Nitride synthesis using ammonia and hydrazine - a thermodynamic panorama

Because of the wide variety of projected applications of ultrapure nitrides in advanced technologies, there is interest in developing new cost-effective methods of synthesis. Explored in this study is the use of ammonia and hydrazine for the synthesis of nitrides from oxides, sulfides and chlorides. Even when the standard Gibbs energy change for the nitridation reactions involved are moderately positive, the reaction can be made to proceed by lowering the partial pressure of the product gas below its equilibrium value. Use of a metastable form of precursor in the nanometric size range is an alternative method to facilitate nitridation. Ellingham-Richardson-Jeffes diagrams are used for a panoramic presentation of the driving force for each set of reactions as a function of temperature. Oxides are the least promising precursors for nitride synthesis; sulfides offer a larger synthetic window for many useful nitrides such as BN, AlN, InN, VN, TiN, ThN and Si3N4. The standard Gibbs free energy changes for reactions involving chlorides with either ammonia or hydrazine are much more negative. Hydrazine is a more powerful nitriding agent than ammonia. The metastability of hydrazine requires that it be introduced into a reactor through a water-cooled lance. The use of volatile halides with ammonia or hydrazine offers the potential for synthesis of pure and doped nanocrystalline nitrides. Nitride thin films can also be prepared by suitable adaptations of the chloride route. (C) 2002 Kluwer Academic Publishers.

The influence of oxygen impurities on the formation of AlN-Al composites by infiltration of molten Al-Mg

The influence of residual oxygen in nitrogen on the formation of AlN-Al matrix by reactive infiltration has been investigated. Increasing the oxygen content from 10 ppm upwards decreased the nitride content in the matrix from 64 to 6%, Based on the analysis of the availability of oxygen at the Al-melt/gas interface, three distinct scenarios have been proposed (i) at lowest values, oxygen does not interfere with either infiltration or nitridation reaction; (ii) at intermediate values, nitridation is suppressed, however infiltration continues; and (iii) at a critical upper value, the melt passivates without any infiltration. This phenomenon offers control of the AlN/Al ratio in the matrix and the possibility of creation of microstructural gradierits by the appropriate choice of gas mixtures. (C) 2002 Elsevier Science B.V. All rights reserved.

The production of AlN-rich matrix composites by the reactive infiltration of Al alloys in nitrogen

Aluminium nitride (AlN)-Al matrices reinforced with Al2O3 particulate have been fabricated by reactive infiltration of Al-2% Mg alloy into Al2O3 preforms in N-2 in the temperature range of 900-1075 degreesC. The growth of composites of useful thickness was facilitated by the presence of a Mg-rich external getter, in the absence of which composite growth is self-limiting and terminates prematurely. Successful growth of composites has been attributed to the reduction in residual oxygen partial pressure brought about by the reaction with oxygen of highly volatile Mg in the getter alloy. The microstructure of the matrix consists of AlN-rich regions contiguous with the particulate with metal-rich channels in-between, thereby suggesting that nitridation initiates by preferential wicking of alloy along the particle surfaces. The increase in nitride content of the matrix with temperature is consistent with hardness values that vary between similar to3 and 10 GPa. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Preparation of β-SiAION from silica-alumina gel

Amorphous aluminosilicate gel powders have been subjected to carbothermal reduction and nitridation reaction at high temperature (1673 K). The influence of Al2O3 content in the gel powder on the nature and structure of the product phases has been examined. Between 5% and 9% Al2O3 in the gel powder, it is found that only β-SiAION is formed as the product of CTR/N reaction.

Determination of MBE grown wurtzite GaN/Ge3N4/Ge heterojunctions band offset by X-ray photoelectron spectroscopy

Hexagonal Ge3N4 layer was prepared on Ge surface by in situ direct atomic source nitridation and it is promising buffer layer to grow GaN on Ge (111). The valence band offset (VBO) of GaN/Ge3N4/Ge heterojunctions is determined by X-ray photoemission spectroscopy. The valence band (VB) of Ge3N4 is found to be 0.38?+/-?0.04?eV above the GaN valance band and 1.14?+/-?0.04?eV below the Ge. The GaN/Ge3N4 and Ge3N4/Ge are found type-II and type-I heterojunctions, respectively. The exact measurements of the VBO and conduction band offset (CBO) are important for use of GaN/Ge3N4/Ge (111) heterosystems.

