We present here a detailed investigation of the optical properties of GaN epilayers grown by low pressure MOVPE on sapphire substrates, using 2K photoluminescence as well as 2K reflectance spectroscopy. A large series of samples has been grown under eclectic conditions (V/III ratio, growth temperature, nitridation steps,...) which allows us to propose the first semi-quantitative investigation of the sample-dependent band gap energies. This dependence of the bandgap is analyzed in terms of i) residual stress, ii) exciton parameters and iii) deformation potential characteristics of the A, B, C excitons. the residual stress cannot be simply explained in terms of the differences between the thermal expansion coefficients of the various compounds, but are strongly correlated to the V/III growth ratio imposed during the growth, and subsequently to the influence of this parameter at the scale of electronic and structural characteristics of the deposited layers.

GaN plays a key role in the exploration of the properties of group-Ill nitrides. As grown GaN often shows a high electron concentration, e.g. 1019 cm−3, of as yet unidentified origin. Applying large hydrostatic pressure we studied the behavior of these donors and a frequently observed strong luminescence band at 3.42 eV. We find a drop of the electron concentration to 3×1017 cm−3 at 27 GPa and derive a binding energy of 126 meV for the neutral singlet donor level at this pressure. Such a pressure behavior of a donor is consistent with the model of strongly localized defects. Within the framework of a bandstructure calculation we predict the neutral level of this donor at 0.40 ± 0.10 eV above the conduction band edge at ambient pressure.

Phonons are thought to play a crucial role in the high thermal conductivity of AIN and ZrN. Using time-of-flight neutron spectroscopy, we have measured the phonon spectra of A1N and ZrN up to 300 meV (2400 cm−1). The one-phonon density of states (DOS) of AIN exhibits relatively sharp bands at about 33, 63, 83 and 91 meV. In addition, distinct multiple-phonon excitations were observed at ∼173 and 255 meV. The phonon DOS of ZrN displays similar features with the corresponding phonon energies shifted toward lower energies. The measured DOS of AIN is compared with results of molecular-dynamics simulations.

We present local density functional theory (DFT-LDA) studies of the structural properties of boron nitride in the layered hexagonal (h-BN), zincblende (c-BN), and wurtzite (w-BN) structures, performed using a fast implementation of the norm-conserving pseud-opotential plane-wave method. Quasiparticle band structures are then calculated for all phases by means of an efficient GW self-energy scheme. To our knowledge, these are the first GW quasiparticle calculations for wurtzite BN including local-field and dynamical screening effects. DFT-LDA band gaps as functions of pressure and uniaxial distorsion for h-BN are also discussed.

We present preliminary results of tight binding molecular dynamics (TBMD) simulations concerning the thermal effects on the structural and electronic properties of GaN. We derived a semiempirical tight binding (TB) potential which is able to reproduce the band structure and the phase diagram of GaN for zincblende, wurtzite and rock-salt phases. We have found that even at few hundreds K above the experimental melting temperature the local ordering is fairly well conserved, with the fraction of wrong bonds quite low. Defects states appear in the gap at approximately 2.3 eV in agreement to the experimental indication for annealed films.

Shallow and deep electronic defects in MOCVD-grown GaN were characterized by variable temperature Hall effect measurements, deep level transient spectroscopy (DLTS) and photoemission capacitance transient spectroscopy (O-DLTS). Unintentionally and Si-doped, n-type and Mg-doped, p-type GaN films were studied. Si introduces a shallow donor level into the band gap of GaN at ∼Ec - 0.02 eV and was found to be the dominant donor impurity in our unintentionally doped material. Mg is the shallowest acceptor in GaN identified to date with an electronic level at ∼Ev + 0.2 eV. With DLTS deep levels were detected in n-type and p-type GaN and with O-DLTS we demonstrate several deep levels with optical threshold energies for electron photoemission in the range between 0.87 and 1.59 eV in n-type GaN.

Various aspects of the electronic structure of the group III nitrides are discussed. The relation between band structures and optical response in the vacuum ultraviolet is analyzed for zincblende and wurtzite GaN and for wurtzite A1N and compared with available experimental data obtained from reflectivity and spectroscopic ellipsometry. The spin-orbit and crystal field splittings of the valence band edges and their relations to exciton fine structure are discussed including substrate induced biaxial strain effects. The band-offsets between the III-nitrides and some relevant semiconductor substrates obtained within the dielectric midgap energy model are presented and strain effects which may alter these values are discussed. The importance of lattice mismatch in bandgap bowing is exemplified by comparing AlxGa1−xN and InxGa1−xN.

