TiN多型体高压相变的第一性原理计算

基于密度泛函理论框架下的赝势平面波方法,计算了B1(氯化钠结构)、B2(氯化铯结构)、B3(闪锌矿结构)、B_k(六方氮化硼结构)、B_h(碳化钨结构)和B8₁(砷化镍结构)6种TiN多型体的晶体结构、体积弹性模量和相对稳定性.计算指出,不存在B4(纤锌矿)结构的TiN.通过不同外压下的晶格弛豫得到每种结构的焓,发现外压 关键词： 氮化钛 赝势 高压相变 密度泛函理论     

Molecular dynamics simulations of phase transition of n-nonadecane under high pressure

The phase transition behavior of n-nonadecane under high pressure was investigated with molecular dynamics (MD) simulations method. A simplified model with amorphous structure and periodic boundary conditions in constant-temperature, constant-pressure ensemble was used in this study. The results showed that the whirling and molecules motion of n-nonadecane chains were restrained by the high pressure. The simulated phase transition temperature of n-nonadecane under high pressure is higher than that under atmospheric pressure. The order parameter of n-nonadecane decreases with the increase in temperature. The simulations reveal that MD is an effective method to understand the phase transition of alkane-based phase change materials on molecular and atomic scale.     

Investigations of the Cathode Spot Dynamics in a Vacuum Arc Coating Process

Influence of cathode materials (Ti, Al, Cu, TiN), ambient gases (Ar, N₂, p = 0.1-1 Pa) and the arc current itself on the motion and the velocity of cathode spots in an arc coating process have been investigated with the help of a new high speed framing camera. It was found, that the cathode material causes different spot currents but in general the spot arrangement and the motion on the surface are similar. Surface contaminations due to ambient gases affect this dynamics in several ways. Insulating layers like AIN can drastically increase the instantaneous spot velocity, for example from <5 m/s on Al up to 170 m/s on AIN contaminated areas. TiN layers with a high conductivity increase the spot mobility at first. But at nearly completely contaminated surfaces (simulated by a TiN cathode), the mobility is strongly decreased. The values change from an average velocity of 6.3 m/s with a diffusion constant of 54 cm²/s (Ti, 0.01 Pa) to 2 m/s and 6.4 cm²/s at TiN. The course of the instantaneous spot velocity during the spot splitting phase was investigated too. The instantaneous spot velocity of each of the two new spots originated from the starting spot is relatively high (30–40 m/s) within the first 50 μs. The cathode material and the ambient gases are of slight influence in this phase. The movement is directed. In the further development the instantaneous spot velocity is decreasing to values under 5–10 m/s. The motion is now more and more random. Additionally it could be proved, that the lower stability limit for a stable discharge is strongly connected with the spot current, which depends on discharge conditions.     

高压下TiN的结构转变、弹性和热力学性质的第一性原理计算

 利用基于密度泛函的第一性原理,计算了高压下TiN的结构转变、弹性和热力学性质。计算结果表明：在压力作用下,TiN经历了从NaCl型结构到CsCl型结构的转变,转变压力为348 GPa;TiN的弹性系数随着压力的增加呈线性增加规律。此外,还给出了德拜温度和热容量这两个重要热力学量与温度和（或）压力的依赖关系。     

Stress anisotropy in liquid crystalline phases

Monte Carlo simulations of bulk liquid crystals in the isotropic, nematic and smectic phases were performed. The simulations were carried out using different box shapes. The diagonal components of the pressure tensor were calculated to verify that the system is in mechanical equilibrium. For simulations in cubic boxes it was found that the three components of the pressure tensor had the same values in the isotropic and nematic phases but they were different in the smectic phase, i.e. the system seemed to be under anisotropic stress. NVT and NPT simulations in the smectic phase were performed by allowing the box sides to fluctuate independently; in this case, the average diagonal components of the pressure tensor had the same value. Inaccurate calculation of the total pressure produces incorrect equilibrium boundaries in the phase diagram. Microphases and poorly defined layering can be found in simulations of smectic phases when they are performed on cubic boxes. Although the pressure anisotropy is relaxed out, the layering structure in smectic phases seems to depend on the initial configuration, regardless of the simulation method.     

