EFFECT OF STRUCTURE ON DEFECT FORMATION IN CRYSTAL OF LITHIUM BORIC OXIDE (LBO)

<正> The effect of structure on the defective formation in non-linear optical crystal of lithium boric oxide(LBO)was studied by X-ray topography.Only a few dislocations with the density less than 50/cm2 occur in the specimen cut far from the seed.Most inclusive formed in the late growth stage show a regular orthorhombic shape with a definite orientation,which are due to the negative crystal growth happened further in the inclusioned melt.The grown-in dislocation takes nearly the screw character with the Burgers vector b almost all in the low index directions,however,the inclusion-induced dislocation is distributed much closely in a network parallel only to the plane of(010)and also takes the screw type with b all in the lowest diretions of this plane.The high movability of lithium ions in open structure and the loosely atmic packings on certain planes were taken into account for the defect formation in addition to for some other crystal properties.     

Atomic simulation of the point defects in three low‐index surfaces of BCC transition metals with the MAEAM

The favorable position of an adatom and the formation energies of a single vacancy and an adatom‐vacancy pair in three low‐index surfaces of body‐centered cubic (BCC) transition metals have been calculated by using the modified analytical embedded atom method (MAEAM). The favorable position of an adatom is at the fourfold and twofold positions above the (100) and (110) surfaces respectively, but it is deviated from the threefold position of the (111) surface. Either the heights of the adatom from the top atomic layer, or the formation energies of a single vacancy, or an adatom‐vacancy pair decrease in sequence of the (110), (100) and (111) surfaces for each metal. Furthermore, the formation energy of an adatom‐vacancy pair is always lower than that of a single vacancy for each low‐index surface of each metal, which shown the formation of adatom‐vacancy pair is more energetically favorable than the vacancy for the BCC transition metals. Copyright © 2007 John Wiley & Sons, Ltd.     

Growth morphology of isotactic polybutene-1

Isotactic polybutene-1 has been crystallized from solution by the film formation method. Well-defined single crystals have been grown from solutions of the polymer in amyl acetate and its mixtures with n-butanol in all the three modifications by varying the concentration and crystallization temperature. Multilayered orthorhombic, tetragonal and hexagonal crystals with spiral ramps and terraces have been obtained from concentrated solutions near the turbidity temperature. Rotation of the screw dislocation as well as interlacing multilayered growth have been observed in the tetragonal morphology. Different types of twinning are commonly observed in the orthorhombic and hexagonal modifications. It is suggested that (a) spiral ramps grow by the mechanism of screw dislocation, (b) terraced crystals grow by the mechanism of Frank-Read source or the basal lamellae being hairy on the molecular level nucleating the next lamella, (c) movement of screw dislocation is very common in the orthorhombic and hexagonal modifications, (d) the solution temperature does not affect the morphology but the solvent concentration and the crystallization temperature decide the growth habit of the single crystals and (e) the growth mechanism of multilayered crystals and twinning are similar to those of monomeric substances.     

Magneto-optical specifications of Rosen-Morse quantum dot with screw dislocation

This is the first study to consider a quantum dot with screw dislocation that has Rosen-Morse (RM) confinement potential, generated by a GaAs/GaAlAs heterostructure. An external magnetic field and Aharonov-Bohm (AB) flux field were also applied on RM quantum dot (RMQD) in order to stave the effects of a screw dislocation defect. The combined effect of the screw dislocation defect, the external magnetic field, and AB flux field on the total refractive index changes (TRICs) and the total absorption coefficients (TACs) of RMQD are thus investigated. Cylindrical coordinates are used due to the direction of application of the torsion and the external fields, as well as due to the structure's symmetry. The effective mass approximation and tridiagonal matrix methods are used in order to obtain the subband energy spectra and electronic wave functions of RMQD. The nonlinear optical specifications of RMQD are checked using compact-density-matrix formalism within the framework of the iterative method. Reviews without screw dislocation are also carried out in order to be able to clarify the effects of a screw dislocation defect on the optical properties, and then, both cases are deliberated. This study is the first attempt to analyze the AB flux field for RMQD without screw dislocation. In the present study, the influences of a screw dislocation defect on RMQD's TRICs and TACs are probed by considering different values of the external magnetic field and AB flux field, and the ranges of corresponding parameters on the optimum of the structure are specified. Moreover, the study also elucidates how to rule out the effects of screw dislocation on optical specifications by means of the external fields. Despite a certain screw dislocation, the frequency range is determined where the structure behaves as if it is perfect (namely, without screw dislocation) for its optimum, which in turn is crucial for experimental applications.     

