We have performed systematic first-principles pseudopotential local density functional calculations of stacking faults in GaN and AlN. Their band offsets and the charge accumulation at stacking fault interfaces has been investigated, taking fully into account the effects of lattice relaxation and electric polarization. We find the stacking fault junctions to be of type I in both materials. However, the intrinsic valence band offsets are close to zero, so that the conduction band offsets result mostly from the differences in the energy gaps between the cubic and wurtzite phases. The charge accumulated at the interface between the cubic and wurtzite phase is found to be 0.009 and 0.003 C/m2 for the AlN and GaN stacking fault, respectively.

Gallium Nitride (GaN) thin films were successfully grown by electron cyclotron resonance molecular beam epitaxy (ECR-MBE), gas source MBE (GSMBE), and chemical beam epitaxy (CBE). Time of flight mass spectroscopy of recoiled ions (TOF-MSRI) and reflection high energy electron diffraction (RHEED) were used in-situ to determine the surface composition, crystalline structure, and growth mode of GaN thin films deposited by the three MBE methods. The substrate nitridation and the buffer layers were monitored and optimized by TOF-MSRI and RHEED. For GSMBE, the gallium to nitrogen ratio is found to correlate well with ex-situ optical properties. In the case of CBE, carbon incorporation determines the surface morphology, crystalline quality and optical activity of the epilayers.

Growth of GaN/Al2O3 layers by MOVPE has been investigated. Precise optimization of the growth parameters results in films with extremely high electron mobility: 900 cm2/Vs at 300K and 4000 cm2/Vs at 77K. The influence of the growth parameters on film properties like morphology, crystallographic structure, and the concentration of electrically active defects is presented. The mechanism of dislocation density reduction is proposed to explain the obtained results.

The electrical and electroluminescent properties of MOVPE GaN p-n homojunctions have been analyzed as a function of temperature and bias. Electroluminescence is observed for V>3 V under dc and ac conditions. The main emission at low T is a donor-acceptor transition involving shallow acceptors, though it disappears at higher T due to the ionization of the acceptors and compensation by ionized donors. Room temperature dc and ac electroluminescence spectra evolve under increasing bias from a blue-shifting visible band involving deep states at the p-type side of the p-n junction, to a band-to-band UV recombination at high bias. In agreement, the superlinear dependence of light-current characteristics at low current injection becomes linear when the defects are saturated. Time analysis of the spectra vs pulse duration and duty cycle allows the determination of the visible radiative recombination and relaxation times associated to the Mg-related deep states, which are found to behave as acceptors lying 0.55 eV above the valence band. A simple 3-level model is able to explain the visible emission, which involves the conduction band (or shallow donor) and those deep acceptors in the p-layer. Optimum UV/visible ratio emission requires intense and relatively long pulses, with a high duty cycle to impede visible recombination.

Microcrystals of BN, AlN and GaN were obtained by the AMMONO method, in which nitridization of metal occurs in supercritical ammonia, at relatively low temperature and pressure conditions (below 550°C and 5 kbar). The reaction rate was regulated by the amount of mineralizers, i.e. alkali metal amides.

All crystals obtained by AMMONO method revealed intense and homogenous luminescence. Significant improvement of the optical properties was observed for crystals grown in the presence of Rare Earth elements. For such GaN crystals, helium temperature photoluminescence spectra were dominated by near-band-gap recombination. Exciton lines were extremely narrow, with full-width half-maximum (FWHM) as low as 1 meV. The concentration of uncompensated shallow donors in AMMONO GaN determined by electron paramagnetic resonance measurements was below 5×1015 cm−3.

Clean and As covered zinc-blende and wurtzite GaN surfaces have been investigated employing density-functional theory calculations. For clean GaN surfaces our calculations indicate the stability of several novel surface structures that are very different from those found on traditional III-V semiconductors. Adding impurities commonly present in significant concentrations during growth strongly modifies surface reconstructions and energies. In particular, we find that arsenic has a low solubility and significantly stabilizes the cubic GaN (001) surface making it interesting as a potential surfactant. Finally, we have studied the diffusion of Ga and N adatoms on both the equilibrium and non-equilibrium surfaces. Our calculations reveal a very different diffusivity for Ga and N adatoms: While Ga adatoms are very mobile at typical growth temperatures, the diffusion of N adatoms is slower by several orders of magnitude. These results give insight into the fundamental growth mechanisms and allow conclusions concerning optimum growth conditions.

