A Computational Study of Aspects of ZnO Nanorod Film Electro-Crystallisation

<p>A new generation of material technologies is being produced by tuning the properties of an existing material through control of the size and shape on the nanoscale. Zinc oxide is an excellent candidate for such an approach due to its possession of a plethora of useful properties, both mechanical and electronic, and a fantastically rich family of morphologies accessible on the nanoscale. A more detailed control over the nano-structure of these materials requires a more detailed understanding of the events that control the growth. We have undertaken computational studies of the electrodeposition of zinc oxide nano-rod films to open up and improve the understanding of the pathways, and events that facilitate the controlled selection of desired structures and therefore properties. We have applied methods that span vastly different scales to provide insight on the continuum and atomistic regimes. Specifically, we have developed a macroscopic transport model to track the evolution of crystallite shape, surrounding concentration distributions, and electric field variation. The macroscopic view is complemented with a classical description of crystal growth, in which we obtain the key parameters using quantum mechanical calculations.</p>

A Computational Study of Aspects of ZnO Nanorod Film Electro-Crystallisation

<p>A new generation of material technologies is being produced by tuning the properties of an existing material through control of the size and shape on the nanoscale. Zinc oxide is an excellent candidate for such an approach due to its possession of a plethora of useful properties, both mechanical and electronic, and a fantastically rich family of morphologies accessible on the nanoscale. A more detailed control over the nano-structure of these materials requires a more detailed understanding of the events that control the growth. We have undertaken computational studies of the electrodeposition of zinc oxide nano-rod films to open up and improve the understanding of the pathways, and events that facilitate the controlled selection of desired structures and therefore properties. We have applied methods that span vastly different scales to provide insight on the continuum and atomistic regimes. Specifically, we have developed a macroscopic transport model to track the evolution of crystallite shape, surrounding concentration distributions, and electric field variation. The macroscopic view is complemented with a classical description of crystal growth, in which we obtain the key parameters using quantum mechanical calculations.</p>

Determining the Preferred Orientation of Silver-Plating via X-ray Diffraction Profile

Determining the preferred orientation of plating film is of practical importance. In this work, the Rietveld method and quantitative texture analysis (RM+QTA) are used to analyze the preferred orientation of plating silver film with XRD profile, whose <311> axial texture can be completely described by a set of exponential harmonics index, extracted from a single XRD profile, C41,1(0.609), C61,1(0.278), C81,1(−0.970). The constructed pole figures with the index of the exponential harmonic are following those measured by the multi-axis diffractometer. The method using exponential harmonic index can be extended to characterize the plating by electroplating in a quantitative harmonic description. In addition, a new dimension involving crystallite shape and size is considered in characterizing the preferred orientation.

Nanoscale imaging of shale fragments with coherent X-ray diffraction

Despite the abundance of shales in the Earth's crust and their industrial and environmental importance, their microscale physical properties are poorly understood, owing to the presence of many structurally related mineral phases and a porous network structure spanning several length scales. Here, the use of coherent X-ray diffraction imaging (CXDI) to study the internal structure of microscopic shale fragments is demonstrated. Simultaneous wide-angle X-ray diffraction (WAXD) measurement facilitated the study of the mineralogy of the shale microparticles. It was possible to identify pyrite nanocrystals as inclusions in the quartz–clay matrix and the volume of closed unconnected pores was estimated. The combined CXDI–WAXD analysis enabled the establishment of a correlation between sample morphology and crystallite shape and size. The results highlight the potential of the combined CXDI–WAXD approach as an upcoming imaging modality for 3D nanoscale studies of shales and other geological formations via serial measurements of microscopic fragments.

