Symmetry Of Substrate Research Articles

Epitaxial Orientation-Controlled High Crystallinity and Ferroelectric Properties in Hf0.5Zr0.5O2 Films.

Hafnium-based binary oxides are essential for fabricating nanoscale high-density ferroelectric memory devices. However, effective strategies to control and improve their thin-film single crystallinity and metastable ferroelectricity remain elusive, hindering potential applications. Here, using NdGaO3 (NGO) substrates with four crystalline orientations, we report a systematic study of the structural characterizations and ferroelectric properties of epitaxial Hf0.5Zr0.5O2 (HZO) films, demonstrating orientation-controlled high crystallinity and enhanced ferroelectric properties. HZO films grown on NGO(001) and NGO(110) substrates exhibit relatively low crystallinity and a significant presence of the monoclinic phase. In contrast, HZO films grown on NGO(100) and NGO(010) possess high single crystallinity and a dominant ferroelectric phase. These differences are attributed to the surface symmetry of the NGO substrate, which favors the formation of 4- or 2-fold domain configurations. Moreover, the optimized HZO films exhibit a large polarization (2Pr) of ∼50 μC/cm2, enhanced fatigue behavior up to 1011 cycles, improved retention of 2Pr ∼ 40 μC/cm2 after 10 years, and characteristic polarization switching speeds in the submicrosecond range. Our results highlight the importance of modulating the single crystallinity and ferroelectric phase fraction of HfO2-based films to enhance ferroelectric properties, further revealing the potential of epitaxial symmetry engineering.

Hexagons on rectangles: Epitaxial graphene on Ru[formula omitted]

Ruthenium is emerging as a promising candidate to replace copper in highly integrated electronics by enabling barrierless metallization in ultrathin interconnects. From this perspective, the study of graphene growth on such surface templates is of paramount importance as a platform for graphene integration in electronic devices. In particular, graphene growth on the Ru(101‾0) surface allows selective growth of different graphene orientations, one-dimensional structures, and reduced substrate interaction compared to the well-established hexagonal Ru(0001) substrate. Real-time growth observations using low-energy electron microscopy and micro-diffraction highlight the influence of substrate symmetry on graphene growth, leading to the formation of rectangular islands with distinct zigzag- or armchair-terminated edges. Bilayer formation on Ru(101‾0) occurs by nucleation of graphene nanoribbons under the monolayer. Micro-spot angle-resolved photoemission spectroscopy shows significantly less charge-transfer doping in these freestanding, zigzag-terminated bilayer graphene nanoribbons, indicating reduced graphene-substrate interaction and hence more effective decoupling as compared to graphene/Ru(0001). Our results show that the growth of graphene on non-hexagonal substrates opens new pathways for tailoring the graphene-substrate interaction at the interface, and thus the properties of graphene beyond the limits imposed by hexagonal substrates.

Polarization-Independent Perfect Absorption in Monolayer Black Phosphorus Metasurfaces at Terahertz Frequencies via Critical Coupling.

Two-dimensional (2D) materials, which possess rich underlying physical properties that can provide the potential for designing more efficient and compact optoelectronic devices, have attracted great interest among scientists. Due to the atomic-scale thickness and the anisotropy of in-plane conductivity, 2D black phosphorus (BP) exhibits a polarization-dependent absorption spectrum with low absorption, which limits its further development in polarization-independent applications such as light absorbers and sensors. In this paper, a polarization-independent perfect absorber in the terahertz band is proposed, which is composed of a patterned BP monolayer deposited on a lossless photonic crystal (PC) slab with a back reflection mirror. The absorption of the patterned BP monolayer can reach 100% at resonant frequencies through the critical coupling mechanism of guided resonance. Moreover, the absorber exhibits polarization-independent absorption characteristics for vertically incident light, which are attributed to the 4-fold rotational symmetry of the PC substrate and the patterned BP monolayer deposited on it. This work opens up the possibility of fabricating optically polarization-independent devices based on single-layer 2D anisotropic materials.

