We study experimentally and theoretically liquid crystal structure of smectic oily streaks, focusing on planar wall defects hosted within smectic flattened hemicylinders (SFHs). The wall configuration is singular both in orientational and translational order and we refer to it as the Total Wall Defect (TWD). Here "singular" refers to nematic director field and smectic phase field. In theoretical analysis of the TWD we use a mesoscopic Landau-de Gennes-Ginsburg approach in terms of the nematic tensor order parameter and smectic A (SmA) complex order parameter field. The smectic layer structure is experimentally determined using polarizing optical microscopy and X-ray diffraction measurements at Synchrotron facilities. We demonstrate theoretically and numerically that the experimentally observed abrupt change of the SmA layering in the centre of the wall defect is realized via nematic order reconstruction mechanism. Our experiments reveal that smectic layer spacing above and below the wall are almost similar. The theoretical analysis suggests that lateral SFH boundary conditions determine the vertical position of TWD.
Smectic liquid crystals can be viewed as model systems for lamellar structures for which there has been extensive theoretical development. We demonstrate that a nonlinear energy description is required with respect to the usual Landau-de Gennes elasticity in order to explain the observed layer spacing of highly curved smectic layers. Using x-ray diffraction we have quantitatively determined the dilation of bent layers distorted by antagonistic anchoring (as high as 1.8% of dilation for the most bent smectic layers) and accurately described it by the minimal nonlinear expression for energy. We observe a 1° tilt of planar layers that are connected to the curved layers. This value is consistent with simple energetic calculations, demonstrating how the bending energy impacts the overall structure of a thin distorted smectic film. Finally, we show that combined x-ray measurements and theoretical modeling allow for the quantitative determination of the number of curved smectic layers and of the resulting thickness of the dilated region with unprecedented precision.
We present an experimental study of the formation of lamellar eutectic grains in thin Al-Al2Cu samples. The coupled growth of the Al-rich solid-state solution alpha and the Al2Cu intermetallic theta is observed in situ by real-time optical microscopy during directional solidification. Crystallographic structural information is probed ex situ by X-ray Laue micro-diffraction (mu-Laue), thus providing non-destructive access to the local orientation of alpha and theta lamellae at the submicrometer scale. The mu-Laue measurements are made on representative specimen zones within distinct eutectic grains located at distances in the order of millimeters to centimeters over the metal film. Three types of crystal orientation relationships (ORs) are identified: the well-known Alpha-4 and Beta-6 ORs in hypereutectic samples, and ORs belonging to the recently identified Type C family in hypoeutectic samples. Direct observations clearly show how remarkable ORs are created during initial nucleation and growth stages, and bring clear evidence for the existence of a selection mechanism depending on the nature of the primary phase. A discussion is proposed on the experimental control of the eutectic-grain structure during early solidification stages, and on pending questions regarding differences between thin and bulk Al-Al2Cu samples.
We studied the formation and growth of locked-lamellar microstructures in a thin sample of a slightly hypoeutectic Al-Al 2 Cu alloy. The coupled-growth dynamics, including early stages and steady-state regimes, was observed optically in real time during directional solidification. The orientation of the α (Al) and θ (Al 2 Cu) crystals was measured ex situ in a series of eutectic grains by X-ray Laue microdiffraction. A nucleation event of a θ crystal on a pre-existing α crystal, and the subsequent growth of a eutectic grain with a type-C orientation relationship, that is, with a coincidence of {123}-α and {100}-θ planes, were observed in situ. In type-C eutectic grains, lamellar locking occurred parallel to the low-energy coincidence plane. A regular ( floating ) coupled-growth dynamics was observed in misoriented eutectic grains.
New collective optical properties have emerged recently from organized and oriented arrays of closely packed semiconducting and metallic nanoparticles (NPs). However, it is still challenging to obtain NP assemblies which are similar everywhere on a given sample and, most importantly, share a unique common orientation that would guarantee a unique behavior everywhere on the sample. In this context, by combining optical microscopy, fluorescence microscopy and synchrotron-based grazing incidence X-ray scattering (GISAXS) of assemblies of gold nanospheres and of fluorescent nanorods, we study the interactions between NPs and liquid crystal smectic topological defects that can ultimately lead to unique NP orientations. We demonstrate that arrays of one-dimensional - 1D (dislocations) and two-dimensional - 2D (grain boundaries) topological defects oriented along one single direction confine and organize NPs in closely packed networks but also orient both single nanorods and NP networks along the same direction. Through the comparison between smectic films associated with different kinds of topological defects, we highlight that the coupling between the NP ligands and the smectic layers below the grain boundaries may be necessary to allow for fixed NP orientation. This is in contrast with 1D defects, where the induced orientation of the NPs is intrinsically induced by the confinement independently of the ligand nature. We thus succeeded in achieving the fixed polarization of assemblies of single photon emitters in defects. For gold nanospheres confined in grain boundaries, a strict orientation of hexagonal networks has been obtained with the 〈10〉 direction strictly parallel to the defects. With such closely packed and oriented NPs, new collective properties are now foreseen.
