Effective reduction of bowing in free-standing GaN by N-face regrowth with hydride vapor-phase epitaxy

Free-standing GaN films prepared with hydride vapor-phase epitaxy (HVPE) technique usually show bowing resulting from the high densities of defects near the N-polar face after separation from the original substrates. To solve the problem, a simple technique has been developed. A GaN layer was regrown on the N-polar face of the free-standing GaN by HVPE. High-resolution X-ray diffraction (HRXRD) measurements were performed to compare the bowings among GaN films before laser lift-off (LLO), after LLO, and after regrowth. The apparent reductions of XRD full-width at half-maximum (FWHM), along with the increase of XRD peak intensity, after regrowth clearly demonstrate the effectiveness of this method to eliminate bowings of the free-standing GaN films.     

Impact of the gas flow ratio on the physical properties of GaN grown by vertical flow metalorganic chemical vapour deposition

We studied the effect of gas flow ratio of the H₂ carrier gas to the NH₃ precursor on the physical and crystal properties of GaN. GaN was grown by vertical reactor metalorganic chemical vapour deposition (MOCVD) on a low-temperature-deposited GaN buffer layer. A (0 0 0 1) sapphire substrate was used. The impact of the gas flow ratio as it was varied from 0.25 to 1 was investigated and discussed. With increase in flow ratio, the concentrations of magnesium and carbon impurities in GaN increased. The flow ratio of 0.5 is the optimum value to minimise the background electron concentration and to maintain crystal quality. The decrease in the background electron concentration is due to the compensation mechanism of acceptor-like magnesium and carbon impurities.     

Ca3N2 as a flux for crystallization of GaN

In this work Ca₃N₂ was investigated as a potential flux for crystallization of GaN. Melting temperature of the potential flux at high N₂ pressure evaluated by thermal analysis as 1380 °C is in good agreement with the theoretical prediction. It is shown that Ca₃N₂ present in the liquid gallium in small amount (1 at%) dramatically accelerates synthesis of GaN from its constituents. On the other hand, it does not influence significantly the rate of GaN crystallization from solution in gallium in temperature gradient for both unseeded and seeded configurations. However the habit and color of the spontaneously grown GaN crystals change drastically. For 10 mol% Ca₃N₂ content in the liquid Ga it was found that the GaN thick layer and GaN crystals (identified by micro-Raman scattering measurements) were grown on the substrate. For growth from molten Ca₃N₂ (100%) with GaN source, the most important observations were (i) GaN source material was completely dissolved in the molten Ca₃N₂ flux and (ii) after experiment, GaN crystals were found on the sapphire substrate.     

The effects of annealing on non-polar (1 1 2¯ 0) a-plane GaN films

Non-polar a-plane (1 1 2¯ 0) GaN films were grown on r-plane sapphire by metal–organic vapor phase epitaxy and were subsequently annealed for 90 min at 1070 °C. Most dislocations were partial dislocations, which terminated basal plane stacking faults. Prior to annealing, these dislocations were randomly distributed. After annealing, these dislocations moved into arrays oriented along the [0 0 0 1] direction and aligned perpendicular to the film–substrate interface throughout their length, although the total dislocation density remained unchanged. These changes were accompanied by broadening of the symmetric X-ray diffraction 1 1 2¯ 0 ω-scan widths. The mechanism of movement was identified as dislocation glide, occurring due to highly anisotropic stresses (confirmed by X-ray diffraction lattice parameter measurements) and evidenced by macroscopic slip bands observed on the sample surface. There was also an increase in the density of unintentionally n-type doped electrically conductive inclined features present at the film–substrate interface (as observed in cross-section using scanning capacitance microscopy), suggesting out-diffusion of impurities from the substrate along with prismatic stacking faults. These data suggest that annealing processes performed close to film growth temperatures can affect both the microstructure and the electrical properties of non-polar GaN films.     

Hydride vapor phase epitaxy of GaN boules using high growth rates

The boule-like growth of GaN in a vertical AIXTRON HVPE reactor was studied. Extrinsic factors like properties of the starting substrate and fundamental growth parameters especially the vapor gas composition at the surface have crucial impact on the formation of inverse pyramidal defects. The partial pressure of GaCl strongly affects defect formation, in-plane strain, and crystalline quality. Optimized growth conditions resulted in growth rates of 300–500 μm/h. GaN layers with thicknesses of 2.6 and of 5.8 mm were grown at rates above 300 μm/h. The threading dislocation density reduces with an inverse proportionality to the GaN layer thickness. Thus, it is demonstrated that growth rates above 300 μm/h are promising for GaN boule growth.     

