Magnetron Sputter Epitaxy of GaN Epilayers and Nanorods
Abstract: In this research, electronic-grade GaN(0001) epilayers and nanorods have been grown onto Al2O3(0001) and Si(111) substrates, respectively, by reactive magnetron sputter epitaxy (MSE) using liquid Ga as a sputtering target. MSE, employing ultra high vacuum conditions, high-purity source materials, and lowenergy ion assisted deposition from substrate biasing, is a scalable method, lending itself to large area GaN synthesis.For the growth of epitaxial GaN films two types of sputtering techniques, direct current (DC) magnetron sputtering and high power impulse magnetron sputtering (HiPIMS) were studied. The GaN epitaxial films grown by DC-MSE directly on to Al2O3(0001) in a mixture of Ar and N2, feature low threading dislocation densities on the order of ? 1010 cm-2, as determined by transmission electron microscopy (TEM) and modified Williamson-Hall plots. X-ray rocking curves reveal a narrow full-width at half maximum (FWHM) of 1054 arcsec of the 0002 reflection. A sharp 4 K photoluminescence (PL) peak at 3.474 eV with a FWHM of 6.3 meV is attributed to intrinsic GaN band edge emission. GaN(0001) epitaxial films grown on Al2O3 substrates by HiPIMS deposition in a mixed N2/Ar discharge contain both strained domains and almost relaxed domains in the same epilayers, which was determined by a combination of x-ray diffraction (XRD), TEM, atomic force microscopy (AFM), ?-Raman microscopy, ?-PL, and Cathodoluminescence (CL). The almost fully relaxed domains show superior structural and optical properties evidenced by a rocking curves with full width at half maximum of 885 arc sec and a low temperature band edge luminescence at 3.47 eV with the FWHM of 10 meV. The other domain exhibits a 14 times higher isotropic strain component, which is due to higher densities of point and extended defects, resulting from bombardment of energetic species during growth.Single-crystal GaN(0001) nanorods have been grown directly on Si(111) substrates by DC-MSE in a pure N2environment. The as-grown GaN nanorods exhibit very high crystal quality from bottom to the top without any stacking faults, as determined by TEM. The crystal quality is found to increase with increasing working pressure. XRD results show that all the rods are highly 0001 oriented. All nanorods exhibit an N-polarity, as determined by convergent beam electron diffraction methods. Sharp and well-resolved 4 K ?-PL peaks at ~3.474 eV with a FWHM ranging from 1.7 meV to 22 meV are attributed to the intrinsic GaN band edge emission and corroborate the exceptional crystal quality of the material. Texture measurements reveal that the rods have random in-plane orientation when grown on Si(111) with its native oxide while they have an inplane epitaxial relationship of GaN[11?20] // Si[1?10] when grown on Si(111) without the surface oxide. The best structural and optical properties of the rods were achieved at N2 partial pressures of 15 to 20 mTorr. By diluting the reactive N2 working gas in DC-MSE with Ar, it is possible to achieve favorable growth conditions for high quality GaN nanorods onto Si(111) at a low total pressure of 5 mTorr. With an addition of small amount of Ar (0.5 mTorr), we observe an increase in nanorod aspect ratio from 8 to ~35, a decrease in average diameter from 74 nm to 35 nm, and a 2-fold increase in nanorod density compared to pure N2 conditions. By further dilution, the aspect ratio continuously decreases to 14 while the diameter increases to 60 nm and the nanorod density increases to a maximum of 2.4×109 cm-1. The changes in nanorod morphology upon Ar-dilution of the N2 working gas are explained by a transition from N-rich growth conditions, promoting the diffusion induced nanorods growth mode, to Ga-rich growth conditions, in qualitative agreement with GaN nanorods growth by MBE. At N2 partial pressure of 2.5 mTorr, the Ga-target is close to a non-poisoned state which gives the most perfect crystal quality which is reflected in an exceptionally narrow band edge emission at 3.479 eV with a FWHM of only 1.7 meV. Such structural and optical properties are comparable to rods previously grown at 3 to 4 time higher total working pressures of pure N2.
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