For years, substituted iron nitrides have been studied by various types of approaches: physical, chemical, and materials engineering, both experimental and theoretical. More recently, substituted iron nitrides have been studied by theoretical models for calculation of electronic structure, presenting the advantage of being economically viable. The properties of these compounds have potential application not only as a recording material but also in other areas: as resistance to corrosion and wear. The changes occurred in the alloys when transformed into nitrides still require further studies. Thus, the electronic and magnetic structure of IrFe3 and Ir3Fe alloys and the changes caused in their ground state properties when the nitrogen atoms were included in their stoichiometry, turning them into substituted iron nitrides type Ir3FeN and IrFe3N, will be investigated in this study. The electronic structure of these compounds was modeled using the linearized augmented plane waves (LAPW), an augmented plane wave (APW – method of Slater) modification. The following methodology was used in this study: the cohesive energy for steady state was calculated and then the ground state properties, such as charge transfer, magnetic moment, hyperfine properties, and the density of states, were obtained. The ground state properties are also assessed from the pressure variation experienced by these compounds, that way, the induced changes in the alloys caused by introducing the nitrogen atom are obtained. This study may assist in obtaining new and better nitrides.

We combine two scanning electron microscopy techniques to investigate the influence of dislocations on the light emission from nitride semiconductors. Combining electron channeling contrast imaging and cathodoluminescence imaging enables both the structural and luminescence properties of a sample to be investigated without structural damage to the sample. The electron channeling contrast image is very sensitive to distortions of the crystal lattice, resulting in individual threading dislocations appearing as spots with black–white contrast. Dislocations giving rise to nonradiative recombination are observed as black spots in the cathodoluminescence image. Comparison of the images from exactly the same micron-scale region of a sample demonstrates a one-to-one correlation between the presence of single threading dislocations and resolved dark spots in the cathodoluminescence image. In addition, we have also obtained an atomic force microscopy image from the same region of the sample, which confirms that both pure edge dislocations and those with a screw component (i.e., screw and mixed dislocations) act as nonradiative recombination centers for the Si-doped c-plane GaN thin film investigated.

Buffer leakage in aluminum gallium nitride/gallium nitride (AlGaN/GaN) heterostructure transistors is recognized as an issue that has deleterious consequences on device performance for high-power, high-frequency transistors and has been related to the presence of uncharged threading screw dislocations. In this study, we demonstrate that measurements of buffer leakage in AlGaN/GaN heterostructures grown on bulk gallium nitride (GaN) substrates are consistent with a mechanism based on the concept of dislocations acting as quantum wires in series with unintentional silicon (Si) impurity incorporation at the bulk GaN substrate/GaN buffer interface. The number of electronic channels N deduced from the leakage data using Landauer’s formula for the quantum resistance of N electronic channels is consistent with the number of dislocations along the ohmic contact pads determined from panchromatic cathodoluminescence and x-ray diffraction measurements of the dislocation density. This mechanism is consistent with Shockley’s suggestion that dislocations can act as one-dimensional conductors due to the presence of edge states along the dislocation core.

The ternary nitridotungstate Li6WN4 has been synthesized via the solid state reaction of lithium subnitride, Li3N, with W under nitrogen. High quality X-ray powder diffraction data were collected for the crystal-structure determination. Li6WN4 crystallizes in the tetragonal system, space group P42∕nmc, with cell parameters a=6.6759(3) Å and c=4.9280(3) Å, Z=2. Preliminary thermal stability measurements of Li6WN4 show that it is sensitive to moisture, even at room temperature, and decomposes at high temperatures below 1000 °C under flowing nitrogen.

Producing high purity aluminum nitride crystals by the sublimation-recondensation technique is difficult due to the inherently reactive crystal growth environment, normally at temperature in excess of 2100 °C. The durability of the furnace fixture materials (crucibles, retorts, etc.) at such a high temperature remains a critical problem. In the present study, the suitability of several refractory materials for AlN crystal growth is investigated, including tantalum carbide, niobium carbide, tungsten, graphite, and hot-pressed boron nitride. The thermal and chemical properties and performance of these materials in inert gas, as well as under AlN crystal growth conditions are discussed. TaC and NbC are the most stable crucible materials with very low elemental vapor pressures in the crystal growth system. Compared with refractory material coated graphite crucibles, HPBN crucible is better for AlN self-seeded growth, as crystals tend to nucleate in thin colorless platelets with low dislocation density.

