Structural stability,electronic structure and mechanical properties of 4d transition metal nitrides TMN (TM=Ru,Rh, Pd)

Ab initio calculations are performed to investigate the structural stability, electronic, structural and mechanical properties of 4d transition metal nitrides TMN (TM=Ru, Rh, Pd) for five different crystal structures, namely NaCl, CsCl, zinc blende, NiAs and wurtzite. Among the considered structures, zinc blende structure is found to be the most stable one among all three nitrides at normal pressure. A structural phase transition from ZB to NiAs phase is predicted at a pressure of 104 GPa, 50.5 GPa and 56 GPa for RuN, RhN and PdN respectively. The electronic structure reveals that these nitrides are metallic. The calculated elastic constants indicate that these nitrides are mechanically stable at ambient condition.     

Stability,structural, elastic and electronic properties of RuN polymorphs from first-principles calculations

First-principles FLAPW–GGA calculations for six possible polymorphs of ruthenium mononitride RuN indicate that the most stable structure is that of zinc blende rather than the rock salt structure recently reported for synthesized RuN samples. The elastic, electronic properties and the features of chemical bonds of zinc-blende RuN polymorph were investigated and discussed in detail.     

Laser synthesis of nitrides on the surface of refractory metals immersed in liquid nitrogen

In this paper we describe an approach for the formation of composite layers on the surface of refractory metals. We show that laser radiation on refractory metals (Ti, V, Zr, Mo, Hf, Ta, and W) immersed in liquid nitrogen can provide a chemical synthesis of nitride phases on the surface of metals. The metals were subjected to pulsed laser radiation with a wavelength of 1.06 μm. The power density ranged from 10⁴ to 10⁹ W cm⁻². The synthesis of nitrides began with the formation of Me_xN_y (x > y) phases with low contents of nitrogen. When the melting point was reached at the metal surface, the quantity of MeN phases increased sharply. Study of the melting zone showed that it contained a non-uniform distribution of nitride phases. The quantity of nitrides was a maximum on the surface and decreased with the increase of the depth of melting zone. Due to the high-cooling rates, titanium nitride crystallized in the form of columns. Maximum microhardness in the Ti surface layer was up to 20,000 MPa.     

Theoretical study of the transition metal ring functionalized tips of open-ended (5,5) boron nitride nanotube (BNNT)

The nanotube with open edges is an excellent candidate for designing efficient tip for atomistic scanning probes or field emission display (FED) devices. In the present work, we have studied the functionalization of an open-ended boron nitride nanotube (BNNT) with a series of transition metal rings and the effects on the properties of open-ended BNNT through density functional theory (DFT) calculations. The results show that the TM-BNNT complexes are energetically favorable. Moreover, it is found that the functionalization (a) significantly decreases the band gap of BNNT to different degrees, which might effectively modify the electronic properties of the open-ended BNNT; and (b) efficiently lowers the work function, which might improve the field emission properties. Our results might be helpful not only to design specific BNNT-based tips but also to further discuss the chemical vapor deposition (CVD) growth of BNNT on nanoparticles.     

贵金属氮化物晶体结构、电子结构和力学性能的实验与理论研究进展

氮化铂（Pt-N）是高温高压条件下合成的第一种块体二元贵金属氮化物，由于该化合物具有高的体弹性模量和特殊的电子结构从而吸引了世界范围内一些理论研究者的目光．Pt-N中金属原子的质量远远大于非金属原子的质量，因此X射线衍射仅能确定Pt原子的位置，拉曼光谱虽然能限制N原子的对称性，但仍不能确定其具体位置．以上因素使得确定这种新合成物质的晶体结构成了理论研究的焦点，这些工作已经在高压科学中开拓了一个新的领域，即贵金属元素氮化物的高压合成与物性研究．     

Thickness-Dependent Phase Transformations in Implanted Iron

The dependence of iron nitride formation and phase transformations on the thickness of the nitrogen implanted Fe layers is investigated. The iron nitrides formation in N-implanted Fe-layers of various thickness (60–860 nm) implanted with 100 keV N₂ ⁺ ions with doses ranging from 1×10¹⁷ to 4.5×10¹⁷ at. N/cm² is studied by CEMS and supplemented by GXRD. It was found that nitride formation is strongly enhanced in thin Fe films as compared to thicker layers or the bulk samples. A given nitride phase is formed in thin (60, 130 nm) Fe layers at significantly lower N-doses and the transformation of the original Fe layer into iron nitrides is more complete than in the bulk -Fe. It is suggested that high stresses in thin Fe layers, revealed by the GXRD measurements, may enhance nitrides formation.     

