Defect-free Lattice Research Articles

Topologically trivial gap-filling in superconducting Fe(Se,Te) by one-dimensional defects

Structural distortions and imperfections are a crucial aspect of materials science, on the macroscopic scale providing strength, but also enhancing corrosion and reducing electrical and thermal conductivity. At the nanometre scale, multi-atom imperfections, such as atomic chains and crystalline domain walls have conversely been proposed as a route to topological superconductivity, whose most prominent characteristic is the emergence of Majorana Fermions that can be used for error-free quantum computing. Here, we shed more light on the nature of purported domain walls in Fe(Se,Te) that may host 1D dispersing Majorana modes. We show that the displacement shift of the atomic lattice at these line-defects results from sub-surface impurities that warp the topmost layer(s). Using the electric field between the tip and sample, we manage to reposition the sub-surface impurities, directly visualizing the displacement shift and the underlying defect-free lattice. These results, combined with observations of a completely different type of 1D defect where superconductivity remains fully gapped, highlight the topologically trivial nature of 1D defects in Fe(Se,Te).

1,1-Diamino-2,2-dinitroethylene: The riddles of thermal decomposition and combustion

The thermal decomposition of deuterium derivatives α-FOX-7 and γ-FOX-7 have been studied using non-isothermal and isothermal kinetic methods. It was found that deuteration only affects the kinetics of the low-temperature decomposition step of α-FOX-7. A unique feature of the low-temperature stage of the decomposition of α-FOX-7 is that topochemical processes on crystal defects lead to intermolecular hydrogen transfer with the formation of its highly reactive aci-form. The decomposition of the aci-form of FOX-7 proceeds in an extremely unusual way via the molecular elimination of nitric acid and formation of nitrile N-oxide. The high-temperature decomposition stage involves the olefinic form of FOX-7 in a defect-free crystal lattice, and the decomposition is initiated by breaking the C–NO2 bond. In the gas phase, the FOX-7 molecule is also in its olefin form and exhibits high thermal stability.The combustion behavior and flame structure of α–FOX-7 and heat-treated substance (γ–FOX-7t) have been studied using a constant-pressure bomb and micro-thermocouple technique. Analysis of the thermocouple measurement data showed that the burning rate of both FOX-7 isomers is controlled by the rate of heat release in the condensed phase. This reaction is the decomposition of the substance in the melt. The higher burning rates of α-FOX-7 were due to the fact that the highly reactive aci-form of FOX-7 formed on the crystal defects remains in the melt and decomposes at the surface temperature. The break in the dependence of the burning rate on pressure observed for the α- and γ-polymorphs is associated with their complete isomerization into the internal aci-form of FOX-7 due to intramolecular hydrogen transfer. In this case, the surface temperature is determined by the vaporization of the internal aci-form of FOX-7, whose enthalpy of vaporization is higher than that of its olefin form.

Oriented-Attachment- and Defect-Dependent PbTe Quantum Dots Growth: Shape Transformations Supported by Experimental Insights and DFT Calculations.

High-resolution transmission electron microscopy results reveal that oriented-attachment- and defect-dependent mechanisms rule the size and shape evolution of the monodispersed PbTe quantum dots (QDs). The former is characterized by the growth of quasi-cubic PbTe QDs, which depends on both the geometric constraints imposed by the {200} facets and the defect-free lattice, while the latter one is a defect-dependent mechanism which gives way to the formation of decahedral PbTe QDs (∼6 nm). Experimentally, formaldehyde is an important parameter for the mechanochemical synthesis of monodispersed PbTe QDs, which has not been studied until now. In a theoretical context, Fukui functions reveal that Pb surface atoms are the most reactive sites toward nucleophilic attacks, and the Lowdin charge analysis shows that formaldehyde molecules tend to donate their electron pairs to Pb atoms. Besides, formaldehyde-molecule-on-PbTe adsorption energies (-4.46 to -21.16 kcal mol-1) agree with ligand-surface polar electrostatic interactions. Based on dispersion-corrected density functional theory calculations, PbTe QDs exhibited decahedral and faceted shapes. According to modified Wulff constructions, the decahedral shape is a result of (111) facets (Δγ = -2.79 meV Å-2), whereas the faceted and rounded shapes are due to the interaction of (100), (110), and (111) facets.

