Honeycomb Superstructure Research Articles

A Cable-Stayed Honeycomb Superstructure to Improve the Stability of Li-Rich Materials via Inhibiting Interlaminar Lattice Strain.

In layered Li-rich materials, over stoichiometric Li forms an ordered occupation of LiTM6 in transition metal (TM)layer, showing a honeycomb superstructure along [001] direction. At the atomic scale, the instability of the superstructure at high voltage is the root cause of problems such as capacity/voltage decay of Li-rich materials. Here a Li-rich material with a high Li/Ni disorder is reported, these interlayer Ni atoms locate above the honeycomb superstructure and share adjacent O coordination with honeycomb TM. These Ni─O bonds act as cable-stayed bridge to the honeycomb plane, and improve the high-voltage stability. The cable-stayed honeycomb superstructure is confirmed by in situ X-ray diffraction to have a unique cell evolution mechanism that it can alleviate interlaminar lattice strain by promoting in-plane expansion along a-axis and inhibiting c-axis stretching. Electrochemical tests also demonstrate significantly improved long cycle performance after 500 cycles (86% for Li-rich/Li half cell and 82% for Li-rich/Si-C full cell) and reduced irreversible oxygen release. This work proves the feasibility of achieving outstanding stability of lithium-rich materials through superstructure regulation and provides new insights for the development of the next-generation high-energy-density cathodes.

Accumulated Lattice Strain as an Intrinsic Trigger for the First-Cycle Voltage Decay in Li-Rich 3d Layered Oxides

Li- and Mn-rich layered oxides (LMLOs) are promising cathode materials for Li-ion batteries (LIBs) owing to their high discharge capacity of above 250 mA h g-1. A high voltage plateau related to the oxidation of lattice oxygen appears upon the first charge, but it cannot be recovered during discharge, resulting in the so-called voltage decay. Disappearance of the honeycomb superstructure of the layered structure at a slow C-rate (e.g., 0.1 C) has been proposed to cause the first-cycle voltage decay. By comparing the structural evolution of Li[Li0.2Ni0.2Mn0.6]O2 (LLNMO) at various current densities, the operando synchrotron-based X-ray diffraction results show that the lattice strain in bulk LLNMO is continuously increased over cycling, resulting in the first-cycle voltage loss upon Li-ion insertion. Unlike the LLNMO, the accumulated average lattice strain of LiNi0.8Co0.1Mn0.1O2 (NCM811) and LiNi0.6Co0.2Mn0.2O2 (NCM622) from the open-circuit voltage to 4.8 V could be released on discharge. These findings help to gain a deep understanding of the voltage decay in LMLOs.

Growth of a quasicrystal-related structure and superstructure for ultrathin Ce-Ti-O films on Pt(111).

Herein, oxide quasicrystal-related (OQC-R) structure and Ce-Ti-O-(3 × 3) superstructure ultrathin films were prepared on Pt(111) and characterized using scanning tunneling microscopy (STM) and low-energy electron diffraction. The OQC-R structure with dodecagonal clusters consisting of triangles, squares, and rhombuses was observed in STM images. The first discovery of the OQC-R structure with a magnetic rare earth metal expands the possibility of discovering new oxide quasicrystals with novel magnetism or superconductivity. By depositing Ti on an OQC-R ultrathin film and post-annealing, a honeycomb lattice of the Ce-Ti-O-(3 × 3) superstructure was prepared. From X-ray photoelectron spectroscopy (XPS) and resonant-photoelectron spectroscopy, the chemical states of the Ce and Ti atoms in the OQC-R structure corresponded to the Ce3+ and Ti2+ states, while those for the Ce-Ti-O-(3 × 3) superstructure corresponded to the Ce3+, Ti3+, and Ti2+ states. The phase transformation from the OQC-R structure to the Ce-Ti-O-(3 × 3) honeycomb superstructure likely occurred when the amount of Ti increased and was more oxidized. The elemental atomic density was also calibrated using XPS and Rutherford backscattering spectroscopy. These results propose tentative structural models of the OQC-R structure as Ce18Ti14O41 and the Ce-Ti-O-(3 × 3) superstructure as CeTi6O9.