Resistive switching and synaptic simulation behaviors of epitaxial ZnO/Nb-doped SrTiO3 heterojunction controlled by the substrate orientation

Zinc oxide (ZnO) films were grown epitaxially on Nb-doped SrTiO3 (NSTO) substrates with different orientations using laser pulse deposition to create the (112¯0)ZnO/(100)NSTO, (0002)ZnO/(110)NSTO and (0002)ZnO/(111)NSTO heterojunctions. Epitaxial ZnO films on the (100) NSTO had two orthorgonal domains, resembling the fourfold symmetry of the (100) NSTO substrate. This good matching between the grown ZnO film and NSTO substrate resulted in a lower growth rate, smoother and denser surface, and a higher density of interface defect states. The interface state density was approximately 4.4 × 1012 eV−1cm−2, which was notably higher than that of the other two heterojunctions. Electrical transport studies revealed that ZnO/(100)NSTO heterojunction demonstrated bipolar resistive switching and negative differential resistance (NDR) due to a higher density of donor interface states from contributions of oxygen vacancies, while both the ZnO/(110)NSTO and ZnO/(111)NSTO heterojunction exhibited typical rectifying behavior. The preliminary investigation into synaptic behaviors suggested that (112¯0) ZnO/(100)NSTO heterojunction holds significant potential in brain-inspired neuromorphic computing systems.

Solvent-free confinement of ordered microparticle monolayers: effect of host substrate and pattern symmetry

We report a solvent-free assembly method where microspheres align on fluorocarbon patterns without rigid boundaries, creating tunable crystal patterns. Our findings highlight the impact of tribocharging and substrate elasticity on particle ordering.

Understanding growth‐faulted GaAsBi samples by Reflectance Anisotropy Spectroscopy.

Reflectance Anisotropy Spectroscopy (RAS) has been recently applied to Molecular Beam Epitaxy (MBE) of GaAsBi alloys. The presence of the voluminous Bi atoms induces strain in the crystal lattice, modifying the substrate symmetry of the centrosymmetric GaAs(001) and then producing clear signatures in the anisotropy spectra of the GaAsBi layers. In particular, the amplitude of the characteristic structure measured below 2.5 eV has been shown to be directly related to the Bi concentration, while the sign has a meaningful correlation to the strain conditions present in the sample. In this paper, we extend the application of RAS to “faulted” GaAsBi samples, i.e. samples that after growth result not satisfactory for research because of problems or errors risen during the complex deposition process (wrong growth temperature, excess or deficiency of Bi flux, formation of dislocations, etc.). We demonstrate that also in these cases RAS offers a useful characterization of the sample, possibly (if RAS runs during the deposition) singling out the occurrence of faults eventuality, and thus validating its potential applicability to an all‐optical real time monitoring of the deposition process.This article is protected by copyright. All rights reserved.

Experimental and Theoretical Exploration of the Kinetics and Thermodynamics of the Nucleophile-Induced Fragmentation of Ylidenenorbornadiene Carboxylates.

Ylidenenorbornadienes (YNDs), prepared by [4 + 2] cycloadditions between fulvenes and acetylene carboxylates, react with thiol nucleophiles to yield mixtures of four to eight diastereomers depending on the symmetry of the YND substrate. The mixtures of diastereomers fragment via a retro-[4 + 2] cycloaddition with a large variation in rate, with half-lives ranging from 16 to 11,000 min at 80 °C. The diastereomer-enriched samples of propane thiol adducts [YND-propanethiol (PTs)] were isolated and identified by nuclear Overhauser effect spectroscopy (NOESY) correlations. Simulated kinetics were used to extrapolate the rate constants of individual diastereomers from the observed rate data, and it correlated well with rate constants measured directly and from isolated diastereomer-enriched samples. The individual diastereomers of a model system fragment at differing rates with half-lives ranging from 5 to 44 min in CDCl3. Density functional theory calculations were performed to investigate the mechanism of fragmentation and support an asynchronous retro-[4 + 2] cycloaddition transition state. The computations generally correlated well with the observed free energies of activation for four diastereomers of the model system as a whole, within 2.6 kcal/mol. However, the observed order of the fragmentation rates across the set of diastereomers deviated from the computational results. YNDs display wide variability in the rate of fragmentation, dependent on the stereoelectronics of the ylidene substituents. A Hammett study showed that the electron-rich aromatic rings attached to the ylidene bridge increase the fragmentation rate, while electron-deficient systems slow fragmentation rates.