Topology optimization of imperfect lattice materials built with process-induced defects via Powder Bed Fusion

Abstract Lattice materials built via additive manufacturing feature process-induced defects that impact their mechanical properties and optimum design. This work presents a methodology to integrate geometric defects in a density-based formulation for topology optimization of additively built lattice materials. The method combines imperfect unit cell models capturing their geometric defects with a homogenization scheme upscaling their effective properties, into a topology optimization formulation. The method is of general application, and it is here demonstrated through the application to two cell topologies, the Tetrahedron-based and the Octet-truss unit cells, called to satisfy specific geometric constraints. Verification is performed through the solution of two well-known benchmark problems in 3D: the fixed-beam and the L-shaped beam, assumed to consist of either defect-free or imperfect lattice materials. The impact of process-induced defects, and cell orientation is demonstrated on the elastic anisotropy of the unit cell, the optimized gradients of relative density and the global compliance of the beams. The results highlight the significance of accounting for geometric defects in topology optimization of additively built lattice materials.

Enhanced thermoelectric performance of Ca3Co4O9 doped with aluminum

Ca3−x AlxCo4O9 polycrystalline ceramics with a small amount of Al (0 ≤ x ≤ 0.4) were fabricated using the sol–gel combustion method with natural starch as a fuel. All synthesized samples were a pure phase with no Al-based secondary phase detected, and a defect-free lattice structure. Their diffraction peaks shifted to higher angle values as doping (x) increased. A mixture of valence states of Co2+, Co3+, and Co4+ were detected in all samples. In the Ca3Co4O9 system, both the Seebeck coefficient and the thermal conductivity are enhanced by a single doping of Al. The maximum power factor (0.348 mW/m K2) and figure of merit (0.14) was obtained for x = 0.1 at 700 K; these values are respectively 3.6% and 28.4% higher than undoped samples. These results indicate that Al is a promising doping element for enhancing the thermoelectric properties of the Ca3Co4O9 system.

Floquet-surface bound states in the continuum in a resonantly driven one-dimensional tilted defect-free lattice

We study the Floquet-surface bound states embedded in the continuum (BICs) and bound states out the continuum (BOCs)in a resonantly driven 1D tilted defect-free lattice. In contrast to fragile single-particle BICs assisted by specially tailored potentials, we find that Floquet-surface BICs, stable against structural perturbations, can exist in a wide range of parameter space. By using a multiple-time-scale asymptotic analysis in the high-frequency limit, the appearance of Floquet-surface bound states can be analytically explained by effective Tamm-type defects at boundaries induced by the resonance between the periodic driving and tilt. The phase boundary of existing Floquet-surface states is also analytically given. Based on the repulsion effect of surface states, we propose to detect transition points and measure the number of Floquet-surface bound states by quantum walk. Our work opens a new door to experimental realization of BICs in quantum system.

New insights into the nature of glauconite

AbstractGlauconite must be assessed as mica-rich mica-smectite R3 interstratified mineral, with the pure end-member mica also having intrinsic K-deficient chemical characteristics (K+ ~ 0.8 apfu). This assertion is in accordance with our X-ray diffraction (XRD) and high-resolution tranmission electron microscopy (HRTEM) studies and chemical analyses by electron probe microanalysis (EPMA) of mature glauconites in Cenozoic Antarctic sediments that indicate that: (1) It consists of a glauconite-smectite (R3 ordered) mixed-layer silicate, composed mainly of mica-type layers (>90%), but displaying slightly different proportions of Fe(III)-smectite layers (<10%). (2) More mature glaucony grains are characterized by major K+ and VIFe2+ (mica layers) and minor VIFe3+ (smectite layers) content in the interstratified glauconite-smectite. (3) Potassium is stabilized at the interlayer site by the octahedrally coordinated Fe2+. (4) Microtexture of the glauconite crystals are comparable with those of other micas and illite minerals, with straight, defect-free lattice fringes of ~10 Å spacings glauconite packets characteristic of mica with minor interstratified poorly crystalline smectite layers. In addition, our new findings give insights into the glauconitization process and at the same time investigate the potassium-deficient character of the dioctahedral mica “glauconite.” These findings show that glauconite crystallizes by a layer-growth mechanism at the expense of a poorly crystalline smectite precursor and that smectiteto-glauconite transformations are accompanied by a gradually higher octahedral charge deficiency (Fe2+/Fe3+) stabilized by K+ uptake into the interlayer sheet.

