Two-dimensional Superstructures Research Articles

Deformation-induced structural multiplicity of tilt boundaries facilitating the formation of two-dimensional interfacial superstructures

Understanding the interfacial structures and the induced solute segregation behaviors at the atomic scale can facilitate the design of high-performance materials. However, the diversity and concealed nature of interfaces often make it challenging to reveal the interfacial microstructures and the accompanying solute segregation phenomena. Here, we report the discovery of 8 types of asymmetric tilt grain boundaries (GBs) with solute segregation in a deformed and annealed Mg-rare-earth binary model alloy, by means of Z-contrast high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) observations. Molecular dynamics (MD) simulations provide a visual depiction of the atomic-scale characteristics of the periodic extension and compression sites in these tilt GBs. The first-principles density functional theory (DFT) calculations unveil the energetics of the well-ordered segregation behavior of solutes at these interfaces. It is confirmed that the selective segregation of solutes at substitutional sites in the periodic misfit-dislocations separated tilt GBs leads to the formation of 8 types of unique two-dimensional interfacial superstructures. Additionally, the MD simulations have revealed that solute segregation plays a pivotal role in governing the shear strength of tilt GBs by influencing the nucleation of dislocations at interfaces. Our atomic-scale insights provide valuable guidance for understanding the formation of tilt GBs within the wrought alloys and their pivotal role in facilitating solute segregation, enabling the creation of specific two-dimensional superstructures at interfaces. Furthermore, these insights hold promise for advancing the design of high-performance alloys through the application of GB engineering.

Designing two-dimensional FeP@C nanoparticle superstructures for efficient hydrogen evolution

Hydrogen evolution reaction (HER) is a promising technology for the production of clean and renewable energy. Iron phosphide (FeP) has attracted significant attention as HER catalysts due to its excellent catalytic activity and low cost. We report herein a new method to construct two-dimensional (2D) superstructures composed of close-packed FeP@C nanoparticles. Such rationally designed FeP@C superstructures, benefiting from their 2D geometry and highly accessible active sites, show excellent activity and stability as HER electrocatalysts.

Two-dimensional interface superstructures assembled by well-ordered solute atoms

Two-dimensional interface superstructures assembled by well-ordered solute atoms

Two-Dimensional Superstructures from the Gas Phase: Directed Assembly of Copper-Sulfide Nanoplatelets.

We report on a novel plasma-assisted approach for the deposition of free-standing two-dimensional superstructures via directed assembly of copper-sulfide nanoplatelets in the gas phase. For this, the copper-organic complex bis-[bis(N,N-diethyldithiocarbamato)-copper(II)] is thermally evaporated and transported into a capacitively coupled rf plasma to form two-dimensional nanoplatelets upon fragmentation. On a substrate, the highly anisotropic platelets are attached in a directed edge-to-edge configuration. We found that a high substrate temperature of 400 °C is necessary for the 2D vertical growth of copper sulfide. Using plasma reinforces the directional assembly and leads to nanowalls which are several micrometers high with the thickness of a single nanoplatelet. The morphology and crystallographic composition of the emerging superstructures were extensively investigated via scanning and transmission electron microscopy as well as electron diffraction. The data reveal the (010) plane to be the preferred axis for the arrangement of the nanoplatelets.

Structural Diversity in Dimension-Controlled Assemblies of Tetrahedral Gold Nanocrystals.

Polyhedron packings have fascinated humans for centuries and continue to inspire scientists of modern disciplines. Despite extensive computer simulations and a handful of experimental investigations, understanding of the phase behaviors of synthetic tetrahedra has remained fragmentary largely due to the lack of tetrahedral building blocks with tunable size and versatile surface chemistry. Here, we report the remarkable richness of and complexity in dimension-controlled assemblies of gold nanotetrahedra. By tailoring nanocrystal interactions from long-range repulsive to hard-particle-like or to systems with short-ranged directional attractions through control of surface ligands and assembly conditions, nearly a dozen of two-dimensional and three-dimensional superstructures including the cubic diamond and hexagonal diamond polymorphs are selectively assembled. We further demonstrate multiply twinned icosahedral supracrystals by drying aqueous gold nanotetrahedra on a hydrophobic substrate. This study expands the toolbox of the superstructure by design using tetrahedral building blocks and could spur future computational and experimental work on self-assembly and phase behavior of anisotropic colloidal particles with tunable interactions.