Effect of in-plane alignment on selective area grown homo-epitaxial nanowires

In-plane selective area growth (SAG) of III–V nanowires (NWs) has emerged as a scalable materials platform for quantum electronics and photonics applications. Most applications impose strict requirements on the material characteristics which makes optimization of the crystal quality vital. Alignment of in-plane SAG NWs with respect to the substrate symmetry is of importance due to the large substrate-NW interface as well as to obtain nanostructures with well-defined facets. Understanding the role of mis-orientation is thus important for designing devices and interpretation of electrical performance of devices. Here we study the effect of mis-orientation on morphology of selectively grown NWs oriented along the [1 1̅ 1̅] direction on GaAs(2 1 1)B. Atomic force microscopy is performed to extract facet roughness as a measure of structural quality. Further, we evaluate the dependence of material incorporation in NWs on the orientation and present the facet evolution in between two high symmetry in-plane orientations. By investigating the length dependence of NW morphology, we find that the morphology of ≈1 μm long nominally aligned NWs remains unaffected by the unintentional misalignment associated with the processing and alignment of the sample under study. Finally, we show that using Sb as a surfactant during growth improves root-mean-square facet roughness for large misalignment but does not lower it for nominally aligned NWs.

Lateral and Vertical Morphology Engineering of Low‐Symmetry, Weakly‐Coupled 2D ReS2

AbstractMorphology significantly affects material's electronic, catalytic, and magnetic properties, especially for 2D crystals. Abundant achievements have been made in the morphology engineering of high‐symmetry 2D materials, but for the emerging low‐symmetry ones, such as ReS2, both the morphology control technique and comprehension are lacking. Here, the lateral shape and vertical thickness engineering of 2D ReS2 by tailoring the growth temperature and the substrate symmetry using chemical vapor deposition, is reported. The temperature increase induces an isotropic‐to‐anisotropic transition of domain shapes, as well as a monotonic decrease of the domain thickness, which promotes the electrocatalytic performance. The substrate rotational symmetry determines the shape anisotropy of polycrystalline ReS2 monolayers via a diffusion‐limited mechanism, leading to highly oriented square, triangular, and strip‐like domains synthesized on the fourfold symmetry SrTiO3 (001), threefold symmetry c‐sapphire, and twofold symmetry a‐sapphire substrates, respectively. Various stacking configurations in bilayers are unclosed at the atomic scale. Some are predicted to adopt a type‐II band alignment with great potential in photovoltaics. The results give insights into the morphological engineering of a unique class of 2D material with low in‐plane lattice symmetry and weak interlayer coupling, which are crucial for their high‐quality synthesis and industrial applications.

Direct Observation of Spin-Orbit Interaction of Light via Chiroptical Responses.

The spin-orbit interaction of light is a fundamental manifestation of controlling its angular momenta with numerous applications in photonic spin Hall effects and chiral quantum optics. However, observation of an optical spin Hall effect, which is normally very weak with subwavelength displacements, needs quantum weak measurements or sophisticated metasurfaces. Here, we theoretically and experimentally demonstrate the spin-orbit interaction of light in the form of strong chiroptical responses by breaking the in-plane inversion symmetry of a dielectric substrate. The chiroptical signal is observed at the boundary of a microdisk illuminated by circularly polarized vortex beams at normal incidence. The generated chiroptical spectra are tunable for different photonic orbital angular momenta and microdisk diameters. Our findings, correlating photonic spin-orbit interaction with chiroptical responses, may provide a route for exploiting optical information processing, enantioselective sensing, and chiral metrology.

Adsorbate chemical environment-based machine learning framework for heterogeneous catalysis

Heterogeneous catalytic reactions are influenced by a subtle interplay of atomic-scale factors, ranging from the catalysts’ local morphology to the presence of high adsorbate coverages. Describing such phenomena via computational models requires generation and analysis of a large space of atomic configurations. To address this challenge, we present Adsorbate Chemical Environment-based Graph Convolution Neural Network (ACE-GCN), a screening workflow that accounts for atomistic configurations comprising diverse adsorbates, binding locations, coordination environments, and substrate morphologies. Using this workflow, we develop catalyst surface models for two illustrative systems: (i) NO adsorbed on a Pt3Sn(111) alloy surface, of interest for nitrate electroreduction processes, where high adsorbate coverages combined with low symmetry of the alloy substrate produce a large configurational space, and (ii) OH* adsorbed on a stepped Pt(221) facet, of relevance to the Oxygen Reduction Reaction, where configurational complexity results from the presence of irregular crystal surfaces, high adsorbate coverages, and directionally-dependent adsorbate-adsorbate interactions. In both cases, the ACE-GCN model, trained on a fraction (~10%) of the total DFT-relaxed configurations, successfully describes trends in the relative stabilities of unrelaxed atomic configurations sampled from a large configurational space. This approach is expected to accelerate development of rigorous descriptions of catalyst surfaces under in-situ conditions.

