Influence Of Structural Disorder Research Articles

Influence of Structural Disorder on the Magnetic Order in FeRhCr Alloys

Magnetic phase transitions in alloys are highly influenced by the sample preparation techniques. In the present research, electronic and magnetic properties of Fe48Cr3Rh49 alloys with varying cooling rates were studied, both experimentally and theoretically. The degree of crystalline ordering was found to depend on the cooling rate employed after annealing the alloy. Modeling of alloy structures with different degrees of crystalline ordering was carried out via strategic selection of substitution positions and distances between chromium atoms. Theoretical calculations revealed significant changes in magnetic and electronic properties of the alloy with different substitutions. A comprehensive analysis of the calculated and experimental data established correlations between structural characteristics and parameters governing the magnetic phase transition. In this study, we also developed a method for evaluating the magnetic properties of the alloys obtained under different heat treatments. The proposed approach integrates atom substitution and heat treatment parameters, offering precise control over alloy manufacturing to effectively tune their essential magnetic properties.

Influence of structural disorder on the elastic, frictional, and electrical properties in functionalized polyaniline thin films at the nanoscale investigated by atomic force microscopy

We investigated the influence of structural order on the elastic, frictional, and electrical properties of butylthio-functionalized PANI (PANI-SBu) films by atomic force microscopy (AFM)-based techniques, including PeakForce quantitative nanomechanical mapping, friction force microscopy, and conductive AFM. The PANI-SBu films were prepared by the drop-cast method from the solution of PANI-SBu in N-methyl-2-pyrrolidone that was continuously stirred. The PANI-SBu films were fabricated after different solution stirring times. The shear force during the mechanical stir will disentangle the highly-coiled PANI-SBu polymer chains in the solution. Therefore, the polymer chains in solution cast on the substrates will progressively self-assemble into a more organized structure when solvents evaporate, leading to PANI-SBu films with improved structural order. Our AFM studies discovered that more structurally-ordered PANI-SBu films have substantially larger out-of-plane elastic moduli and charge mobility but smaller kinetic friction coefficients. The denser packing of polymer molecules increases film elasticities and promotes chain-to-chain charge transport. In addition, stiffer PANI-SBu film surfaces are more difficult to deform when sheared by the sliding AFM probe, resulting in less energy dissipation during AFM friction measurements. Thus, smaller kinetic friction coefficients were found. Conversely, more structurally-disordered PANI-SBu films have smaller elasticity and charge mobility but larger kinetic friction coefficients. Our results demonstrate that it is possible to manipulate the elastic, frictional, and electrical properties of PANI-SBu films by controlling their structural order, which can be essential for developing polymer-based composite materials and flexible electronic devices.

Memory Effects in the Nonequilibrium Critical Behavior of the Two-Dimensional XY Model in the Low-Temperature Berezinskii Phase

The Monte Carlo study of nonequilibrium memory effects in the two-dimensional pure and structurally disordered XY model in the low-temperature Berezinskii phase has been performed. Features of the correlation between memory and aging effects have been demonstrated. A qualitatively novel phenomenon for memory effects has been revealed: dynamic curves of the autocorrelation function in the thermal cycling time interval tend to the dynamic curves with the initial temperature. A unique implementation of memory effects has been demonstrated at both cooling and heating cycling of the system under the condition that cooling and heating temperatures are in the low-temperature Berezinskii phase. The influence of structural disorder on memory effects has been analyzed. It has been found that they are enhanced in the structurally disordered system owing to the enhancement of aging effects.