Flat Bands in Network Superstructures of Atomic Chains

We investigate the origin of the ubiquitous existence of flat bands in the network superstructures of atomic chains, where one-dimensional (1D) atomic chains array periodically. While there can be many ways to connect those chains, we consider two representative ways of linking them, the dot-type and triangle-type links. Then, we construct a variety of superstructures, such as the square, rectangular, and honeycomb network superstructures with dot-type links and the honeycomb superstructure with triangle-type links. These links provide the wavefunctions with an opportunity to have destructive interference, which stabilizes the compact localized state (CLS). In the network superstructures, there exist multiple flat bands proportional to the number of atoms of each chain, and the corresponding eigenenergies can be found from the stability condition of the compact localized state. Finally, we demonstrate that the finite bandwidth of the nearly flat bands of the network superstructures arising from the next-nearest-neighbor hopping processes can be suppressed by increasing the length of the chains consisting of the superstructures.

On the Formation of Honeycomb Superlattices from PbSe Quantum Dots: The Role of Solvent-Mediated Repulsion and Facet-to-Facet Attraction in NC Self-Assembly and Alignment.

Semiconductor superstructures made from assembled and epitaxially connected colloidal nanocrystals (NCs) hold promise for crystalline solids with atomic and nanoscale periodicity, whereby the band structure can be tuned by the geometry. The formation of especially the honeycomb superstructure on a liquid substrate is far from understood and suffers from weak replicability. Here, we introduce 1,4-butanediol as an unreactive substrate component, which is mixed with reactive ethylene glycol to tune for optimal reactivity. It shows us that the honeycomb superlattice has a NC precursor state before oriented attachment occurs, in the form of a self-assembled hexagonal bilayer. We propose that the difference between the formation of the square or honeycomb superstructure occurs during the self-assembly phase. To form a honeycomb superstructure, it is crucial to stabilize the hexagonal bilayer in the presence of solvent-mediated repulsion. In contrast, a square superstructure benefits from the contraction of a hexagonal monolayer due to the absence of a solvent. A second experiment shows the very last stage of the process, where the increasing alignment of NCs is quantified using selected-area electron diffraction (SAED). The combination of transmission electron microscopy (TEM), SAED, and tomography used in these experiments shows that the (100)/(100) facet-to-facet attraction is the main driving force for NC alignment and attachment. These findings are validated by coarse-grained molecular dynamic simulations, where we show that an optimal NC repulsion is crucial to create the honeycomb superstructure.

Bulk O2 formation and Mg displacement explain O-redox in Na0.67Mn0.72Mg0.28O2

Summary O-redox in compounds with Li on the transition-metal layers (TML) has recently been attributed to the formation of molecular O2 on charge, trapped in the lattice. Here, we show that a similar process occurs for P2-Na0.67[Mn0.72Mg0.28]O2, which contains Mg2+ on the TML. The molecular O2 is identified by high-resolution RIXS and quantified by magnetometry, showing that it equates to the charge passed. This O2 is trapped in voids that are formed by Mg2+ out-of-plane displacement and Mn4+ in-plane disordering and is then reduced on discharge associated with a large voltage hysteresis. In contrast to compounds containing Li+ in the TML, in which the honeycomb ordering and the high-voltage plateau are irreversibly lost after the first cycle, in P2-Na0.67[Mn0.72Mg0.28]O2, the plateau reappears partially on the second charge due to the partial reversibility of Mn in-plane and Mg out-of-plane migration and the local reformation of the honeycomb ordering.

High Pressure Effect on Structural and Electrochemical Properties of Anionic Redox-Based Lithium Transition Metal Oxides

Summary The richness of anionic redox chemistry in the solid state offers new opportunities and a possible paradigm shift in energy storage. The excess capacity that goes beyond conventional theoretical values is attributed to the anionic redox in Li-rich transition metal oxide cathodes for Li-ion batteries. Their electrochemical behavior is thermodynamically determined by structural evolution. To better understand the electrochemical dependence on structural factors, we have induced structural modifications in pristine and electrochemically activated Li1.144Ni0.136Co0.136Mn0.544O2 through high-pressure treatment. A unique cyclical change of structural reordering is observed in the anionic redox-activated material during operando pressure sweep, characterized by a periodic evolution of superlattice peak intensity in synchrotron X-ray diffraction patterns. During the structural reordering period, the bulk compressibility of the material decreases, even becoming negative. These insights elucidate the structural flexibility and metastability of anionic redox-based materials, which can undergo large compressions and structural modifications while delivering good electrochemical properties.

