Uncovering the internal structure of five-fold twinned nanowires through 3D electron diffraction mapping

Five-fold twinned nanostructures are intrinsically strained or relaxed by extended defects to satisfy the space-filling requirement. Although both of metallic and semiconductor five-fold twinned nanostructures show inhomogeneity in their cross-sectional strain distribution, the evident strain concentration at twin boundaries in the semiconductor systems has been found in contrast to the metallic systems. Naturally, a problem is raised how the chemical bonding characteristics of various five-fold twinned nanosystems affects their strain-relieving defect structures. Here using three-dimensional(3 D)electron diffraction mapping methodology, the intrinsic strain and the strain-relieving defects in a pentagonal Ag nanowire and a star-shaped boron carbide nanowire, both of them have basically equal radial twin-plane width about 30 nm, are nondestructively characterized. The non-uniform strain and defect distribution between the five single crystalline segments are found in both of the five-fold twinned nanowires. Diffraction intensity fine structure analysis for the boron carbide five-fold twinned nanowire indicates the presence of high-density of planar defects which are responsible for the accommodation of the intrinsic angular excess. However, for the Ag five-fold twinned nanowire, the star-disclination strain field is still present, although is partially relieved by the formation of localized stacking fault layers accompanied by partial dislocations.Energetic analysis suggests that the variety in the strain-relaxation ways for the two types of five-fold twinned nanowires could be ascribed to the large difference in shear modulus between the soft noble metal Ag and the superhard covalent compound boron carbide.     

Cold welding of copper nanowires with single-crystalline and twinned structures: A comparison study

In this article, molecular simulations were adopted to explore the cold welding processes of copper nanowires with both single-crystalline and fivefold twinned structures. It was verified that the twinned nanowires exhibited enhanced strength but lowered elastic limit and ductility. Both nanowires could be successfully welded through rather small loadings, although their stress–strain responses toward compression were different. Meanwhile, more stress was accumulated in the twinned nanowire due to repulsive force of the twin boundaries against the nucleation and motions of dislocations. Moreover, by characterizing the structure evolutions in the welding process, it can be ascertained that perfect atomic order was finally built at the weld region in both nanowires. This comparison study will be of great importance to future mechanical processing of metallic nanowires.     

First principles study of the electronic properties of twinned SiC nanowires

The electronic properties of saturated and unsaturated twinned SiC nanowires grown along [111] direction and surrounded by {111} facets are investigated using first-principles calculations with density functional theory and generalized gradient approximation. All the nanowires considered, including saturated and unsaturated ones, exhibit semiconducting characteristics. The saturated nanowires have a direct band gap and the band gap decreases with increasing diameters of the nanowires. The hexagonal (2H) stacking inside the cubic (3C) stacking has no effect on electronic properties of the SiC nanowires. The highest occupied molecular orbitals and the lowest unoccupied molecular orbitals are distributed along the nanowire axis uniformly, which indicates that the twinned SiC nanowires are good candidates in realizing nano-optoelectronic devices.     

Investigation of mechanical properties of twin gold crystal nanowires under uniaxial load by molecular dynamics method

Twin gold crystal nanowires, whose loading direction is parallel to the twin boundary orientation, are simulated.We calculate the nanowires under tensile or compressive loads, different length nanowires, and different twin boundary nanowires respectively. The Young modulus of nanowires under compressive load is about twice that under tensile load.The compressive properties of twin gold nanowires are superior to their tensile properties. For different length nanowires,there is a critical value of length with respect to the mechanical properties. When the length of nanowire is greater than the critical value, its mechanical properties are sensitive to length. The twin boundary spacing hardly affects the mechanical properties.     

