The effect of high temperature, high pressure annealing on morphology, optical and structural properties of free-standing GaN films grown by hydride vapor phase epitaxy is studied. The annealing is found to change the intensities of the photoluminescence peaks as a result of a redistribution of the impurities and native defects in the thick GaN films. A positron annihilation study shows a decrease of the Ga vacancy-related defects below the detection limit after the annealing. The defect redistribution is correlated with a flattening of the stress distribution across the thickness, as revealed by micro Raman study, and with a decrease of the curvature of the annealed free-standing films.

We used single crystals of GaN, obtained from high-pressure synthesis, as substrates for Metalorganics Vapor Phase Epitaxy growth of violet and UV laser diodes. The use of high-quality bulk GaN leads to the decrease of the dislocation density to the low level of 105 cm−2, i.e. two orders of magnitude better than typical for the Epitaxial Lateral Overgrowth laser structures fabricated on sapphire. The low density and homogeneous distribution of defects in our structures enables the realization of broad stripe laser diodes. We demonstrate that our laser diodes, having 15 μm wide stripes, are able to emit 1.3-1.9 W per facet (50% reflectivity) in 30 ns long pulses. This result, which is among the best ever reported for nitride lasers, opens the path for the development of a new generation of high power laser diodes.

We used high-pressure grown GaN single crystal substrates to fabricate dislocation free optoelectronic devices like light emitting diodes and laser diodes structures. The latter ones demonstrated laser action under optical pumping condition with the threshold of about 200 kW/cm2 at room temperature. In the present paper we would focus on the specific aspects of the homoepitaxial growth by MOVPE method including epi-ready substrate preparation and surface polarity choice. We believe that our results demonstrate clearly the feasibility of device fabrication based on high-pressure grown GaN bulk crystals.

In this paper we review studies aiming at elucidation of the mechanisms responsible for anomalously low pressure coefficients of the light emission energy, dEE/dP, observed in quantum structures of InGaN/GaN and GaN/AlGaN. We have established that in hexagonal InGaN/GaN and GaN/AlGaN structures the main mechanism involved is related to the pressure induced increase of the piezoelectric field which determines also the strong red shift of the emission energy with thickness of the quantum well. To reproduce the experimental findings in InGaN/GaN case, it is necessary to take into account the dependence of the piezoelectric constants on the volume-conserving strain. Whereas the experimental results on a decrease of dEE/dP in GaN/AlGaNstructures can be fully accounted for within the linear elasticity theory. In contrast to these findings, dEE/dP magnitude measured in cubic InGaN/GaN quantum structures shows value close to changes of the InGaN bangap with pressure obtained from first principle calculations. The latter result is consistent with the absence of the built-in electric fields in the cubic nitride structures.

Using free standing layer of InGaAsN we have succeeded in measuring the optical absorption in very broad spectral range (0.8-2.5eV). This gave us an insight into the conduction band density of states for the energies higher than the energy gap of this compound. By combining Hall effect measurements with determination of plasma edge frequency in infrared reflectivity for differently doped samples we were able to deduce the density of states, conduction band electrons effective mass and dispersion relation. In particular it turned out that both i) experimentally measured dispersion relation of the conduction band shows extremely high degree of nonparabolicity and consistently ii) the effective mass of electrons is few times larger than that corresponding to GaAs of the same electron concentration. So far the obtained experimental results are in line with recently proposed band anticrossing model of the electronic structure of III-N-V alloys.

We have studied an influence of pressure on the emission and absorption spectra measured from various types of InGaN structures such as epilayers, quantum wells and quantum dots. While the known pressure coefficients of GaN and InN bandgaps are in the range 40-25 meV/GPa, the experimental observation for the light emission shift with pressure for InGaN alloys is dramatically different. With the increasing In content and thus decreasing emission energy the observed pressure coefficients become very small eventually reaching zero or even slightly negative values! We have observed a much weaker trend for the decrease of the pressure coefficient for the absorption edges of InGaN. First principle calculations of InGaN band structure and its modification with a pressure are not able to explain the huge effect observed in the emission experiment but are in a good agreement with the results obtained in optical absorption measurements. We discuss here the possible mechanisms which can account for extremely low pressure coefficient of the light emission and the discrepancy between sensitivity light emission and absorption on applied pressure in InGaN alloys.

