, Schewski, Robert, Irmscher, Klaus, Klimm, Detlef, Kwasniewski, Albert, Pietsch, Mike, Fiedler, Andreas, Schulze-Jonack, Isabelle, Albrecht, Martin, Schröder, Thomas, Bickermann, Matthias
Truly bulk ZnGa2O4 single crystals were obtained directly from the melt. High melting point of 1900 ± 20 °C and highly incongruent evaporation of the Zn- and Ga-containing species impose restrictions on growth conditions. The obtained crystals are characterized by a stoichiometric or near-stoichiometric composition with a normal spinel structure at room temperature and by a narrow full width at half maximum of the rocking curve of the 400 peak of (100)-oriented samples of 23 arcsec. ZnGa2O4 is a single crystalline spinel phase with the Ga/Zn atomic ratio up to about 2.17. Melt-grown ZnGa2O4 single crystals are thermally stable up to 1100 and 700 °C when subjected to annealing for 10 h in oxidizing and reducing atmospheres, respectively. The obtained ZnGa2O4 single crystals were either electrical insulators or n-type semiconductors/degenerate semiconductors depending on growth conditions and starting material composition. The as-grown semiconducting crystals had the resistivity, free electron concentration, and maximum Hall mobility of 0.002–0.1 Ωcm, 3 × 1018–9 × 1019 cm−3, and 107 cm2 V−1 s−1, respectively. The semiconducting crystals could be switched into the electrically insulating state by annealing in the presence of oxygen at temperatures ≥700 °C for at least several hours. The optical absorption edge is steep and originates at 275 nm, followed by full transparency in the visible and near infrared spectral regions. The optical bandgap gathered from the absorption coefficient is direct with a value of about 4.6 eV, close to that of β-Ga2O3. Additionally, with a lattice constant of a = 8.3336 Å, ZnGa2O4 may serve as a good lattice-matched substrate for magnetic Fe-based spinel films.
Cobalt as a promising dopant for producing semi-insulating β -Ga2O3crystals: Charge state transition levels from experiment and theory
2022, Seyidov, Palvan, Varley, Joel B., Galazka, Zbigniew, Chou, Ta-Shun, Popp, Andreas, Fiedler, Andreas, Irmscher, Klaus
Optical absorption and photoconductivity measurements of Co-doped β-Ga2O3 crystals reveal the photon energies of optically excited charge transfer between the Co related deep levels and the conduction or valence band. The corresponding photoionization cross sections are fitted by a phenomenological model considering electron-phonon coupling. The obtained fitting parameters: thermal ionization (zero-phonon transition) energy, Franck-Condon shift, and effective phonon energy are compared with corresponding values predicted by first principle calculations based on density functional theory. A (+/0) donor level ∼0.85 eV above the valence band maximum and a (0/-) acceptor level ∼2.1 eV below the conduction band minimum are consistently derived. Temperature-dependent electrical resistivity measurement at elevated temperatures (up to 1000 K) yields a thermal activation energy of 2.1 ± 0.1 eV, consistent with the position of the Co acceptor level. Furthermore, the results show that Co doping is promising for producing semi-insulating β-Ga2O3 crystals.