Combustion synthesis of SiC-based ceramics reinforced by discrete carbon fibers with in situ grown SiC nanowires

This study proposes a combustion-based ceramic matrix composite processing technique intended on single-step in situ deposition of single-crystal SiC nanowires (SiCnw) on the surface of carbon fibers (Cf) and formation of SiCnw–reinforced SiC matrix. This was accomplished by Ta-catalyzed combustion of poly-(C2F4)-containing reactive mixtures with pre-mixed chopped Cf. Depending on the combustion conditions, carbon fiber surface is subjected either to formation of diffusion layers, ceramic particle incrustation or growth of continuous arrays of carbon-coated single-crystal SiCnw with a nearly defect-free lattice, 10–50 nm diameter and 15–20 μm length. Thermodynamics, phase and structure formation mechanisms are explored, and the optimal conditions are outlined for reproducible Cf/in situ SiCnw dual reinforcement of SiC-based ceramics. Hot pressing at 1500 °C produced Cf/in situ SiCnw-reinforced ceramic SiC–TaSi2 specimens with a relative density of 97%, 19 GPa Vickers hardness, 3-point flexural strength σ = 420 ± 70 MPa and fracture toughness K1C = 12.5 MPa m1/2.

Large influence of vacancies on the elastic constants of cubic epitaxial tantalum nitride layers grown by reactive magnetron sputtering

We report a comprehensive study on the structure and elastic constants of epitaxial cubic δ-TaxN (x ≈ 1) layers deposited by reactive magnetron sputtering at 570 °C on MgO(001), MgO(110) and MgO(111) substrates. X-ray diffraction shows that all layers are single-phase and have a single-crystal rocksalt-structure, growing with an epitaxial cube-on-cube relationship with respect to their MgO substrates. For (001)-orientation, Brillouin light scattering provides the measurement of c44 (137 ± 3 GPa) and c12 (130 ± 5 GPa) single-crystal elastic constants, while picosecond laser ultrasonics (PLU) provides the third independent one, c11 (530 ± 10 GPa). For (110)- and (111)-orientations, PLU provides selectively the following combinations, (c11+c12+2c44)/2 and (c11+2c12+4c44)/3, respectively. Electrical resistivity measurements show evidence of point defects in the films despite a composition close to 1:1 stoichiometry. Point defects (metal and nitrogen vacancies) are considered in our first-principles calculations to find closer agreement between experimental and theoretical lattice parameter, mass density, sound velocities and elastic constants. Sound velocities and elastic constants are found to be particularly sensitive to the presence of vacancies, resulting into a more compliant and less anisotropic material. While only ∼ − 1% mismatch is found between predicted defect-free and experimental lattice parameters, huge differences of −27% and +180% are observed for c11 and c44, respectively. These discrepancies can be rationalized by considering the presence of point defects (metal vacancy and/or Schottky defect) in concentration ∼11% in the as-deposited TaN films, a compositional value that corresponds to the lowest formation energy of δ-TaNx structure.