Influence of structural disorder on plasmonic metasurfaces and their colors—a coupled point dipole approach: tutorial

The optical properties of plasmonic metasurfaces are determined not only by the shape and size of the constituting nanostructures, but also by their spatial arrangement. The fast progress in nanofabrication has facilitated the emergence of many advanced metasurface designs that enable controlling the propagation of light on the nanoscale. While simple metasurface designs can be derived from theoretical considerations, it is inevitable to employ computational approaches for complex manipulations of incident light. However, most of the currently available full-wave simulation approaches such as the finite element method (FEM) or finite difference time domain method come with drawbacks that limit the applicability to certain usually simplified or less complex geometries. Within this tutorial, different approaches are outlined for modeling light propagation in complex metasurfaces. We focus on an approach that approximates the nanostructure ensemble as a coupled set of point dipoles and determine their far-field response via the reciprocity theorem. This coupled point dipole approximation (CPDA) model is used to examine randomly distributed, oriented, and scaled nanostructure ensembles. A disorder formalism to introduce the randomness is developed that allows one to progressively perturb periodic arrangements of identical nanostructures and thereby investigate the effects of disorder and correlation. Several disorder metrics are provided that allow one to quantify the disorder, and the relation with the far-field scattering properties is discussed. Spatially and angle resolved hyperspectral datasets are computed for various disordered metasurfaces to assess the capabilities of the CPDA model for different polarization states and incidence angles, among others. The hyperspectral datasets are converted into sRGB color space to deduce the appearances in the image and Fourier planes. Very good agreement of the simulation results with Mie theory, FEM results, and experiments is observed, and possible reasons for the present differences are discussed. The presented CPDA model establishes a highly efficient approach that provides the possibility to rapidly compute the hyperspectral scattering characteristics of metasurfaces with more than 10,000 structures with moderate computational resources, such as state-of-the-art desktop computers with sufficient memory; 16 GB allow for the simulations in this paper, whereas scaling to up to more memory by the factor of N2 allows for the simulation of N times more dipoles. For that reason, the CPDA is a suitable approach for tailoring the bidirectional reflectance distribution function of metasurfaces under consideration of structural perturbations and experimental parameters.

Optical phonons of GeSbTe alloys: Influence of structural disorder

Phase-change materials such as pseudobinary GeSbTe (GST) alloys are widely used for fabrication of rewritable and nonvolatile memory devices and also reveal perspective thermoelectric parameters. Their electron spectrum demonstrates the topological insulator behavior. These promising properties are related to unique structural features of a lattice, study of which attracts much attention since full clarity was not achieved so far. Here, we study Raman spectra of monocrystalline GST alloys to examine influence of lattice structure on phonon spectrum. In the Raman spectra, the broad bands typical for the amorphous state and sharp lines of the crystalline one are observed. The use of a one-dimensional harmonic chain model of atoms composing the lattice unit cell allows us to explain the origin of these features. It is shown that the first component is related to dispersion of phonon frequencies in the different lattice unit cells, which is caused by Ge/Sb disorder. The sharp spectral lines are attributed to phonons originated from those of Sb2Te3 as the structural basis of GST. Their frequencies are invariants relative to Ge/Sb disorder, and GST alloy is an ordered crystal for these modes.

Spectral variability of the uranyl silicates uranophane-α and uranophane-β: polymorphism and luminescence

The luminescence of the uranyl cation UO22+ depends on the local crystalline environment and is sensitive to structural influences. Steady-state photoluminescence emission spectra of the related uranyl silicates uranophane-α, uranophane-β, sklodowskite and haiweeite from various locations are presented and discussed in the light of structure–property relation. The four mineral species were chosen for their close relationships: uranophane-α and uranophane-β are polymorphs and share the underlaying topology with sklodowskite. Haiweeite, with different topology, shares the composing elements Ca, U, Si, O with uranophane, while in sklodowskite Mg replaces Ca. All species show some variability in their spectra, parameterized as a variation of the centroid wavelength. Those variations are linked to defects and structural disorder, relevant in studies of uranyl speciation and migration. We present empiric spectra of the four mineral species with the least influence of structural disorder. As an unexpected feature, a prominent—partly dominating—double peak structure occurs in the case of uranophane-α only, while it is absent in the spectra of the other species. Considering a model of luminescent transitions in the uranyl ion in more detail, this observation is discussed in the light of the polymorphism of uranophane. We show evidence that variable amounts of uranophane-β phase embedded in uranophane-α are possibly at the origin of this spectral signature. Growth of those uranophane-β clusters might be induced by defects in the uranophane-α lattice and further promoted by the polymorphism of uranophane.

