Crystalline Sheets Research Articles

Surface plasmon resonance properties of silver nanoparticle 2D sheets on metal gratings.

Grating-coupled propagating surface plasmons associated with silver-nanoparticle 2D crystalline sheets exhibit sensitive plasmonic resonance tuning. Multilayered silver-nanoparticle 2D crystalline sheets are fabricated on gold or silver grating surfaces by the Langmuir– Blodgett method. We show that the deposition of Ag crystalline nanosheets on Au or Ag grating surfaces causes a drastic change in propagating surface plasmon resonance (SPR) both in angle measurements at fixed wavelengths and in fixed incident-angle mode by irradiation of white light. The dielectric constant of the multilayered silver nanosheet is estimated by a rigorous coupled-wave analysis. We find that the dielectric constant drastically increases as the number of silver-nanosheet layers increases. The experimentally obtained SP dispersions of Ag crystalline nanosheets on Au and Ag gratings are compared with the calculated SP dispersion curves. The drastic change in the surface plasmon resonance caused by the deposition of Ag-nanoparticle 2D crystalline sheets on metal grating surfaces suggests the potential for applications in highly sensitive sensors or for plasmonic devices requiring greatly enhanced electric fields.Electronic supplementary materialThe online version of this article (doi:10.1186/2193-1801-3-284) contains supplementary material, which is available to authorized users.

Uniform Ti-doped Sb2Te3 materials for high-speed phase change memory applications

Compared with pure Sb2Te3, Ti0.32Sb2Te3 (TST) phase change material has larger resistance ratio, higher crystallization temperature and better thermal stability. The sharp decrease in mobility is responsible for the increasing amorphous and crystalline sheet resistance. The uniform crystalline structure of TST film is very benefit for the endurance characteristic. The Set and Reset operation voltages for TST-based phase change memory device are much lower than those of conventional Ge2Sb2Te5-based one. Remarkably, the device presents extremely rapid Set operation speed (∼6 ns). Furthermore, up to 1 × 106 programming cycles are obtained with stable Set and Reset resistances.

Controlled Nucleation and Growth of Pillared Paddlewheel Framework Nanostacks onto Chemically Modified Surfaces

The nucleation and growth of metal-organic frameworks onto functional surfaces stands to facilitate the utility of these supramolecular crystalline materials across a wide range of applications. Here, we demonstrate the solvothermal nucleation and growth of a pillared paddlewheel porphyrin framework 5 (PPF-5) onto semiconductor surfaces modified with carboxylic acids. Using versatile diazonium and catechol chemistries to modify silicon and titania surface chemistries, we show that solvothermally grown PPF-5 selectively nucleates and grows as stacked crystalline sheets with preferential (001), (111), and (110) crystallographic orientations. Furthermore, variations in the synthesis temperature produce modified stack morphologies that correlate with changes in the surface-nucleated PPF-5 photoluminescence.

An unsaturated hydrogen bonded network generated from three-fold symmetric carbamates

A new crystalline sheet spontaneously assembled under mild conditions from tri-carbamates. The discovery of the unsaturated hydrogen bonded sheet further demonstrated the variety and adaptability of the sheet structures.

Silicon sheets by redox assisted chemical exfoliation

In this paper, we report the direct chemical synthesis of silicon sheets in gram-scale quantities by chemical exfoliation of pre-processed calcium disilicide (CaSi2). We have used a combination of x-ray photoelectron spectroscopy, transmission electron microscopy and energy-dispersive x-ray spectroscopy to characterize the obtained silicon sheets. We found that the clean and crystalline silicon sheets show a two-dimensional hexagonal graphitic structure.

Employment of boron-doped carbon materials for the anode materials of lithium ion batteries

Abstract Plasma carbon and boron-doped carbons are prepared by gas phase synthesis technique using a plasma arc torch apparatus. The effects of boron doping on the microstructure and electrochemical performance are investigated. Transmission electron microscopy results indicate that crystalline graphitic sheets are formed when the content of boron in the carbon is higher than around 1.00 wt.% X-ray diffraction (XRD) and Raman analysis also reveal that the increased amount of boron doping results in decreased interlayer spacing and increased crystallite size of the boron-doped carbons. The boron-doped carbons exhibit not only higher reversible capacity, but also better rate capability than undoped plasma carbon, due to the formation of nano-structured carbon composite composed of both spherically shaped amorphous (hard carbon-like) and paper-shaped crystalline (graphite-like) phases. The reversible capacity remained over 390 mAh g −1 even after 200 cycles at a current density of 300 mA g −1 for the 1.00 wt.% boron-doped carbon.