Tunable Orientation and Assembly of Polymer-Grafted Nanocubes at Fluid–Fluid Interfaces

Self-assembly of faceted nanoparticles is a promising route for fabricating nanomaterials; however, achieving low-dimensional assemblies of particles with tunable orientations is challenging. Here, we demonstrate that trapping surface-functionalized faceted nanoparticles at fluid-fluid interfaces is a viable approach for controlling particle orientation and facilitating their assembly into unique one- and two-dimensional superstructures. Using molecular dynamics simulations of polymer-grafted nanocubes in a polymer bilayer along with a particle-orientation classification method we developed, we show that the nanocubes can be induced into face-up, edge-up, or vertex-up orientations by tuning the graft density and differences in their miscibility with the two polymer layers. The orientational preference of the nanocubes is found to be governed by an interplay between the interfacial area occluded by the particle, the difference in interactions of the grafts with the two layers, and the stretching and intercalation of grafts at the interface. The resulting orientationally constrained nanocubes are then shown to assemble into a variety of unusual architectures, such as rectilinear strings, close-packed sheets, bilayer ribbons, and perforated sheets, which are difficult to obtain using other assembly methods. Our work thus demonstrates a versatile strategy for assembling freestanding arrays of faceted nanoparticles with possible applications in plasmonics, optics, catalysis, and membranes, where precise control over particle orientation and position is required.

Twin Boundary Superstructures Assembled by Periodic Segregation of Solute Atoms.

Twinning is a common deformation mechanism in metals, and twin boundary (TB) segregation of impurities/solutes plays an important role in the performances of alloys such as thermostability, mobility, and even strengthening. The occurrence of such segregation phenomena is generally believed as a one-layer coverage of solutes alternately distributed at extension/compression sites, in an orderly, continuous manner. However, in the Mn-free and Mn-containing Mg-Nd model systems, we reported unexpected three- and five-layered discontinuous segregation patterns of the coherent {101̅1} TBs, and not all the extension sites occupied by solutes larger in size than Mg, and even some larger sized solutes taking the compression sites. Nd/Mn solutes selectively segregate at substitutional sites and thus to generate two new types of ordered two-dimensional TB superstructures or complexions. These findings refresh the understanding of solute segregation in the perfect coherent TBs and provide a meaningful theoretical guidance for designing materials via targeted TB segregation.

Crystallization-Mediated Magnetoelectric Response in Two-Dimensional Molecular Charge Transfer Crystals

Two-dimensional films and organic superstructures held by nonconvalent interaction with optoelectronic and magnetoelectric properties are of vital importance for sustainable energy and spintronics. Here, a bottom-up approach is proposed to organize tetrathiafulvalene and C60 into free-standing millimeter-sized single crystallized two-dimensional films by noncovalent charge transfer interactions. Opto-magnetoelectric properties of amorphous and crystallized films are compared. In addition, a high, broadband, and fast photoresponse from the UV to near-infrared region for the crystallized film is promising for flexible, lightweight photodetectors. The method proposed here is promising for scalable fabrication of other two-dimensional molecular films.

Vacuum-tuned-atmosphere induced assembly of Au@Ag core/shell nanocubes into multi-dimensional superstructures and the ultrasensitive IAPP proteins SERS detection

Utilizing vacuum-tuned-atmosphere induced dip coating method, we achieve the cross-dimensional macroscopic diverse self-assemblies by using one building block with one chemical functionality. Coordinated modulating the vacuum degree, colloid concentration and evaporation atmosphere, Au@Ag core/shell NCs can controllably assemble into diverse multi-dimensional superstructures. Under 0.08 MPa, we obtained the two-dimensional (2D) stepped superstructures with continuously tunable step width. In addition, we generated a series of tailorable nanoscale-roughened 2D Au@Ag NCs superstructures at 0.04 MPa, which exhibited the label-free ultrasensitive SERS detection for the different mutants of IAPP8-37 proteins. Under 0.01 MPa, we obtained the cross-dimensional tailorable Au@Ag NCs assemblies from random to macroscale 2D and three-dimensional (3D) densest superstructures by adjusting the capping ligand-environmental molecule interactions. This is a flexible method to generate as-prepared Au@Ag core/shell NCs into well-defined macroscopic diverse superstructures and to promote the exploitation into biological applications.