GaN undoped layers of good morphology, good crystallinity and electrical properties were grown on c-plane sapphire substrates by the atmospheric pressure MOVPE technique using a new multi-buffer growth approach. A suitable buffer layer growth technique was worked out which enabled growth of GaN layers with properties superior to those grown in a conventional process scheme. Additional buffer layers, deposited with increasing temperature and increasing V/III molar ratio, were inserted between the low temperature buffer layer and the high temperature GaN layer grown on it. The c and a lattice constants of the high temperature GaN overgrown layer were evaluated from X-ray data. The layer mosaicity and c-lattice parameter variation were determined. The relationship between c and a lattice parameters and the second buffer layer growth scheme has been studied. The effect of second buffer layer growth conditions, buffer layer annealing time as well as the influence of V/III molar ratio during the high temperature GaN deposition on the crystalline and electrical properties of overgrown GaN epitaxial layers are presented. Characterization includes surface morphology examination by SEM and Nomarski optical microscope, X-ray diffraction and C-V measurements.

Thick AlGaN layers and GaN/AlGaN heterostructures were grown by low pressure MOCVD on (0001) sapphire substrates utilizing a low temperature AlGaN buffer layer. The distribution of Al in the thick AlGaN layers was observed to be non-uniform as a function of depth. The Al content gradually increases from the substrate towards the epilayer surface. Moreover, fluctuations of Al content are also noticeable. The saturation of impurity-related emission with increasing current density was observed in EL spectra of LEDs consisting of AlGaN/GaN/AlGaN DH sandwiched by a 2 μm-thick bottom layer of GaN:Si and 0.5 μm-thick layer of GaN:Mg. The dominant near-band edge emission of the GaN active layer was found to be strongly absorbed in the thick bottom layer. Utilizing a 2 μm-thick AlGaN bottom layer instead of the GaN one allowed the absorption edge to be shifted towards higher energies. A single peak at 362 nm with FWHM of 14 nm was observed in this type of LED. Luminescence properties of various types of heterostructures are also discussed.

Optical properties of the GaNxAs1−x layers grown on (001) GaAs substrates by molecular beam epitaxy have been studied. The samples can be classified into three categories with respect to the concentration of N, as determined by x-ray diffraction and secondary-ion mass spectrometry: (i) with doping nitrogen concentration, (ii) with average content of N less than 30 %, and (iii) with x close to 100 %. From optical measurements of photoluminescence and Raman scattering, combined with analysis of x-ray diffraction spectra, different phases are observed in the GaNxAs1−x layers: GaAs, GaN and the solid ternary solution GaNxAs1−x. We have estimated the fundamental band-gap energy in the GaNxAs1−x alloy with low nitrogen concentration (up to x = 0.04) from absorption measurements, and in GaNxAs1−x with low arsenic concentration (up to 1−x = 0.04) - from photoluminescence spectra. An analysis of the dependence of the experimental values of the GaNxAs1−x band-gap energy on the nitrogen composition indicates a constant bowing parameter b as large as b = -18 eV.

A database for thermodynamic properties of group-III nitrides and relevant species involved into growth of these materials is developed in this paper. Standard formation enthalpies of materials and coefficients of polynomial approximations of the reduced Gibbs free energies are collected in the tables. They allow one to determine the Gibbs free energy, enthalpy, entropy and specific heat of a species as a function of temperature. The database covers solid and gaseous group-III nitrides, elemental species, gaseous metal-organic compounds, chlorides and hydrides of group-III elements, nitrogen containing precursors and organic byproducts of various chemical reactions proceeding during growth processes. Thermodynamic properties of adducts which can be formed in the vapor phase while mixing ammonia and metal-organic compounds are presented in the database as well. Much of the data given in this paper is presented for the first time. All the data are checked for self-consistency and therefore can be used for thermodynamic calculations.

A study of the optoelectronic properties of strained 40 nm Ga1−xInxN layers on GaN films is presented. The fact of pseudomorphic strain leads to a new interpretation of the film composition when derived from x-ray scattering. In addition we directly confirm that strain induces huge piezoelectric fields in this uniaxial system by the observation of Franz-Keldysh oscillations in photoreflection. As a function of composition (0 < x < 0.2) and strain we derive the electronic band gap energy and the piezoelectric field strength. We interpret both in terms of effective bowing parameters and piezoelectric coefficients, respectively. From a spatially resolved micro photoluminescence at room temperature we find no evidence for spatial band gap or composition variations of more than 60 meV over the length scale from 1 to 50 μm (x=0.187) in our material. At the same time, an observed discrepancy between photoluminescence peak energy and photoreflection band gap energy increases with x to some 160 meV. We attribute this redshift to photon assisted tunneling in the huge piezoelectric fields (Franz-Keldysh effect).