Superconductivity in Crystallographically Disordered LaHg6.4

The influence of structural disorder on superconductivity is not yet fully understood. A concurrent examination of crystallographic and physical properties of LaHg6.4 reveals that this material enters a superconducting state below Tc = 2.4 K while showing crystallographic disorder in one dimension. Lanthanum mercuride, which crystallizes in a new structure type (space group Cmcm, a = 9.779(2) Å, b = 28.891(4) Å, c = 5.0012(8) Å, Z = 8), has remained out of reach for nearly 50 years. In this crystal structure, strong disorder is present in the channels that propagate along the [001] direction. By implementing a combination of cutting-edge synthesis and characterization techniques, we were able to circumvent the complexity associated with the low formation temperature and chemical reactivity of this substance and study the superconductivity of LaHg6.4 in detail.

Influence of structural disorder on the photocatalytic properties of ZnS nanocrystals prepared by the one-pot solvothermal approach

This study focuses on the impact of the sulfur vacancies on the photocatalytic response of the ZnS nanocrystals synthesized by solvothermal method varying the concentration of zinc acetate/thiourea precursors. XRD patterns show that these samples have a hexagonal structure with different degrees of crystallinity, varying the crystallite size from 2.48 to 2.85 nm. The UV-Vis data reveals an absorption peak (at about 320 nm) characteristic of ZnS nanocrystals. As a result, a decrease in the bandgap value of these materials was observed from 3.78 to 3.62 eV. In principle, a comparison of these results and theoretical calculations reveals the formation of intermediate levels inside the bandgap due to structural polarization. These findings also corroborate the zeta potential measured for these samples, evidenced by an increase of positive charge of ZnS surfaces. Also, the low Miller-index surfaces, such as (100), (110) and (0001), were investigated by periodic density functional theory calculations, in nice agreement with the experimental data. A photocatalysis mechanism was investigated and confirmed the formation of reactive oxygen species.

On the Possible Nature of Armchair-Zigzag Structure Formation and Heat Capacity Decrease in MWCNTs.

Structural disorder and temperature behavior of specific heat in multi walled carbon nanotubes (MWCNTs) have been investigated. The results of X-ray diffractometry, Raman spectroscopy, and transmission electron microscopy (TEM) images are analyzed. The thermodynamic theory of the zigzag-armchair domain structure formation during nanotube synthesis is developed. The influence of structural disorder on the temperature behavior of specific heat is investigated. The size of domains was estimated at ~40 nm. A decrease in heat capacity is due to this size effect. The revealed dependence of the heat capacity of MWCNTs on the structural disorder allows control over thermal properties of nanotubes and can be useful for the development of thermoelectric, thermal interface materials and nanofluids based on them.

Формирование Ферми-дуг при T<< T-=SUB=-c-=/SUB=- в окрестности d-волновых узлов структурно неоднородных ВТСП YBa-=SUB=-2-=/SUB=-Cu-=SUB=-3-=/SUB=-O-=SUB=-6.92-=/SUB=-

The effect of structural inhomogeneity on the superconducting gap near d-wave for optimally doped high-Tc superconductors YBa2Cu3O6.92 sites is considered. For this purpose, the heat capacity was investigated in the temperature range T = 2-10 K and in magnetic fields H = 0-9 T for a series of fine-crystalline samples with different degrees of controlled structural disordering. The information on the features of superconducting gap near d-wave sites in structurally disordered samples is obtained. It is shown that the d-wave sites inherent in an ideal crystal structure under the influence of structural disorder are modified with the formation of small Fermi arcs in the vicinity of nodal points at T << Tc, not covered by a superconducting gap. In this case, the gap itself remains at T ≤ Tc in other directions of the Brillouin zone and coexists with the Fermi arcs. This transformation is accompanied by an increase in the steepness of the nodal slope, a decrease of the Volovik effect, and the generation of a linear term γ (0) T of the metallic type in the temperature dependence of heat capacity, which should not be present in superconductors with an ideal crystal structure and the nature of which has not yet been established.