Electronic structure of twinned ZnS nanowires

The electronic properties of twinned ZnS nanowires (NWs) with different diameters were investigated based on first-principles calculations. The energy band structures, projected density of states and the spatial distributions of the bottom of conduction band and the top of the valence band were presented. The results show that the twinned nanowires exhibit a semiconducting character and the band gap decreases with increasing nanowire diameter due to quantum confinement effects. The valence band maximum and conduction band minimum originate mainly from the S-p and Zn-s orbitals at the core of the nanowires, respectively, which was confirmed by their spatial charge density distribution. We also found that no heterostructure is formed in the twinned ZnS NWs since the valence band maximum and conduction band minimum states are distributed along the NW axis uniformly. We suggest that the hexagonal (2H) stacking inside the cubic (3C) stacking has no effect on the electronic properties of thin ZnS NWs.     

Atomistic simulation study on twin orientation and spacing distribution effects on nanotwinned Cu films

Affected by twin orientation and spacing distribution, different deformation and failure mechanisms of nanotwinned (NT) Cu films are discovered. For films with the same twin spacing, transition from brittle to ductile and ductile to localized necking with the increase of the slanted angle of twin boundary (TB) from 0° to 90° is examined. Two dominant slip mechanisms: (1) slip intersecting with the TBs; (2) slip parallel to the TBs can uncover the transition mechanisms with consideration of twin orientation. To maintain both relatively high strength and good ductility, the slanted angle can be set close to the ductile to localized necking transition border. Besides, the stress–strain curves obtained in this article show that the mechanical responses on both sides of the turning point 45° are asymmetric. On the other hand, the twin spacing distributions affect the ductility of NT Cu films and have almost no contribution to strengthening. The strength of the NT Cu films mainly depends on the twin density. NT Cu films with different twin spacing have worse ductility than equal twin spacing films due to the local twin spacing asymmetry. The failures can be predicted appearing at TBs adjacent to large twin spacing regions, and the failure propagation direction can also be predicted by knowing the obtuse angle decided by stacking faults and TBs.     

Growth and characterization of type-II ZnO/ZnTe core-shell nanowire arrays for solar cell applications

Large area, well-aligned type-II ZnO/ZnTe core-shell nanowire arrays have been fabricated on an a-plane sapphire substrate. The ZnO nanowires were grown in a furnace by chemical vapor deposition with gold as catalyst and then were coated with a ZnTe shell on the ZnO nanowires surface by a metal-organic chemical deposition chamber. The morphology and size distribution of the ZnO/ZnTe core-shell nanowire arrays were studied by scanning electron microscopy (SEM) and the crystal structure was examined by x-ray diffraction (XRD). Transmission measurement was used to study the optical properties of the core-shell nanowires. The results indicated that the ZnO/ZnTe core-shell nanowire arrays have good crystalline quality. In addition, it was found that the nanowire arrays have good light absorption characteristics and these properties make it suitable for making photovoltaic devices.     

Strengthening effects of various grain boundaries with nano-spacing as barriers of dislocation motion from molecular dynamics simulations

Strengthening in metals is traditionally achieved through the controlled creation of various grain boundaries (GBs), such as low-angle GBs, high-angle GBs, and twin boundaries (TBs). In the present study, a series of large-scale molecular dynamics simulations with spherical nanoindentation and carefully designed model were conducted to investigate and compare the strengthening effects of various GBs with nano-spacing as barriers of dislocation motion. Simulation results showed that high-angle twist GBs and TBs are similar barriers and low-angle twist GBs are less effective in obstructing dislocation motion. Corresponding atomistic mechanisms were also given. At a certain indentation depth, dislocation transmission and dislocation nucleation from the other side of boundaries were observed for low-angle twist GBs, whereas dislocations were completely blocked by high-angle twist GBs and TBs at the same indentation depth. The current findings should provide insights for comprehensive understanding of the strengthening effects of various GBs at nanoscale.     

