Luminescence, induced absorption and degenerate four-wave mixing experiments are perform on GaN epilayers grown on a sapphire substrate by MOCVD.

We measure the nonlinear behavior of the luminescence spectra near the excitonic resonance, by using an excitation at 4.026 eV from an excimer laser. At low intensities of excitation, spectra show a saturation of the I2 line due to the finite donor density in the sample. Higher intensities of excitation induce collision processes between photo-created quasi-particles.

Using a dye laser as a pump beam, we measure the induced variation of absorption of a probe beam as a function of the intensity and of the wavelength of the excitation. With increasing intensities of the pump beam, transmission spectra show a red-shift of the absorption edge and of the excitonic resonance.

Pulsed degenerate four-wave mixing experiments were performed using the third harmonic of a picosecond Nd-YAG laser at 3.492 eV. A characteristic time constant of 16 ps has been measured, which is independent of the temperature, spacing of the interference fringe and of the intensity of the pump beams.

We have studied the dependence of the absorption edge and the refractive index of wurtzite AlxGa1−xN films on composition using transmission, ellipsometry and photothermal deflection spectroscopy. The Al molar fraction of the AlxGa1−xN films grown by plasma-induced molecular beam epitaxy was varied through the entire range of composition (0 ≤ x ≤ 1). We determined the absorption edges of AlxGa1−xN films and a bowing parameter of 1.3 ± 0.2 eV. The refractive index below the bandgap was deduced from the interference fringes, the dielectric function between 2.5 and 25 eV from ellipsometry measurements. The measured absorption coefficients and refractive indices were used to calculate the design and reflectivity of AlGaN-based Bragg reflectors working in the blue and near-ultraviolet spectral region.

Au/GaN and Pt/GaN contacts have been studied with XPS. According to XPS depth profiling, the N signal is weak in the region below the metal contact and the Pt or Au signal decreases much more slowly than expected for a sharp interface. Next, we have performed in situ studies of the formation of Au contacts on GaN. In contrast to the results from depth profiling, we observe 2D growth and little or no chemical interaction between Au and GaN. This suggests that conventional calculations of sputtering yields and ion-beam-induced mixing cannot be applied to the analysis of noble metal/GaN depth profiles. Heating during or after Au deposition results in strong clustering, observed by both XPS and AFM. The Schottky barrier height measured by XPS is 1.15 eV.

We present four wave mixing experiments on GaN. We find an intrinsic homogeneous broadening of the A-exciton of 1.67 meV. A pronounced beating with a period of 0.52 ps is observed at excitation energies between the A- and the B-exciton and corresponds to an energy splitting of 7.98 meV of A- and B-exciton.

High-excitation processes like biexciton decay and recombination of an electron-hole-plasma are discussed as efficient mechanisms for lasing in blue laser diodes [1]. Therefore, the investigation of these processes is of fundamental importance to the understanding of the properties of GaN as a basic material for optoelectronical applications. We report on comprehensive photoluminescence and gain measurements of highly excited GaN epilayers grown by metal-organic chemical vapor deposition (MOCVD) over a wide range of excitation densities and temperatures. For low temperatures the decay of biexcitons and the electron-hole-plasma dominate the spontaneous-emission and gain spectra. A spectral analysis of the lineshape of these emissions is performed and the properties of the biexciton and the electron-hole-plasma in GaN will be disscused in comparison to other wide-gap materials. At increased temperatures up to 300 K exciton-exciton-scattering and band-to-band recombination are the most efficient processes in the gain spectra beside the electron-hole-plasma.

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.

The ternary alloy GaAlN has been grown by low pressure MOVPE (76 Torr) using triethylgallium, trimetylaluminum and ammonia as precursors. The alloy layers were grown on (0001) sapphire substrates using a low temperature AlN buffer. All layers were deposited at a growth temperature of 980°C. Only the aluminum/gallium ratio in the gas phase was changed, keeping the total group III molar flow rate and V/III molar ratio constant.

The aluminum incorporation versus gas phase composition was determined experimentally, using energy dispersive analysis of X-rays (EDAX), and X-ray diffraction. We propose a model, taking into account kinetically limited mass transport of group III species in the gas phase, which describes well the data.

The structural quality of the layers was investigated using X-ray diffraction and TEM experiments.

A degradation of the materials quality is observed with increasing Al content. In this case, growth originate on the buffer grains facets resulting in a “ two directional » growth. This phenomenon, being markedly enhanced when increasing the Al content will be detailed in this paper.

Optical thresholds, that correspond to a level located at 1 eV above the valence band, are observed by photocapacitance techniques in n-type Mg-doped GaN. In undoped GaN, this level has been previously related to the yellow emission detected by photoluminescence. In Mg-doped GaN, this yellow luminescence is only observed for excitation energies below the Mg-related band (2.9 - 3 eV). This result evidences that Mg-doping may reduce but not avoid the formation of the yellow band related defects in n-type and semiinsulating Mg-doped samples. The fact that the yellow luminescence is not observed for excitation energies above the bandgap may be justified by a higher efficiency of the Mg-related recombination path.