Two-dimensional superstructures filled into polysulfone membranes for highly improved ultrafiltration: The case of cuprous iodide nanosheets

Mixed-matrix membranes blended with nanosized inorganic fillers have been widely used in ultrafiltration (UF) for large molecule separation. In this work, we provide a feasible route to construct mixed-matrix polysulfone (PSf) UF membranes via the nonsolvent-induced phase inversion process, utilizing sheet-like copper iodide superstructures (s-CuI) as fillers. The size of s-CuI in lateral dimension reaches micrometer scale, but the nanosheets can be well embedded in the polymer matrix with their 2D basal planes parallel to the membrane surface. On account of the stacking straight-through channel structure of s-CuI and its large dimension spanning across multiple membrane pores within the layer, the PSf membrane blended with 0.8 wt% content of s-CuI displays optimal UF performance with a pure water permeation (PWP) of 1473 L/(m2 h bar) and a bovine serum albumin (BSA) rejection of 92%. In contrast, the pure PSf membrane only presents a PWP of 556 L/(m2 h bar) and a BSA rejection of 58.2%. Besides, the enhancement of mechanical stability for the PSf/s-CuI 0.8% membrane is significant and the leakage of the s-CuI filler is negligible. Though the antifouling performance of the PSf/s-CuI 0.8% membrane against the protein BSA is limited, its flux is always 2–3 times higher than that of the pure PSf membrane in each step during a sequential test of fouling behavior. This study indicates that it is highly promising to employ designable superstructures as functional fillers to construct novel mixed-matrix membranes with good interfacial compatibility and superior performance.

Chemistry of cysteine assembly on Au(100): electrochemistry, in situ STM and molecular modeling

Cysteine (Cys) is an essential amino acid with a carboxylic acid, an amine and a thiol group. We have studied the surface structure and adsorption dynamics of l-cysteine adlayers on Au(100) from aqueous solution using electrochemistry, high-resolution electrochemical scanning tunnelling microscopy (in situ STM), and molecular modelling. Cys adsorption on this low-index Au-surface has been much less studied than Cys adsorption on Au(111)- and Au(110)-electrode surfaces. Chronopotentiometry was employed to monitor the adsorption dynamics at sub-second resolution and showed that adsorption is completed in 30 minutes at Cys concentrations above 100 μM. Two consecutive steps could be fitted to these data. Two separate reductive desorption peaks of Cys adlayers on Au(100) with a total coverage of 2.52 (±0.15) × 10-10 mol cm-2 were observed. In situ STM showed that the adsorbed Cys is organized in stripes with "fork-like" features which co-exist in (11 × 2)-2Cys and (7 × 2)-2Cys lattices, quite differently from Cys adsorption on Au(111)-electrode surfaces. Stripe structures with bright STM contrast in the center suggest that a second Cys adlayer on top of a first adlayer is formed, supporting the dual-peak reductive desorption of Cys adlayers. In addition, monolayers of both pure l-Cys and pure d-Cys and a 1 : 1 racemic mixture of l- and d-Cys on Au(100) were studied. Virtually identical macroscopic electrochemical features were found, but in situ STM discloses many more defects for the racemic mixture than for the pure enantiomers due to structural mismatch of l- and d-Cys. Density functional theory (DFT) calculations combined with a cluster model for the Au(100) surface were carried out to investigate the adsorption energy and geometry of the adsorbed monomer and dimer Cys species in different orientations, with detailed attention to the chirality effects. Optimized DFT geometries were used to construct model STM images, and kinetic Monte Carlo simulations undertaken to illuminate the growth of adsorbate rows and the mechanism of the adlayer formation as well as the Cys adsorption patterns specific to the Au(100)-electrode surface.

Intrinsic stacking domains in graphene on silicon carbide: A pathway for intercalation

Graphene on silicon carbide (SiC) bears great potential for future graphene electronic applications because it is available on the wafer-scale and its properties can be custom-tailored by inserting various atoms into the graphene/SiC interface. It remains unclear, however, how atoms can cross the impermeable graphene layer during this widely used intercalation process. Here we demonstrate that, in contrast to the current consensus, graphene layers on SiC are not homogeneous, but instead composed of domains of different crystallographic stacking. We show that these domains are intrinsically formed during growth and that dislocations between domains dominate the (de)intercalation dynamics. Tailoring these dislocation networks, e.g. through substrate engineering, will increase the control over the intercalation process and could open a playground for topological and correlated electron phenomena in two-dimensional superstructures.

