Polarity issues affecting III-V nitride semiconductors are reviewed with respect to their determination and control. A set of conditions crucial to the polarity control of GaN is provided for each of the following growth techniques; molecular beam epitaxy (MBE), pulsed laser deposition (PLD) and hydride vapor phase epitaxy (HVPE). Although GaN films might have been deposited by identical growth methods using the same buffer layer technologies, there is often a conflict between the resulting polarities achieved by different research groups. In this paper, we present the implications of the conditions used in each of the processes used for two-step metalorganic chemical vapor deposition (MOCVD), demonstrating systematic control of the polarity of GaN films on sapphire substrates. The potential for confusion in polarity control will be explained, taking into account the implications clarified in our studies. The correlation between the polarity and the growth conditions will be discussed in order to provide a mechanism for the determination and control of the crystal polarity during the growth of GaN films.

We report the growth of high quality GaN epitaxial layers by rf-plasma MBE. The unique feature of our growth process is that the GaN epitaxial layers are grown on top of a double layer that consists of an intermediate-temperature buffer layer (ITBL), which is grown at 690°C and a conventional low-temperature buffer layer deposited at 500°C. It is observed that the electron mobility increases steadily with the thickness of the ITBL, which peaks at 377 cm2V−1s−1 for an ITBL thickness of 800 nm. The PL also demonstrated systematic improvements with the thickness of the ITBL. Our analyses of the mobility and the photoluminescence characteristics demonstrate that the utilization of an ITBL in addition to the conventional low-temperature buffer layer leads to the relaxation of residual strain within the material resulting in improvement in the optoelectronic properties of the films. A maximum electron mobility of 430 cm2V−1s−1 can be obtained using this technique and further optimizing the growth conditions for the low-temperature buffer layer.

We developed a unique preparation technique to eliminate surface damage on the c-plane of sapphire and render it atomically flat. AFM images of c-plane sapphire annealed at 1380 °C for 1hour show terrace-like features with about 0.2 μm long terraces. The GaN layers grown by MBE on annealed sapphire have [0 0 2] symmetric and [1 0 4] asymmetric full width at half maximum (FWHM) of about 60 and 132 arcsec, respectively. This compares with 408 and 600 arcsec, respectively, for GaN grown on sapphire having gone through conventional chemical cleaning.

The growth rate evolution versus V/III ratio and substrate temperature was studied by means of optical reflectivity during MBE of GaN layers using NH3 as nitrogen source. The GaN desorption becomes observable at temperatures above 800°C and causes the reduction of growth rate accompanied with the surface roughening at temperatures above 850-870°C. Unlike GaAs, which evaporates in accordance with the action mass law, the desorption rate of GaN is found to be almost independent of V/III ratio within the N-rich growth conditions. The activation energy for GaN desorption during the growth is found to be (3.2±0.1)eV. This value is very close to the activation energy for free evaporation. At V/III ratio values exceeding 200 the GaN growth rate reduction caused by violation of the molecular flow regime is observed. The Mg-doped samples grown under these extreme conditions tend to have improved acceptor activation and thus p-type conductivity.

Molecular beam epitaxy growth utilising an RF-plasma nitrogen source was used to study surface reconstruction and surface morphology of GaN on GaAs (001) at 580 °C. While both the nitrogen flow and plasma excitation power were constant, the grown layers were characterised as a function of Ga-flux. In the initial growth stage a (3×3) surface reconstruction was observed. This surface periodicity only lasted up to a maximum thickness of 2.5 ML, followed by a transition to the unreconstructed surface. Samples grown under N-rich, Ga-rich and stoichiometric conditions were characterised by high-resolution scanning electron microscopy and atomic force microscopy. We found that the smoothest surfaces were provided by the N/Ga-ratio giving the thickest layer at the (3×3)=>(1×1) transition. The defect formation at the GaN/GaAs interface also depended on the N/Ga-flux ratio.

Low temperature photoluminescence spectra of Be-doped layers grown on Si (111) by molecular beam epitaxy have been analyzed. Emissions at 3.466 eV and 3.384 eV, and a broad band centered at 2.4-2.5 eV are observed. Their evolution with temperature and excitation power, and time resolved PL measurements ascribe an excitonic character for the luminescence at 3.466 eV, whereas the emission at 3.384 eV is associated with a donor-acceptor pair transition. This recombination involves residual donors and Be-related acceptors, which are located around 90meV above the valence band, confirming Be as the shallowest acceptor reported in GaN. The intensity of the band at 2.4-2.5 eV increases with the Be content. This emission involves a band of deep acceptors generated by Be complex defects, as suggested by the parameter g = 2.008 ± 0.003 obtained by photoluminescence-detected electron paramagnetic resonance.

A quasi-thermodynamic model accounting for kinetics of molecular nitrogen evaporation is applied to simulate the growth of binary and ternary group-III nitrides using atomic group-III elements and molecular ammonia as the sources. The values of the molecular nitrogen evaporation coefficients from the surface of GaN and AlN necessary for the simulation are extracted from experiments on free evaporation of the crystals in vacuum, while for InN only estimates are available. The growth process of AlN and InN is studied by analyzing the composition of the desorbed vapor species that are thought to influence the native defect formation in group-III nitrides. Different channels of desorption from the surfaces of group-III nitrides (related either to group-III atoms or to their hydrides) are compared. Specific features of the growth processes under the metal-rich and N-rich conditions are analyzed. The developed approach is extended to study the growth of the ternary compounds GaInN and AlGaN. The growth rate of ternary compounds versus temperature shows a two-drop behavior corresponding to the rapid increase of the respective group-III atom desorption. The effect is accompanied by a corresponding stepwise change in the solid phase composition. Factors retarding the growth of ternary compounds — the miscibility gap related to internal strain accumulated in the solid phase due to the lattice mismatch of binary constituents, and the extra liquid phase formation during growth — are discussed with respect to GaInN.