In this Letter, we show how advanced hierarchical structures of topological defects in the so-called smectic oily streaks can be used to sequentially transfer their geometrical features to gold nanospheres. We use two kinds of topological defects, 1D dislocations and 2D ribbon-like topological defects. The large trapping efficiency of the smectic dislocation cores not only surpasses that of the elastically distorted zones around the cores but also surpasses the one of the 2D ribbon-like topological defect. This enables the formation of a large number of aligned NP chains within the dislocation cores that can be quasi-fully filled without any significant aggregation outside of the cores. When the NP concentration is large enough to entirely fill the dislocation cores, the LC confinement varies from 1D to 2D. We demonstrate that the 2D topological defect cores induce a confinement that leads to planar hexagonal networks of NPs. We then draw the phase diagram driven by NP concentration, associated with the sequential confinements induced by these two kinds of topological defects. Owing to the excellent large-scale order of these defect cores, not only the NP chains but also the NP hexagonal networks can be oriented along the desired direction, suggesting a possible new route for the creation of either 1D or 2D highly anisotropic NP networks. In addition, these results open rich perspectives based on the possible creation of coexisting NP assemblies of different kinds, localized in different confining areas of a same smectic film that would thus interact thanks to their proximity but also would interact via the surrounding soft matter matrix.
Liquid Crystal (LC) topological defects have been shown to trap nanoparticles (NPs) in the defect cores. The LC topological defects may thus be used as a matrix for new kinds of NP organizations templated by the defect geometry. We here study composites of LC smectic dislocations and gold NPs. Straight NP chains parallel to the dislocations are obtained leading to highly anisotropic optical absorption of the NPs controlled by light polarization. Combining Grazing Incidence Small Angle X-ray scattering (GISAXS), Rutherford Back Scattering (RBS), Spectrophotometry and the development of a model of interacting NPs, we explore the role of the Np size regarding the dislocation core size. We use NPs of diameter D = 6 nm embedded in an array of different kinds of dislocations. For dislocation core larger than the NP size, stable long chains are obtained but made of poorly interacting NPs. For dislocation core smaller than the NP size, the disorder is induced outside the dislocation cores and the NP chains are not equilibrium structures. However we show that at least half of these small dislocations can be filled, leading to chains with strongly enhanced electromagnetic coupling between the NPs. These chains are more probably stabilized by the elastic distortions around the defect cores, the distortion being enhanced by the presence of the grain boundary where the dislocations are embedded.
We present an experimental and k⋅p theoretical study on the origin of the strong in-plane uniaxial magnetic anisotropy in (Ga,Mn)As layers, unexpected from the cubic crystalline structure. The symmetry lowering can be accounted for by structural or effective shear strains. We find theoretically out-of-plane and in-plane magnetic anisotropy constants being linear with the shear strain. Searching for a real shear strain arising from lattice relaxation, we perform two types of measurements: anomalous x-ray diffraction and strain-induced optical birefringence, at room temperature. Working on a strongly anisotropic (Ga,Mn)As layer, the estimated ϵxy=10−4 was not found although it lied an order of magnitude above the detection threshold. This ensemble of results indicates as unlikely a relaxation-driven uniaxial anisotropy. As previously suggested theoretically, the magnetic symmetry-lowering could instead originate from the anisotropic incorporation of Mn atoms during growth. This would yield a perfectly in-plane matched lattice, with an anisotropy that could nevertheless be modeled as an effective shear strain and modified by an external shear stress, in agreement with the existing experimental literature.
Au-Cu bimetallic nanoparticles (NPs) grown on TiO2(110) have been followed in situ using grazing incidence X-ray diffraction and X-ray photoemission spectroscopy from their synthesis to their exposure to a CO/O2 mixture at low pressure (P < 10-5 mbar) and at different temperatures (300 K-470 K). As-prepared samples are composed of two types of alloyed NPs: randomly oriented and epitaxial NPs. Whereas the introduction of CO has no effect on the structure of the NPs, an O2 introduction triggers a Cu surface segregation phenomenon resulting in the formation of a Cu2O shell reducible by annealing the sample over 430 K. A selective re-orientation of the nanoparticles, induced by the exposure to a CO/O2 mixture, is observed where the randomly oriented NPs take advantage of the mobility induced by the Cu segregation to re-orient their Au-rich core relatively to the TiO2(110) substrate following specifically the orientation ((111)NPs//(110)TiO2) when others epitaxial relationships were observed on the as-prepared sample.