Three-phase osmotic equilibria using the Gibbs ensemble simulation method

The Gibbs Ensemble Monte Carlo method has been used to simulate osmotic equilibria for Lennard-Jones mixtures. When the simulations are performed with two independent boxes, one containing solvent and the other a mixture of solute and solvent significantly negative osmotic pressures (Π) develop. Following a sugestion of Powles et al. (1997, Molec. Phys., 90, 665), we have extended these simulations to include a third box and the possibility of modelling three coexisting phases. The simulations show that the two phase equilibria with negative values of 77 are metastable and that the system spontaneously separates into three phases: pure solvent, dilute solute-solvent and dense solute-solvent with a resulting osmotic pressure that is normally small and positive.     

Interdiffusion reaction in the CrN interlayer in the NiCrAlY/CrN/DSM11 system during thermal treatment

During thermal treatment, a series of chemical reactions took place in the CrN interlayer in the NiCrAlY/CrN/DSM11 system. The CrN phase in the interlayer was first transformed to intermediate AlN and Cr₂N phases during vacuum heat treatment, and thereafter both changed to TiN phase after thermal exposure. The formation of TiN is beneficial to the suppression of elemental interdiffusion. With the good barrier ability and strong interfacial bonding, the CrN interlayer acts as an excellent diffusion barrier.     

Amorphous silicon hexaboride at high pressure

ABSTRACT

We investigate the pressure-induced structural phase transformation of amorphous silicon hexaboride (a-SiB₆) using a constant pressure first principles approach. a-SiB₆ is found to undergo a gradual phase transformation to a high-density amorphous phase (HDA) in which the average coordination number of both B and Si atoms is about 6. The HDA phase consists of differently coordinated motifs ranging from 4 to 8. B₁₂ icosahedra are found to persist during compression of a-SiB₆ and the structural modifications primarily occur around Si atoms and in the regions linking pentagonal pyramid-like configurations to each other. Upon pressure release, an amorphous structure, similar to the uncompressed one, is recovered, indicating a reversible amorphous-to-amorphous phase change in a-SiB_6. When the electronic structure is considered, the HDA phase is perceived to have a wider forbidden band gap than the uncompressed one.     

溅射压强对TiN/SiNx纳米多层膜微观结构及力学性能的影响

利用磁控溅射方法在不同溅射压强条件下制备了TiN/SiN_x纳米多层膜.多层膜的微观结构及力学性能分别用X射线衍射仪、原子力显微镜及纳米压痕仪来表征.结果表明随着溅射压强的增大,多层膜的界面变模糊,TiN层的择优取向由(200)晶面过渡到(111)晶面.与此同时,多层膜的表面粗糙度增大,硬度和弹性模量随溅射压强的增大而减小.多层膜力学性能的差异主要是由于薄膜的周期性结构及致密度存在差异所致. 关键词： x多层膜')" href="#">TiN/SiN_x多层膜 界面宽度 表面形貌     

Optimization of plasma parameters for high rate deposition of titanium nitride films as protective coating on bell-metal by reactive sputtering in cylindrical magnetron device

Nano-structured titanium nitride (TiN) thin film coating is deposited by reactive sputtering in cylindrical magnetron device in argon and nitrogen gas mixtures at low temperature. This method of deposition using DC cylindrical magnetron configuration provides high uniform yield of film coating over large substrate area of different shapes desirous for various technological applications. The influence of nitrogen gas on the properties of TiN thin film as suitable surface protective coating on bell-metal has been studied. Structural morphological study of the deposited thin film carried out by employing X-ray diffraction exhibits a strong (2 0 0) lattice texture corresponding to TiN in single phase. The surface morphology of the film coating is studied using scanning electron microscope and atomic force microscope techniques. The optimized condition for the deposition of good quality TiN film coating is found to be at Ar:N₂ gas partial pressure ratio of 1:1. This coating of TiN serves a dual purpose of providing an anti-corrosive and hard protective layer over the bell-metal surface which is used for various commercial applications. The TiN film's radiant golden colour at proper deposition condition makes it a very suitable candidate for decorative applications.     