Large-scale and low cost synthesis of graphene as high capacity anode materials for lithium-ion batteries

Graphene has emerged as an intriguing and attractive functional material for a wide range of applications, owing to its unique physical, chemical and mechanical properties. Herein, we report large-scale production of high quality single crystalline graphene sheets based on the ambient pressure chemical vapor deposition (APCVD) method using acetylene (C2H2) as the carbon source and coral-like iron with body-centered-cubic structure as the catalyst. The process can be scaled up for large quantity production at a low cost. The optimum APCVD temperature has been identified to be 850°C, which is much lower than that catalyzed by other metals. Transmission electron microscopy (TEM), atomic force microscopy, Raman spectroscopy and X-ray photoemission spectroscopy characterizations show the single crystalline and high quality nature of the as-prepared graphene produced by the bottom-up APCVD approach. A new horizontal “dissolution–deposition–growth” mechanism is proposed and verified by high resolution TEM. When applied as anode materials in lithium ion batteries, graphene sheets exhibited a high lithium storage capacity and an excellent cyclability. The capability of preparing crystalline graphene on a large scale with low cost opens an avenue for technological applications of graphene in many fields.

Universal collapse of stress and wrinkle-to-scar transition in spherically confined crystalline sheets

Imposing curvature on crystalline sheets, such as 2D packings of colloids or proteins, or covalently bonded graphene leads to distinct types of structural instabilities. The first type involves the proliferation of localized defects that disrupt the crystalline order without affecting the imposed shape, whereas the second type consists of elastic modes, such as wrinkles and crumples, which deform the shape and also are common in amorphous polymer sheets. Here, we propose a profound link between these types of patterns, encapsulated in a universal, compression-free stress field, which is determined solely by the macroscale confining conditions. This "stress universality" principle and a few of its immediate consequences are borne out by studying a circular crystalline patch bound to a deformable spherical substrate, in which the two distinct patterns become, respectively, radial chains of dislocations (called "scars") and radial wrinkles. The simplicity of this set-up allows us to characterize the morphologies and evaluate the energies of both patterns, from which we construct a phase diagram that predicts a wrinkle-scar transition in confined crystalline sheets at a critical value of the substrate stiffness. The construction of a unified theoretical framework that bridges inelastic crystalline defects and elastic deformations opens unique research directions. Beyond the potential use of this concept for finding energy-optimizing packings in curved topographies, the possibility of transforming defects into shape deformations that retain the crystalline structure may be valuable for a broad range of material applications, such as manipulations of graphene's electronic structure.

Shubnikov de Haas quantum oscillation of the surface states in the metallic Bismuth Telluride sheets

Metallic Bi2Te3 crystalline sheets with the room-temperature resistivity of above 10 m{\Omega} cm were prepared and their magnetoresistive transport was measured in a field of up to 9 Tesla. The Shubnikov de Haas oscillations were identified from the secondly-derived magnetoresistance curves. While changing the angle between the field and normal axis of the sheets, we find that the oscillation periods present a cosine dependence on the angle. This indicates a two-dimensional transport due to the surface state. The work reveals a resolvable surface contribution to the overall conduction even in a metallic topological insulator.

A Bottom-Up Approach toward Fabrication of Ultrathin PbS Sheets

Two-dimensional (2D) sheets are currently in the spotlight of nanotechnology owing to high-performance device fabrication possibilities. Building a free-standing quantum sheet with controlled morphology is challenging when large planar geometry and ultranarrow thickness are simultaneously concerned. Coalescence of nanowires into large single-crystalline sheet is a promising approach leading to large, molecularly thick 2D sheets with controlled planar morphology. Here we report on a bottom-up approach to fabricate high-quality ultrathin 2D single crystalline sheets with well-defined rectangular morphology via collective coalescence of PbS nanowires. The ultrathin sheets are strictly rectangular with 1.8 nm thickness, 200-250 nm width, and 3-20 μm length. The sheets show high electrical conductivity at room and cryogenic temperatures upon device fabrication. Density functional theory (DFT) calculations reveal that a single row of delocalized orbitals of a nanowire is gradually converted into several parallel conduction channels upon sheet formation, which enable superior in-plane carrier conduction.