Using an analytically tractable example, the pseudomorphic inclusion, this article examines the influence of elastic deformations on the form factor of polyhedral nanocrystals. A control parameter, the total amplitude of the variation of the complex density phase, is identified and it is shown that for low enough deformations the characteristic asymptotic behaviours as a function of the scattering vector associated with the polyhedral crystal shape are preserved, leading to a strong contrast in the dependence of the form factor on orientation. Using the sections method, it is explained why these results can be generalized to more realistic elastic situations.
Strained epitaxial SiGe on vicinal Si(001) substrates develops a morphological instability perpendicular to the steps unlike the usual growth instabilities on vicinal substrates, eventually leading to planar nanowires. We assess both theoretically and experimentally the effect of strain anisotropy on the 1D elongation of the Asaro-Tiller-Grinfel'd (ATG) instability. The anisotropy of strain relaxation due to the presence of step edges is considered in a continuum model with two different effective strains in the surface plane. We show that the measured in-plane strain anisotropy and the theoretical model are consistent with the experimental morphologies. Nice network of ultrasmall aligned elongations are predicted resulting from a complex interplay of kinetic and energetic phenomena associated with strain anisotropy.
An analytical method, the sections method, is developed to build a close link between the singularities of the surface of a body and the asymptotic behaviour of its amplitude form factor at large scattering vector, q . In contrast with a sphere, for which the asymptotic behaviour is in q −2 , surface singularities lead to both narrow regions, for which the amplitude form factor exhibits trailing behaviour, and extended regions, for which it exhibits a rapid decrease. A numerical study of a simple example, the fourfold truncated sphere, illustrates the usefulness of these analytical predictions.
Surface acoustic waves are used in magnetism to initiate magnetization switching, in microfluidics to control fluids and particles in lab-on-a-chip devices, and in quantum systems like two-dimensional electron gases, quantum dots, photonic cavities, and single carrier transport systems. For all these applications, an easy tool is highly needed to measure precisely the acoustic wave amplitude in order to understand the underlying physics and/or to optimize the device used to generate the acoustic waves. We present here a method to determine experimentally the amplitude of surface acoustic waves propagating on Gallium Arsenide generated by an interdigitated transducer. It relies on Vector Network Analyzer measurements of S parameters and modeling using the Coupling-Of-Modes theory. The displacements obtained are in excellent agreement with those measured by a very different method based on X-ray diffraction measurements.
A general and compact formula is established for the form factor of any polyhedron, which involves only the apex coordinates and the apex connections. For large diffusion vector q , the form factor behaves like q −3 for generic directions, but it exhibits q −2 singularities in the directions perpendicular to the edges and q −1 singularities in the directions normal to the faces. General results are established for these singularities. Using a Python implementation, illustrative examples are discussed. The generality of the formula and of its singularities are likely to be important for any discussion of scattering from polyhedral particles.
A hybrid disklike/rodlike molecule comprising central triphenylene core symmetrically substituted with six azobenzene moieties (C-12) has been adsorbed at the 1,2,4 trichlorobenzene/Au(111) interface, revealing the potential of azobenzene moieties for the control of two-dimensional (2D) chiral networks. The C-12, which due to its complex molecular structure possesses a relatively large number of degrees of freedom, surprisingly forms monolayers of only one kind of structure, namely a hexagonal network of large period, 3.5 nm. By combining scanning tunneling microscopy (STM) and DFT calculations, we evidence that this specific 2D-ordering is due to cooperative weak hydrogen bonds between neighboring azobenzenes and azobenzene-Au(111) interactions. The crystallographic network is hexagonal, but azobenzene-azobenzene pairing, associated with hydrogen bonding renders the network chiral with a chirality spanning all ranges, from the molecular C-12 configuration, to the configuration of the azobenzene dimers, the rosettelike azobenzene network and the C-12 network orientation on Au(111) rotated by +/- 8 degrees from the main crystallographic direction Au<110>, depending on the handedness of the molecular network. This chiral 2D system thus paves the way for the formation of macroscopic 2D molecular crystals of unique handedness, if additional enantiomeric chiral dopants can be used.