Ab initio calculations of yttrium nitride: structural and electronic properties

Using first principles total energy calculations within the full-potential linearized augmented plane wave method, we have studied the structural and electronic properties of yttrium nitride (YN) in the three phases, namely wurtzite, caesium chloride and rocksalt structures. The calculations are performed at zero and under hydrostatic pressure. In agreement with previous findings, it is found that the favored phase for YN is the rocksalt-like structure. We predict that at zero pressure YN in the rocksalt structure is a semiconductor with an indirect bandgap of 0.8 eV. A phase transition from a rocksalt to a caesium chloride structure is found to occur at ∼134 GPa. Besides, a transition from an indirect (Γ−X) bandgap semiconductor to a direct (X−X) one is predicted at pressure of ∼84 GPa. For the electron effective mass of rocksalt YN, these are the first results, to our knowledge. The information derived from the present study may be useful for the use of YN as an active layer in electronic devices such as diodes and transistors.     

铁冲击相变的分子动力学研究

用分子动力学方法模拟了单晶铁(Fe)在一定初始温度下冲击相变(α相→ε相)的微观过程，结果显示温度会导致冲击相变压力阈值降低.基于此微观过程，对加卸载波系的传播规律进行了相应计算和分析，结果表明在卸载过程中逆相变波(ε相→α相)相对于波前以当地纵波声速传播，而相对波后以亚声速传播，这可由卸载压力-密度曲线给出相应解释；计算了不同初态的卸载压力-密度状态曲线，并给出了逆相变带的分布，其分布规律显示了卸载过程逆相变的滞后现象. 关键词： 分子动力学 多体势 冲击波 相变     

First-Order Phase Transitions in One-Dimensional Steady States

The steady states of the two-species (positive and negative particles) asymmetric exclusion model of Evans, Foster, Godrèche, and Mukamel are studied using Monte Carlo simulations. We show that mean-field theory does not give the correct phase diagram. On the first-order phase transition line which separates the CP-symmetric phase from the broken phase, the density profiles can be understood through an unexpected pattern of shocks. In the broken phase the free energy functional is not a convex function, but looks like a standard Ginzburg–Landau picture. If a symmetry-breaking term is introduced in the boundaries, the Ginzburg–Landau picture remains and one obtains spinodal points. The spectrum of the Hamiltonian associated with the master equation was studied using numerical diagonalization. There are massless excitations on the first-order phase transition fine with a dynamical critical exponent z = 2, as expected from the existence of shocks, and at the spinodal points, where we find z = 1. It is the first time that this value, which characterizes conformal invariant equilibrium problems, appears in stochastic processes.     

Pressure dependence of crystal structure and molecular packing in anthracene

Anthracene molecular crystal has been investigated up to a pressure of 10.5 GPa at room temperature using variable shape variable size Monte Carlo simulations in an isothermal–isobaric ensemble. We have reported various structural quantities, such as cell parameters and unit cell volume, as a function of pressure and compared them with the experimental results [J. Chem. Phys. 119, 1078 (2003)]. The pressure dependence of angles θ, δ and χ which describe the relative packing of molecules in the crystal has been calculated. We report that anthracene molecular crystal does not exhibit any first order phase transition up to a pressure of 10.5 GPa which is consistent with the experimental observations by Oehzelt et al. [Phys. Rev. B 66, 174104 (2002)]. The calculated equation of state (EOS) has been fitted to a Murnaghan-type EOS with good agreement. The calculated bulk modulus and the pressure derivative of bulk modulus are 8.2 GPa and 8.9 respectively which are in agreement with the experimentally calculated values.     

Pressure-induced phase transition of zinc-blende AlN: An ab initio molecular dynamics study

An ab initio constant pressure technique is carried out to study the pressure-induced phase transition of the zinc blende AlN (aluminum nitride). A first order phase transformation into a rock salt structure is observed in the constant pressure simulations. The transformation is accompanied by an initial tetragonal distortion and a subsequent shearing, similar to that found in the other zinc blende structured materials. This phase transition should occur around 6.2 GPa based upon the enthalpy calculations.     