Coulomb blockade transport emerged in quasi one-dimensional PEDOT: PSS fiber

In organic materials, peculiar nonlinearity to current voltage appears, thought a general and comprehensive explanation of them is still controversial. Conductive segments in poorly conductive organic materials are expected to have a smaller electrical capacity, leading to a higher critical temperature for the blockade effect. Here we show an experimental evidence of Coulomb blockade taking place on quasi one-dimensional conductive polymer, PEDOT:PSS [poly (3, 4-ethylenedioxy-thiophene) doped with poly (styrene sulfonate) anions], fibers. The PEDOT:PSS wire grows through electro-polymerization, and bridges between electrodes immersed in EDOT monomer solution. Conducting measurement for the dried fibers shows clear nonlinear behaviour in the current-voltage characteristics as temperature decreases. The non-zero threshold voltage, which increased with decreasing temperature, appears in the current flows through a thinnest fiber. The effective percolative transport passes in thin fiber is able to consists of the connection of the Coulomb blockade islands. By considering both the charge blockade effect and the influence of structural disorder and dimensionality, it is hoped that a clear understanding of charge transport in organic materials can be achieved.

Disorder-driven glasslike thermal conductivity in colusite Cu26V2Sn6S32 investigated by Mössbauer spectroscopy and inelastic neutron scattering

The influence of structural disorder on the thermal transport in the colusite $\mathrm{C}{\mathrm{u}}_{26}{\mathrm{V}}_{2}\mathrm{S}{\mathrm{n}}_{6}{\mathrm{S}}_{32}$ has been investigated by means of low-temperature thermal conductivity and specific heat measurements (2--300 K), $^{119}\mathrm{Sn}$ M\"ossbauer spectroscopy and temperature-dependent powder inelastic neutron scattering (INS). Variations in the high-temperature synthesis conditions act as a key parameter for tuning the degree of disorder in colusite compounds. Intriguingly, we find that all synthesized samples are disordered, the degree of which varies with the synthesis conditions used. M\"ossbauer data clearly evidence that Sn atoms do not solely occupy the $6c$ site of the crystal lattice but are present on possibly both the Cu and V sites, leading to a random distribution of these three cations within the unit cell. Increasing the disorder in these materials tends to lead to a smearing out of the main features in the phonon density of states measured by INS. Although the evolution of the inelastic signal upon warming is well described by a quasiharmonic approximation, elastic properties calculations indicate large average Gr\"uneisen parameters, consistent with those determined experimentally from thermodynamic data. Increasing the level of disorder results in a decreased average Gr\"uneisen parameter suggesting that the lowered lattice thermal conductivity is not driven by enhanced anharmonicity. These results provide experimental evidence to support that the remarkable changeover in the lattice thermal conductivity from crystalline to glasslike is solely driven by enhanced disorder accompanied by local lattice distortions.

The Effect of Anti-Site Disorder on Structural and Magnetic Properties of Ni–Co–Mn–In Alloys: <italic>Ab Initio</italic> and Monte Carlo Studies

In this paper, we report on the effect of partial structural B2-like disorder on martensitic transformation and thermomagnetization curves in Ni–Co–Mn–In alloy by using the theoretical approach involving first principles and Monte Carlo methods. In case of ground-state electronic calculations, the off-stoichiometric composition was treated by using both supercell and coherent potential approaches. It is found that the increase of a structural disorder degree leads to decrease the energy difference between austenite and martensite phases, which corresponds to a decrease in the martensitic transformation temperature according to $\Delta E \approx k_{B}T_{m}$ . Besides, the magnetic exchange interaction constants for both martensite and austenite are slightly weakened by influence of structural disorder. Using calculated exchange coupling constants in the effective Potts–Blume–Emery–Griffiths Hamiltonian, a set of magnetization curves for the studied system is simulated. It is shown that the account of disorder results in a decrease in the magnetization value around the magnetostructural transformation. Theoretical results reproduce well the experimental ones.