Modulating the Yield But Not Pathway of Protein Self-Assembly by the Surface-Layer Protein SbpA in Solution

Surface layer (S-layer) proteins form a highly ordered crystalline, yet porous, layer on the outermost cell surface of most species of bacteria and archaea. S-layers not only provide the cell a layer for protection, they are postulated to mediate several functions such as cell adhesion, drug resistance and providing a scaffold for mineralization. Thus, S-layers provide a robust in vitro model system to test our understanding of the dynamics of self-assembly pathways, as well as a biological scaffold for hierarchical assembly of nano-materials. The SbpA protein from Lysinibacillus sphaericus is a well characterized S-layer protein that forms Ca2+ dependent, 2D crystals in solution with square symmetry. Here we use ensemble techniques to study the self-assembly process in solution. We use light scattering to follow assembly kinetics and determine a phase a diagram for crystallization; moreover we use electron microscopy and SAXS to confirm that SbpA forms large crystalline sheets in solution, detectable by our assay. Surprisingly, we find that while SbpA requires a minimal amount of Ca2+ to crystallize, excess divalent ions in solution inhibit interaction between subunits and thus self-assembly. In addition, we find that the crystallization of SbpA does not require the formation of a nucleus, and that all the steps for self-assembly are energetically favorable. We propose a model in which SbpA monomers that lack significant tertiary structure aggregate rapidly in solution to form dense protein clusters, which then order into crystalline sheets.

Mechanical and Electrical Properties of Au-Ni-C Alloy Films Produced by Pulsed Current Electrodeposition

Au-Ni-C alloys films electrodeposited by a pulsed current method were investigated to assess the crystalline structure, sheet resistance, and wear resistance, for use as an electronic contact material. In particular, we have analyzed the effects of citric acid concentration and pulse off-time on the mechanical and electrical properties of the electrodeposited Au-Ni-C alloy films. The electrodeposition bath used in this study was composed of K[Au(CN)2] and NiSO4·6H2O as precursors, and citric acid as the complexing agent. The film microstructure and composition were controlled by adjusting the interval of pulse off-time and the concentration of citric acid. With the prolongation of the pulse off-time interval, XRD results indicated that the amorphous structure with high Ni and C contents was transformed into a nanocrystalline structure, followed by the formation of crystals with small Ni and C contents. The amorphous and nanocrystalline films showed a high Knoop hardness of ca. 500 kg mm−2, while that of the crystalline films was found to be 300 kg mm−2. The wear resistance of the film electrodeposited by the pulsed current method was remarkably good compared to that of the direct-current electrodeposition films, even though both films exhibited essentially identical microstructure and composition. The wear property was considered to be relevant to the restoration of the surface flatness of the film by the galvanic displacement deposition of Au during the pulse off time.

Semiconductor nanomembranes: a platform for new properties via strain engineering

New phenomena arise in single-crystal semiconductors when these are fabricated in very thin sheets, with thickness at the nanometer scale. We review recent research on Si and Ge nanomembranes, including the use of elastic strain sharing, layer release, and transfer, that demonstrate new science and enable the fabrication of materials with unique properties. Strain engineering produces new strained forms of Si or Ge not possible in nature, new layered structures, defect-free SiGe sheets, and new electronic band structure and photonic properties. Through-membrane elastic interactions cause the double-sided ordering of epitaxially grown nanostressors on Si nanomembranes, resulting in a spatially and periodically varying strain field in the thin crystalline semiconductor sheet. The inherent influence of strain on the band structure creates band gap modulation, thereby creating effectively a single-element electronic superlattice. Conversely, large-enough externally applied strain can make Ge a direct-band gap semiconductor, giving promise for Group IV element light sources.

Polysorbate20 adsorption layers below and above the critical micelle concentration over aluminum; cloud point and inhibitory role investigations at the solid/liquid interface

Non‐ionic polysorbate20 surfactant was used to produce adsorption protective layers below and above its critical micelle concentration (CMC) at the liquid/solid interface. The well‐ordered accumulation of surfactant molecules on the metal surface below the CMC led to the formation of oriented surfactant monolayers. On the other hand, as the surfactant concentration increased above the CMC, the monodisperse micelles, free surfactant molecules and oriented surfactant monolayers undergo aggregate formation and produce a turbid solution. The gradual increase in the number and size of aggregates leads to phase separation and hence disassembled protective layers that allow easier penetration of corrosive HCl at a metal surface. This was demonstrated by inhibition efficiency, activation energy, enthalpy and entropy of activation values. Two‐dimensional irregular crystalline sheets accumulated at the surface of aluminum, as shown by scanning electron micrographs. Adsorption of polysorbate20 at the aluminum surface exhibited a Temkin isotherm fit. Larger desorption processes at the cloud point demonstrate aggregate formation and phase separation, and hence poorer adsorption layers at the metal surface. Copyright © 2012 John Wiley & Sons, Ltd.