We have investigated the properties of InGaN grown at low temperature on glass substrates by a plasma enhanced MBE process. The goal of this study was to evaluate the potential of InGaN as an oxide-free, transparent conductor material which could be deposited at or slightly above room temperature with minimal interaction or damage to the underlying material. InxGa1−xN films deposited on glass, even without substrate heating, are highly crystalline, but the crystallinity as measured by x-ray degrades at x < 0.5. The microstructure observed by TEM of InGaN films deposited on unheated substrates is highly columnar, with typical column widths of ~10 nm. The optical absorption spectra of InGaN/glass have a distinct absorption edge at the bandgap, but also high background absorption in the bandgap. InxGa1−xN grown on glass (x > 0.5) is conductive due to its high electron concentration. InN electron Hall mobilities > 20 cm2/Vs when grown at 400°C, and ~ 7 cm2/Vs on unheated substrates were obtained. The addition of GaN degraded the electrical properties of the films to a greater extent than it improved the transparency. As a result, the best transparent conductor films were pure InN which, when deposited at 400°C, were half as transparent in the green as an indium tin oxide film having the same sheet resistance.

The (1 0 0) face of γ-LiAlO2 has attracted attention as a possible substrate for GaN epitaxial growth. This is partly because this face has an excellent lattice and structural match to (1 0 0) GaN. This orientation would have a misfit of only −1.4% along the c-direction and −0.1% along the b-direction of LiAlO2. We find that in practice this orientation relationship does not occur; instead, (0 0 0 1) oriented GaN grows with a small tilt (0.6° towards the c-direction) between the film and substrate. Although the misfit along the substrate b direction is large (−6.3%) for this orientation, the tilt perfectly accommodates the −1.4% misfit in the c direction. We present characterization of these films by RHEED, X-ray diffraction, and TEM. We propose that the tilt is driven by a reduction of interface energy which occurs in polar, incoherent interfaces.

In this paper we examine a series of four GaN epilayers grown by MOVPE on sapphire substrates with different AlN buffer layer thicknesses. We examine the effect of the buffer layer thickness on the physical and optical properties of the samples via optical microscopy, cathodoluminescence imaging and photoluminescence and cathodoluminescence spectroscopy. While the morphological and optical properties of all the films (excepting that with the thinnest buffer layer of 30 nm) are good, i.e., the films are smooth and the luminescence is dominated by excitonic luminescence, a number of circular island like features are observed in all the films whose density decrease with increasing buffer layer thickness. A large circular island present on the sample with the thinnest buffer layer and surrounded by cracks in the directions, displays some interesting acceptor related luminescence.

Time-resolved photoluminescence spectra have been recorded on three GaN epitaxial layers of thickness 2.5 μm, 7 μm and 16 μm, at various temperatures ranging from 8K to 300K. The layers were deposited by MOVPE on (0001) sapphire substrates with standard AlN buffer layers. To achieve good homogeneities, the growth was in-situ monitored by laser reflectometry. All GaN layers showed sharp excitonic peaks in cw PL and three excitonic contributions were seen by reflectivity. The recombination dynamics of excitons depends strongly upon the layer thickness. For the thinnest layer, exponential decays with τ ~ 35 ps have been measured for both XA and XB free excitons. For the thickest layer, the decay becomes biexponential with τ1 ~ 80 ps and τ2 ~ 250 ps. These values are preserved up to room temperature. By solving coupled rate equations in a four-level model, this evolution is interpreted in terms of the reduction of density of both shallow impurities and deep traps, versus layer thickness, roughly following a L−1 law.

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.

We report both cw and time resolved optical investigations performed on an InGaN/GaN multiple quantum well grown by MOVPE on <0001>-oriented sapphire substrate. At low temperature we find a strong “blue” luminescence band, of which energy position corresponds well with the wavelength of stimulated emission when excited with a nitrogen laser. We show that this PL band appears systematically red-shifted with respect to the QWs features, which supports a standard picture of fluctuations of the indium composition. Coming to the time-resolved data, we find at low temperature at least two “blue” band components which are both associated with long decay times (up to 4-5 ns at 8K). The decay time is temperature dependent and, when rising the temperature, the recombination rate increases. At room temperature, we reach typical values in the range ~100 to 500 ps.