GaNxAs1−x-layers were grown by solid source molecular beam epitaxy using N2 and excitation by RF-plasma source. The average nitrogen concentration, x, determined by secondary ion mass spectrometry, ranges from isovalent nitrogen doping in GaAs up to GaN. X-ray diffraction revealed two peaks, close to the ones for GaAs(002) and the GaN(002) diffraction, respectively. The position of both peaks moved slightly as a function of nitrogen content. Scanning electron microscopy indicated a rough surface structure with improved smoothing for low and high nitrogen compositions. The rough surface is partly due to crystallite formation when mixing arsenic and nitrogen as a result of phase separation between the GaAs and GaN. In ternary films with very high nitrogen composition there were structural features with a different contrast. These were crystallites that arose at the interface and grew up to the surface.

Heteroepitaxy of hexagonal symmetry materials is more complicated than in the more usual case of cubic systems. In the growth of layers on the (0001) surfaces, the misfit dislocations always exhibit a screw component that leads to rotation of the epilayer in a 3 dimensional growth mode. The size of the islands will depend on many factors among which the substrate surface treatment, prior to growth, may be a predominant one. In this work, a comparative study is carried out for samples grown on plasma treated samples, with and without additional substrate annealing prior to epitaxy. It is found that the defect density can be brought below 109 cm−2, which is better than one order of magnitude in comparison to the layers grown on sapphire substrates. On top of the annealed substrates, the island growth is not obvious. Whereas, misorientations as large as a few degrees can be measured inside the layers on top of non annealed substrates, justifying the occurrence of high densities of threading dislocations.

Ammonia is investigated as nitrogen precursor for molecular beam epitaxy of group III nitrides. With the particular on-surface cracking approach, NH3 is dissociated directly on the growing surface. By this technique, molecular beam epitaxy becomes a serious competitor to metal organic vapor phase epitaxy. Thermodynamic calculations as well as experimental results reveal insights into the growth mechanisms and its differences to the conventional plasma approach. With this knowledge, homoepitaxially GaN can be grown with record linewidths of 0.5 meV in photoluminescence (4 K). GaN layers on c-plane sapphire also reveal reasonable material properties (photoluminescence linewidth 5 meV, n ≈ 1017 cm−3, μ ≈ 220 cm2/Vs). Beside GaN growth, p- and n-doping of GaN as well as the growth of ternary nitrides are discussed. Using the presented ammonia approach UV-LEDs emitting at 370 nm with linewidths as narrow as 12 nm have been achieved.

High quality AlN layers with full widths at half maximum values of 10 arcmin and average surface roughness (rms) of 48Å were grown by molecular beam epitaxy on Si(111) substrates. A systematic study and optimization of the growth conditions was performed in order to use these AlN layers as buffers in the growth of GaN films. Atomic force microscopy (AFM) and X-ray diffraction (XRD) techniques were employed to determine the surface and structural quality of the layers. Best AlN films were obtained at high substrate temperatures (Tsubs>900°C) and III/V ratios close to stoichiometry. Growth conditions with III/V ratios beyond stoichiometry (Al-rich) did not further improve the crystal quality. In these cases a higher substrate temperature is needed to prevent condensation of Al on the surface. GaN films with full width at half maximum of 10 arcmin and improved optical properties were grown on top of optimized AlN buffer layers.

In order to identify the strain relaxation mechanism, Molecular Beam Epitaxy of wurtzite GaN on AlN was monitored in situ using Reflection High Energy Electron Diffraction (RHEED). In the substrate temperature range between 620°C and 720°C, a Stransky-Krastanov (SK) transition was evidenced, resulting in a 2D-3D transition after completion of 2 monolayers, with subsequent coalescence of 3D islands, eventually resulting in a smooth surface. Quantitative analysis of the RHEED pattern allowed us to determine that island formation is associated with elastic relaxation. After island coalescence, a progressive plastic relaxation is observed. The size and density of 3D islands was varied as a function of the growth parameters. AFM experiments revealed that the size of the GaN islands, about 8 nm large and 2 nm high, was small enough to expect quantum effects. It was found that capping of the islands by AlN resulted in a smooth surface after deposition of a few monolayers allowing us to grow a »superlattice» of islands by periodically repeating the process.

In N-rich growth conditions, prismatic domains were formed in the initial stage of a cyclotron assisted MBE of GaN over 6H-SiC (0001). They exhibit {10 0} facets and are either voids or amorphous phase. Their density is of a few 109 cm−2 and they are located in a 50 nm layer closest to the substrate surface.

We report the growth of AlxGa1−xN alloys on (0001) sapphire by the method of Electron Cyclotron Resonance-assisted Molecular Beam Epitaxy (ECR-MBE). The films were doped n-type with silicon at carrier concentration levels from 1016 to 1019 cm−3. SEM studies reveal smooth surface morphology consistent with the observed 3×4 surface reconstruction in the RHEED pattern. Independent determination of the Al-concentration and the lattice constant of the alloys shows that Vegard’s rule is obeyed in the pseudo-binary GaN-AlN system. The bandgap of the alloys, determined by transmission and photoluminescence measurements, was found to depend linearly on Al-concentration.