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Effect of Thermal Oxidation on the Structure, Surface Texturing, and Microstructure Evolution in Nanocrystalline Ga-O-N Films

An extensive examination of the nanoscale, crystallographic growth dynamics of the system, which is impacted by the thermal energy given to the GaN, is carried out to derive a deeper understanding of the growth kinetics, morphology and microstructure evolution, chemical bonding, and optical properties of Ga-O-N films. Thermal annealing of GaN films is performed in the temperature range of 900–1200 °C. Crystal structure, phase formation, chemical composition, surface morphology, and microstructure evolution of Ga-O-N films are investigated as a function of temperature. Increasing temperature induces surface oxidation, which results in the formation of stable β-Ga2O3 phase in the GaN matrix, where the overall film composition evolves from nitride (GaN) to oxynitride (Ga-O-N). While GaN surfaces are smooth, planar, and featureless, oxidation induced granular-to-rod shaped morphology evolution is seen with increasing temperature to 1200 °C. The considerable texturing and stability of the nanocrystalline Ga-O-N on Si substrates can be attributed to the surface and interface driven modification because of thermal treatment. Corroborating with structure and chemical changes, Raman spectroscopic analyses also indicate that the chemical bonding evolution progresses from fully Ga-N bonds to Ga-O-N. While the GaN oxidation process starts with the formation of β-Ga 2 O 3 at an annealing temperature of 1000 °C, higher annealing temperatures induce structural distortion with the potential formation of Ga-O-N bonds. The structure-phase-chemical composition correlation, which will be useful for nanocrystalline materials for selective optoelectronic applications, is established in Ga-O-N films made by thermal treatment of GaN.

36 MATERIALS SCIENCE↗

Materials Data on GaN by Materials Project

GaN is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ga3+ is bonded to six equivalent N3- atoms to form a mixture of edge and corner-sharing GaN6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Ga–N bond lengths are 2.14 Å. N3- is bonded to six equivalent Ga3+ atoms to form a mixture of edge and corner-sharing NGa6 octahedra. The corner-sharing octahedral tilt angles are 0°.

36 MATERIALS SCIENCE↗

Materials Data on GaN by Materials Project

GaN is Wurtzite structured and crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. Ga3+ is bonded to four equivalent N3- atoms to form corner-sharing GaN4 tetrahedra. All Ga–N bond lengths are 1.97 Å. N3- is bonded to four equivalent Ga3+ atoms to form corner-sharing NGa4 tetrahedra.

36 MATERIALS SCIENCE↗

Materials Data on GaN by Materials Project

GaN is Zincblende, Sphalerite structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. Ga3+ is bonded to four equivalent N3- atoms to form corner-sharing GaN4 tetrahedra. All Ga–N bond lengths are 1.97 Å. N3- is bonded to four equivalent Ga3+ atoms to form corner-sharing NGa4 tetrahedra.

36 MATERIALS SCIENCE↗

Materials Data on GaN by Materials Project

GaN is Boron Nitride-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is two-dimensional and consists of two GaN sheets oriented in the (0, 0, 1) direction. Ga3+ is bonded in a trigonal planar geometry to three equivalent N3- atoms. All Ga–N bond lengths are 1.85 Å. N3- is bonded in a trigonal planar geometry to three equivalent Ga3+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on GaN by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