Toward High-Energy Batteries: High-Voltage Stability via Superstructure Control

One pathway to higher energy density batteries is by way of intercalation cathodes that operate at high voltage, storing charge on both the oxide and transition metal ions. In the January 23, 2020 issue of Nature, Peter Bruce and colleagues illuminate the mechanism by which the honeycomb superstructure of most O-redox compounds is lost, along with the high energy density, upon first-cycle charging. The secret of certain intercalation compounds maintaining the desired high-voltage electrochemistry upon cycling is in their unique superstructures that resist molecular O2 formation.

Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes.

In conventional intercalation cathodes, alkali metal ions can move in and out of a layered material with the charge being compensated for by reversible reduction and oxidation of the transition metal ions. If the cathode material used in a lithium-ion or sodium-ion battery is alkali-rich, this can increase the battery's energy density by storing charge on the oxide and the transition metal ions, rather than on the transition metal alone1-10. There is a high voltage associated with oxidation of O2- during the first charge, but this is not recovered on discharge, resulting in reduced energy density11. Displacement of transition metal ions into the alkali metal layers has been proposed to explain the first-cycle voltage loss (hysteresis)9,12-16. By comparing two closely related intercalation cathodes, Na0.75[Li0.25Mn0.75]O2 and Na0.6[Li0.2Mn0.8]O2, here we show that the first-cycle voltage hysteresis is determined by the superstructure in the cathode, specifically the local ordering of lithium and transition metal ions in the transition metal layers. The honeycomb superstructure of Na0.75[Li0.25Mn0.75]O2, present in almost all oxygen-redox compounds, is lost on charging, driven in part by formation of molecular O2 inside the solid. The O2 molecules are cleaved on discharge, reforming O2-, but the manganese ions have migrated within the plane, changing the coordination around O2- and lowering the voltage on discharge. The ribbon superstructure in Na0.6[Li0.2Mn0.8]O2 inhibits manganese disorder and hence O2 formation, suppressing hysteresis and promoting stable electron holes on O2- that are revealed by X-ray absorption spectroscopy. The results show that voltage hysteresis can be avoided in oxygen-redox cathodes by forming materials with a ribbon superstructure in the transition metal layers that suppresses migration of the transition metal.

Intrinsic superstructure near atomically clean armchair step edges of graphite

We investigated the electronic superstructure of graphite surface in the vicinity to monoatomic armchair step edges with scanning tunneling microscopy and spectroscopy. Only the ($\sqrt{3}\times\sqrt{3}$)$\textit{R}$30$^{\circ}$ superstructure is visualized near atomically clean armchair edges, while the honeycomb superstructure is absent. The spectroscopic mapping near the clean armchair edge clearly reveals the ($\sqrt{3}\times\sqrt{3}$)$\textit{R}$30$^{\circ}$ superstructure on both sides of the step edge. We have also visualized a mixture of ($\sqrt{3}\times\sqrt{3}$)$\textit{R}$30$^{\circ}$ and honeycomb superstructures near structurally defective armchair edges. Our results suggest that the honeycomb superstructure pattern results from superposition of two sets of ($\sqrt{3}\times\sqrt{3}$)$\textit{R}$30$^{\circ}$ superstructure with different phases. Our observation solves the mystery of the coexistence of two types of superstructures reported by prior studies.

Resolving the Controversial Existence of Silicene and Germanene Nanosheets Grown on Graphite.

The highly oriented pyrolytic graphite (HOPG) surface, consisting of a dangling bond-free lattice, is regarded as a potential substrate for van der Waals heteroepitaxy of two-dimensional layered materials. In this work, the growth of silicon and germanium on HOPG is investigated with scanning tunneling microscopy by using typical synthesis conditions for silicene and germanene on metal surfaces. At low coverages, the deposition of Si and Ge gives rise to tiny and sparse clusters that are surrounded by a honeycomb superstructure. From the detailed analysis of the superstructure, its comparison with the one encountered on the bare and clean HOPG surface, and simulations of the electron density, we conclude that the superstructure is caused by charge density modulations in the HOPG surface. At high coverages, we find the formation of clusters, assembled in filamentary patterns, which indicates a Volmer-Weber growth mode instead of a layer-by-layer growth mode. This coverage-dependent study sets the stage for revisiting recent results alleging the synthesis of silicene and germanene on the HOPG surface.