Semipolar and nonpolar GaN epi-films grown on m-sapphire by plasma assisted molecular beam epitaxy

We hereby report the development of non-polar epi-GaN films of usable quality, on an m-plane sapphire. Generally, it is difficult to obtain high-quality nonpolar material due to the planar anisotropic nature of the growth mode. However, we could achieve good quality epi-GaN films by involving controlled steps of nitridation. GaN epilayers were grown on m-plane (10-10) sapphire substrates using plasma assisted molecular beam epitaxy. The films grown on the nitridated surface resulted in a nonpolar (10-10) orientation while without nitridation caused a semipolar (11-22) orientation. Room temperature photoluminescence study showed that nonpolar GaN films have higher value of compressive strain as compared to semipolar GaN films, which was further confirmed by room temperature Raman spectroscopy. The room temperature UV photodetection of both films was investigated by measuring the I-V characteristics under UV light illumination. UV photodetectors fabricated on nonpolar GaN showed better characteristics, including higher external quantum efficiency, compared to photodetectors fabricated on semipolar GaN. X-ray rocking curves confirmed better crystallinity of semipolar as compared to nonpolar GaN which resulted in faster transit response of the device. (C) 2014 AIP Publishing LLC.

Trap modulated photoresponse of InGaN/Si isotype heterojunction at zero-bias

n-n isotype heterojunction of InGaN and bare Si (111) was formed by plasma assisted molecular beam epitaxy without nitridation steps or buffer layers. High resolution X-ray diffraction studies were carried out to confirm the formation of epilayers on Si (111). X-ray rocking curves revealed the presence of large number of edge threading dislocations at the interface. Room temperature photoluminescence studies were carried out to confirm the bandgap and the presence of defects. Temperature dependent I-V measurements of Al/InGaN/Si (111)/Al taken in dark confirm the rectifying nature of the device. I-V characteristics under UV illumination, showed modest rectification and was operated at zero bias making it a self-powered device. A band diagram of the heterojunction is proposed to understand the transport mechanism for self-powered functioning of the device. (c) 2015 AIP Publishing LLC.

β-Ga2O3 单晶NH3中氮化的研究

为了将β-Ga2O3单晶应用于作为外延生长优质GaN薄膜的衬底材料，本文对β-Ga2O3 (100)进行了氮化处理，并且主要讨论了氮化温度以及β-Ga2O3表面的粗糙程度对GaN形成的影响。我们发现，最理想的氮化温度在900oC。此时，在抛光的β-Ga2O3的表面上生成了一层具有六方结构并且有择优取向的GaN层。本文同时也对氮化的机理进行了讨论。

Plasma stabilisation of metallic nanoparticles on silicon for the growth of carbon nanotubes

Ammonia (NH 3) plasma pretreatment is used to form and temporarily reduce the mobility of Ni, Co, or Fe nanoparticles on boron-doped mono- and poly-crystalline silicon. X-ray photoemission spectroscopy proves that NH 3 plasma nitrides the Si supports during nanoparticle formation which prevents excessive nanoparticle sintering/diffusion into the bulk of Si during carbon nanotube growth by chemical vapour deposition. The nitridation of Si thus leads to nanotube vertical alignment and the growth of nanotube forests by root growth mechanism. © 2012 American Institute of Physics.

Synthesis of composite AIN powder mixed with sintering additives by the Lanxide method

Composite AlN powder, mixed with the sintering additive Y2O3, was synthesized by the direct nitridation of molten Al-Mg-Y alloys. The character of products was determined by means of electron microscopy, X-ray diffraction, granularmetric analysis and chemical composition analysis etc. The results show that the nitridation rate of the raw alloys is higher, and the nitridation products axe porous enough to be easily crushed. Composite AlN powder, obtained by the Lanxide method, has excellent characters such as high purity, especially low oxygen content, and narrow well-distributed grain size and so on.