Ruthenium adsorption and diffusion on the GaN(0 0 0 1) surface

We report first principles calculations to analyze the ruthenium adsorption and diffusion on GaN(0 0 0 1) surface in a 2×2geometry. The calculations were performed using the generalized gradient approximation (GGA) with ultrasoft pseudopotential within the density functional theory (DFT). The surface is modeled using the repeated slabs approach. To study the most favorable ruthenium adsorption model we considered T₁, T₄ and H₃ special sites. We find that the most energetically favorable structure corresponds to the Ru- T₄ model or the ruthenium adatom located at the T₄ site, while the ruthenium adsorption on top of a gallium atom (T₁ position) is totally unfavorable. The ruthenium diffusion on surface shows an energy barrier of 0.612 eV. The resultant reconstruction of the ruthenium adsorption on GaN(0 0 0 1)- 2×2 surface presents a lateral relaxation of some hundredth of Å in the most stable site. The comparison of the density of states and band structure of the GaN(0 0 0 1) surface without ruthenium adatom and with ruthenium adatom is analyzed in detail.     

Ab initio simulations on the atomic and electronic structure of single-walled BN nanotubes and nanoarches

To simulate the perfect single-walled boron nitride nanotubes and nanoarches with armchair- and zigzag-type chiralities and uniform diameter of ∼5 nm, we have constructed their one-dimensional (1D) periodic models. In this study, we have compared the calculated properties of nanotubes with those for both hexagonal and cubic phases of bulk: bond lengths, binding energies per B-N bond, effective atomic charges as well as parameters of total and projected one-electron densities of states. For both phases of BN bulk, we have additionally verified their lattice constants. In the density functional theory (DFT), calculations performed using formalism of the localized Gaussian-type atomic functions as implemented in the CRYSTAL-06 code we have applied Hamiltonians containing either PWGGA or hybrid (DFT+HF) B3PW exchange-correlation functionals. After calculation of Hessian matrix for the optimized structures of BN bulk (both phases) and nanotubes (both chiralities) using the CRYSTAL code we have estimated their normal phonon modes within the harmonic approximation. Applying both atomistic and continuum models we have calculated the elastic energies and moduli for SW BN nanoarches. Our calculations clearly show a reproducibility of the atomic structure, effective charges and total energy, as well as phonon and elastic properties when using either PWGGA or hybrid B3PW Hamiltonians. On other hand, there is a high sensitivity of the discrete energy spectra parameters (including band gap) to the choice of the first principles approach (the hybrid method reproduce them noticeably better).     

First principles study of structural stability,electronic structure and mechanical properties of ReN and TcN

The crystal structure, structural stability, electronic and mechanical properties of ReN and TcN are investigated using first principles calculations. We have considered five different crystal structures: NaCl, zinc blende (ZB), NiAs, tungsten carbide (WC) and wurtzite (WZ). Among these ZB phase is found to be the lowest energy phase for ReN and TcN at normal pressure. Pressure induced structural phase transitions from ZB to WZ phase at 214 GPa in ReN and ZB to NiAs phase at 171 GPa in TcN are predicted. The electronic structure reveals that both ReN and TcN are metallic in nature. The computed elastic constants indicate that both the nitrides are mechanically stable. As ReN in NiAs phase has high bulk and shear moduli and low Poisson's ratio, it is found to be a potential ultra incompressible super hard material.     

立方氮化硅及其冲击波合成

 立方氮化硅是高温高压研究近期合成得到的一种新物相，与已经在工业上普遍使用的氮化硅的两种六方物相（α相和β相）相比，新物相的密度增加了26%，预期是一种新型功能材料。简要综述了立方氮化硅的研究进展和存在的问题，讨论了立方氮化硅的人工合成和相关物性研究、Ⅳ(A)族氮化物（Ge₃N₄、Sn₃N₄、C₃N₄）的高密度物相研究，以及后尖晶石相氮化物的实验和理论探索等问题。介绍了作者最近利用炸药爆轰加载技术开展的冲击波合成实验结果，以α相氮化硅为冲击压缩前驱体，实现了在单次冲击波压缩实验中合成出了克量级立方氮化硅粉体，为进一步开展立方氮化硅的性能研究奠定了基础。     