Growth and dislocation studies of β-HMX

Background

The defect structure of organic materials is important as it plays a major role in their crystal growth properties. It also can play a subcritical role in “hot-spot” detonation processes of energetics and one such energetic is cyclotetramethylene-tetranitramine, in the commonly used beta form (β-HMX).

Results

The as-grown crystals grown by evaporation from acetone show prismatic, tabular and columnar habits, all with {011}, {110}, (010) and (101) faces. Etching on (010) surfaces revealed three different types of etch pits, two of which could be identified with either pure screw or pure edge dislocations, the third is shown to be an artifact of the twinning process that this material undergoes. Examination of the {011} and {110} surfaces show only one type of etch pit on each surface; however their natural asymmetry precludes the easy identification of their Burgers vector or dislocation type. Etching of cleaved {011} surfaces demonstrates that the etch pits can be associated with line dislocations. All dislocations appear randomly on the crystal surfaces and do not form alignments characteristic of mechanical deformation by dislocation slip.

Conclusions

Crystals of β-HMX grown from acetone show good morphological agreement with that predicted by modelling, with three distinct crystal habits observed depending upon the supersaturation of the growth solution. Prismatic habit was favoured at low supersaturation, while tabular and columnar crystals were predominant at higher super saturations. The twin plane in β-HMX was identified as a (101) reflection plane. The low plasticity of β-HMX is shown by the lack of etch pit alignments corresponding to mechanically induced dislocation arrays. On untwinned {010} faces, two types of dislocations exist, pure edge dislocations with b?=?[010] and pure screw dislocations with b?=?[010]. On twinned (010) faces, a third dislocation type exists and it is proposed that these pits are associated with pure screw dislocations with b?=?[010].

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Graphical abstract Etch pits on the twinned (010) face of β-HMX.

     

Formic acid self-poisoning on bismuth-modified Pt(755) and Pt(775) electrodes

This paper reports the effect of bismuth on the formation of CO from formic acid on platinum stepped surfaces containing six atoms wide (111) terraces and monoatomic steps having (110) or (100) symmetry. In both cases the steps were elaborated by irreversibly adsorbed bismuth in such a way that CO should be produced on the remaining terrace sites. It was found that bismuth decoration of (100) steps causes a large decrease in CO formation, whereas the effect of the same adatom when adsorbed on (110) steps is almost negligible. In this latter case it is necessary to adsorb bismuth on the terrace sites in order to obtain a similar inhibition of the poisoning reaction.     

Slip-step on polyoxymethylene crystals

Crystals of polyoxymethylene have been grown from solution in bromobenzene. In many growth features, which are similar to those for monomeric crystals, the movement of dislocation can be traced by a slip-step raised in the growth surface. Such slip-steps are associated with single spirals, two spirals of opposite senses and two spirals of the same sense. Anomalies in the growth patterns of crystals have also been observed and attributed to the movement of screw dislocation long before the cessation of growth.     

Theory of the vibrational line shape of an adatom at a bridge site

The homogeneous vibrational line shape of an adatom on a surface is determined by its interactions with other localized and delocalized modes of the adsorbate and substrate. These interactions include anharmonic bonds between the adatom and the surface, and also between the substrate atoms themselves at the adsorption site. The line width and frequency shift of the perpendicular vibrational mode of an adatom at a bridge site is calculated as a function of temperature, due to coupling to phonon modes of a semi-infinite elastic continuum. A self energy formulation is employed, using perturbative methods in a quantum field theory. The effects of anharmonicity of both the adsorption bonds and of the interatomic bonds between substrate atoms at the bridge site, on the vibrational line shape, are compared. Energy relaxation by two-phonon emission is found to describe well the temperature-dependent line width in the O/Cu(110) system.     

Excitation in low-energy Li+ collisions with cesiated W(110) surfaces: alignment and orientation of the collisionally excited Li(2p) state

The linear and circular polarization of the Li(2p?2s) emission has been measured for Li⁺ collisions with cesiated and oxydized cesiated W(110) surfaces, Cs-W(110) and O/Cs-W(110), at impact energies below 1 keV for an incidence angle of 5 degrees with respect to the surface plane. The cesium coverage has been varied between zero and the saturation coverage at room temperature. Although the excitation of the projectile seems to occur in a binary collision with only one Cs adatom, the presence of the surface influences the total photon yield by Auger deexcitation, and the circular polarization by affecting the energetic separation of the Li(2p) substates close to the surface.     