Deposition of Chiral Heptahelicene Molecules on Ferromagnetic Co and Fe Thin-Film Substrates.

The discovery of chirality-induced spin selectivity (CISS), resulting from an interaction between the electron spin and handedness of chiral molecules, has sparked interest in surface-adsorbed chiral molecules due to potential applications in spintronics, enantioseparation, and enantioselective chemical or biological processes. We study the deposition of chiral heptahelicene by sublimation under ultra-high vacuum onto bare Cu(111), Co bilayer nanoislands on Cu(111), and Fe bilayers on W(110) by low-temperature spin-polarized scanning tunneling microscopy/spectroscopy (STM/STS). In all cases, the molecules remain intact and adsorb with the proximal phenanthrene group aligned parallel to the surface. Three degenerate in-plane orientations on Cu(111) and Co(111), reflecting substrate symmetry, and only two on Fe(110), i.e., fewer than symmetry permits, indicate a specific adsorption site for each substrate. Heptahelicene physisorbs on Cu(111) but chemisorbs on Co(111) and Fe(110) bilayers, which nevertheless remain for the sub-monolayer coverage ferromagnetic and magnetized out-of-plane. We are able to determine the handedness of individual molecules chemisorbed on Fe(110) and Co(111), as previously reported for less reactive Cu(111). The demonstrated deposition control and STM/STS imaging capabilities for heptahelicene on Co/Cu(111) and Fe/W(110) substrate systems lay the foundation for studying CISS in ultra-high vacuum and on the microscopic level of single molecules in controlled atomic configurations.

Hydrodynamic synchronization and clustering in ratcheting colloidal matter.

Ratchet transport systems are widespread in physics and biology; however, the effect of the dispersing medium in the collective dynamics of these out-of-equilibrium systems has been often overlooked. We show that, in a traveling wave magnetic ratchet, long-range hydrodynamic interactions (HIs) produce a series of remarkable phenomena on the transport and assembly of interacting Brownian particles. We demonstrate that HIs induce the resynchronization with the traveling wave that emerges as a “speed-up” effect, characterized by a net raise of the translational speed, which doubles that of single particles. When competing with dipolar forces and the underlying substrate symmetry, HIs promote the formation of clusters that grow perpendicular to the driving direction. We support our findings both with Langevin dynamics and with a theoretical model that accounts for the fluid-mediated interactions. Our work illustrates the role of the dispersing medium on the dynamics of driven colloidal matter and unveils the growing process and cluster morphologies above a periodic substrate.

Tailoring sheet resistance through laser fluence and study of the critical impact of a V-shaped plasma plume on the properties of PLD-deposited DLC films for micro-pattern gaseous detector applications

Diamond-like carbon (DLC) is an attractive inexpensive alternative to diamond. The control of the C (sp3)/C(sp2) ratio, influencing the material properties, is fundamental for its use in dedicated applications like, for example, the fabrication of a particular class of gas detectors for ionizing particles termed Micro-Pattern Gaseous Detectors (MPGDs).A deposition technique enabling control on the amount of C(sp3) hybridized bonds, hydrogen content and disorder is pulsed lased deposition (PLD).In this paper, we report on the preparation of hydrogen-free DLC films by nanosecond excimer laser-based ablation of a graphite target correlating the laser fluence with the electrical properties of the DLC films to be used as protective resistive layers in MPGD detectors.Moreover, unprecedented physical insight and discussion are provided about the critical aspects of both occurrence of a V-branched plume and its composition on the spatial distribution of C(sp3) bonds and film uniformity. Improvement strategies are demonstrated by comparing and discussing two classes of PLD experiments: ON-axis (coaxial plasma expansion axis and substrate symmetry axis) and OFF-axis (substrate-axis shifted with respect to the plume-axis and rotating substrate). Optimally working OFF-axis configuration conditions are shown to lead to fine tuning of resistivity and uniformity of composition of C(sp3) bonding over a few cm2 extended areas. Sheet resistance (3.1 ± 0.3) × 109 Ω/sq., corresponding to C(sp3) bonding concentration of ~86%, is reported in OFF-axis experiments at a fluence of 5.5 J/cm2 onto kapton substrates which are used for the realization of MPGDs.

