Properties of Ge-doped,high-quality bulk GaN crystals fabricated by hydride vapor phase epitaxy

We investigated the properties of Ge-doped, high-quality bulk GaN crystals with Ge concentrations up to 2.4×10¹⁹ cm⁻³. The Ge-doped crystals were fabricated by hydride vapor phase epitaxy with GeCl₄ as the dopant source. Cathodoluminescence imaging revealed no increase in the dislocation density at even the highest Ge concentration, with values as low as 3.4×10⁶ cm⁻². The carrier concentration, as determined by Hall measurement, was almost identical to the combined concentration of Ge and unintentionally incorporated Si. The electron mobilities were 260 and 146 cm² V⁻¹ s⁻¹ for n=3.3×10¹⁸ and 3.35×10¹⁹ cm⁻³, respectively; these values are markedly larger than those reported in the past for Ge-doped GaN thin films. The optical absorption coefficient was quite small below the band gap energy; it slightly increased with increase in Ge concentration. Thermal conductivity, estimated by the laser-flash method, was virtually independent of Ge concentration, maintaining an excellent value around 2.0 W cm⁻¹ K⁻¹. Thermal expansion coefficients along the a- and m-axes were approximately constant at 5.0×10⁻⁶ K⁻¹ in the measured doping concentration range.     

Electrical characterisation of AlGaN/GaN heterostructure wafers for high-power HFETs

Undoped 28 nm AlGaN on 1 μm GaN was grown by MOVPE for high power microwave HFETs. Non-destructive methods for rapid characterisation of the layers are described. Double contact mercury probe capacitance voltage measurements gave valuable information on AlGaN layer leakage, thickness and quality, but only gave an estimate of the carrier concentration and pinch-off voltage due to the absence of an ohmic contact to the 2DEG layer. A non-contact resistivity mapping system gave accurate average sheet resistance, but underestimated the cross-wafer variation.     

Impedance spectroscopy analysis of AlGaN/GaN HFET structures

For HFET application a series of samples with 30 nm Al_xGa_1−xN (x=0.02–0.4) layers deposited at 1040°C onto optimised 2 μm thick undoped GaN buffers were fabricated. The Al_xGa_1−xN/GaN heterostructures were grown on c-plane sapphire in an atmospheric pressure, single wafer, vertical flow MOVPE system. Electrical properties of the Al_xGa_1−xN/GaN heterostructures and thick undoped GaN layers were evaluated by impedance spectroscopy method performed in the range of 80 Hz–10 MHz with an HP 4192A impedance meter using a mercury probe. The carrier concentration distribution through the layer thickness and the sheet carrier concentration were evaluated. A non-destructive, characterisation technique for verification of device heterostucture quality from the measured C–V and G–V versus frequency characteristics of the heterostructure is proposed.     

Polarization induced 2D hole gas in GaN/AlGaN heterostructures

The generation of high density 2D hole gases is crucial for further progress in the electronic and optoelectronic nitride devices. In this paper, we present systematic theoretical studies of Mg-doped GaN/AlGaN gated heterostructures and superlattices. Our calculations are based on a self-consistent solution of the multiband k.p Schrödinger and Poisson equation and reveal that the hole 2D sheet density is mainly determined by the polarization induced interface charges. For an aluminium concentration of 30%, the induced hole density in the heterostructure can reach values up to 1.5×10¹³ cm⁻². In the GaN/AlGaN superlattices, the hole sheet density increases with the superlattice period and saturates for a period of 40 nm at a value of 1.5×10¹³ cm⁻².     

Liquid phase epitaxy (LPE) of GaN on c- and r-faces of AlN substrates

We present the optical properties of MBE-grown GaAs–AlGaAs core–shell nanowires (NWs) grown on anodized-aluminum-oxide (AAO) patterned-Si (1 1 1) substrate using photoluminescence and Raman scattering spectroscopy. The GaAs NWs were grown via the vapor–liquid–solid method with Au-nanoparticles as catalysts. Enhancement in emission of at least an order of magnitude was observed from the GaAs–AlGaAs core–shell NWs as compared to the bare GaAs NWs grown under similar conditions, which is an indication of improved radiative efficiency. The improvement in radiative efficiency is due to the passivating effect of the AlGaAs shell. Variation in bandgap emission energy as a function of temperature was analyzed using the semi-empirical Bose–Einstein model. Results show that the free exciton energy of the GaAs core–shell agrees well with the known emission energy of zinc blende (ZB) bulk GaAs. Further analysis on the linear slope of the temperature dependence curve of photoluminescence emission energy at low temperatures shows that there is no difference between core–shell nanowires and bulk GaAs, strongly indicating that the grown NWs are indeed predominantly ZB in structure. The Raman modes show downshift and asymmetrical broadening, which are characteristic features of NWs. The downshift is attributed to lattice defects rather than the confinement or shape effect.     

