We report on growth and electrical properties of α-Ga2O3 films prepared by halide vapor phase epitaxy (HVPE) at 500 °C on α-Cr2O3 buffers predeposited on sapphire by magnetron sputtering. The α-Cr2O3 buffers showed a wide microcathodoluminescence (MCL) peak near 350 nm corresponding to the α-Cr2O3 bandgap and a sharp MCL line near 700 nm due to the Cr+ intracenter transition. Ohmic contacts to Cr2O3 were made with both Ti/Au or Ni, producing linear current–voltage ( I– V) characteristics over a wide temperature range with an activation energy of conductivity of ∼75 meV. The sign of thermoelectric power indicated p-type conductivity of the buffers. Sn-doped, 2- μm-thick α-Ga2O3 films prepared on this buffer by HVPE showed donor ionization energies of 0.2–0.25 eV, while undoped films were resistive with the Fermi level pinned at EC of 0.3 eV. The I– V and capacitance–voltage ( C– V) characteristics of Ni Schottky diodes on Sn-doped samples using a Cr2O3 buffer indicated the presence of two face-to-face junctions, one between n-Ga2O3 and p-Cr2O3, the other due to the Ni Schottky diode with n-Ga2O3. The spectral dependence of the photocurrent measured on the structure showed the presence of three major deep traps with optical ionization thresholds near 1.3, 2, and 2.8 eV. Photoinduced current transient spectroscopy spectra of the structures were dominated by deep traps with an ionization energy of 0.95 eV. These experiments suggest another pathway to obtain p–n heterojunctions in the α-Ga2O3 system.
High-temperature β-Ga2O3:Cr2O3-based sensors sensitive to oxygen- and hydrogen-containing gases have been developed and studied. Magnetron cosputtering is the method of choice for the thin film synthesis as an industry-compatible technique. The composition-structure-properties relationship has been revealed. An introduction of 0.04–0.14 wt. % Cr leads to a significant increase in the response of the O2 sensors over the temperature range 250–400 °C. The highest response in the above-mentioned temperature range has been achieved for a Cr addition of 0.14 wt. %. An increase in the Cr content from 0.04 to 0.22 wt. % leads to a decrease in the β-Ga2O3-based sensors’ response time, especially for low O2 concentrations (≤10 vol. %). Reliable control of the β-Ga2O3:Cr2O3-based sensors’ selectivity to industry-relevant reducing gases—hydrogen, carbon monoxide, and toluene—is demonstrated. β-Ga2O3 films with a Cr incorporation content of 0.04 and 0.06 wt. % have a high response to toluene at operating temperatures 300–500 °C, while the films with 0.14 and 0.22 wt. % Cr have a high response to H2 in the range 400–500 °C. Regardless of the Cr content in β-Ga2O3 thin films, all sensors considered demonstrate a weak response to CO within the operating temperature range 250–500 °C. The results attained are of certain technological importance, i.e., in terms of the development of cost-effective methods for the synthesis of materials and systems for monitoring and control of industry-relevant gases for an environmentally friendly and sustainable growth.
Heavily Sn doped films of α-Ga2O3 were grown by Halide Vapor Phase Epitaxy (HVPE) on basal plane c-sapphire and on (10-12) r-sapphire substrates with and without α-Cr2O3 thin buffers prepared by magnetron sputtering and annealing in air at 500oC for 3 hours. For both substrate orientations, the use of the α-Cr2O3 buffers led to three major effects. The first was a substantial decrease of the half-width of the symmetric and asymmetric x-ray reflections. The second effect was an order of magnitude decrease of the net donor concentration produced by flowing the same amounts of Sn into the reactor. Thirdly, there was a reduction in the concentration of the major electron trap in the films near Ec-1 eV by more than a factor of 2. These results show the major influence of sapphire substrate orientation on the electrical and structural properties of α-Ga2O3 grown by HVPE.
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