Crystal morphology of GaN layers grown on Si(111) evolves from whisker-like microcrystals to compact films as a function of the III/V ratio. Small changes in the III/V ratio (from Ga-rich to N-rich) during the growth of a compact layer result in the appearance of microcrystals on the top of the layer, indicating a sharp transition between the two growth regimes.

Four different morphologies are obtained by increasing the III/V ratio: a) completely columnar whisker-like samples exhibiting a pair of intense excitonic emissions at 3.471−3.478 eV; b) a mixture of compact regions with columnar microcrystals showing two pairs of excitonic emissionsnbsp c) compact layers with very small microcrystals on the top surface with a weaker dominant transition at 3.415 eV (±5meV) and, d) full compact and smooth layers with a single dominant excitonic emission at 3.466 eV. A combination of PL measurements with SEM photographs and CL imaging reveals that both pairs of emissions in samples b) come from the columnar microcrystals. The high energy pair (3.471−3.478eV) is attributed to the free-exciton A and a donor-bound exciton while the low energy pair (3.452−3.458eV) is assigned to acceptor-bound excitons associated to valence bands Γ9v and Γ7uv. Power and temperature dependence together with time-resolved data show that the dominant peak at 3.415eV (± 5meV) present in samples c) correspond to a donor-acceptor transition. CL measurements as a function of electron beam energy (depth) also indicate that this emission is more intense towards the interface between the layer and the sample. Finally, the excitonic emission in samples d) is shifted to lower energies due to residual biaxial tensile strain of thermal origin.

Far infrared magnetooptical investigations of shallow donors in epitaxial MOCVD GaN layers show two types of shallow donors. In relaxed layers, a donor with an ionization energy of 35 meV was found. In strained, undoped and Si doped samples, a donor with ionization energy 32.5 meV was observed. From the p state splitting in magnetic field, the cyclotron effective mass for conduction electrons was found to be m*=0.222 m0.

Investigations of luminescence and ESR of silicon doped GaN layers are presented. The room temperature electron concentration in the investigated layers ranged from 1.7×1017 cm−3to 7×1018 cm−3. The layer with the highest electron concentration has metallic conductivity. The ESR investigation revealed the presence of a characteristic asymmetric resonance whose intensity grows with increasing silicon impurity concentration. This resonance, corresponding to perpendicular g=1.985 and parallel g=1.983 has been observed in Si doped layers with electron concentration below the Mott transition. It seems that the ESR resonance is due to isolated Si donors. It has been found that the total PL emission increases with the silicon concentration, and is strongest in the layer with metallic conductivity. This indicates that silicon impurities eliminate non-radiative recombination centers or they create a new path of radiative recombination. The AFM and low temperature PL measurements indicate that strain relief via creation of pinholes may be responsible for the increase of radiative emission in GaN:Si epilayers.

A detailed threshold analysis of room-temperature pulsed operation of GaN/AlGaN/AlN vertical-cavity surface-emitting lasers (VCSELs) is carried out. The model takes advantage of the latest results concerning gain in active regions, material absorption in the cladding layers, as well as cavity diffraction and scattering losses. The simulation showed that although VCSELs with single (S) or multiple (M) quantum-well (QW) active regions exhibit lower threshold currents, they are much more sensitive to any increase in optical losses than their bulk counterparts. In particular, decreasing the active region radius of gain-guided QW VCSELs below 5 μm (which increases diffraction losses) or increasing dislocation densities (which, in turn, raises scattering losses) gives an enormous rise to their threshold currents. Therefore small-size GaN VCSELs should have an index-guided structure. In the case of MQW VCSELs, the optimal number of quantum wells strongly depends on the reflectivities of resonator mirrors. According to our study, MQW GaN lasers usually require noticeably lower threshold currents compared to SQW lasers. The optimal number of QW active layers is lower in laser structures exhibiting lower optical losses. Although the best result occurred for an active region thickness of 4 nm, threshold currents for the various sizes differ insignificantly.