Hydrogen and nitrogen ambient effects on epitaxial growth of GaN by hydride vapour phase epitaxy

This study presents the influence of the composition of the carrier gas on the growth of GaN by HVPE. Since no hydrogen is introduced in the vapour phase, the deposition is expected to be controlled by Cl desorption in the form of GaCl₃, as has been proposed for GaAs. However, our published model predicts much lower growth rates than those observed. We can account for both the observed parasitic deposition and GaN growth rate if we assume that GaCl₃ is not at its equilibrium pressure in the deposition zone and where nucleation takes place on the walls as well as on the substrate. This yields a high rate of parasitic nucleation even though the nominal supersaturation is vanishing small. Very little growth takes place on the substrate where the equilibrium pressure of GaCl₃ is reached. We describe similar experiments performed with a H₂/N₂ mixture as the carrier gas. In this case, we expect GaN deposition to be controlled by desorption of Cl as HCl, which is known as the H₂ mechanism. It is speculated that the results show the existence of a new growth mechanism.     

Method for HVPE growth of thick crack-free GaN layers

Twenty-five micrometer thick GaN was grown with hydride vapor phase epitaxy (HVPE) on metal-organic chemical vapor deposition (MOCVD) grown templates on sapphire substrates with the gallium treatment step (GTS) technique with varying buffer layer thickness. The samples are studied with atomic force microscopy (AFM), etching and scanning electron microscopy (SEM), photo-luminescence (PL), X-ray diffraction (XRD) and optical microscopy. The results show that the thickness of the buffer layer is not important for the layer quality once the growth in MOCVD starts to make the transition from 3D growth to 2D growth and HVPE continues in the same growth mode. We show that the MOCVD templates with GTS technique make excellent templates for HVPE growth, allowing growth of GaN without cracks in either sapphire or GaN.     

The influences of supersaturation on LPE growth of GaN single crystals using the Na flux method

The dependency of LPE growth rate and dislocation density on supersaturation in the growth of GaN single crystals in the Na flux was investigated. When the growth rate was low during the growth of GaN at a small value of supersaturation, the dislocation density was much lower compared with that of a substrate grown by the Metal Organic Chemical Vapor Deposition method (MOCVD). In contrast, when the growth rate of GaN was high at a large value of supersaturation, the crystal was hopper including a large number of dislocations. The relationship between the growth conditions and the crystal color in GaN single crystals grown in Na flux was also investigated. When at 800 °C the nitrogen concentration in Na–Ga melt was low, the grown crystals were always tinted black. When the nitrogen concentration at 850 °C was high, transparent crystals could be grown.     

Synthesis of GaN nanospindles via a facile solid-state reaction route

Gallium nitride (GaN) nanospindles have been synthesized via a solid-state reaction at a low-temperature condition. X-ray powder diffraction (XRD), Raman spectrum and high-resolution transmission electron microscopy (HRTEM) revealed that the synthesized GaN crystallized in a hexagonal structure and displaying spindly particles morphology has an average diameter of 100 nm and length of 400 nm X-ray photoelectron spectroscopy (XPS) of the sample gave the atomic ratio of Ga and N of 1.04:1. Room-temperature photoluminescence (PL) spectrum showed that the as-prepared product had a peak emission at 372 nm. The possible formation mechanism of the wurtzite GaN is briefly discussed.     

Influence of growth parameters on crack density in thick epitaxially lateral overgrown GaN layers by hydride vapor phase epitaxy

Using hydride vapor phase epitaxy the influence of growth parameters on the crack density is studied for thick epitaxially lateral overgrown (ELOG) GaN layers. Reactor pressure, growth rate, and substrate temperature are key factors to obtain crack-free thick GaN layers. The cracking mechanism is discussed and void formation on top of the SiO₂ stripes is proposed to play a key role in stress relaxation and crack suppression.     

In situ optical monitoring of AlGaN thickness and composition during MOVPE growth of AlGaN/GaN microwave HFETs

Real-time spectral reflectometry has been implemented to monitor the MOVPE growth of AlGaN/GaN microwave HFET structures. The aim is to monitor and control the thickness and composition of the thin AlGaN layer during growth. In order to extract useful information from the in situ spectra the optical constants of AlGaN as a function of alloy composition are required at the growth temperature (1050°C). As the first step to obtaining the high temperature optical constants, a room temperature spectroscopic ellipsometry study (energy range 1.65–4.95 eV) has been carried out on thin AlGaN films of various thickness (30 and 100 nm) and aluminium content (0.15 and 0.25). The multilayer model of each sample from the ellipsometry study is used to generate a reflectance spectrum which is compared with the in situ spectral reflectometry spectrum of the same sample acquired at room temperature to verify the technique. Further work is in progress to model the bandgap and optical constants of GaN and AlGaN at growth temperature.     

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.     

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.     