We have investigated the high-pressure high-temperature annealing of Mg/P-implanted GaN films using visible and ultraviolet (UV) micro-Raman spectroscopy. The results illustrate the use of Raman spectroscopy to monitor processing of GaN where fast feedback is required. The structural quality and the stress in ion-implanted GaN films was monitored in a 40nm-thin surface layer of the sample as well as averaged over the sample layer thickness. We find the nearly full recovery of the crystalline quality of ion-implanted GaN films after annealing at 1400-1500°C under nitrogen overpressures of 1.5GPa. No significant degradation effects occurred in the GaN surface layer during the annealing. The high nitrogen overpressures proved very effective in preventing the nitrogen out-diffusion from the GaN surface. Stress introduced during the annealing was monitored. Raman spectra of ion-implanted GaN films were investigated at different temperatures and excitation wavelengths to study the GaN phonon density of states.

Epitaxial growth on GaN single bulk crystals sets new standards in GaN material quality. The outstanding properties provide new insights into fundamental material parameters (e.g. lattice constants, exciton binding energies, etc.) being not accessible by heteroepitaxial growth on sapphire or SiC. With MOVPE and MBE we realized unstrained GaN layers with dislocation densities about six orders of magnitude lower than in heteroepitaxy. Those layers revealed an exceptional optical quality as determined by a reduction of the photoluminescence linewidth from 5 to 0.1 meV and a reduced XRD rocking curve width from 400 to 20 arcsec.

Only recently, progress in surface preparation allowed morphologies of the layers suitable for device applications. We report on InGaN/GaN MQW structures as well as the first GaN pn- and InGaN/GaN double heterostructure LEDs on GaN single bulk crystals. Those LEDs are twice as bright as their counterparts grown on sapphire. In addition they reveal an improved high power characteristics, which is attributed to an enhanced crystal quality and an increased p-doping. Time resolved electroluminescence measurements proof that band/band recombination is the dominant emission mechanism for the InGaN/GaN LEDs.

Interdiffusion of In and Ga is observed in InGaN multiple-quantum-well superlattices for annealing temperatures of 1250 to 1400°C. Hydrostatic pressures of up to 15 kbar were applied during the annealing treatments to prevent decomposition of the InGaN and GaN. In as-grown material, x-ray diffraction spectra show InGaN superlattice peaks up to the fourth order. After annealing at 1400°C for 15 min, only the zero-order InGaN peak is observed, a result of compositional disordering of the superlattice. Composition profiles from secondary ion mass spectrometry indicate significant diffusion of Mg from the p-type GaN layer into the quantum well region. This Mg diffusion may lead to an enhancement of superlattice disordering. For annealing temperatures between 1250 and 1300°C, a blue shift of the InGaN spontaneous emission peak is observed, consistent with interdiffusion of In and Ga in the quantum-well region.

We have investigated the high-pressure high-temperature annealing of Mg/P-implanted GaN films using visible and ultraviolet (UV) micro-Raman spectroscopy. The results illustrate the use of Raman spectroscopy to monitor processing of GaN where fast feedback is required. The structural quality and the stress in ion-implanted GaN films was monitored in a 40nm-thin surface layer of the sample as well as averaged over the sample layer thickness. We find the nearly full recovery of the crystalline quality of ion-implanted GaN films after annealing at 1400-1500°C under nitrogen overpressures of 1.5GPa. No significant degradation effects occurred in the GaN surface layer during the annealing. The high nitrogen overpressures proved very effective in preventing the nitrogen out-diffusion from the GaN surface. Stress introduced during the annealing was monitored. Raman spectra of ion-implanted GaN films were investigated at different temperatures and excitation wavelengths to study the GaN phonon density of states.

Epitaxial growth on GaN single bulk crystals sets new standards in GaN material quality. The outstanding properties provide new insights into fundamental material parameters (e.g. lattice constants, exciton binding energies, etc.) being not accessible by heteroepitaxial growth on sapphire or SiC. With MOVPE and MBE we realized unstrained GaN layers with dislocation densities about six orders of magnitude lower than in heteroepitaxy. Those layers revealed an exceptional optical quality as determined by a reduction of the photoluminescence linewidth from 5 to 0.1 meV and a reduced XRD rocking curve width from 400 to 20 arcsec.