Infrared measurements on wurzite GaN codoped with Mg and H reveal strong absorption at 3125 cm−1. Theorectical work provides strong evidence for the H being antibonding to N. We have performed an ab-initio study of Mg-H complexes in wurzite GaN, using the Local Density Approximation on a large H-terminated cluster MgHGa25N26H42. We have investigated the physical properties of three neutral configurations along the c direction. In all configurations Mg sits in a gallium substitutional site. H is then located in the Mg-N bond centre (BC), in the antibonding site on nitrogen side (ABN) or in the antibonding position on magnesium side (ABMg). We found the lowest total energy configuration is hydrogen in the antibonding on the nitrogen site. The stretch mode in this configuration is calculated at 3277 cm−1 which agrees with experiment and previous LDA calculations and we predict an unreported infra red active wag mode at 1311 cm−1. The experimental isotopic shift with D is well reproduced. The BC and ABMg configurations are 0.5 and 3.7 eV higher, producing local modes at 3645 and 2144 cm−1, respectively. No wag modes appear for the BC and ABMg configurations.

Even in good quality undoped GaN samples, as assessed by the intense excitonic emission, the yellow band is present. This band has been attributed either to a shallow donor to deep double donor pair recombination [1], to a deep donor to a shallow acceptor [2] or to a shallow donor and a deep state [3]. However, its origin is not yet clear. We present data on time resolved spectroscopy compared with steady state results. These results indicate that there is no difference in band shape between steady state and time resolved spectra at all temperatures. However, in some samples there is an increase in intensity of the yellow band. It is concluded that besides a fast emission, due to prompt excitation of the centre, an indirect path from a trap 13.7 meV below the shallow donor is responsible for the long component of the decay and the intensity increase. An emission with a lifetime of ca. 300 ms is also present with a maximum at 2.35 eV.

Mg has been widely used as p-doping species despite its intrinsic difficulties. It is nowadays well established that during the growth process of Mg doped GaN, atomic H is generated from the decomposition of NH3 and Mg-H complexes are formed in the layer. This has been for instance shown by the occurrence of LO mode in IR absorption, and by the observation of the Mg-H local vibration modes. This H passivation limits the electrical activity of Mg, therefore an activation process is required to get full activation of the Mg atoms. In the present study, bismethylcyclopentadienyl magnesium [(MeCp)2Mg] was used as precursor. However, this precursor reacts in the gas phase with NH3 to produce tiny solid particles as evidenced by a very bright diffuse emission visible along the laser beam used for reflectometry measurements. This simplest obvious product would be [(MeCp)Mg(NH2)]m(m≥2). To limit this drawback, Ga and Mg precursor lines have been separated. With proper in situ heat treatment, doping densities up to 1.5×1018 cm−3 have been obtained. PL spectra of lightly Mg doped samples (1016 cm−3) are dominated by shallow donor-acceptor pairs whereas for higher doping densities ( 1018 cm−3), the luminescence is dominated by a broad band in the 2.7-2.9 eV range. GaN LEDs were fabricated from Si doped (n-type) and Mg-doped (p-type) GaN, these LEDs emit in the blue-UV range.

E-beam pumped lasers are attractive for Laser Cathode Ray Tubes (LCRT) in projection displays and a variety of applications typically associated with optically pumped lasers. For the first time an InGaN/GaN multiple quantum well (MQW) in-plane laser pumped by surface normal pulse and scanning electron beams was demonstrated. Pumping at room temperature (RT) and 80 K showed peak stimulated emission wavelengths of 402 and 409 nm with a full width half maximum (FWHM) of 0.6 nm and 1.2 nm, respectively. The threshold electron beam current densities have been estimated as 60 A/cm2 for 35 keV electron energy at 80 K using scanning e-beam pumping and 200-300 A/cm2 at RT using pulsed e-beam pumping with a maximum electron energy of 150 keV. At 80 K, light output of 150 mW was measured out of one facet at an e-beam current of 1.7 mA.

Free standing GaN platelets were fabricated by hydride vapor phase epitaxy (HVPE). The platelets having a current maximum size of 7×6×0.1 mm3 were obtained by HVPE growth of ~100 μm thick GaN layers on SiC substrates and subsequent removal of the substrates by reactive ion etching (RIE). Surface of the GaN platelets was characterized by reflectance high energy election diffraction (RHEED), and Auger electron spectroscopy (AES). Crystal structure and optical properties of the platelets were studied by x-ray diffraction and photoluminescence (PL), respectively. Raman spectroscopy was also applied for material characterization. Residual strain was detected in the crystals. The stress was eliminated by high temperature anneal.

Long wavelength optical phonons of AlxGa1−xN solid solutions have been identified in the whole compositional range by Raman spectroscopy. The frequencies of A1 and E1 polar phonons increase continuously with x from one-member crystal to the other. A generalization of the dielectric model of Hon and Faust is used to treat the coupling of the longitudinal optic (LO) mode. This approach accounts for the observed frequencies and confirms the so-called one-mode behaviour of polar LO phonons. Moreover,a signature of the coupling of a discrete mode (tentatively associated to silent q=0 B1 mode) with an unidentified continuum has been obtained.