Three silicon-doped 3 µm thick GaN epilayers were grown simultaneously by metalorganic chemical vapour deposition on (0001) sapphire substrates misorientated by 0°, 4° and 10° toward the m-plane (100). A comparative study of these epilayers was undertaken using photoluminescence (PL) spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), cathodoluminescence (CL) imaging, CL spectroscopy and Hall effect measurements. Low temperature PL of the 0° and 4° epilayers shows donor bound exciton (BE) emission between 3.47 and 3.48 eV and a low level of yellow band emission. The peak intensities of both emission bands are a factor of 2 higher for the 4° layer. In the 10° epilayer, the BE band is 3x stronger than in the 0° epilayer but there is no discernible yellow band. However, a number of additional bands appear at 3.459, 3.417, 3.362, 3.345, 3.309, and 3.285 eV. These bands, some of which are acceptor related, may be attributed to the presence of structural defects in this epilayer, pointing to an abrupt degradation of its structural quality compared to the others. This degradation is confirmed by AFM studies. On a 20 µm x 20 µm image the 0° and 4° epilayers exhibit smooth surface morphologies, while the 10° epilayer shows a high density of hexagonal pits. Finally, SEM images reveal the surface of the 10° epilayer to be “streaked” and pitted. Low temperature CL images at 3.48 eV (bound exciton region) show random spotty emission, while those at 3.28 eV and 3.41 eV exhibit a streaky appearance similar to the SEM image. This suggests that these luminescence bands are indeed associated with structural defects.

Au Schottky diodes were prepared by vacuum evaporation or by plasma sputtering on n-AlGaN(Si) films with Al mole fractions of 0, 0.11 or 0.23. The barrier heights were deduced from C-V and I-T measurements. The difference between the C-V and I-T results was less than 0.1 eV for the barriers deposited at 300 °C on HF etched samles with prior in situ heating at 450 °C. For low deposition temperatures (about 150°C) C-V and I-T methods give results differing by some tenths of an eV. For deposition temperatures exceeding 450°C the diodes were very leaky. The barrier heights were 0.8 eV, 0. 9 eV and 1.1 eV for AlGaN with compositions of 0, 0.11 and 0.23. For plasma sputtered diodes on GaN and AlGaN (x=0.11) samples, the difference in C-V and I-T results was quite considerable and admittance spectroscopy indicated the presence of deep electron traps at 0.12-0.14 eV that were absent in vacuum evaporated diodes. For similar diodes on AlGaN(x=0.23) samples the results of C-V and I-T measurements were very close and no traps at 0.12-0.14 eV could be detected. This difference is most likely due to damage caused by low energy ions. More Al-rich films are less susceptible to such damage. Persistent photocapacitance was observed in n-AlGaN Schottky diodes after illumination at 85K.

Using optimised growth processes for an AIX 2000 HT Planetary® Reactor a high material quality and high potential device yield are demonstrated. Doping levels for GaN single layers from 1·1020 cm−3 free electrons to semi-insulating to 1·1018 cm−3 free holes with state-of-the-art layer resistance uniformities especially for n-type layers are shown. Both AlGaN and GaInN with composition homogeneities of better than 1 nm photoluminescence peak-wavelength standard deviation are displayed. Finally, examination of optically pumped laser action in simple double-hetero structures is quoted to prove the quality of the material.

We analyse by means of transmission electron microscopy (TEM) and atomic force microscopy (AFM) the strain relaxation mechanisms in InGaN layers on GaN as dependent on the In content. At the experimentally given thickness of 100 nm, the layers remain coherently strained, up to an In concentration of 14 %. We show that part of the strain is reduced elastically by formation of hexagonally facetted pinholes. First misfit dislocations are observed to form at pinholes that reach the InGaN/GaN interface. We discuss these results in the framework of the Matthews-Blakeslee model for the critical thickness considering the Peierls force for glide of threading dislocations in the different slip systems of the wurtzite lattice.

We report ongoing experiments on the growth of GaN by hydride vapor phase epitaxy (HVPE), using a newly designed Aixtron horizontal reactor. Growth was carried out on c-plane Al2O3 substrates on which a thin GaN layer had been predeposited by MOVPE and patterned using a dielectric mask. The mask pattern was designed to give information on the growth rate and morphology along different directions, and contained both a star-shaped pattern and arrays of parallel stripes of various widths and orientations. All growths were performed at atmospheric pressure and ~1050°C deposition temperature. For the range of experimental conditions investigated the maximum ratios of lateral to vertical growth velocities of around 2 and coalescence of the layer after approximately 10 μm of growth were observed for stripes oriented along the <100> direction.