Group III selenides: Controlling dimensionality, structure, and properties through defects and heteroepitaxial growth

This Review describes behaviors and mechanisms governing heteroepitaxial nucleation and growth of group III (Al, Ga, and In)–selenium (Se) based semiconductors by molecular beam epitaxy and the properties of the resultant nanoscale films. With nine bonding electrons per AIII–BVI pair, these chalcogenide semiconductors crystallize in a variety of locally tetrahedral bulk structures that incorporate intrinsic vacancies (atom-sized voids) lined with doubly occupied lone-pair orbitals, including layered, defected zinc blende and defected wurtzite structures. During heteroepitaxial growth, the choice of how the vacancies order and which phase results, as well as interface reactions, intermixing, surface passivation, and film morphology, are controlled by electron counting, substrate symmetry, and size mismatch. Nucleation and growth of AlxSey, GaxSey, and InxSey compounds on Si and GaAs, including initial reactions, layer nucleation, symmetry, crystal structure, defects, dimensionality, and stoichiometry, were studied with a combination of techniques, including photoelectron spectroscopy, x-ray photoelectron diffraction, scanning tunneling microscopy, x-ray absorption spectroscopy, and low energy electron diffraction. The unique crystal structure of Ga2Se3 was also investigated as a novel platform for doping with transition metals to create a dilute magnetic semiconductor: Cr:Ga2Se3 is ferromagnetic at room temperature, while Mn:Ga2Se3 results in the precipitation of MnSe. The present study provides new insight into growing interest in variable dimensional materials, using group III selenides as prototypes, to address the basic physical chemistry governing the heteroepitaxy of dissimilar materials.

Nanopatterns of molecular spoked wheels as giant homologues of benzene tricarboxylic acids.

Molecular spoked wheels with D3h and Cs symmetry are synthesized by Vollhardt trimerization of C2v-symmetric dumbbell structures with central acetylene units and subsequent intramolecular ring closure. Scanning tunneling microscopy of the D3h-symmetric species at the solid/liquid interface on graphite reveals triporous chiral honeycomb nanopatterns in which the alkoxy side chains dominate the packing over the carboxylic acid groups, which remain unpaired. In contrast, Cs-symmetric isomers partially allow for pairing of the carboxylic acids, which therefore act as a probe for the reduced alkoxy chain nanopattern stabilization. This observation also reflects the adsorbate substrate symmetry mismatch, which leads to an increase of nanopattern complexity and unexpected templating of alkoxy side chains along the graphite armchair directions. State-of-the-art GFN-FF calculations confirm the overall structure of this packing and attribute the unusual side-chain orientation to a steric constraint in a confined environment. These calculations go far beyond conventional simple space-filling models and are therefore particularly suitable for this special case of molecular packing.

9,10-Anthraquinones Disubstituted with Linear Alkoxy Groups: Spectroscopy, Electrochemistry, and Peculiarities of Their 2D and 3D Supramolecular Organizations.