In situ TEM study of mechanical behaviour of twinned nanoparticles

There is strong interest in studying changes in mechanical properties with reducing grain size. The rational is that consequent dislocation glide cannot be sustained, resulting in an increase in material strength. However, this comes with the cost of a reduction in ductility. It has been shown that coherent twin boundaries in nanostructured Cu improve the ductility to 14% [Lu et al., Science 324 (2009) p. 349]. In this paper, we report for the first time the compression of individual nanoparticles using an in situ force probing holder in the transmission electron microscope. Four types of nanoparticles were tested, three with twin boundaries (decahedra, icosahedra and a single twin) and one free of defects (octahedral). Our results indicate the yield strength of the twinned nanoparticles is between 0.5 and 2.0 GPa. The total malleability for the twinned particles range from 80 to 100%. In addition, experimental results were reproduced by MD simulations of the compression phenomena and suggest that the outstanding mechanical properties are related with partial dislocation multiplication at twin boundaries.     

Atomic and electronic structure of mixed Au-Co nanowires: Ab initio molecular dynamics study

The atomic and electronic structure of uniformly and nonuniformly mixed Au-Co nanowires have been studied using the ab initio molecular dynamics method. The effect of elastic stretching/contraction deformations on the stability and electronic properties of mixed Au-Co nanowires has been studied. It is established that Co dimers are formed in a nonuniformly mixed nanowire. The formation of CO₂ dimers results in a non-uniform distribution of the electron density and interactomic distances along the wire and leads to accelerated rupture of the wire between Au atoms under stretching. Only a uniformly mixed Au-Co nanowire composed of regularly alternating Au and Co atoms is stable under stretching up to large interactomic distances.     

Direct insight into grain boundary reconstruction in polycrystalline Cu(In,Ga)SE2 with atomic resolution

This work presents results from high-resolution scanning transmission electron microscopy and electron energy-loss spectroscopy on twin boundaries (TBs) and nontwin grain boundaries (GBs) in Cu(In,Ga)Se(2) thin films. It is shown that the atomic reconstruction is different for different symmetries of the grain boundaries. We are able to confirm the model proposed by Persson and Zunger [Phys. Rev. Lett. 91, 266401 (2003)] for Se-Se-terminated Σ3 {112} TBs, showing Cu depletion and In enrichment in the two atomic planes closest to the TB. On the contrary, Cu depletion without In enrichment is detected for a cation-Se-terminated TB. At nontwin GBs, always a strong anticorrelation of Cu and In signals is detected suggesting that the formation of In(Cu) or Cu(In) antisites within a very confined region of smaller than 1 nm is an essential element in the reconstruction of these GBs.     

Crossover between channeling and pinning at twin boundaries in YBa2Cu3O7 thin films

The critical current (Jc) of highly twinned YBa2Cu3O7 films has been measured as a function of temperature, magnetic field, and angle. For much of the parameter space we observe a strong suppression of Jc for fields in the twin boundary (TB) directions; this is quantitatively modeled as flux-cutting-mediated vortex channeling. For certain temperatures and fields a crossover occurs to a regime in which channeling is blocked and the TBs act as planar pinning centers so that TB pinning enhances the overall Jc. In this regime, intrinsic pinning along the TBs is comparable to that between the twins.     

Fano resonance in asymmetric gold nano-dimers with square and rectangular sections

The Fano resonances of the asymmetric dimers of gold nanowires with square and rectangular sections are investigated by using the finite-difference time-domain (FDTD) method. It is found that the Fano resonance peak can be switched on and off by laying or removing the rectangular section nanowire aside the square section one. There is only one dipole resonance mode of a single gold nanowire with a square section on the dielectric substrate, and it redshifts obviously accompanied with the FWHM being broadened along with the side width of the nanowire increasing. A Fano resonance appears when another gold nanowire with the rectangular section is laid aside the one with a square section. The peak value and FWHM of the Fano resonance mode increase obviously with the distance between the two nanowires getting larger. Meanwhile, it can be modulated by the height of the rectangular section nanowire. In addition, they can be regulated by the width and rotating angle of the rectangular section nanowire, but the peak value stays the same. The mechanisms for these behaviors are associated with the interaction of the superradiant and subradiant modes, and the corresponding electric field distributions are plotted to verify this. It is expected that the results will be useful for the design of wavelength biosensing and other new optical devices.     