Aluminum nitride substrates for ultraviolet light-emitting diode structures

Currently, wafers of aluminum nitride cut from bulk aluminum nitride crystals (AlN) grown by sublimation are considered promising substrates for obtaining light-emitting diode structures based on nitrides of the third group. In this study, the structural characteristics and electrical properties of AlN, as a prospective substrate material for light-emitting diode heterostructures based on AlGaN/GaN, were investigated. The substrate working surface ((0001) plane, Al-polar) was specifically prepared for epitaxial growth using chemical-mechanical polishing. The surface roughness (“epi-ready”), as estimated by atomic force microscopy, did not exceed 0.3 nm.     

Raman characteristics of carbon nitride synthesized by nitrogen-ion-beam-assisted pulsed laser deposition

Raman characteristics of carbon nitride films synthesized by nitrogen-ion-beam-assisted pulsed laser deposition were investigated. In addition to the D (disorder) band and G (graphitic) band commonly observed in carbon nitride films, two Raman bands located at 1080–1100 and 1465–1480 cm^-1 were found from our carbon nitride films. These two bands were well matched with the predicted Raman frequencies for βC₃N₄ and the observed Raman bands reported for carbon nitride films, indicating their relation to carbon-nitrogen stretching vibrations. Furthermore, the relative intensity ratio of the two Raman bands to the D and G bands increased linearly with increasing nitrogen content of the carbon nitride films. Received: 30 October 2000 / Accepted: 5 February 2001 / Published online: 2 October 2001     

Full potential calculation of structural, elastic properties and high-pressure phase of binary noble metal carbide: ruthenium carbide

We present in this paper the results of an ab initio theoretical study within the local density approximation (LDA) to determine in rock-salt (B1), cesium chloride (B2), zinc-blende (B3), and tungsten carbide (WC) type structures, the structural, elastic constants, hardness properties and high-pressure phase of the noble metal carbide of ruthenium carbide (RuC).The ground state properties such as the equilibrium lattice constant, elastic constant, the bulk modulus, its pressure derivative, and the hardness in the four phases are determined and compared with available theoretical data. Only for the three phases B1, B3, and WC, is the RuC mechanically stable, while in the B2 phase it is unstable, but in B3 RuC is the most energetically favourable phase with the bulk modulus 263 GPa, and at sufficiently high pressure (P_t=19.2 GPa) the tungsten carbide (WC) structure would be favoured, where ReC-WC is meta-stable.The highest bulk modulus values in the B3, B2, and WC structures and the hardnesses of H(B3)=36.94 GPa, H(B1)=25.21 GPa, and H(WC)=25.30 GPa indicate that the RuC compound is a superhard material in B3, and is not superhard in B1 and WC structures compared with the H(diamond)=96 GPa.     

Critical layer thickness of GaIn(N)As(Sb) QWs on GaAs and InP substrates for (001) and (111) orientations

The aim of this work is to examine the effect of dilute nitride and/or antimonite on the critical layer thickness of GaInAs quantum wells on GaAs and InP substrates by means of Matthews and Blakeslee force model. The study provides a comparison of the critical layer thickness of the related GaIn(N)As(Sb) QWs in (001) and (111) orientation. Our calculations indicate the importance of antimonite and the proper usage of it with dilute nitrides in order to tailor the active layer thickness and emission wavelength of quantum well laser devices.     

An ab initio study of 5d noble metal nitrides: OsN2, IrN2, PtN2 and AuN2

The crystal structure, phonon stability, elasticity and electronic properties of four noble metal nitrides (PtN₂, IrN₂, OsN₂ and AuN₂) with three structural types (pyrite, marcasite and CoSb₂ structure) were studied by first principles calculations. In agreement with experiments and previous theoretical predictions, it is found that the most stable structure for OsN₂ is marcasite, for PtN₂ is pyrite, and for IrN₂ is the CoSb₂ structure. It is found that these three compounds are thermodynamically metastable with respect to solid N₂ and the metal at zero pressure. The structures are mechanically and dynamically stable. The lowest energy structure of AuN₂ is the CoSb₂ structure. The formation energy of AuN₂ is found to be very high compared to the other three nitrides studied here. This underlies the experimental difficulty in the synthesis of this compound. OsN₂ is found to be metallic, while IrN₂ and PtN₂ are both semiconductors.     