A study of the degree of relaxation of AlGaN epilayers on GaN template

The strain state of 570 nm Al_xGa_1−xN layers grown on 600 nm GaN template by metal organic chemical vapor deposition was studied using Rutherford backscattering (RBS)/channeling and triple-axis X-ray diffraction measurements. The results showed that the degree of relaxation (R) of Al_xGa_1−xN layers increased almost linearly when x0.42 and reached to 70% when x=0.42. Above 0.42, the value of R varied slowly and Al_xGa_1−xN layers almost full relaxed when x=1 (AlN). In this work the underlying GaN layer was in compressive strain, which resulted in the reduction of lattice misfit between GaN and Al_xGa_1−xN, and a 570 nm Al_xGa_1−xN layer with the composition of about 0.16 might be grown on GaN coherently from the extrapolation. The different shape of (0 0 0 4) diffraction peak was discussed to be related to the relaxation.     

Experimental and theoretical investigations of the electrical properties of undoped and magnesium-doped GaN layers

The ac characteristics of GaN : Mg and undoped GaN layers, grown by MOVPE on sapphire substrates, are measured for a wide range of temperature and bias conditions, in order to investigate the effect of the magnesium-related level on the transport properties. Two peaks, whose height and position depend on the measurement temperature, are observed in the admittance curves (G/ω versus frequency) of the Mg-doped samples, whereas only one peak appears in undoped samples. The study of the frequency dependence of the impedance, with a model including the two metallic Au/GaN junctions, the GaN layer itself, shows that, besides the effect of the differential resistance of the layer which plays a role in both sample types, the presence of a Mg-related deep level contributes to the observed variations of the peaks in the admittance curves of the p-doped samples. Results of a theoretical steady-state and small-signal analysis based on numerical modelling of the Au/GaN/Au heterostructure complete our analysis.     

Surface chemistry and transport effects in GaN hydride vapor phase epitaxy

A simple quasi-thermodynamic model of surface chemistry in GaN hydride vapor phase epitaxy (HVPE) is presented. The model is coupled with the detailed 3D simulations of species transport in a horizontal-tube reactor and validated by the comparison with the data on the GaN growth rate obtained by laser reflectometry. Parametric study of the growth rate as a function of temperature and species flow rates has been performed over a wide range of growth conditions. The important role of species transport in an HVPE reactor is demonstrated. In particular, a strong effect of the natural concentration convection resulting in the formation of recirculation zones and in a non-uniform vapor composition is revealed by modeling. The impact of these effects on the GaN growth rate and V/III ratio on the growth surface is discussed in detail.     

Revealing extended defects in HVPE-grown GaN

In this communication we will summarize the results of a complementary study of structural and chemical non-homogeneities that are present in thick HVPE-grown GaN layers. It will be shown that complex extended defects are formed during HVPE growth, and are clearly visible after photo-etching on both Ga-polar surface and on any non-polar cleavage or section planes. Large chemical (electrically active) defects, such as growth striations, overgrown or empty pits (pinholes) and clustered irregular inclusions, are accompanied by non-uniform distribution of crystallographic defects (dislocations). Possible reasons of formation of these complex structures are discussed. The nature of defects revealed by selective etching was subsequently confirmed using TEM, orthodox etching and compared with the CL method. The non-homogeneities were studied in GaN crystals grown in different laboratories showing markedly different morphological characteristics.     

Industrial production of GaN and InGaN-light emitting diodes on SiC-substrates

Blue light emitting diodes (LEDs) based on GaN or InGaN have a large market, e.g. for communication, industry and automotive applications. Since 1998, OSRAM Opto Semiconductors has been producing blue LEDs on a large scale, concentrating on the automotive market. LEDs in the wavelength range 450–480 nm are grown by metalorganic vapour phase epitaxy (MOVPE) on SiC. This substrate material offers many advantages from the epitaxial and device processing points of view. To fulfil the strong consumer recommendations not only do the epitaxial processes have to be developed, but also improvements in chip technology and package design help to stabilise electrical and optical properties on these high level demands. For example, low forward voltages, high light output powers at 20 mA, low reverse currents, long term stability and high electrostatic discharge robustness have to be guaranteed in a temperature range of −55–+85°C and at a maximum humidity of 85%. Electrical and optical parameters were tested on every produced chip not only to remove LEDs before packaging, which do not meet the specifications, but to control and optimise the applied technological steps. As an example we demonstrate a testing method for controlling the process and optimising the p-contact.Optimisation of n- and p-contact as well as the improvement of epitaxy helped to increase the light output power from 1 mW in 1998 to more than 6 mW at present when mounted in a 5 mm radial lamp. All electrical parameters of these high brightness LEDs could also be improved or at least kept in the demanded specification range.     

Ab initio study of the effect of doping on stacking faults in GaN

The influence of impurities on the basal plane stacking fault energy in GaN is investigated using density functional theory. It is found that silicon, indium, magnesium and carbon impurities each reduce the stacking fault energy by introducing changes to the bonding properties of the material. These bonding properties are analysed in terms of Mulliken charges and bond populations. It is found that the reduction in stacking fault energy correlates both with a reduction in the average anion charge and with an increase in the overlap population.