Helical gold nanotube synthesized at 150 K

Gold nanowires were synthesized at 150 K by electron beam thinning of a gold thin foil in an UHV electron microscope. The gold nanowires were found to have a helical multishell structure (HMS). One particular nanowire, which was thinner than the 7-1 HMS nanowire, was found to have a tubular structure. The gold single wall nanotube is composed of five atomic rows that coil about the tube axis. The diameter was 0.4 nm and the pitch was 11 nm. The stability of the (5,3) nanotube was discussed in terms of the shear deformation of the triangular network of gold atoms.     

多晶银纳米线拉伸变形的分子动力学模拟研究

纳米尺度金属Ag以其独特的导电和导热性,广泛应用于微电子、光电子学、催化等领域,特别是在纳米微电极和纳米器件方面的应用.本文采用分子动力学方法模拟了不同晶粒尺寸下多晶银纳米线的拉伸变形行为,详细分析了晶粒尺寸对多晶银纳米线弹性模量、屈服强度、塑性变形机理的影响.发现当晶粒尺寸小于13.49 nm时,多晶Ag纳米线呈现软化现象,出现反Hall-Petch关系,此时的塑性变形机理主要以晶界滑移、晶粒转动为主,变形后期形成五重孪晶;当晶粒尺寸大于13.49 nm时,塑性变形以位错滑移为主,变形后期产生大量的孪晶组织.     

Straight single-crystalline germanium nanowires and their patterns grown on sol-gel prepared gold/silica substrates

Straight single-crystalline Ge nanowires with a uniform diameter distribution of 50-80 nm and lengths up to tens of micrometers were grown in a high yield on sol-gel prepared gold/silica substrates by using Ge powder as the Ge source. Detailed electron microscopy analyses show that the nanowires grow through a vapor-liquid-solid growth mechanism with gold nanoparticles located at the nanowire tips. By using transmission electron microscope grids as the shadow mask, the sol-gel technique can be readily adapted to prepare patterned film-like gold/silica substrates, so that regular micropatterns of Ge nanowires were obtained, which could facilitate the integration of Ge nanowires for characterization and devices.     

The effect of surface roughness on lattice thermal conductivity of silicon nanowires

A theoretic model is presented to take into account the roughness effects on phonon transport in Si nanowires (NWs). Based on the roughness model, an indirect Monte Carlo (MC) simulation is carried out to predict the lattice thermal conductivities of the NWs with different surface qualities. Through fitting the experimental data with the MC predictions, the scattering strength on phonons from the boundary, umklapp phonon-phonon processes and impurities can be estimated. It is found that the scattering on phonons by the roughness cell boundaries in a rough nanowire can reduce the phonon mean free path to be smaller than the nanowire diameter, the Casimir limit of the phonon mean free path in a flat nanowire for phonons engaged in completely diffused boundary scattering processes.     

Functional twin boundaries

Functional interfaces are at the core of research in the emerging field of ‘domain boundary engineering’ where polar, conducting, chiral, and other interfaces and twin boundaries have been discovered. Ferroelectricity was found in twin walls of paraelectric CaTiO₃. We show that the effect of functional interfaces can be optimized if the number of twin boundaries is increased in densely twinned materials. Such materials can be produced by shear in the ferroelastic phase rather than by rapid quench from the paraelastic phase.     

金属纳米线弹性性能的尺寸效应及其内在机理的模拟研究

本文应用分子动力学(MD)方法和改进分析型嵌入原子模型(MAEAM)研究了Ni, Al和V纳米线的弹性性能尺寸效应及表面对其影响, 并计算了相应完整晶格材料的弹性性能. 结果表明本文计算完整晶格材料的弹性性能与已有实验和理论的结果相符合. 而计算所得各金属纳米线的体模量明显低于相应块体材料的结果, 且随纳米线的尺寸增加而呈指数增加, 并接近于常数. 在此基础上, 通过研究Ni, Al和V纳米线表面能的尺寸效应及其分布特征进一步探讨了自由表面在尺寸影响纳米线弹性性能过程中的作用及其内在机理.