We report on the investigation of GaN(0001)−1×1 using synchrotron radiation x-ray excited photoelectron spectra from the core levels Ga 3p and N 1s, as well as from the contaminants O 1s and C 1s. Measurements were done after outgassing (a) and during three surface treatment methods performed in sequence; (b) ammonia (NH3) flux anneals, (c) Ga deposition with sample held at room temperature followed by vacuum anneal, and (d) Ga deposition on a heated sample followed by Ga desorption during NH3 flux anneal. We have found that the initial NH3 flux anneals increased the amount of present N on the surface and enabled the formation of a well-ordered surface structure, according to the low energy electron diffraction (LEED) pattern. After treatment (b) and (d) the core level spectra of Ga 3p are much improved showing clearly distinct features indicative of increased Ga-N bonding. The Ga to N concentration ratio decreases during the surface treatments from 4.0 to 1.1, hence towards stoichiometry. The amounts of C (and O) present on the surface after outgassing corresponded to 1.1 (0.9) monolayers (ML) but reduced to 0.1 (0.1) ML after the final treatment (d). The Fermi level position in the band gap shifts down by 0.55 eV during the surface treatments, indicating a change of states present in the band gap. We have also found strong support that this Ga-polar sample is initially Ga-terminated.

This work is a modern revisitation of an old idea of great chemists of the past such as Berthelot, Mendeleev, Cloez and Moissan: the formation of organic matter under pre-biotic conditions starting from the hydrolysis of metal carbides. This idea was originally proposed for the formation of petroleum in the Earth and was extended to other bodies of the solar system by Sokolov at the end of the 19th century. The reason for this revisitation lies in the fact that complex organic matter resembling a petroleum fraction may exist in certain protoplanetary nebulae. The present work starts with a survey of the theory of the inorganic origin of petroleum and reports on current evidence for its derivation from residues of formerly living matter, but also considers theories that admit both a biogenic and an abiogenic origin for petroleum. By considering the cosmic abundance of elements and the evidence concerning the presence of carbides in meteorites, we discuss the formation, structure and hydrolysis products derived from the metal carbides of the iron peak of cosmic elemental abundance. Chromium carbide (Cr3C2) has then been used as a model compound for all the key carbides of the iron peak of the cosmic abundance (Cr, Fe, Ni, V, Mn, Co) and it has been hydrolysed under different conditions and the hydrocarbons formed have been analysed using electronic spectroscopy, high-performance liquid chromatography with a diode-array detector (HPLC-DAD) and by Fourier-transform infrared (FT-IR) spectroscopy. Methane, a series of about 20 different alkenes with single and conjugated double bonds have been detected. Paraffins are formed simultaneously with the alkene series but no acetylenic hydrocarbons have been detected. This study confirms early works considering the easy hydrolysis of the carbides of Cr, Fe, Ni, Mn and Co with the formation of H2, a series of alkanes including methane and a series of alkenes including ethylene. The peculiar behaviour of copper carbide (copper is inside the iron peak of the cosmic abundances) has been discussed as well. A survey of the hydrolytic behaviour of other carbides has been included so that all lanthanides and actinides are considered as well as carbides of the second and third groups of the periodic table of elements and highly refractory carbides such as those of Ti, Zr, Ta and W have been briefly discussed. Furthermore, the hydrolysis of mixed metal carbides and nitrides is discussed, which gives a mixture of extremely interesting molecules that are considered the raw materials for the formation of the molecules of life: guanidine, methyl hydrazine, formic acid, hydrogen cyanide, urea, cyanamide, methylamine and formaldehyde. The hydrolysis of metal carbides has also been discussed within the framework of other reactions that are well considered in the present day in an astrochemical context: the ion–molecule reaction, the Miller–Urey and the Sagan–Kaare synthesis as well as the catalytic Fischer–Tropsch synthesis and the radiation-driven Fischer–Tropsch synthesis.

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.

Isotopic labeling experiments have revealed correlations between hydrogen reactions, Ga desorption, and ammonia decomposition in GaN CVD. Low energy electron diffraction (LEED) and temperature programmed desorption (TPD) were used to demonstrate that hydrogen atoms are available on the surface for reaction after exposing GaN(0001) to deuterium at elevated temperatures. Hydrogen reactions also lowered the temperature for Ga desorption significantly. Ammonia did not decompose on the surface before hydrogen exposure. However, after hydrogen reactions altered the surface, N15H3 did undergo both reversible and irreversible decomposition. This also resulted in the desorption of N2 of mixed isotopes below the onset of GaN sublimation. This suggests that the driving force of the high nitrogen-nitrogen bond strength (226 kcal/mol) can lead to the removal of nitrogen from the substrate when the surface is nitrogen rich. Overall, these findings indicate that hydrogen can influence GaN CVD significantly, being a common factor in the reactivity of the surface, the desorption of Ga, and the decomposition of ammonia.

Electroluminescence spectra of light-emitting diodes based on InGaN/AlGaN/GaN heterostructures with single and multiple quantum wells (QWs) are analyzed by models of radiative recombination in 2D-structures with band tails. Equations of the model fit spectra quite good in a wide range of currents. Parameters of the fit are discussed and compared for single and multiple QWs. Tunnel effects play a sufficient role in blue LEDs with single QWs at low currents; they can be neglected in LEDs with multiple QWs. A new spectral band was detected at the high energy side of the spectra of green LEDs with multiple QWs; it is attributed with large scale inhomogenities of In distribution in InGaN QWs.*)

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.