Topological Insulators from Electronic Superstructures

The possibility of realizing topological insulators by spontaneous formation of electronic superstructure is theoretically investigated in a minimal two-orbital model including both the spin-orbit coupling and electron correlations on a triangular lattice. Using the mean-field approximation, we show that the model exhibits several different types of charge ordered insulators, where the charge disproportionation forms a honeycomb or kagome superstructure. We find that the charge ordered insulators in the presence of strong spin-orbit coupling can be topological insulators showing quantized spin Hall conductivity. Their band gap is dependent on electron correlations as well as the spin-orbit coupling, and even vanishes with showing the massless Dirac dispersion at the transition to a trivial charge ordered insulator. Our results suggest a new route to realize and control topological states of quantum matter by the interplay between the spin-orbit coupling and electron correlations.

A Filled-Honeycomb-Structured Crystal Formed by Self-Assembly of a Janus Polyoxometalate-Silsesquioxane (POM-POSS) Co-Cluster.

Clusters with diverse structures and functions have been used to create novel cluster-assembled materials (CAMs). Understanding their self-assembly process is a prerequisite to optimize their structure and function. Herein, two kinds of unlike organo-functionalized inorganic clusters are covalently linked by a short organic tether to form a dumbbell-shaped Janus co-cluster. In a mixed solvent of acetonitrile and water, it self-assembles into a crystal with a honeycomb superstructure constructed by hexagonal close-packed cylinders of the smaller cluster and an orderly arranged framework of the larger cluster. Reconstruction of these structural features via coarse-grained molecular simulations demonstrates that the cluster crystallization and the nanoscale phase separation between the two incompatible clusters synergistically result in the unique nano-architecture. Overall, this work opens up new opportunities for generating novel CAMs for advanced future applications.

A Filled‐Honeycomb‐Structured Crystal Formed by Self‐Assembly of a Janus Polyoxometalate–Silsesquioxane (POM–POSS) Co‐Cluster

AbstractClusters with diverse structures and functions have been used to create novel cluster‐assembled materials (CAMs). Understanding their self‐assembly process is a prerequisite to optimize their structure and function. Herein, two kinds of unlike organo‐functionalized inorganic clusters are covalently linked by a short organic tether to form a dumbbell‐shaped Janus co‐cluster. In a mixed solvent of acetonitrile and water, it self‐assembles into a crystal with a honeycomb superstructure constructed by hexagonal close‐packed cylinders of the smaller cluster and an orderly arranged framework of the larger cluster. Reconstruction of these structural features via coarse‐grained molecular simulations demonstrates that the cluster crystallization and the nanoscale phase separation between the two incompatible clusters synergistically result in the unique nano‐architecture. Overall, this work opens up new opportunities for generating novel CAMs for advanced future applications.

Delocalized Surface State in Epitaxial Si(111) Film with Spontaneous √3 × √3 Superstructure.

The “multilayer silicene” films were grown on Ag(111), with increasing thickness above 30 monolayers (ML). Scanning tunneling microscopy (STM) observations suggest that the “multilayer silicene” is indeed a bulk-like Si(111) film with a (√3 × √3)R30° honeycomb superstructure on surface. The possibility for formation of Si(111)(√3 × √3)R30°-Ag reconstruction on the surface can be distinctively ruled out by peeling off the surface layer with the STM tip. On this surface, delocalized surface state as well as linear energy-momentum dispersion was observed from quasiparticle interference patterns. Our results indicate that a bulklike silicon film with diamondlike structure can also host delocalized surface state, which is even more attractive for potential applications, such as new generation of nanodevices based on Si.

Self-Assembled Si(111) Surface States: 2D Dirac Material for THz Plasmonics.