We report on conductance and cyclotron resonance (CR) experiments on GaN epitaxial films grown by the OMVPE and HVPE techniques. From a precise determination of the electron effective mass the donor binding energy in the effective mass approximation (EMT) is calculated. We obtain 31.7 meV. The transport experiments on the HVPE films show that the conductance is thermally activated with an activation energy of 15 meV in contrast to the OMVPE films which showed temperature independent conductivity for temperatures between 4 and 100 K.

Wide bandgap III-V nitrides, such as GaN and AlN, have become topical in the near-term technology of blue lasers. We report detailed electronic band-structure calculations for (AlN)m(GaN)n [001] zinc-blende superlattices (SL), with m + n ≤ 12, using the all-electron full-potential linear-muffin-tin-orbital method. For n ≥ 3, the SL are found to have a direct band gap. For n ≤ 2 and m ≥ 3, all the band gaps are indirect. In ultrathin SL, m ≤ 3 and n ≤ 2, only (m, n)= (3,1) is found to have an indirect gap. The band offsets are estimated by calculating the core-level shifts of nitrogen atoms in the central planes of the GaN and A1N layers. The calculated densities of states, electron- and hole- effective masses (m), etc., as a function of m and n, are reported; a remarkable dependence of m on the number of layers is revealed.

In this paper, we present ensemble Monte Carlo based calculations of the steady state hole transport properties, i.e. average energy, drift velocity, and band occupancy of zincblende GaN. The Monte Carlo calculation includes the full details of the valence bands and a numerically determined scattering rate derived from an empirical pseudopotential calculation. Calculations are made for electric field strengths up to 1000 kV/cm. It is found that the average hole energies are much lower than the corresponding electron energies at comparable electric field strengths, and that some anisotropy in the drift velocity and average energy appears at the higher fields examined here.

Excitonic recombination processes in GaN films grown by low pressure metalorganic chemical vapor deposition technique have been studied in the temperature range between 6K to 320K by photoluminescence spectroscopy. Low temperature photoluminescence spectra of high resistivity films show well-resolved spectral features associated with the excitonic interband transitions. A detailed spectral analysis allowed us to estimate the exciton binding energy and the energy gap. Spectral studies of Si-doped GaN films demonstrate that the high energy recombination processes in these films are dominated by excitons bound to neutral Si donors. Comparison between the recombination channels in high resistivity and in Si-doped films indicated that Si has a larger exciton binding energy than the unknown pervasive donor in undoped materials. These results confirm the excellent electronic properties of the undoped and doped films.

We present a photoluminescence study of residual transition metal contaminants in hexagonal GaN layers. We observe three no-phonon lines peaking at 1.3 eV, 1.19 eV and 1.047 eV. The no-phonon line at 1.3 eV is caused by the internal electronic transition 4T 1→ 6A1 of Fe3+. The 1.19 eV emission, which was first attributed to Cr4+, is caused by Ti2+. GaN layers intentionally doped with Cr, V, or Ti during growth have been investigated. Only the Ti doped samples snow an intense sienal of the 1.19 eV emission. The experimental data of the luminescence center at 1.047 ev, which appears as natural contaminant only in GaN layers grown by the sandwich technique, fit best to the 4T2(F) → 4A2(F) transition of Co2+. The three no-phonon lines show characteristic phonon sidebands. Most of them correspond to phonon modes observed in Raman spectroscopy.

P-type GaN films were grown on sapphire substrates in a horizontal metalorganic chemical vapor deposition system using (C5H5)2Mg (Cp2Mg) as the p-dopant source. It is found that the acceptor concentration in the post-growth annealed GaN samples increases with the Mg flow rate and reaches a peak value of 1×1019 cm−3 at Mg flow rate of 0.84 ĉmol/min. The films remain semi-insulating even after annealing when the Mg flow rate is higher than 1.08 ĉmol/min. The effects of annealing temperature and duration on the electrical properties of GaN are also investigated. The results confirm that a 800 °C, 30 minutes post-growth annealing in N2 ambient is sufficient to activate most of the Mg atoms. In addition, study of rapid thermal annealing of Mg-doped GaN was carried out and the results show that the p-type acceptor concentration obtained is comparable to the results obtained using furnace annealing process. Finally, GaN light emitting diodes (LEDs) are demonstrated using undoped layer as the n-type base layer in a p-on-n structure. The light emission spectra are dominated by the 430 nm peak, accompanied with two relatively weak peaks located at 380nm and 550nm.