Ab initio calculations of the physical properties of transition metal carbides and nitrides and possible routes to high-<Emphasis Type="Italic">T</Emphasis><Subscript>c</Subscript> superconductivity

We report ab initio linear-response calculations of the phonon spectra and the electron-phonon interaction for several transition metal carbides and nitrides in a NaCl-type structure. For NbC, the kinetic, optical, and superconducting properties are calculated in detail at various pressures and the normal-pressure results are found to agree well with the experiment. Factors accounting for the relatively low critical temperatures T _c in transition metal compounds with light elements are considered and the possible ways of increasing T _c are discussed. The text was submitted by the author in English.     

Adsorption configuration of magnesium on wurtzite gallium nitride surface using first-principles calculations

First-principles calculations of magnesium adsorption at the Ga-terminated and N-terminated {0 0 0 1} basal plane wurtzite gallium nitride surfaces have been carried out to explain the atomic-scale insight into the initial adsorption processes of magnesium doping in gallium nitride. The results reveal that magnesium adsorption on N-terminated surfaces is preferred than that on Ga-terminated surfaces. Furthermore, the surface diffusivity of magnesium atom on the N-terminated surface is much lower than that on the Ga-terminated surface, which is due to both the larger average adsorption energies and the lower adsorption distance on N-terminated surface than that on Ga-terminated surface. The results indicate that the p-type doping on the Ga-terminated surface will be better distributed than that on the N-terminated surface.     

Equation of state for technetium from X‐ray diffraction and first-principle calculations

The ambient temperature equation of state (EoS) of technetium metal has been measured by X-ray diffraction. The metal was compressed using a diamond anvil cell and using a 4:1 methanol-ethanol pressure transmitting medium. The maximum pressure achieved, as determined from the gold pressureEquation of state for technetium from X-ray diffraction and first-principle calculations scale, was 67 GPa. The compression data shows that the HCP phase of technetium is stable up to 67 GPa. The compression curve of technetium was also calculated using first-principles total-energy calculations. Utilizing a number of fitting strategies to compare the experimental and theoretical data it is determined that the Vinet equation of state with an ambient isothermal bulk modulus of B_0T=288 GPa and a first pressure derivative of B′=5.9(2) best represent the compression behavior of technetium metal.     

Density functional studies of selected metal dioxides

This study investigates the optical properties of selected metal oxides due to their high dielectric constants. The local-spin-density approximation plus Hubbard U (commonly called LDA+U) is used in a study of the structural, mechanical and optical properties of UO₂. The inclusion of a Hubbard U correction to 5f electrons of uranium changes UO₂ from a metal to an insulator and, therefore, has a dramatic effect on the localisation of the electron spin and charge density of uranium. However although the band gap can be reproduced using the effective U parameter, which is equal to 3.5 eV and optical properties were calculated in our previous work, it is difficult to calculate ionic contribution to the static dielectric constant within LDA+U formalism for this compound. It is shown in the present work that the electronic structures of both ceria and thoria exhibit similarities to urania within LDA or PBE functional implementations. Within this functional and linear response theory one can easily calculate static dielectric permittivity and it is shown that in agreement with experiment the predicted values are an order of magnitude larger than the dielectric constant of SiO₂. In this work, high accuracy, first-principles calculations are also used to compare properties of urania versus ceria and thoria and how these similarities can help in understanding these compounds. It is also shown that the B3LYP functional predicts slightly overestimated band gaps for ceria and thoria as well as smaller than experimentally observed electronic contribution to the static dielectric constant, while the index of refraction is well reproduced for thoria.     

Ground-state structure determination and mechanical properties of palladium seminitride

Combining first-principles calculations with the particle swarm optimization （PSO） algorithm, we have explored the ground-state structure of Pd2N, whose structure is in debate although it is the first synthesized binary platinum group nitride. The ground-state structure is predicted to be tetragonal with space group P^-4m2, which is energetically more favorable than the previously proposed orthorhombic Co2N-type structure. The stability is confirmed by the subsequent calculations on the phonon dispersion curves and elastic constants. Furthermore, the calculated mechanical properties indicate that Pd2N has low incompressibility and is a common hard material.