Fabrication of a freestanding GaN layer by direct growth on a ZnO template using hydride vapor phase epitaxy

A new hydride vapor phase epitaxy (HVPE)-based approach for the fabrication of freestanding GaN (FS-GaN) substrates was investigated. For the direct formation of low-temperature GaN (LT-GaN) layers, the growth parameters were optimized: the polarity of ZnO, the growth temperature, and the V/III ratio. The FS-GaN layer was achieved by gas etching in an HVPE reactor. A fingerprint of Zn out-diffusion was detected in the photoluminescence measurements, especially for the thin (80 μm) FS-GaN film; however, a thicker film (400 μm) was effectively reduced by optimization of GaN growth.     

Growth of GaN based structures on Si(1 1 0) by molecular beam epitaxy

The growth of GaN based structures on Si(1 1 0) substrates by molecular beam epitaxy using ammonia as the nitrogen precursor is reported. The structural, optical and electrical properties of such structures are assessed and are quite similar to the ones obtained on Si(1 1 1) in-spite of the very different substrate surface symmetry. A threading dislocation density of 3.7×10⁹ cm⁻² is evaluated by transmission electron microscopy, which is in the low range of typical densities obtained on up to 2 μm thick GaN structures grown on Si(1 1 1). To assess the potential of such structure for device realization, AlGaN/GaN high electron mobility transistor and InGaN/GaN light emitting diode heterostructures were grown and their properties are compared with the ones obtained on Si(1 1 1).     

Enhanced growth rates and reduced parasitic deposition by the substitution of Cl2 for HCl in GaN HVPE

The main limitation in the application of hydride vapor phase epitaxy for the large scale production of thick free-standing GaN substrates is the so-called parasitic deposition, which limits the growth time and wafer thickness by blocking the gallium precursor inlet. By utilizing Cl₂ instead of the usual HCl gas for the production of the gallium chlorine precursor, we found a rapid increase in growth rate from ∼80 to ∼400 μm/h for an equally large flow of 25 sccm. This allowed us to grow, without any additional optimization, 1.2 mm thick high quality GaN wafers, which spontaneously lifted off from their 0.3° mis-oriented GaN on sapphire HCl-based HVPE templates. These layers exhibited clear transparencies, indicating a high purity, dislocation densities in the order of 10⁶ cm⁻², and narrow rocking curve XRD FWHMs of 54 and 166 arcsec in for the 0002 and 101−5 directions, respectively.     

The influence of the Al pre-deposition on the properties of AlN buffer layer and GaN layer grown on Si (1 1 1) substrate

The influence of Al pre-deposition on the properties of AlN buffer layer and GaN layer grown on Si (1 1 1) substrate by metalorganic chemical vapor deposition (MOCVD) has been systematically studied. Compared with the sample without Al pre-deposition, optimum Al pre-deposition time could improve the AlN buffer layer crystal quality and reduce the root mean square (RMS) roughness. Whereas, overlong Al-deposition time deteriorated the AlN crystal quality and Al-deposition patterns could be found. Cracks and melt-back etching patterns appeared in the GaN layer grown without Al pre-deposition. With suitable Al-deposition time, crack-free 2.0 μm GaN was obtained and the full-width at half-maximum (FWHM) of (0 0 2) plane measured by double crystal X-ray diffraction (DCXRD) was as low as 482 arcsec. However, overlong Al-deposition time would result in a great deal of cracks, and the crystal quality of GaN layer deteriorated. The surface of GaN layer became rough in the region where the Al-deposition patterns were formed due to overlong Al-deposition time.     

Homoepitaxial growth and electrical characterization of GaN-based Schottky and light-emitting diodes

Homoepitaxial growth of GaN epilayers on free-standing hydride vapor phase epitaxy (HVPE) GaN substrates offered a better control over surface morphology, defect density, and doping concentration compared to conventional heteroepitaxial growth. The FWHM of the (0 0 0 2) X-ray diffraction (XRD) rocking curve from homoepitaxial GaN was measured to be as low as 79 arcsec, much smaller than 230 arcsec for GaN grown on sapphire. Schottky diodes grown on GaN substrates exhibited sharper breakdown characteristics and much lower reverse leakage than diodes on sapphire. However, the homoepitaxial devices had poor scalability due to the presence of yield-killing defects originating from the substrate surface. Vertical InGaN/GaN light-emitting diodes (LEDs) on GaN substrates showed reduced series resistance and reverse leakage compared to lateral LEDs on sapphire. Wafer mapping demonstrated that the distribution of leaky homoepitaxial devices correlated well with that of macroscopic defects in the GaN substrates.     