Energetics and heterodiffusion of Cu on Ag(110) stepped surfaces

A molecular‐dynamics simulation study has been performed to investigate the Cu adatom diffusion on the (110) stepped surfaces of Ag, using interatomic potentials described by the embedded atom method. We have systematically calculated the energy barriers for different possible diffusion mechanisms, which occur on the terrace and near the step edge. Our findings show that the predominant atomistic diffusion process at step edge and on the terrace is the exchange mechanism with anES barrier about 220 meV lower than that via jumping (290 meV), indicating that the incorporation of Cu adatom into Ag(110) is ‘easier’ than making a jump on the surface. On the other hand, the calculation of the Ehrlich–Schwoebel (ES) barrier demonstrates that this quantity is equal to 0 meV for the exchange process near the step edge and about 60 meV for channel–channel migration. Thus, the mass transport across steps may be important due to the lack of the ES barriers for exchange mechanism, revealing the possible layer‐by‐layer growth mode for our heterogeneous system. Copyright © 2015 John Wiley & Sons, Ltd.     

Structure Sensitivity in the Decomposition of Ethylene Carbonate on Si Anodes

The interaction of ethylene carbonate (EC) with Si surfaces is studied by density functional theory. The results show a strong structure sensitivity in the adsorption of EC on Si surfaces. While the adsorbed EC molecule readily decomposes on the Li/Si(111) surface, it does not dissociate on the Li/Si(100) and Li/Si(110) surfaces. On Si(111), the O atom at the top of EC is detached from the EC molecule and binds to the Li adatom, forming Li?O molecules. The mechanism of EC decomposition is the transfer of 2.4 electrons from the surface to the EC molecule, as well as the formation of a covalent bond between the Li adatom and the EC molecule. This result shows that in lithium‐ion batteries with Si anodes, dissociation of the solvent and formation of a solid electrolyte interphase layer start as soon as the Li atoms cover the anode surface.     

Fundamental aspects of HCOOH oxidation at platinum single crystal surfaces with basal orientations and modified by irreversibly adsorbed adatoms

Oxidation of formic acid at Pt(hkl) electrodes with basal orientations and modified by irreversibly adsorbed adatoms is revisited. It was shown that the adatoms of the nitrogen group enhance the electrocatalytic activity through long-range electronic effects in the case of Pt(111) substrates or through shorter third-body effects when adsorbed at Pt(100) electrodes. In both cases, it appears that free platinum sites were required. Special attention is given here to the reactivity at Pt(110) substrates. It is found that maximum electrocatalysis is observed at fully blocked surfaces. This result points out again structure sensitivity effects for this characteristic reaction. Unlike the more compact planes, in which the enhancement of the oxidation rate was explained through essentially rigid models for the adlayer, it is suggested that the resulting enhancement observed at Pt(110) substrates could be explained if some adatom mobility is considered.     

Interaction of Pt clusters with the anatase TiO(2)(101) surface: a first principles study

The adsorption of Pt(n)() (n = 1-3) clusters on the defect-free anatase TiO(2)(101) surface has been studied using total energy pseudopotential calculations based on density functional theory. The defect-free anatase TiO(2)(101) surface has a stepped structure with a step width of two O-Ti bond distances in the (100) plane along the [10] direction and the edge of the step is formed by 2-fold-coordinated oxygen atoms along the [010] direction. For a single Pt adatom, three adsorption sites were found to be stable. Energetically, the Pt adatom prefers the bridge site formed by 2 2-fold-coordinated oxygen atoms with an adsorption energy of 2.84 eV. Electronic structure analysis showed that the Pt-O bonds formed upon Pt adsorption are covalent. Among six stable Pt(2) adsorption configurations examined, Pt(2) was found to energetically favor the O-O bridge sites on the step edge along [010] with the Pt-Pt bond axis perpendicular to [010]. In these configurations, one of the Pt atoms occupies the same O-O bridge site as for a single Pt adatom and the other one either binds a different 2-fold-coordinated oxygen atom on the upper step or a 5-fold-coordinated Ti atom on the lower terrace. Three triangular and three open Pt(3) structures were determined as minima for Pt(3) adsorption on the surface. Platinum trimers adsorbed in triangular structures are more stable than in open structures. In the most stable configuration, Pt(3) occupies the edge O-O site with the Pt(3) plane being upright and almost perpendicular to the [001] terrace. The preference of Pt(n)() to the coordinately unsaturated 2-fold-coordinated oxygen sites indicates that these sites may serve as nucleation centers for the growth of metal clusters on the oxide surface. The increase in clustering energy with increasing size of the adsorbed Pt clusters indicates that the growth of Pt on this surface will lead to the formation of three-dimensional particles.     