Only recently, progress in surface preparation allowed morphologies of the layers suitable for device applications. We report on InGaN/GaN MQW structures as well as the first GaN pn- and InGaN/GaN double heterostructure LEDs on GaN single bulk crystals. Those LEDs are twice as bright as their counterparts grown on sapphire. In addition they reveal an improved high power characteristics, which is attributed to an enhanced crystal quality and an increased p-doping. Time resolved electroluminescence measurements proof that band/band recombination is the dominant emission mechanism for the InGaN/GaN LEDs.

Interdiffusion of In and Ga is observed in InGaN multiple-quantum-well superlattices for annealing temperatures of 1250 to 1400°C. Hydrostatic pressures of up to 15 kbar were applied during the annealing treatments to prevent decomposition of the InGaN and GaN. In as-grown material, x-ray diffraction spectra show InGaN superlattice peaks up to the fourth order. After annealing at 1400°C for 15 min, only the zero-order InGaN peak is observed, a result of compositional disordering of the superlattice. Composition profiles from secondary ion mass spectrometry indicate significant diffusion of Mg from the p-type GaN layer into the quantum well region. This Mg diffusion may lead to an enhancement of superlattice disordering. For annealing temperatures between 1250 and 1300°C, a blue shift of the InGaN spontaneous emission peak is observed, consistent with interdiffusion of In and Ga in the quantum-well region.

Positron annihilation experiments have been performed to identify native point defects in GaN bulk crystals as well as in epitaxial layers. The results show that Ga vacancies are present at concentrations of 1017 – 1018 cm−3 in undoped GaN bulk crystals and layers, whereas the Mgdoped samples are free of Ga vacancies. The Ga vacancies are negatively charged and their concentration correlates with the intensity of the yellow luminescence. We conclude that the Ga vacancies contribute to the electrical compensation of n-type GaN and their acceptor levels are involved in the yellow luminescence transition.

The recent progress in high pressure crystallization of GaN is reported. The results of the growth from the solutions of atomic nitrogen in pure Ga and in its alloys with Mg, Ca and Zn are discussed. It is shown that the growth mechanisms and the physical properties of the crystals depend on the type of dopant added into the solution. In particular, high resistivity (104-106Ωcm) GaN crystals of improved structural quality can be grown from solutions containing Mg. It was also observed that the addition of Mg, Ca and Zn suppress yellow photoluminescence commonly observed in GaN crystals grown without an intentional doping. The preparation of surfaces of GaN substrates for homoepitaxy by mechanical and mechanochemical polishing is discussed. It is shown that atomically flat, thermally stable surfaces are possible to obtain by the applied procedures.

Some most interesting results concerning homoepitaxial growth by MOCVD and MBE is shortly reviewed. In particular, it is shown that perfectly matched (strain free) GaN layers can be deposited on the highly resistive GaN:Mg substrates.

Lattice parameters of semiconductors depend on the concentration of free electrons via the deformation potentials of the occupied minima of the conduction bands. In the presented work we examined the lattice parameters of variously doped GaN samples (epitaxial layers on sapphire and on SiC, bulk crystals grown at high hydrostatic pressure and homoepitaxial layers). The following dopants were used: Si, Mg and O. The measurements were performed using high resolution X-ray diffractometry. The results indicate that free electrons expand the lattice what confirms a negative value of the deformation potential of the Γ minimum of the conduction band. However, for Mg-doping (acceptor) we observed the lattice expansion as well. This violates the Vegard's law, as Mg ions are smaller than Ga ions.

Properties of GaN and its alloys are strongly controlled by impurities and strain. Using large hydrostatic and biaxial pressure we identify the role of donor dopants and stress induced fields. The doping of Si and 0 as relevant representatives of group-IV and group-VI impurities are studied in Raman spectroscopy. For pressures above 20 GPa we find that oxygen induces a strongly localized gap state while Si continues to behave as a hydrogenic donor. Such a DX-like behavior of 0 indicates and corresponds to doping limitations in AIGaN alloys. The site specific (ON, SiGa) formation of a gap-state is attributed to bond strengths of the respective neighbors. In photoreflection of pseudomorphic GaInN we observe pronounced Franz-Keldysh oscillations corresponding to piezoelectric fields of 0.6 MV/cm. An observed redshift of the luminescence is found to originate in electric field induced tailstates. A reduced but similar effect is expected for GaN possibly explaining observations of persistent photoconductivity in a wide range of materials.