(Invited) Lithium Ion Conductors – between Model Systems and Battery Materials

Lithium ion conductors continue to attract huge attention mainly due to the need for improved Li ion batteries, although “post-Li” energy storage systems are also being explored. In any case, basic research dealing with, e.g., the elementary ion jump process, the dimensionality of diffusion or the influence of structural disorder – besides being a field in its own right – is indispensable for those applications, too. Here, exemplary results of our group on Li ion conductors are reviewed. Interestingly, materials used as model systems for basic questions quite often are also potential battery materials, i.e. solid electrolytes or electrodes, and vice versa. An early example of a cathode material has been the intercalation compound LixTiS2 which turned out to be a model system for two-dimensional Li diffusion, involving a unique jump process over many decades, as was proven by a combination of nuclear magnetic resonance (NMR) techniques. Besides the layer-structured also the cubic modification as well as nanocrystalline and amorphous forms were examined with respect to dimensionality and disorder effects.. Anode materials studied by us primarily from a fundamental point of view have been Li x C6 (0<x≤1), Li4+x Ti5O12 (0<x<3) and, as one of the silicides, Li12Si7. In Li12Si7 very fast quasi one-dimensional Li diffusion was detected. Among the potential electrolytes for all-solid-state Li ion batteries, Li7La3Zr2O12 was investigated in some detail also with respect to the influence of doping and defects on Li diffusivity. The examples to be presented extensively involve NMR, which now is an established materials science method for Li ion dynamics [1, 2], but also impedance spectroscopy [3], mass spectrometry [4] and neutron reflectometry [5] have been applied in the Li ion transport studies.[1] C. V. Chandran, P. Heitjans, Solid-State NMR Studies of Lithium Ion Dynamics Across Materials Classes, Annual Reports on NMR Spectroscopy 89 (2016) 1-102.[2] K. Volgmann, V. Epp, J. Langer, B. Stanje, J. Heine, S. Nakhal, M. Lerch, M. Wilkening, P. Heitjans, Solid-State NMR to Study Translational Li Ion Dynamics in Solids with Low-Dimensional Diffusion Pathways, Z. Phys. Chem. 231 (2017) 1215–1241. [3] J. Rahn, E. Hüger, L. Dörrer, B. Ruprecht, P. Heitjans, H. Schmid, Li Self-Diffusion in Lithium Niobate Single Crystals at Low Temperatures, Phys. Chem. Chem. Phys. 116 (2012) 2427–2433. [4] A.-M. Welsch, H. Behrens, I. Horn, S. Roß, P. Heitjans, Self-Diffusion of Lithium in LiAlSi2O6 Glasses Studied Using Mass Spectrometry, J. Phys. Chem. A 116 (2012) 309–318. [5] F. Strauß, E. Hüger, P. Heitjans, T. Geue, J. Stahn, H. Schmidt, Li Permeation through Thin Lithium-Silicon Films for Battery Applications Investigated by Neutron Reflectometry, Energy Technology 12 (2016) 1582–1587.

The influence of structural disorder and phonon on metal-to-insulator transition of VO2

We used temperature-dependent x-ray absorption fine structure (XAFS) measurements to examine the local structural properties around vanadium atoms at the V K edge from VO2 films. A direct comparison of the simultaneously-measured resistance and XAFS regarding the VO2 films showed that the thermally-driven structural transition occurred prior to the resistance transition during a heating, while this change simultaneously occured during a cooling. Extended-XAFS (EXAFS) analysis revealed significant increases of the Debye-Waller factors of the V-O and V-V pairs in the {111} direction of the R-phase VO2 that are due to the phonons of the V-V arrays along the same direction in a metallic phase. The existance of a substantial amount of structural disorder on the V-V pairs along the c-axis in both M1 and R phases indicates the structural instability of V-V arrays in the axis. The anomalous structural disorder that was observed on all atomic sites at the structural phase transition prevents the migration of the V 3d1 electrons, resulting in a Mott insulator in the M2-phase VO2.