We present ab-initio calculations on energetics and geometries of atomic hydrogen, of several candidate acceptors, and of H-acceptor complexes in wurtzite GaN For the H-Mg complex in Mg-doped GaN, we calculate the vibrational frequencies of H. Hydrogen is found to be a negative-U center. H-acceptor complex formation is always exothermic. Substitutional Be has a low formation energy and a shallow impurity level, which makes it a good candidate for p-doping in MBE growth. CN appears not to be shallow. Atomic hydrogen incorporation in undoped GaN is disfavored in an H2 atmosphere; it becomes favorable in p and n-type conditions in atomic H environments.

A nitrogen vacancy in zinc-blende structure gallium nitride (c-GaN) is investigated by the plane-wave pseudopotential (PWPP) and tight binding-linear combination of muffin tin orbitals (TB-LMTO) methods using 32- and 64- atom supercells. The relaxation of the nearest Ga atom to the vacancy site is found to be inward by 0.069 a.u., with a relaxation energy of 0.04 eV/N-atom vacancy. The shell-projected, total and partial densities of states and the charge density maps are obtained to provide detailed information on energy and spatial localization of the N vacancy states.

Ab initio local-density-functional calculations are presented for bulk A1N, GaN, and InN in the wurtzite, zincblende, and rocksalt structures. Structural transition pressures and deformation potentials of electronic gaps are investigated. In addition, we study the band offset at the polar (0001) and non-polar (1010) AIN/GaN interfaces. Within AIN-on-GaN epitaxial conditions, we obtain valence-band offset values close to 0.7 eV for both interfaces. From the macroscopic field appearing along the growth direction of the polar interface (tentatively attributed to AIN macroscopic polarization), an estimate of the macroscopic dielectric constant of GaN is extracted. All calculations employed conjugate-gradient total-energy minimizations, ultrasoft pseudopotentials, and plane waves at 25 Ryd cutoff.

We have investigated the relationship of the Hall electron mobility to the background carrier concentration in low pressure MOCVD grown GaN. The highest electron mobility (400 cm2 /V•s) of the unintentionally doped GaN was obtained at a carrier concentration of 1×1017 cm−3 and samples with carrier concentrations lower than this exhibited lower mobilities. SIMS analysis shows C and O concentrations in the range of 2–3×1016 cm−3 and H in the 2–3×1017 cm−3 range. Structural defects, stoichiometry and impurities in the GaN films grown under different conditions are investigated to understand their relationship to the electron Hall mobilities. In particular, different growth temperatures and pressures were used to grow undoped GaN and modify the background doping effect of the impurities.

GaN films and GaN/AlGaN heterostructures have been gro wn by MBE. GaN films doped with varying levels of Mg indicate effective mass acceptor at low doping concentrations, as determined from strong photoluminescence emission at about 380 nm. As the Mg concentration is increased the photoluminescence emission line red shifts considerably, indicating the formation of Mg-related or induced complexes whose lifetimes are relatively short. GaN/AlGaN separate confinement heterostructures grown on sapphire show strong near ultraviolet stimulated emission at room temperature in a side-pumping configuration. The pumping threshold for stimulated emission at room temperature was found to be ∼90 kW/cm2. Initial GaN films grown on ZnO substrates show the A exciton in low temperature photoluminescence. ZnO is being considered for nitride growth because of its stacking order and close lattice match.

In this paper we demonstrate the feasibility of growing III-N semiconductors on novel lattice-matched oxide substrates. Although the growth parameters are not yet optimal, acceptable GaN layers have been grown.

The optical second-harmonic (SH) response of a reverse biased gallium nitride (GaN) film was investigated for SH photon energies near the fundamental absorption edge. With the application of a DC electric field (∼ 100 to 220 kV/cm) along the optical axis of the sample, a strong two-photon resonance was observed in the specular reflected SH signal. This resonance was attributed to electric-field induced SH generation, EFISH, a third-order nonlinear response which arises from an induced polarization that is linearly dependent on the amplitude of the DC field. The EFISH contribution was spectrally localized at the bandedge, demonstrating the potential of SH spectroscopy for analysis of critical points in the band structure of semiconductors.