Fractal MTW Zeolite Crystals: Hidden Dimensions in Nanoporous Materials

Screw dislocation structures in crystals are an origin of symmetry breaking in a wide range of dense‐phase crystals. Preparation of such analogous structures in framework‐phase crystals is of great importance in zeolites but is still a challenge. On the basis of crystal‐structure solving and model building, it was found that the two specific intergrowths in MTW zeolite produce this complex fractal and spiral structure. With the structurally determined parameters (spiral pitch h, screw angle θ, and spatial angle ψ) of Burgers circuit, the screw dislocation structure can be constructed by two different dimensional intergrowth sections. Thus the reported complexity of various dimensions in diverse crystals can be unified.     

Dissociation mechanism of 2-propanol on a Si(111)-(7x7) surface studied by scanning tunneling microscopy

Adsorption of 2-propanol, (CH3)2CHOH, on a Si(111)-7x7 surface was studied by scanning tunneling microscopy. (CH3)2CHOH adsorbs equally on the faulted and unfaulted half unit cells by forming Si-OCH(CH3)2 and Si-H on an adatom and rest atom pair. Si-OCH(CH3)2 is consecutively increased in each half unit cell, and the adsorption is saturated when every half unit cell has three Si-OCH(CH3)2, which corresponds to 0.5 of the adatom coverage. The sticking probability for the dissociation of (CH3)2CHOH is independent of the adatom coverage from 0 to 0.4, but it depends on coverage at higher than 0.4. By counting the darkened adatoms, Si-OCH(CH3)2 on the center adatom (m) and that on the corner adatom (n), it was found the m/n ratio is ca. 4 for the first dissociation of (CH3)2CHOH in virgin half unit cell, but it becomes ca. 1.9 and 1.8 when two and three Si-OCH(CH3)2 are contained in a half unit cell. This result reveals that the dissociation probability of (CH3)2CHOH at the adatom-rest atom pair site is influenced by the nearest Si-OCH(CH3)2 in the half unit cell.     

Structure of the core of a screw dislocation in smectic A liquid crystals

The structure of the core region of a screw dislocation in smectic A liquid crystals is investigated by a Ginzburg-Landau type expansion of the smectic order parameter. The core radius and the energy of a screw dislocation are discussed.     

Diffusion of Formaldehyde on Rutile TiO2(110) Assisted by Surface Hydroxyl Groups

As the photo-dissociation product of methanol on the TiO₂(110) surface,the diffusion and desorption processes of formaldehyde (HCHO) were investigated by using scanning tunneling microscope (STM) and density functional theory (DFT).The molecular-level images revealed the HCHO molecules could diffuse and desorb on the surface at 80 K under UV laser irradiation.The diffusion was found to be mediated by hydrogen adatoms nearby,which were produced from photodissociation of methanol.Diffusion of HCHO was significantly decreased when there was only one H adatom near the HCHO molecule.Furthermore,single HCHO molecule adsorbed on the bare TiO₂(110) surface was quite stable,little photo-desorption was observed during laser irradiation.The mechanism of hydroxyl groups assisted diffusion of formaldehyde was also investigated using theoretical calculations.     

氧原子在Pt低指数面上的吸附和振动

应用原子和表面簇合物相互作用的5参数Morse势方法（简称5-MP）对O-Pt低指数表面体系进行了研究,并获得了全部临界点特性.计算结果表明,氧原子在Pt(100)面上只存在四重吸附态.在缺行重构的(110)面上,氧原子仍吸附于三重位,随着覆盖度的增加还会嵌切吸附于长桥位;通过分析三重态振动指纹性质的遗传和遗变,确认实验观察到的59.49和40.90 meV损失谱分别为氧原子在三重位和长桥位吸附态的表面垂直振动.     

Atomic structures of the defective SrTiO3 (001) surface

Surface structures of defective SrTiO(3) (001) have been studied by using scanning probe microscopy and density functional theory calculations. We observed several defective surface structures with true atomic resolution under reducing ultrahigh vacuum conditions. It is found that all the defects are terminated by (001), (100) and (010) microfacets of the TiO(2) plane. We propose microfaceting TiO(2) termination with Sr adatom models. The formation of various types of defects is driven by the changes of the surface stoichiometry depending on surface preparations.     

Adsorption effects on resonant charge transfer in atom-surface scattering

The probability of positive ionization of an atom impinging on a solid surface is calculated by numerical solution of the equations of motion of the time-dependent molecular orbitals of the system. The model is applied to the scattering of Na atoms, in the energy range 50–1000 eV, from a W(110) surface. The presence of Na adatoms is considered and found to hinder the ionization process. This reduction in the charge-transfer probability arises because of the lowering of the surface work function brought about by increasing adatom concentration.