Formation and Mechanical Behavior of Nanocomposite Superstructures from Interlayer Bonding in Twisted Bilayer Graphene.

We report a comprehensive study on the design of two-dimensional graphene-diamond nanocomposite superstructures formed through interlayer covalent bonding of twisted bilayer graphene with commensurate bilayers. The interlayer bonding is induced by patterned hydrogenation that leads to the formation of superlattices of two-dimensional nanodiamond domains embedded between the two graphene layers. We generalize a rigorous algorithm for the formation of all possible classes of these superstructures: the structural parameters employed to design such carbon nanocomposites include the commensurate bilayer's twist angle, the stacking type of the nanodomains where the interlayer bonds are formed, the interlayer bond pattern, and the interlayer C-C bond density that is proportional to the concentration of sp3-hybridized interlayer-bonded C atoms. We also analyze systematically the mechanical behavior of these nanocomposite superstructures on the basis of molecular-dynamics simulations of uniaxial tensile straining tests according to a reliable interatomic bond-order potential. We identify a range of structural parameters over which the fracture of these superstructures is ductile, mediated by void formation, growth, and coalescence, contrary to the typical brittle fracture of graphene. We introduce a ductility metric as an order parameter for the brittle-to-ductile transition, demonstrate its direct dependence on the fraction of sp3-hybridized interlayer-bonded C atoms, and show that increasing the fraction of interlayer-bonded C atoms beyond a critical level in certain classes of these superstructures induces their ductile mechanical response.

Mono- and Multilayer Silicene-Type Honeycomb Lattices by Oriented Attachment of PbSe Nanocrystals: Synthesis, Structural Characterization, and Analysis of the Disorder.

Nanocrystal (NC) solids are commonly prepared from nonpolar organic NC suspensions. In many cases, the capping on the NC surface is preserved and forms a barrier between the NCs. More recently, superstructures with crystalline connections between the NCs, implying the removal of the capping, have been reported, too. Here, we present large-scale uniform superstructures of attached PbSe NCs with a silicene-type honeycomb geometry, resulting from solvent evaporation under nearly reversible conditions. We also prepared multilayered silicene honeycomb structures by using larger amounts of PbSe NCs. We show that the two-dimensional silicene superstructures can be seen as a crystallographic slice from a 3-D simple cubic structure. We describe the disorder in the silicene lattices in terms of the nanocrystals position and their atomic alignment. The silicene honeycomb sheets are large enough to be used in transistors and optoelectronic devices.

Superstructures at Te/Au(111) interface evolving upon increasing Te coverage

By in-situ low temperature scanning tunneling microscopy, we systematically investigated the superstructure evolution at Te/Au(111) interface upon increasing Te coverage. Te atoms form one-dimensional 3R30∘ chains at ∼0.10 monolayer (ML) coverage. Two two-dimensional chiral superstructures, (111×111)R4.7∘ and (321×321)R10.9∘, are selectively formed with the Te coverage below and above 1/3 ML, respectively. The two chiral superstructures can be converted to each other reversibly by adding Te atoms or moderately annealing. A honeycomb-like superstructure, decorated with adatoms that are distributed in quasi-one-dimensional chains, is observed by further increasing the Te coverage to 4/9 ML. At the Te/Au(111) interface, an interfacial state at −0.65 eV to −0.55 eV below the Fermi level is also resolved by scanning tunneling spectroscopy. The formation of these Te-induced high-order superstructures is accompanied by relaxation of gold atoms in the surface layer, indicating a strong Te–Au interaction. Our work demonstrates a reliable method to fabricate Te nanostructures on noble metals in a controlled way.

In situ study of the formation mechanism oftwo-dimensional superlattices from PbSenanocrystals.

Oriented attachment of PbSe nanocubes can result in the formation of two-dimensional (2D) superstructures with long-range nanoscale and atomic order. This questions the applicability of classic models in which the superlattice grows by first forming a nucleus, followed by sequential irreversible attachment of nanocrystals, as one misaligned attachment would disrupt the 2D order beyond repair. Here, we demonstrate the formation mechanism of 2D PbSe superstructures with square geometry by using in situ grazing-incidence X-ray scattering (small angle and wide angle), ex situ electron microscopy, and Monte Carlo simulations. We observed nanocrystal adsorption at the liquid/gas interface, followed by the formation of a hexagonal nanocrystal monolayer. The hexagonal geometry transforms gradually through a pseudo-hexagonal phase into a phase with square order, driven by attractive interactions between the {100} planes perpendicular to the liquid substrate, which maximize facet-to-facet overlap. The nanocrystals then attach atomically via a necking process, resulting in 2D square superlattices.