Dynamics of soliton crystals in optical microresonators

Dissipative Kerr solitons in optical microresonators provide a unifying framework for nonlinear optical physics with photonic-integrated technologies and have recently been employed in a wide range of applications from coherent communications to astrophysical spectrometer calibration. Dissipative Kerr solitons can form a rich variety of stable states, ranging from breathers to multiple-soliton formations, among which, the recently discovered soliton crystals stand out. They represent temporally-ordered ensembles of soliton pulses, which can be regularly arranged by a modulation of the continuous-wave intracavity driving field. To date, however, the dynamics of soliton crystals remains mainly unexplored. Moreover, the vast majority of the reported crystals contained defects - missing or shifted pulses, breaking the symmetry of these states, and no procedure to avoid such defects was suggested. Here we explore the dynamical properties of soliton crystals and discover that often-neglected chaotic operating regimes of the driven optical microresonator are the key to their understanding. In contrast to prior work, we prove the viability of deterministic generation of $\mathrm{perfect}$ soliton crystal states, which correspond to a stable, defect-free lattice of optical pulses inside the cavity. We discover the existence of critical pump power, below which the stochastic process of soliton excitation suddenly becomes deterministic enabling faultless, device-independent access to perfect soliton crystals. Furthermore, we demonstrate the switching of soliton crystal states and prove that it is also tightly linked to the pump power and is only possible in the regime of transient chaos. Finally, we report a number of other dynamical phenomena experimentally observed in soliton crystals including the formation of breathers, transitions between soliton crystals, their melting, and recrystallization.

Molecular dynamics study of two-dimensional discrete breather in nickel

A discrete breather (DB) is a spatially localized vibrational mode of large amplitude in a defect-free anharmonic lattice. Generally, zero-dimensional DB is considered to be localized in all [Formula: see text] directions of the [Formula: see text]-dimensional lattice. However, the question of existence of DBs localized in [Formula: see text]–[Formula: see text] directions and delocalized in other [Formula: see text] directions remains open. In the present paper, for the first time, the case of [Formula: see text] and [Formula: see text] is considered by constructing a two-dimensional (2D) DB in the fcc nickel lattice using molecular dynamics methods. In order to excite such DB, one of the delocalized vibrational modes of the triangular lattice was used (the (111) plane in fcc crystal is a triangular lattice). All simulations were carried out at zero temperature. The investigated 2D DB demonstrates hard-type nonlinearity, when its oscillation frequency increases with increasing amplitude. The oscillation frequencies of the DB are above the upper edge of the phonon spectrum for nickel, which is 10.3[Formula: see text]THz. The maximum DB lifetime is found to be 9.5[Formula: see text]ps. The obtained results expand our understanding of diversity of nonlinear spatially localized vibrational modes in nonlinear lattices.

Surfactant-free electrochemical synthesis of fluoridated hydroxyapatite nanorods for biomedical applications

Abstract Fluoridated hydroxyapatite (FHA) [Ca10(PO4)6Fx(OH)2−x, x = 0–2] is believed to be a promising calcium phosphate (CaP) to replace pure hydroxyapatite (HA) for next-generation implants, owing to its better biocompatibility, higher antibacterial activity, and lower solubility. Notably, the shape and size of the CaP crystals play key roles in their performance and can influence their applications. One-dimensional (1D) FHA nanorods are important CaP materials which have been widely used in regenerative medicine applications such as restorative dentistry. Unfortunately, the traditional synthesis methods for FHA nanorods either employ surfactants or take a relatively long time. In this study, we aimed to propose a facile synthesis route to fabricate FHA nanorods without any surfactants using an electrochemical deposition method for the first time. This study focused on preparing FHA nanorods without the assistance of any surfactant, unlike the traditional synthesis methods, to avoid chemical impurities. FHA nanorods with lengths of 124–2606 nm, diameters of 28–211 nm, and aspect ratios of 4.4–21.8 were synthesized using the electrochemical method, followed by a heat treatment. For the as-synthesized FHA nanorods, the Ca/P ratio was 1.60 and the atomic concentration of F was 2.06 at.%. An ultrastructure examination revealed that each FHA nanorod possessed long-range order, good crystallinity, and a defect-free lattice with a certain crystallographic plane orientation along the whole rod. In short, we propose a novel, surfactant-free, cost-saving, and more efficient route to synthesize FHA nanorods which can be widely applied in multiple biomedical applications, including drug delivery, bone repair, and restorative dentistry.