The Stability of a Nanoparticle Diamond Lattice Linked by DNA

The functionalization of nanoparticles (NPs) with DNA has proven to be an effective strategy for self-assembly of NPs into superlattices with a broad range of lattice symmetries. By combining this strategy with the DNA origami approach, the possible lattice structures have been expanded to include the cubic diamond lattice. This symmetry is of particular interest, both due to the inherent synthesis challenges, as well as the potential valuable optical properties, including a complete band-gap. Using these lattices in functional devices requires a robust and stable lattice. Here, we use molecular simulations to investigate how NP size and DNA stiffness affect the structure, stability, and crystallite shape of NP superlattices with diamond symmetry. We use the Wulff construction method to predict the equilibrium crystallite shape of the cubic diamond lattice. We find that, due to reorientation of surface particles, it is possible to create bonds at the surface with dangling DNA links on the interior, thereby reducing surface energy. Consequently, the crystallite shape depends on the degree to which such surface reorientation is possible, which is sensitive to DNA stiffness. Further, we determine dependence of the lattice stability on NP size and DNA stiffness by evaluating relative Gibbs free energy. We find that the free energy is dominated by the entropic component. Increasing NP size or DNA stiffness increases free energy, and thus decreases the relative stability of lattices. On the other hand, increasing DNA stiffness results in a more precisely defined lattice structure. Thus, there is a trade off between structure and stability of the lattice. Our findings should assist experimental design for controlling lattice stability and crystallite shape.

Simulating the diffraction line profile from nanocrystalline powders using a spherical harmonics expansion

An accurate description of the diffraction line profile from nanocrystalline powders can be obtained by a spherical harmonics expansion of the profile function. The procedure outlined in this work is found to be computationally efficient and applicable to the line profile for any crystallite shape and size. Practical examples of the diffraction pattern peak profiles resulting from cubic crystallites between 1 and 100 nm in size are shown.

Синтез высокоориентированных пленок оксида цинка на аморфных подложках методом магнетронного распыления на постоянном токе

We describe the technology of obtaining highly oriented zinc-oxide (ZnO) films on amorphous substrates at high growth rates (up to 7 nm/s) by means of direct-current magnetron sputtering. It is suggested to optimize the substrate position with respect to magnetron and consider the floating potential to which the substrate is charged in magnetron discharge plasma as one of the main technological parameters. Electrondiffraction study of the structural characteristics of the obtained ZnO films showed that increase in the substrate temperature was accompanied by transformation of the crystallite shape from platelike to columnar.

AFM Studies on the Effect of Crystalline Interphase on Adhesion of Polyurethane Thin Film to Al Substrate

Polyurethanes crystallized at the aluminum surface, but the crystalline interphase varied with polyol OH number. Early stage of spherulite formation was characterized using AFM after removing amorphous polyurethane. The crystallite shapes of polyurethanes were correlated with the bond strength measured from indentation debonding. Interestingly, the samples involving non-specific shape of crystallites displayed high bond strength, while the polyurethanes with rod-like crystallite poorly adhered to aluminum substrate. Although crystallite shape did not unequivocally relate to bond strength, the results propose that there is a probable correlation.

On the Modelling of Diffraction Line Profiles from Nanocrystalline Materials

Recent advances in Line Profile Analysis of powder diffraction patterns must be paralleled by increasing attention to the quality and quantity of experimental data. The analysis of simulated data with different noise levels demonstrates the importance of statistical quality to reveal fine details of interest in the analysis of nanocrystalline materials, like the crystallite shape. It is also shown how synchrotron radiation diffraction can improve data quality with respect to laboratory measurements, both in terms of statistical quality and in terms of accessible information.

Rietveld analysis of mechanically activated BaCO3–TiO2 system

BaTiO3 powders were prepared through mechanical activation chemistry and analyzed by Rietveld refinement with X-ray diffraction data. Raw BaCO3 and TiO2 powders were dry milled for 5 and 20 h and then calcinated for 2 and 4 h at 800 °C. The milling process was found to have broken up the BaCO3 and TiO2 crystals into smaller crystals and formed only small amounts (<1.5 wt%) of BaTiO3. Subsequence calcinations for 2 and 4 h at 800 °C successfully produced large amounts (>97.7 wt%) of BaTiO3 crystals. The calcination process also generated microstrains and crystallite-size anisotropy in BaTiO3. An increase in the calcination time from 2 to 4 h increased the BaTiO3 weight percentage and the crystallite-shape anisotropy, but decreased the tetragonal distortion anisotropic microstrains in BaTiO3 crystals.