Metal catalysis-free, direction-controlled planar growth of single-crystalline alpha-Si3N4 nanowires on Si(100) substrate

Single-crystalline alpha-Si3N4 nanowires are controlled to grow perpendicular to the wet-etched trenches in the SiO0.94 film on the plane of the Si substrate without metal catalysis. A detailed characterization is carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The photoluminescence at 600 nm from alpha-Si3N4 nanowires is attributed to the recombination at the defect state formed by the Si dangling bond N3 equivalent to Si-center dot. The growth mechanism is considered to be related to the catalysis and nitridation of SiO nanoclusters preferably re-deposited around the inner corner of the trenches, as well as faster Si diffusion along the slanting side walls of the trenches. This simple direction-controlled growth method is compatible with the CMOS process, and could facilitate the fabrication of alpha-Si3N4 nanoelectronic or nanophotonic devices on the Si platform.

Thermodynamics and kinetics analysis of in-situ synthesizing AlN

AIN powders were prepared by in-situ synthesis technique. It is a reaction of binary molten Al-Mg alloys with highly pure nitrogen. It was confirmed through thermodynamics calculation that Mg element in Al-Mg alloys can decrease oxygen content in the reacting system. Thus, nitridation reaction can be performed to form AIN. Moreover, an analysis of kinetics shows that the nitridation reaction of Al-Mg alloys can be accelerated and transferred rapidly with the increment of Mg content.

Investigation of GaN layer grown on Si(111) substrate using an ultrathin AlN wetting layer

High-quality GaN epilayers were grown on Si (1 1 1) substrate by metalorganic chemical vapor deposition. The growth process was featured by using an ultrathin AlN wetting layer (WL) in combination with a low-temperature (LT) GaN nucleation layer (NL). The full-width at half-maximum (FWHM) of the X-ray rocking curve for the GaN (0 0 0 2) diffraction was 15 arcmin. The dislocation density estimated from TEM investigation was found to be of the order of 10(9)cm(-2). The FWHM of the dominant band edge emission peak of the GaN was measured to be 47 meV by photoluminescence measurement at room temperature. The ultrathin AlN WL was produced by nitridation of the aluminium pre-covered substrate surface. The reflection high-energy electron diffraction showed that the AlN WL was wurtzite and the surface morphology was like the nitridated surface of sapphire by the atomic force microscopy measurement. X-ray photoelectron spectroscopy measurement showed that Si and SixNy at a certain concentration were intermixed in the AlN WL. This study suggests that by employing an appropriate WL combined with a LT NL, high-quality heteroepitaxy is achievable even with large mismatch. (C) 2002 Elsevier Science B.V. All rights reserved.

Investigation on quality of cubic GaN/GaAs(100) by double-crystal X-ray diffraction

Cubic GaN was grown on GaAs(100) by low pressure metal organic chemical vapor deposition (MOCVD). X-ray diffraction, scanning electron microscope (SEM) and photoluminescence (PL) spectra were performed to characterize the quality of the GaN film. The PL spectra of cubic GaN thin films being thicker than 1.5 mu m were reported. Triple-crystal diffraction to analyze orientation distributions and strain of the thin films was also demonstrated.

Gallium diffusion through cubic GaN films grown on GaAs(100) at high-temperature using low-pressure MOVPE

Cubic GaN films were grown on GaAs(1 0 0) substrates by low-pressure metalorganic vapor-phase epitaxy at high temperature. We have found a nonlinear relation between GaN film thickness and growth timer and this nonlinearity becomes more obvious with increasing growth temperature. We assumed it was because of Ga diffusion through the GaN film, and developed a model which agrees well with the experimental results. These results raise questions concerning the role of Ga diffusion through the GaN film, which may affect the electrical and optical properties of the material. (C) 1998 Published by Elsevier Science B.V. All rights reserved.