高压下TiN等结构相变的第一性原理研究

 利用基于密度泛函理论的赝势平面波方法和线性响应理论,研究了TiN的物态方程、电子能带结构和声子色散曲线随压强的变化关系。结果表明：TiN 的电子能带结构并未随着压强的增加而出现反常,没有出现电子的拓扑结构相变;零压下出现软化的声子模式并没有随着压强的增加而继续软化。因此可以认为在0～12 GPa 压强范围内,TiN 发生等结构相变的原因不是由于电子的拓扑形貌发生变化和声子软化引起的。     

Amorphous boron nitride at high pressure

The pressure-induced phase transformation in hexagonal boron nitrite and amorphous boron nitrite is studied using ab initio molecular dynamics simulations. The hexagonal-to-wurtzite phase transformation is successfully reproduced in the simulation with a transformation mechanism similar to one suggested in experiment. Amorphous boron nitrite, on the other hand, gradually transforms to a high-density amorphous phase with the application of pressure. This phase transformation is irreversible because a densified amorphous state having both sp³ and sp² bonds is recovered upon pressure release. The high-density amorphous state mainly consists of sp³ bonds and its local structure is quite similar to recently proposed intermediate boron nitrite phases, in particular tetragonal structure (P4₂/mnm), rather than the known the wurtzite or cubic boron nitrite due to the existence of four membered rings and edge sharing connectivity. On the basis of this finding we propose that amorphous boron nitrite might be best candidate as a starting structure to synthesize the intermediate phase(s) at high pressure and temperature (probably below 800 °C) conditions.     

Transitioning model potentials to real systems

The parameters of two pair potentials that describe argon over its entire liquid phase at a fixed pressure were optimized through a novel application of constant temperature and pressure molecular dynamics (NPT-MD) and Monte Carlo (NPT-MC) computer simulations. The forms of these potentials were those of a modified Lennard-Jones potential and a Lennard-Jones potential. The optimized potential determined using NPT-MD simulations reproduces experimental densities, internal energies and enthalpies with an error less than 1% over most of the liquid range and yields self-diffusion coefficients that are in excellent agreement with experiment. The results using the potential determined by NPT-MC simulations are in almost as good agreement with deviations from experiment of no more than 5.89% for temperatures up to vaporization. Additionally, molar volumes predicted using this potential at pressures in the range 100–600 atm and over temperatures in the range 100–140K were within 0.83% of experimental values. These results show that, when properly parametrized, Lennard-Jones-like potentials can describe a system well over a large temperature range. Further, the method introduced is easy to implement and is independent of the form of the interaction potential used.     

Effects of mesonic correlations in the QCD phase transition

The finite-temperature phase transition of strongly interacting matter is studied within a nonlocal chiral quark model of the NJL type coupled to a Polyakov loop. In contrast to previous investigations which were restricted to the mean-field approximation, mesonic correlations are included by evaluating the quark-antiquark ring sum. For physical pion masses, we find that the pions dominate the pressure below the phase transition, whereas above T _c the pressure is well described by the mean-field-approximation result. For large pion masses, as realized in lattice simulations, the meson effects are suppressed. The text was submitted by the authors in English.     

Phase transitions in diglyceride monolayers studied by computer simulations,pressure-area isotherms and X-ray diffraction

Summary 1,2-sn-diglyceride monolayers exhibit unique and complex phase transitions as a function of surface pressure. The dynamical response of the layer on expanding the film has been investigated by computer simulations, (π-A) isotherms and grazing-incidence X-ray diffraction. Good agreement is found between the simulations and experiments. The Langmuir film undergoes two phase transitions occurring at 38.3 and 39.8 ?²/molecule. The transition at low surface density is associated with a tilt of ≈14° in the direction close to nearest neighbour. The first transition is unique for the diglyceride molecules and has not been observed for other amphiphilic molecules. It is driven by a competition of hydrophobic/hydrophilic and intra/intermolecular forces and can be pictured as a ?seesaw? mechanism. Due to the close packing of the chains at high surface pressure, thesn-1 ester group aligns with the alkyl chain, and only thesn-2 ester group is favoured to lay at the aqueous interface. Hydrophilic forces attract thesn-1 ester group, but its motion towards the aqueous subphase is hindered by intra- and intermolecular chain interactions. On expansion, the intermolecular interaction decreases, and at the first transition, the intramolecular interaction between the two chains is strong enough to cause a ?swelling? of the molecules. The diffraction pattern determined in the different mesophases reveals that the layer maintains its hexagonal structure up to the second phase. Concomitant with the tilt, the structure relaxed from a hexagonal to a distorted hexagonal lattice. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.