Theoretical Aspects of Spinodal Decomposition in Fe-C

Carbon redistribution is known to occur during room temperature aging of Fe-C martensite. One of the proposed mechanisms in the literature by which carbon redistributes is spinodal decomposition, a thermodynamically driven reaction in which the alloy undergoes separation into carbon-rich and carbon-poor regions, giving rise to modulations in carbon concentration. Despite the substantial experimental evidence supporting the occurrence of spinodal decomposition in Fe-C, its theoretical formulation requires attention. In the present study, a theoretical framework based on the regular solution model is built for evaluating the thermodynamics of the Fe-C system, with particular emphasis on the interstitial nature of carbon atoms within the ferrite lattice. Assuming a defect-free lattice, the model explains a miscibility gap in the Fe-C system. The limitations of the current model are critically evaluated.

Defect-free atomic array formation using the Hungarian matching algorithm

Deterministic loading of single atoms onto arbitrary two-dimensional lattice points has recently been demonstrated, where by dynamically controlling the optical-dipole potential, atoms from a probabilistically loaded lattice were relocated to target lattice points to form a zero-entropy atomic lattice. In this atom rearrangement, how to pair atoms with the target sites is a combinatorial optimization problem: brute-force methods search all possible combinations so the process is slow, while heuristic methods are time-efficient but optimal solutions are not guaranteed. Here, we use the Hungarian matching algorithm as a fast and rigorous alternative to this problem of defect-free atomic lattice formation. Our approach utilizes an optimization cost function that restricts collision-free guiding paths so that atom loss due to collision is minimized during rearrangement. Experiments were performed with cold rubidium atoms that were trapped and guided with holographically controlled optical-dipole traps. The result of atom relocation from a partially filled 7-by-7 lattice to a 3-by-3 target lattice strongly agrees with the theoretical analysis: using the Hungarian algorithm minimizes the collisional and trespassing paths and results in improved performance, with over 50\% higher success probability than the heuristic shortest-move method.

Localized vibrational modes in diamond

Discrete breather (DB) or, synonymously, intrinsic localized mode (ILM) is a spatially localized and time-periodic vibrational mode in a defect-free nonlinear lattice, e.g., in a crystal lattice. Standing DB and DB clusters (double and triple) are studied in diamond using molecular dynamics method with the AIREBO interatomic potentials. Single DB can be easily excited by applying initial shifts, A0, to a pair of nearest atoms along the valence bond in the opposite directions. Admissible excitation amplitudes are 0.09≤A0/a0≤0.12, where a0 is the equilibrium interatomic distance. The core of a DB is a pair of nearest carbon atoms oscillating out-of-phase, while the neighboring atoms oscillate with one order of magnitude lower amplitudes. DB frequency is above the top of the phonon spectrum and increases with the oscillation amplitude. DB lives for more than 100 oscillation periods which approximately corresponds to 2 ps. The range of initial amplitudes and other conditions necessary for the excitation of double and triple DB clusters as well as their lifetime are investigated in detail. Two different mechanisms of energy exchange between DBs in the DB clusters are revealed, which is the main result of the present study. Our results contribute to a deeper understanding of the nonlinear lattice dynamics of diamond.

Differentiating Defect and Basal Plane Contributions to the Surface Energy of Graphite Using Inverse Gas Chromatography

Historically, reported values for the surface energy of graphite have covered a very wide range. Here, we use finite-dilution inverse gas chromatography (FD-IGC) to show that the dispersive component of the surface energy of graphite has contributions from edge and basal plane defects as well as from the hexagonal carbon lattice. The surface energy associated with the defect-free hexagonal lattice is measured at high probe-coverage to be 63 ± 7 mJ/m2, independent of graphite type. However, the surface energy measured at low probe coverage varied from 125 to 175 mJ/m2 depending on the graphite type. Simulation of the FD-IGC output for different binding site distributions allows us to associate this low-coverage surface energy with the binding of probe molecules to high energy defect sites. Importantly, we find the rate of decay of surface energy with probe coverage to carry information about the defect density. By analyzing the dependence of these properties on flake size, it is possible to separate out th...