We study by grazing incidence x-ray diffraction the strain field induced by periodic double steps on a Si(1 1 15) surface that is a vicinal of a Si(001) surface misoriented by 5.4. towards the < 110 > direction. The best fit of the experimental structure factors is reached on the basis of the rebonded D-B step edge model and the displacement field is well characterized assuming that steps are described by parallel rows of extended buried elastic dipoles. The dipole characteristics are the dipole position with respect to the step edge, the dipole amplitude (2.0 +/- 0.5 nN), and the lever arm Omega = 5.3 degrees and force Phi = 3.7 degrees orientations. We show that the dipole is dominated by a large stretch component localized between the lower and the upper corners of the step, which we assign to the presence of the rebonded atom at the step.
Surface acoustic waves of micrometre wavelength travelling on a monocrystal give diffraction satellites around each Bragg peak in an X-ray diffraction diagram. By using a four-crystal monochromator, a secondary two-crystal analyser and masks reducing the footprint to the part of the crystal containing the acoustic modulation, it is possible to observe these satellites on a GaAs (001) surface using a laboratory diffractometer. The finite extension of the satellite diffraction rods and of the crystal truncation rod perpendicular to the surface leads to geometrical correction factors when convoluted with the instrumental resolution function, which had previously been ignored. The calculation of these geometrical correction factors in the framework of the kinematic approximation allows the determination of the surface acoustic wave amplitude, and the study of its attenuation and its dependence on radiofrequency power and duty cycle. The ability to perform such determinations with a laboratory diffractometer should prove useful in optimizing surface acoustic waves, which are presently used in a broad range of condensed matter physics studies.
Controlling aging of catalysts is of crucial importance to preserve their properties, in particular for bimetallic nanoparticles (NPs) where reaction can modify the composition. Herein, we have studied the stability upon oxygen exposure of gold-copper NPs supported on rutile. We have used in situ scanning tunneling microscopy to follow the evolution of individual Au, Cu and Au-Cu NPs with various compositions grown on the TiO2(110) surface, during each step from their nucleation to their modification with oxygen. We demonstrated a direct relation between the stability of the nanoparticles and their Au concentration. Whereas pure Cu nanoparticles dissociate under O2, Au-Cu NPs containing at least 20% Au are stable. This is explained by a modification of the local density of states of Cu atoms upon alloying.
Scanning tunneling microscopy (STM) and grazing-incidence x-ray diffraction (GIXD) have been used to follow in situ the growth and the structure of Au-Cu nanoparticles (NPs) formed on TiO2(110) by successive metal evaporations. STM observations of the same area of the substrate highlight the strong dependence between the sequence of deposition and the final result. Deposition of Cu first leads to a system where both Au-Cu and pure Au NPs coexist. Deposition of Au first ensures growing mostly bimetallic NPs. GIXD results show that Cu alloys instantaneously with Au NPs at room temperature. Similar observations during evaporation of Au on Cu NPs show that some of the Au atoms alloy with Cu whereas the rest remain at the NP shell. This is attributed both to kinetics and thermodynamics origins.
We investigate the expression of chirality in a monolayer formed spontaneously by 2,3,6,7,10,11-pentyloxytriphenylene (H5T) on Au(111). We resolve its interface morphology by combining scanning tunneling microscopy (STM) with theoretical calculations of intermolecular and interfacial interaction potentials. We observe two commensurate structures. While both of them belong to a hexagonal space group, analogical to the triangular symmetry of the molecule and the hexagonal symmetry of the substrate surface, they surprisingly reveal a 2D chiral character. The corresponding breaking of symmetry arises for two reasons. First it is due to the establishment of a large molecular density on the substrate, which leads to a rotation of the molecules with respect to the molecular network crystallographic axes to avoid steric repulsion between neighboring alkoxy chains. Second it is due to the molecule-substrate interactions, leading to commensurable large crystallographic cells associated with the large size of the molecule. As a consequence, molecular networks disoriented with respect to the high symmetry directions of the substrate are induced. The high simplicity of the intermolecular and molecule-substrate van der Waals interactions leading to these observations suggests a generic character for this kind of symmetry breaking. We demonstrate that, for similar molecular densities, only two kinds of molecular networks are stabilized by the molecule-substrate interactions. The most stable network favors the interfacial interactions between terminal alkoxy tails and Au(111). The metastable one favors a specific orientation of the triphenylene core with its symmetry axes collinear to the Au⟨110⟩. This specific orientation of the triphenylene cores with respect to Au(111) appears associated with an energy advantage larger by at least 0.26 eV with respect to the disoriented core.