GaN semiconductor is characterized by strong bonding and high vapor pressure of nitrogen. The strong bonds limit an efficiency of annealing procedures required for variety of semiconductor technologies, for example, post-implantation annealing, or doping by diffussion. Maximum temperatures employed up to now (at ambient pressure) in GaN annealing have not exceeded about 1100°C. A desired increase of annealing temperatures would cause a decomposition of GaN unless an elevated pressure of N2 is supplied. In this work, we report onapplication of high pressure annealing procedures (temperatures up to 1550°C and pressures up to 16 kbar) which enabled us to study variation of the properties of epitaxial films and bulk crystal of GaN. In particular, we discuss the following results obtained using high pressure annealing: i) structural quality improvement and increase of the thermal strain in as grown epitaxial layers of GaN/A12O3, The annealing at above 1300°C resulted in the decrease of the X-ray rocking curve width from about 700 arc sec. down to 470 arc sec., ii) drastic increase of bandedge (bound exciton) photoluminescence intensity iii) enhancement in removal of implant damage, iv) increase of diffusivity of Zn and Mg atoms (introduced by implantation and/or diffusion from external source). For Zn in epitaxial layers of GaN/A12O3 a diffusion starts at 1200–1250°C, v) enhancement of the blue-photoluminescence intensity in Zn and Mg implanted GaN. The performed experiments give an evidence of the importance of the defect (dislocations) in diffusion of Zn and Mg in the GaN semiconductor.

Heterostructure modulation doped transistors (MODFETs) based on AlGaN/GaN structures have demonstrated impressive DC and microwave performance often despite high transistor access resistance. One approach to reducing the access resistance is to use selective area Si-implantation. While several reports exist on Si-implantation in GaN, little work has been done on implantation in AlGaN. In addition, more information on the annealing of implantation damage in GaN is needed to optimize its use in FETs and thyristors.

We report the electrical and structural properties of Si-implanted Al0.15Ga0.85N based on Hall measurements and Rutherford Backscattering (RBS) spectra, respectively. Al0.15Ga0.85N shows less damage accumulation than GaN for a room temperature Si-implant dose of 5×1015 cm-2 based on the minimum channeling yield (26% for AlGaN as compared to 34% for GaN), however, as with GaN, this damage is difficult to remove by thermal annealing at °C.

We continue our investigations into the optical activation of Zn-implanted GaN annealed under ever higher N2 overpressure. The samples studied were epitaxial GaN/sapphire layers of good optical quality which were implanted with a 1013 cm−2 dose of Zn+ ions at 200 keV, diced into equivalent pieces and annealed under 10 kbar of N2. The N2 overpressure permitted annealing at temperatures up to 1250°C for 1 hr without GaN decomposition. The blue Zn-related photoluminescence (PL) signal rises sharply with increasing anneal temperature. The Zn-related PL intensity in the implanted sample annealed at 1250°C exceeded that of the epitaxially doped GaN:Zn standard proving that high temperature annealing of GaN under kbar N2 overpressure can effectively remove implantation damage and efficiently activate implanted dopants in GaN. We propose a lateral LED device which could be fabricated using ion implanted dopants activated by high temperature annealing at high pressure.

Bulk single crystals of GaN were used for epitaxial growth of GaN films by molecular beam epitaxy. Low temperature photoluminescence yields much higher intensity emission in the near bandedge region for epitaxial films with respect to the situation in bulk crystals. Character of this luminescence changes also. Dominant band-to-band transitions in the bulk crystals are exchanged by bound exciton and/or donor-acceptor pair transitions observed in the epitaxial layers. We will compare the obtained results with the available data on the homoepitaxial samples grown by metalorganic chemical vapor deposition method and discuss the importance of establishing the basic information on energetic positions of excitonic transitions in stress free samples.