Study of LiFePO4 cathode modified by graphene sheets for high-performance lithium ion batteries

Here three kinds of graphene preparation strategies, namely, chemical vapor deposition (CVD), Wurtz-type reductive coupling reaction and chemical exfoliation, respectively, have been developed to synthesize large-scale high-quality graphene for improving the electrochemical properties of LiFePO4 (LFP) cathodes. The flexible graphene sheets as effective conduction channels possess larger surface area to load more LFP nanoparticles (NPs). The amount of the 5wt% graphene additive greatly reduces the contact resistance between LFP NPs, and dramatically enhances the electrical conductivity and electrochemical performances of the cathodes. Particularly, when the large-size, defect-free and highly crystalline CVD graphene sheets are used to modify LFP cathodes, the capacities reach up to 132mAhg−1 and 80mAhg−1 at 1C and 20C discharge rates, and the corresponding capacity decay rates are 3.1% and 6.5% after 100 cycles, respectively. The excellent performance shows that the graphene-modified LFP is promising cathodes for high rate lithium ion batteries.

Amorphous graphene: a realization of Zachariasen’s glass

Amorphous graphene is a realization of a two-dimensional Zachariasen glass as first proposed 80 years ago. Planar continuous random networks of this archetypal two-dimensional network are generated by two complementary simulation methods. In the first, a Monte Carlo bond switching algorithm is employed to systematically amorphize a crystalline graphene sheet. In the second, molecular dynamics simulations are utilized to quench from the high temperature liquid state. The two approaches lead to similar results as detailed here, through the pair distribution function and the associated diffraction pattern. Details of the structure, including ring statistics and angular distortions, are shown to be sensitive to preparation conditions, and await experimental confirmation.

Tuning Colors of Silver Nanoparticle Sheets by Multilayered Crystalline Structures on Metal Substrates

We report a new concept of tuning plasmonic colors of two-dimensional crystalline silver nanoparticle sheets with layer-by-layer structures. The multilayered crystalline sheets fabricated by the Langmuir–Schaefer method keep the localized surface plasmon resonance bands at the same position (λmax = 465 nm) on quartz, while they change their colors drastically on metal substrates depending on the number of layers (one to five layers). The response of the absorption spectra was absolutely nonlinear, with maximum absorption for two or three layers. The obtained results were well reproduced by the finite difference time domain simulation. The simulation confirmed that these plasmonic colors originate not only from near-field coupling of plasmon resonance but also far-field nano-optics of the multilayered silver nanoparticle sheets.

Extremes of heat conduction―Pushing the boundaries of the thermal conductivity of materials

Abstract

An atomistic-based foliation model for multilayer graphene materials and nanotubes

We present a three-dimensional continuum model for layered crystalline materials made out of weakly interacting two-dimensional crystalline sheets. We specialize the model to multilayer graphene materials, including multi-walled carbon nanotubes (MWCNTs). We view the material as a foliation, partitioning of space into a continuous stack of leaves, thus loosing track of the location of the individual graphene layers. The constitutive model for the bulk is derived from the atomistic interactions by appropriate kinematic assumptions, adapted to the foliation structure and mechanics. In particular, the elastic energy along the leaves of the foliation results from the bonded interactions, while the interaction energy between the walls, resulting from van der Waals forces, is parametrized with a stretch transversal to the foliation. The resulting theory is distinct from conventional anisotropic models, and can be readily discretized with finite elements. The discretization is not tied to the individual walls and allows us to coarse-grain the system in all directions. Furthermore, the evaluation of the non-bonded interactions becomes local. We test the accuracy of the foliation model against a previously proposed atomistic-based continuum model that explicitly describes each and every wall. We find that the new model is very efficient and accurate. Furthermore, it allows us to rationalize the rippling deformation modes characteristic of thick MWCNTs, highlighting the role of the van der Waals forces and the sliding between the walls. By exercising the model with very large systems of hollow MWCNTs and suspended multilayer graphene, containing up to 109 atoms, we find new complex post-buckling deformation patterns.

Production of thin graphite sheets for a high electrical conductivity film by the mechanical delamination of ternary graphite intercalation compounds

Herein we propose a production scheme for conductive films composed of thin graphite sheets with high crystallinity and polymeric resin. The crystalline graphite sheets were successfully produced from natural graphite powder by solution-phase synthesis of graphite intercalation compounds (GICs), following a wet planetary-ball milling under mild conditions. The shear forces in the milling pot lead to a peeling of graphite flakes. Taking into consideration the interlayer bonding force, the delamination should be preferentially done from the expanded GICs interlayer rather than intrinsic graphite one. Some composite films derived from the phenolic resin and flaky graphite sheets displayed much higher electrical conductivities compared to the film from the feed graphite particles. We also demonstrate the stage structure of synthetic GICs affected the film conductivity. The composite films made from exfoliated products of ground (around stage IV) GICs exhibited high electrical conductivity with a small amount of the graphite sheets.