Slow Lithium Transport in Metal Oxides on the Nanoscale

Abstract This article reports on Li self-diffusion in lithium containing metal oxide compounds. Case studies on LiNbO3, Li3NbO4, LiTaO3, LiAlO2, and LiGaO2 are presented. The focus is on slow diffusion processes on the nanometer scale investigated by macroscopic tracer methods (secondary ion mass spectrometry, neutron reflectometry) and microscopic methods (nuclear magnetic resonance spectroscopy, conductivity spectroscopy) in comparison. Special focus is on the influence of structural disorder on diffusion.

Stepwise Structural Evolution of a DTS-F2BT Oligomer and Influence of Structural Disorder on Organic Field Effect Transistors and Organic Photovoltaic Performance

An A–D–A oligomer, DTS(F2BT)2, was synthesized; its structural evolution was studied with DSC, POM, 2D-WAXD, and in-situ GI-XRD. The structural evolution of DTS(F2BT)2 is stepwise and kinetically slow. Both rapid drying and the presence of PC71BM trapped DTS(F2BT)2 in a less ordered nematic (N) phase. PDMS-assisted crystallization enabled a pristine DTS(F2BT)2 thin film to attain a more ordered equilibrium phase, and enhanced the OFET mobility of DTS(F2BT)2. In OPV devices, DIO additive drove the DTS(F2BT)2 domains in the DTS(F2BT)2:PC71BM blended film from the N phase toward the equilibrium phase, and resulted in enhanced OPV performances. These results reveal the slow ordering process of the A–D–A oligomer, and the importance of monitoring the degree of structural evolution of the active thin films in organic optoelectronics.

Influence of structural disorder on soft x-ray optical behavior of NbC thin films

Structural and chemical properties of compound materials are modified, when thin films are formed from bulk materials. To understand these changes, a study was pursued on niobium carbide (NbC) thin films of different thicknesses deposited on Si (100) substrate using ion beam sputtering technique. Optical response of the film was measured in 4–36 nm wavelength region using Indus-1 reflectivity beamline. A discrepancy in soft x-ray performance of NbC film was observed which could not be explained with Henke's tabulated data (see http://henke.lbl.gov/optical_constants/). In order to understand this, detailed structural and chemical investigations were carried out using x-ray reflectivity, grazing incidence x-ray diffraction, x-ray absorption near edge structure, extended x-ray absorption fine structure, and x-ray photoelectron spectroscopy techniques. It was found that the presence of unreacted carbon and Nb deficiency due to reduced Nb-Nb coordination are responsible for lower soft x-ray reflectivity performance. NbC is an important material for soft x-ray optical devices, hence the structural disorder need to be controlled to achieve the best performances.

Getting real: influence of structural disorder on the performance of plasmonic hole array sensors fabricated by a bottom-up approach

Periodic hole arrays in gold films showing extraordinary transmission of light are fabricated using solely chemical methods. The degree of order of the hole arrays has a strong impact on their transmission properties, which can be utilized for a spectral quality control of the produced plasmonic sensors.

Theoretical and experimental studies on the electronic structure of crystalline and amorphous ZnSnO3 thin films

The influence of structural disorder on the electronic structure of amorphous ZnSnO3 was examined by ab-initio calculations. The calculation results are compared with the experimental results using as-deposited and annealed ZnSnO3 films grown by atomic layer deposition. The O K-edge X-ray absorption spectroscopy, X-ray diffraction, and thin-film transistors were employed in the experiment. The conduction band minima of amorphous and crystalline ZnSnO3 mainly consisted of Sn 5s state, while a higher non-uniform localization of these states was observed in the amorphous phase compared with the crystalline counterpart. The experimental results coincide well with the theoretical results.