Inversion domains and parallel growth in ammonothermally grown GaN crystals

Macro-defects such as twins, inversion domains, crevices, and columnar growth occasionally appear in ammonothermally grown GaN crystals. Twinning mechanisms and parallel growth are proposed to explain the formation of these defects. As a polar crystal with wurtzite structure, GaN can have several different kinds of twins depending on the polarity arrangement of each individual twin. Inversion domains are formed in one of the twinning mechanisms. Parallel growth is used to explain the formation of pits on the nitrogen face and the columnar growth on the gallium face. Etching in hot H₃PO₄ is used to reveal the polarities and defects of GaN crystals when they are indistinguishable. Optical microscopy, scanning electron microscope, and cathodoluminescence are also employed to study these defects. In addition, seed quality, avoidance of macro-defect formation, and impurity effects are also discussed.     

Hydride-assisted growth of GaN nanowires on Au/Si(0 0 1) via the reaction of Ga with NH3 and H2

High quality, straight GaN nanowires (NWs) with diameters of 50 nm and lengths up to 3 μm have been grown on Si(0 0 1) using Au as a catalyst and the direct reaction of Ga with NH₃ and N₂:H₂ at 900 °C. These exhibited intense, near band edge photoluminescence at 3.42 eV in comparison to GaN NWs with non-uniform diameters obtained under a flow of Ar:NH₃, which showed much weaker band edge emission due to strong non-radiative recombination. A significantly higher yield of β-Ga₂O₃ NWs with diameters of ≤50 nm and lengths up to 10 μm were obtained, however, via the reaction of Ga with residual O₂ under a flow of Ar alone. The growth of GaN NWs depends critically on the temperature, pressure and flows in decreasing order of importance but also the availability of reactive species of Ga and N. A growth mechanism is proposed whereby H₂ dissociates on the Au nanoparticles and reacts with Ga giving Ga_xH_y thereby promoting one-dimensional (1D) growth via its reaction with dissociated NH₃ near or at the top of the GaN NWs while suppressing at the same time the formation of an underlying amorphous layer. The higher yield and longer β-Ga₂O₃ NWs grow by the vapor liquid solid mechanism that occurs much more efficiently than nitridation.     

The K2S2O8–KOH photoetching system for GaN

A recently developed photoetching system for n-type GaN, a KOH solution containing the strong oxidizing agent potassium peroxydisulphate (K₂S₂O₈), was studied in detail. By careful selection of the etching parameters, such as the ratio of components and the hydrodynamics, two distinct modes were defined: defect-selective etching (denoted by KSO-D) and polishing (KSO-P). Both photoetching methods can be used under open-circuit (electroless) conditions. Well-defined dislocation-related etch whiskers are formed during KSO-D etching. All types of dislocations are revealed, and this was confirmed by cross-sectional TEM examination of the etched samples. Extended electrically active defects are also clearly revealed. The known relationship between etch rate and carrier concentration for photoetching of GaN in KOH solutions was confirmed for KSO-D etch using Raman measurements. It is shown that during KSO-P etching diffusion is the rate-limiting step, i.e. this etch is suitable for polishing of GaN. Some constraints of the KSO etching system for GaN are discussed and peculiar etch features, so far not understood, are described.     

Studies on the effect of ammonia flow rate induced defects in gallium nitride grown by MOCVD

Gallium nitride (GaN) epitaxial layers were grown with different V/III ratios by varying the ammonia (NH₃) flow rate, keeping the flow rate of the other precursor, trimethylgallium (TMG), constant, in an MOCVD system. X-ray rocking curve widths of a (1 0 2) reflection increase with an increase in V/III ratio while the (0 0 2) rocking curve widths decrease. The dislocation density was found to increase with an increase in ammonia flow rate, as determined by hot-wet chemical etching and atomic force microscopy. 77 K photoluminescence studies show near band emission at 3.49 eV and yellow luminescence peaking at 2.2 eV. The yellow luminescence (YL) intensity decreases with an increase in V/III ratio. Positron annihilation spectroscopy studies show that the concentration of Ga-like vacancies increases with an increase in ammonia flow rate. This study confirms that the yellow luminescence in the GaN arises due to deep levels formed by gallium vacancies decorated with oxygen atoms.     