Graphene, the first discovered 2D Dirac material, has had a profound impact on science and technology. In the last decade, we have witnessed huge advances in graphene related fundamental and applied research. Here, based on first-principles calculations, we propose a new 2D Dirac band on the Si(111) surface with 1/3 monolayer halogen coverage. The sp(3) dangling bonds form a honeycomb superstructure on the Si(111) surface that results in an anisotropic Dirac band with a group velocity (∼10(6) m/s) comparable to that in graphene. Most remarkably, the Si-based surface Dirac band can be used to excite a tunable THz plasmon through electron-hole doping. Our results demonstrate a new way to design Dirac states on a traditional semiconductor surface, so as to make them directly compatible with Si technology. We envision this new type of Dirac material to be generalized to other semiconductor surfaces with broad applications.

Implantation Length and Thermal Stability of Interstitial Ar Atoms in Boron Nitride Nanotents

Hyperthermal atoms may be implanted beneath single layers of graphene or hexagonal boron nitride (h-BN) on a substrate. For the case of h-BN on rhodium, which is a corrugated honeycomb superstructure with a periodicity of 3.2 nm, Ar atoms are implanted at distinct interstitial sites within the supercell, where the h-BN is weakly bound to the substrate. These peculiar structures are reminiscent of "nanotents" with an ultimately thin "rainfly". Here we explore the implantation length (i.e., the distance the atoms move before they come to rest as interstitial defects) and the thermal stability of these atomic agglomerates above room temperature. The results are obtained by variable-temperature scanning tunneling microscopy and density functional theory calculations.

Immobilizing Individual Atoms beneath a Corrugated Single Layer of Boron Nitride

Single atoms, and in particular the least reactive noble gases, are difficult to immobilize at room temperature. Ion implantation into a crystal lattice has this capability, but the randomness of the involved processes does not permit much control over their distribution within the solid. Here we demonstrate that the boron nitride nanomesh, a corrugated single layer of hexagonal boron nitride (h-BN) with a 3.2 nm honeycomb superstructure formed on a Rh(111) surface, can trap individual argon atoms at distinct subsurface sites at room temperature. A kinetic energy window for implantation is identified where the argon ions can penetrate the h-BN layer but not enter the Rh lattice. Scanning tunneling microscopy and photoemission data show the presence of argon atoms at two distinct sites within the nanomesh unit cell, confirmed also by density functional theory calculations. The single atom implants are stable in air. Annealing of implanted structures to 900 K induces the formation of highly regular holes of 2 nm diameter in the h-BN layer with adjacent flakes of the same size found on top of the layer. We explain this "can-opener" effect by the presence of a vacancy defect, generated during the penetration of the Ar ion through the h-BN lattice, and propagating along the rim of a nanomesh pore where the h-BN lattice is highly bent. The reported effects are also observed in graphene on ruthenium and for neon atoms.

The reduction and oxidation of Fe2O3(0001) surface investigated by scanning tunneling microscopy

By using scanning tunneling microscopy (STM), we study the structure of the (0001) surface of hematite (α-Fe2O3) pre.pared by ultra-high vacuum treatment. The surface is reduced into a Fe3O4(111) phase by Ar ion sputtering followed by annealing in vacuum, while it is oxidized to a honeycomb superstructure by annealing in O2. High-resolution STM images reveal that the O-terminated FeO(111), Fe- and O-terminated Fe2O3(0001) domains coexist with each other in the superstructure. Unlike the reduction of Fe2O3(0001) whose depth increases with repeated annealing in vacuum, the oxidation of Fe3O4(111) occurs only partially on the top layers by annealing in O2.

Monte Carlo study of the honeycomb structure of anthraquinone molecules on Cu(111)

Using Monte Carlo calculations of the two-dimensional (2D) triangular lattice gas model, we demonstrate a mechanism for the spontaneous formation of honeycomb structure of anthraquinone (AQ) molecules on a Cu(111) plane. In our model long-range attractions play an important role, in addition to the long-range repulsions and short-range attractions proposed by Pawin, Wong, Kwon, and Bartels [Science 313, 961 (2006)]. We provide a global account of the possible combinations of long-range attractive coupling constants which lead to a honeycomb superstructure. We also provide the critical temperature of disruption of the honeycomb structure and compare the critical local coverage rate of AQ's where the honeycomb structure starts to form with the experimental observations.