Discrete breathers in crystals: Energy localization and transport

Discrete breather (DB) is spatially localized vibrational mode in defect-free nonlinear lattice. Frequency of DB must lie outside the spectrum of small-amplitude traveling waves. It neither does resonate with traveling waves and nor does it lose energy to their excitation. Theoretically DB can maintain its vibrational energy forever in the absence of thermal vibrations and other perturbations. Crystals are nonlinear discrete systems and they also support existence of DB. Experimental studies of DB run into considerable technical difficulties, and the main tool of their study is by far the atomistic computer simulations. Having gained confidence in the existence of DB in crystals, we still poorly understand their role in solid state physics. This review covers issues specific to the physics of real crystals, which were not considered in the classical works on DB. Focus is placed on the energy transport through crystal lattice assisted by moving DB and by energy exchange between DB.

Multistep Relaxations in a Spin-Crossover Lattice with Defect: A Spatiotemporal Study of the Domain Propagation

We study the spatio-temporal formation and spreading of the low-spin state (LS) during the thermal spin transition and the cooperative relaxation of the photo-induced metastable high spin (HS) state at low temperature, in the presence of a structural defect. The model is made of a two-dimensional rectangular-shaped lattice with discrete spins coupled by springs. The investigations are performed for a perfect lattice and a lattice with a hole (simulating the defect) with a fixed size. We found that the presence of the defect affects the thermal equilibrium by reducing the size of the thermal hysteresis at the transition, although the transition temperature remains unchanged. The study of the low-temperature relaxation of the defect-free lattice from HS to LS state indicated the existence of three different regimes of the growth process: (i) a first regime of growth from one corner of the rectangle along the width, then followed by (ii) a second regime of longitudinal propagation at almost constant velocity, and (iii) a third rapid regime when the system feels the surface or the border of the crystal. When a hole is injected inside the lattice, it results in (i) the deformation of the HS/LS interface’s shape when it approaches the defect position; and (ii) the slowing down of its propagation velocity. These results, which are in good agreement with available experimental data, are discussed in terms of elastic energy stored in the system during the relaxation process.

Carrier localization, Anderson transitions and stripe formation in hole-doped cuprates

Three distinctly different scenarios are proposed for the carrier localization in three- dimentional (3D) lightly doped cuprates in which the self-trapping and pairing of hole carriers (i) near the small-radius dopants and (ii) in a defect-free deformable lattice lead to the formation of the extrinsic and intrinsic (bi)polaronic states in the charge-transfer gap of the cuprates, and (iii) the self-trapping of hole carriers away from the large-radius dopants results in the formation of the in-gap hydrogenic impurity states. We have shown that the extrinsic and intrinsic 3D large bipolarons exist in La-based lightly doped cuprates at η = ɛ∞/ɛ0 < 0:127 and η < 0:138, respectively, where ɛ∞/ɛ0 is the optic (static) dielectric constant. We use the uncertainty relation to obtain the specificc conditions for the Anderson and new MITs in cuprates. The applicability limits of these MITs in La-based cuprates are clarified. Our results are in good agreement with the existing experiments on La-based cuprates.

Molecular dynamics simulations of void defects in the energetic material HMX

A molecular dynamics (MD) simulation was carried out to characterize the dynamic evolution of void defects in crystalline octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine (HMX). Different models were constructed with the same concentration of vacancies (10 %) to discuss the size effects of void. Energetic ground state properties were determined by annealing simulations. The void formation energy per molecule removed was found to be 55-63 kcal/mol(-1), and the average binding energy per molecule was between 32 and 34 kcal/mol(-1) according to the change in void size. Voids with larger size had lower formation energy. Local binding energies for molecules directly on the void surface decreased greatly compared to those in defect-free lattice, and then gradually increased until the distance away from the void surface was around 10 Å. Analysis of 1 ns MD simulations revealed that the larger the void size, the easier is void collapse. Mean square displacements (MSDs) showed that HMX molecules that had collapsed into void present liquid structure characteristics. Four unique low-energy conformers were found for HMX molecules in void: two whose conformational geometries corresponded closely to those found in HMX polymorphs and two, additional, lower energy conformers that were not seen in the crystalline phases. The ratio of different conformers changed with the simulated temperature, in that the ratio of α conformer increased with the increase in temperature.