Oleic Acid-Induced Atomic Alignment of ZnS Polyhedral Nanocrystals.

Ordered two-dimensional (2D) superstructures of colloidal nanocrystals (NCs) can be tailored by the size, shape, composition, and surface chemistry of the NC building blocks, which can give directionality to the resulting superstructure geometry. The exact formation mechanism of 2D NC superstructures is however not yet fully understood. Here, we show that oleic acid (OA) ligands induce atomic alignment of wurtzite ZnS bifrustum-shaped NCs. We find that in the presence of OA ligands the {002} facets of the ZnS bifrustums preferentially adhere to the liquid-air interface. Furthermore, OA ligands induce inter-NC interactions that also orient the NCs in the plane of the liquid-air interface, resulting in atomically aligned 2D superstructures. We follow the self-assembly process in real-time with in situ grazing incidence small-angle X-ray scattering and find that the NCs form a hexagonal superstructure at early stages after which they come closer over time, resulting in a close-packed NC superstructure. Our results demonstrate the profound influence that surface ligands have on the directionality of 2D NC superstructures and highlight the importance of detailed in situ studies in order to understand the self-assembly of NCs into 2D superstructures.

Superstructural defects and superlattice domains in stacked graphene

Recently there has been interest in two-dimensional graphene-based superstructures, such as twisted bilayer or trilayer graphene or graphene on hexagonal boron nitride, stacked one on top of the other. These superstructures are expected to have electronic and optical properties that depend on even small changes in the twist angles. By structural mapping in the micrometer scale, we demonstrate that superstructures consist of stacking-induced ‘superlattice domains’. The rotational disorder between domains created by the superstructural defects, such as wrinkles, folds and grain boundaries, and guest species intercalated between stacked layers, was analyzed at a resolution of sub-one degree. This comprehensive approach provides crucial structural information on graphene-based superstructures.

The quantum nature of C-H···metal interaction: vibrational spectra and kinetic and geometric isotope effects of adsorbed cyclohexane.

The nature of C-H···M (M = metal surface) interactions is reviewed based mainly on our recent investigations of cyclohexane on Rh(111). Infrared reflection-absorption spectroscopy measurements at low temperature (∼20 K) have shown that the softened CH stretching band consists of several sharp peaks. At temperatures above 80 K, each peak is broadened, most probably by anharmonic coupling with thermally excited low-energy frustrated translational modes. The origin of fine structure in this band and its similarity to that in hydrogen bond systems are discussed. In addition, novel isotope effects were observed in desorption kinetics and adsorption geometry of cyclohexane on Rh(111) using temperature programmed desorption, ultraviolet photoelectron spectroscopy, and spot profile analysis low-energy electron diffraction. The desorption energy of deuterated cyclohexane (C6 D12 ) is lower than that of C6 H12 (inverse kinetic isotope effect). In addition, the work function change by adsorbed C6 D12 is smaller than that by adsorbed C6 H12 . These results indicate that C6 D12 molecules are slightly more distant from the surface than C6 H12 molecules (vertical geometric isotope effect). A lateral geometric isotope effect was also observed for the two-dimensional cyclohexane superstructures as a result of the repulsive interaction between interfacial dipoles (= work function change). These isotope effects are ascribed to the quantum nature of hydrogen involved in the C-H···M interaction.

Self-Assembly of Colloidal Hexagonal Bipyramid- and Bifrustum-Shaped ZnS Nanocrystals into Two-Dimensional Superstructures

We present a combined experimental, theoretical, and simulation study on the self-assembly of colloidal hexagonal bipyramid- and hexagonal bifrustum-shaped ZnS nanocrystals (NCs) into two-dimensional superlattices. The simulated NC superstructures are in good agreement with the experimental ones. This shows that the self-assembly process is primarily driven by minimization of the interfacial free-energies and maximization of the packing density. Our study shows that a small truncation of the hexagonal bipyramids is sufficient to change the symmetry of the resulting superlattice from hexagonal to tetragonal, highlighting the crucial importance of precise shape control in the fabrication of functional metamaterials by self-assembly of colloidal NCs.