Spectroscopic, electrochemical, and structural properties of 2,6-dialkoxy-9,10-anthraquinones (Anth-OCn, n = 4, 6, 8, 10, and 12) of increasing alkoxy substituents length were investigated. UV–vis spectroscopy showed a substitution-induced bathochromic shift of the least energetic band from 325 nm in the case of unsubstituted anthraquinone to ca. 350 nm for the studied derivatives. Similarly as unsubstituted anthraquinone, the studied compound showed two reversible one electron reductions to a radical anion and spinless anions, respectively. The first reduction was affected by electron-donating properties of the substituents, its potential being shifted to ca. −1.5 V (vs Fc/Fc+), i.e., by 80 to 95 mV as compared to the case of unsubstituted anthraquinone. This corresponded to a decrease of |EA| from 3.27 to 3.19–3.17 eV. The experimental spectroscopic and electrochemical data were in full agreement with the DFT calculations. The introduction of the alkoxy substituent improved solution processibility of the studied compounds and facilitated the formation of their ordered supramolecular 2D aggregation on HOPG as well as single crystal growth from solutions. Comparative structural investigations carried out on single crystals and monolayers deposited on HOPG revealed two, mutually related, effects of the substituent length on the resulting supramolecular organization. The first one concerns both the 2D organization in the monolayers and 3D molecular arrangement in crystals: increasing substituent length evolution of the structure occurs from herringbone-type to lamellar. The second effect, observed in monolayers of the derivatives with longer substituents, concerns gradual evolution of their lamellar structures with increasing substituent length. This evolution is induced by the structure of the graphite substrate and involves increasing correlation of the molecules orientation (anthraquinone cores as well as alkoxy substituents) with the symmetry of the graphite substrate. As a result, their 2D and 3D structures become dissimilar.

Effect of substrate symmetry on the orientations of MoS2 monolayers

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) are promising platforms for developing next-generation electronic and optoelectronic devices due to their unique properties. To achieve this, the growth of large single-crystal TMDs is a critical issue. Unraveling the factors affecting the nucleation and domain orientation should hold fundamental significance. Herein, we design the chemical vapor deposition growth of monolayer MoS2 triangles on Au(111) and Au(100) facets, for exploring the substrate facet effects on the domain orientations. According to multi-scale characterizations, we find that, the obtained triangular MoS2 domains present two preferential orientations on the six-fold symmetric Au(111) facet, whereas four predominant orientations on the four-fold symmetric Au(100) facet. Using on-site scanning tunneling microscopy, we further reveal the preferred alignments of monolayer MoS2 triangles along the close-packed directions of both Au(111) and Au(100) facets. Moreover, bunched substrate steps are also found to form along the close-packed directions of the crystal facets, which guides the preferential nucleation of monolayer MoS2 along the step edges. This work should hereby deepen the understanding of the substrate facet/step effect on the nucleation and orientation of monolayer MoS2 domains, thus providing fundamental insights into the controllable syntheses of large single-crystal TMD monolayers.

Directional locking effects for active matter particles coupled to a periodic substrate.

Directional locking occurs when a particle moving over a periodic substrate becomes constrained to travel along certain substrate symmetry directions. Such locking effects arise for colloids and superconducting vortices moving over ordered substrates when the direction of the external drive is varied. Here we study the directional locking of run-and-tumble active matter particles interacting with a periodic array of obstacles. In the absence of an external biasing force, we find that the active particle motion locks to various symmetry directions of the substrate when the run time between tumbles is large. The number of possible locking directions depends on the array density and on the relative sizes of the particles and the obstacles. For a square array of large obstacles, the active particle only locks to the x, y, and 45^{∘} directions, while for smaller obstacles, the number of locking angles increases. Each locking angle satisfies θ=arctan(p/q), where p and q are integers, and the angle of motion can be measured using the ratio of the velocities or the velocity distributions in the x and y directions. When a biasing driving force is applied, the directional locking behavior is affected by the ratio of the self-propulsion force to the biasing force. For large biasing, the behavior resembles that found for directional locking in passive systems. For large obstacles under biased driving, a trapping behavior occurs that is nonmonotonic as a function of increasing run length or increasing self-propulsion force, and the trapping diminishes when the run length is sufficiently large.

Magnetic domain engineering in SrRuO3 thin films

Magnetic domain engineering in ferromagnetic thin films is a very important route toward the rational design of spintronics and memory devices. Although the magnetic domain formation has been extensively studied, artificial control of magnetic domain remains challenging. Here, we present the control of magnetic domain formation in paradigmatic SrRuO3/SrTiO3 heterostructures via structural domain engineering. The formation of structural twin domains in SrRuO3 films can be well controlled by breaking the SrTiO3 substrate symmetry through engineering miscut direction. The combination of x-ray diffraction analysis of structural twin domains and magnetic imaging of reversal process demonstrates a one-to-one correspondence between structural domains and magnetic domains, which results in multi-step magnetization switching and anomalous Hall effect in films with twin domains. Our work sheds light on the control of the magnetic domain formation via structural domain engineering, which will pave a path toward desired properties and devices applications.