Polar dependence of impurity incorporation and yellow luminescence in GaN films grown by metal-organic chemical vapor deposition

We have investigated the unintentional impurities, oxygen and carbon, in GaN films grown on c-plane, r-plane as well as m-plane sapphire by metal-organic chemical vapor deposition. The GaN layer was analyzed by secondary ion mass spectroscopy. The different trend of the incorporation of oxygen and carbon has been explained in the polar (0 0 0 1), nonpolar (1 1 2¯ 0) and semipolar (1 1 2¯ 2) GaN by a combination of the atom bonding structure and the origin direction of the impurities. Furthermore, it has been found that there is a stronger yellow luminescence (YL) in GaN with higher concentration of carbon, suggesting that C-involved defects are originally responsible for the YL.     

Characterization of bulk GaN crystals grown from solution at near atmospheric pressure

The properties of GaN crystals grown from solution at temperatures ranging from 780 to 810 °C and near atmospheric pressure ∼0.14 MPa, have been investigated using low temperature X-band (∼9.5 GHz) electron paramagnetic resonance spectroscopy, micro-Raman spectroscopy, photoluminescense spectroscopy, and photoluminescence imaging. Our samples are spontaneously nucleated thin platelets of approximate dimensions of 2×2×0.025 mm³, or samples grown on both polycrystalline and single crystal HVPE large-area (∼3×8×0.5 mm³) seeds. Electron paramagnetic resonance spectra consists of a single Lorentzian line with axial symmetry about the c-axis, with approximate g-values, g_∥=1.951 and g_⊥=1.948 and a peak-to-peak linewidth of∼4.0 G. This resonance has been previously assigned to shallow impurity donors/conduction electrons in GaN and attributed to Si- and/or O impurities. Room temperature photoluminescence and photoluminescence imaging data from both Ga- and N-faces show different dominant emission bands, suggesting different incorporation of impurities and/or native defects. Raman scattering and X-ray diffraction show moderate to good crystalline quality.     

Development of m-plane GaN anisotropic film properties during MOVPE growth on LiAlO2 substrates

The anisotropic film properties of m-plane GaN deposited by metal organic vapour phase epitaxy (MOVPE) on LiAlO₂ substrates are investigated. To study the development of layer properties during epitaxy, the total film thickness is varied between 0.2 and 1.7 μm. A surface roughening is observed caused by the increased size of hillock-like features. Additionally, small steps which are perfectly aligned in (1 1 −2 0) planes appear for samples with a thickness of ∼0.5 μm and above. Simultaneously, the X-ray rocking curve (XRC) full width at half maximum (FWHM) values become strongly dependent on incident X-ray beam direction beyond this critical thickness. Anisotropic in-plane compressive strain is initially present and gradually relaxes mainly in the [1 1 −2 0] direction when growing thicker films. Low-temperature photoluminescence (PL) spectra are dominated by the GaN near-band-edge peak and show only weak signal related to basal plane stacking faults (BSF). The measured background electron concentration is reduced from ∼10²⁰ to ∼10¹⁹ cm⁻³ for film thicknesses of 0.2 μm and ∼1 μm while the electron mobilities rise from ∼20 to ∼130 cm²/V s. The mobilities are significantly higher in [0 0 0 1] direction which we explain by the presence of extended planar defects in the prismatic plane. Such defects are assumed to be also the cause for the observed surface steps and anisotropic XRC broadening.     

Thermogravimetric analysis and microstructural observations on the formation of GaN from the reaction between Ga2O3 and NH3

Thermogravimetric analysis (TGA) and microstructural observations were carried to investigate the nitridation mechanism of β-Ga₂O₃ powder to GaN under an NH₃/Ar atmosphere. Non-isothermal TGA showed that nitridation of β-Ga₂O₃ starts at ∼650 °C, followed by decomposition of GaN at ∼1100 °C. Isothermal TGA showed that nitridation follows linear kinetics in the temperature range 800–1000 °C. At an early stage of nitridation, small GaN particles (∼5 nm) are deposited on the β-Ga₂O₃ crystal surface and they increase with time. We proposed a mechanism for the nitridation of Ga₂O₃ by NH₃ whereby nitridation of β-Ga₂O₃ proceeds via the intermediate vapor species Ga₂O(g).     

Droplet epitaxy of zinc-blende GaN quantum dots

Zinc-blende GaN quantum dots were grown on 3C-AlN(0 0 1) by a vapor–liquid–solid process in a molecular beam epitaxy system. We were able to control the density of the quantum dots in a range of 5×10⁸–5×10¹² cm⁻². Photoluminescence spectroscopy confirmed the optical activity of the GaN quantum dots in a range of 10¹¹–5×10¹² cm⁻². The data obtained give an insight to the condensation mechanism of the vapor–liquid–solid process in general, because the GaN quantum dots condense in metastable zinc-blende crystal structure supplied by the substrate, and not in the wurtzite crystal structure expected from free condensation in the droplet.