Surface reconstructions during homoepitaxial growth of GaN (0001) are studied using reflection high-energy electron diffraction and scanning tunneling microscopy. In agreement with previous workers, a distinct transition from rough to smooth morphology is seen as a function of Ga to N ratio during growth. However, in contrast to some prior reports, no evidence for a 2×2 reconstruction during GaN growth is observed. Observations have been made using four different nitrogen plasma sources, with similar results in each case. A 2×2 structure of the surface can be obtained, but only during nitridation of the surface in the absence of a Ga flux.

Undoped and Si-doped GaN films were grown by low pressure MOCVD on (0001) sapphire substrates. The angular distribution of the X-ray diffraction corresponding to the (0002), (0004), (100), (200), and (114) reflections has been measured by means of double- and triple -crystal diffractometry with Mo Kα1 and Cu Kα1 radiation under conditions of symmetrical and asymmetrical Bragg- and Laue-geometry. In our experiments a non-coplanar geometry was also applied. On the basis of the performed studies, five independent components of the tensor of microdistortion were evaluated and the average grain-size in two directions was determined. The type, position, and density of dislocations were established as well. The role of dislocations in strain relaxation and their influence on the optical and electrical properties are discussed.

GaN, AlN and InGaN have a polar wurtzite structure and epitaxial films of these materials typically grow along the polar axis. Although the polarity of these nitrides has been studied by quite a number of techniques, many results in the literature are in conflict. In this paper an attempt is made to lay out a set of polarity assignments to provide a context for discussion of these results. A “standard framework” is proposed to correlate the disparate results, and the framework is used to draw general conclusions about the polarity of bulk crystals, VPE and MBE epitaxial films, and devices.

Selective and lateral overgrowth by Metal Organics Vapour Phase Epitaxy (MOVPE) was carried out until coalescence to produce smooth and optically flat thick GaN layers. A GaN epitaxial layer is first grown using atmospheric pressure Metalorganic Vapour Phase Epitaxy on a {0001} Al2O3. substrate. Then a 30Å silicon nitride dielectric film is deposited in-situ by reaction of silane and ammonia to form a selective mask. Afterwards, the openings and the figures in the dielectric films are achieved using standard photolithographic technology. Stripes openings in the mask, revealing free GaN surface, are aligned in the 〈100〉 direction. Typical stripes spacing and width are 10 µm and 5 µm respectively. These patterned layers are further on used for epitaxial regrowth of GaN by MOVPE. The growth anisotropy and therefore the coalescence process is achieved by introducing (MeCp)2Mg in the vapour phase. A two-step process is reported which allows a dramatic reduction of threading dislocations density not only above the masked areas but also above the windows opened in the mask. With this process, very sharp bound exciton luminescence peaks are measured at low temperature in the overgrown GaN.

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.

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.

In this paper, we report on the selective area growth (SAG) of GaN directly on patterned c-plane sapphire substrates by hydride vapor phase epitaxy (HVPE). A number of researchers have reported that the HVPE growth technique, unlike the MBE and MOCVD methods, is capable of producing device quality GaN films without the need for any low temperature nucleation/buffer layers. The density of edge dislocations in these HVPE films decreases dramatically as the film thickness is increased, and the dislocation density values for thick films (> 10μm) are comparable to those reported for the best GaN films grown by other methods on c-sapphire. These advantages of the HVPE growth technique makes it possible to achieve high quality selective area growth of GaN directly on c-sapphire substrates.

C-plane sapphire substrates were coated with PECVD SiO2 and photolithographically patterned with different size and shape openings. Subsequently, these patterned substrates were introduced in a horizontal, hot-wall quartz reactor for the GaN growth. It was observed that single crystal GaN growth was preferentially initiated in the openings in the oxide layer. This selective area growth was followed by epitaxial lateral overgrowth (ELO), leading to the formation of hexagonal GaN prisms terminated in smooth, vertical (100) facets. We have been successful in shearing these pyramid structures from the sapphire substrates as individual devices, which do not require any post-growth etching for feature definition. This procedure allows for the dramatic reduction of the process complexity and the duration and expense for GaN growth for device applications. Stimulated emission results on these self-formed optical cavities are also presented.

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.

The electronic structure of defects produced by 2.5-MeV electron irradiation and their effect on optical properties of GaN are investigated using photoluminescence (PL) and optically detected magnetic resonance (ODMR) techniques. The electron irradiation is shown to produce, in particular, a deep PL band with a no-phonon line at around 0.88 eV followed by a phonon-assisted sideband. We suggest that this emission is caused by an internal transition between excited and ground state of a deep defect. The excited state is a multiple-level state, as revealed from temperature dependent PL and level anti-crossing experiments. The electronic structure of the 0.88 eV defect is shown to be sensitive to the internal strain in the GaN epilayers. The ODMR studies reveal that the principal axis of the defect coincides with the c-axis of the host lattice and should therefore be either an on-site point defect or an axial complex defect along the c-axis.