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Showing papers in "Nature Materials in 2007"


Journal ArticleDOI
TL;DR: Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena can now be mimicked and tested in table-top experiments.
Abstract: Graphene is a rapidly rising star on the horizon of materials science and condensed-matter physics. This strictly two-dimensional material exhibits exceptionally high crystal and electronic quality, and, despite its short history, has already revealed a cornucopia of new physics and potential applications, which are briefly discussed here. Whereas one can be certain of the realness of applications only when commercial products appear, graphene no longer requires any further proof of its importance in terms of fundamental physics. Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena, some of which are unobservable in high-energy physics, can now be mimicked and tested in table-top experiments. More generally, graphene represents a conceptually new class of materials that are only one atom thick, and, on this basis, offers new inroads into low-dimensional physics that has never ceased to surprise and continues to provide a fertile ground for applications.

35,293 citations


Journal ArticleDOI
TL;DR: In this paper, it was shown that micrometre-size sensors made from graphene are capable of detecting individual events when a gas molecule attaches to or detaches from graphene's surface.
Abstract: The ultimate aim of any detection method is to achieve such a level of sensitivity that individual quanta of a measured entity can be resolved. In the case of chemical sensors, the quantum is one atom or molecule. Such resolution has so far been beyond the reach of any detection technique, including solid-state gas sensors hailed for their exceptional sensitivity1, 2, 3, 4. The fundamental reason limiting the resolution of such sensors is fluctuations due to thermal motion of charges and defects5, which lead to intrinsic noise exceeding the sought-after signal from individual molecules, usually by many orders of magnitude. Here, we show that micrometre-size sensors made from graphene are capable of detecting individual events when a gas molecule attaches to or detaches from graphene's surface. The adsorbed molecules change the local carrier concentration in graphene one by one electron, which leads to step-like changes in resistance. The achieved sensitivity is due to the fact that graphene is an exceptionally low-noise material electronically, which makes it a promising candidate not only for chemical detectors but also for other applications where local probes sensitive to external charge, magnetic field or mechanical strain are required.

7,318 citations


Journal ArticleDOI
TL;DR: A coarse-grained classification into primarily thermal, electrical or ion-migration-induced switching mechanisms into metal-insulator-metal systems, and a brief look into molecular switching systems is taken.
Abstract: Many metal–insulator–metal systems show electrically induced resistive switching effects and have therefore been proposed as the basis for future non-volatile memories. They combine the advantages of Flash and DRAM (dynamic random access memories) while avoiding their drawbacks, and they might be highly scalable. Here we propose a coarse-grained classification into primarily thermal, electrical or ion-migration-induced switching mechanisms. The ion-migration effects are coupled to redox processes which cause the change in resistance. They are subdivided into cation-migration cells, based on the electrochemical growth and dissolution of metallic filaments, and anion-migration cells, typically realized with transition metal oxides as the insulator, in which electronically conducting paths of sub-oxides are formed and removed by local redox processes. From this insight, we take a brief look into molecular switching systems. Finally, we discuss chip architecture and scaling issues.

4,547 citations


Journal ArticleDOI
TL;DR: It is found that even a weak magnetoelectric interaction can lead to spectacular cross-coupling effects when it induces electric polarization in a magnetically ordered state.
Abstract: Magnetism and ferroelectricity are essential to many forms of current technology, and the quest for multiferroic materials, where these two phenomena are intimately coupled, is of great technological and fundamental importance. Ferroelectricity and magnetism tend to be mutually exclusive and interact weakly with each other when they coexist. The exciting new development is the discovery that even a weak magnetoelectric interaction can lead to spectacular cross-coupling effects when it induces electric polarization in a magnetically ordered state. Such magnetic ferroelectricity, showing an unprecedented sensitivity to ap plied magnetic fields, occurs in 'frustrated magnets' with competing interactions between spins and complex magnetic orders. We summarize key experimental findings and the current theoretical understanding of these phenomena, which have great potential for tuneable multifunctional devices.

3,683 citations


Journal ArticleDOI
TL;DR: Novel device paradigms based on magnetoelectric coupling are discussed, the key scientific challenges in the field are outlined, and high-quality thin-film multiferroics are reviewed.
Abstract: Multiferroic materials, which show simultaneous ferroelectric and magnetic ordering, exhibit unusual physical properties — and in turn promise new device applications — as a result of the coupling between their dual order parameters. We review recent progress in the growth, characterization and understanding of thin-film multiferroics. The availability of high-quality thin-film multiferroics makes it easier to tailor their properties through epitaxial strain, atomic-level engineering of chemistry and interfacial coupling, and is a prerequisite for their incorporation into practical devices. We discuss novel device paradigms based on magnetoelectric coupling, and outline the key scientific challenges in the field.

3,472 citations


Journal ArticleDOI
TL;DR: By incorporating a few volume per cent of alkanedithiols in the solution used to spin-cast films comprising a low-bandgap polymer and a fullerene derivative, the power-conversion efficiency of photovoltaic cells is increased from 2.8% to 5.5% through altering the bulk heterojunction morphology.
Abstract: High charge-separation efficiency combined with the reduced fabrication costs associated with solution processing and the potential for implementation on flexible substrates make 'plastic' solar cells a compelling option for tomorrow's photovoltaics. Attempts to control the donor/acceptor morphology in bulk heterojunction materials as required for achieving high power-conversion efficiency have, however, met with limited success. By incorporating a few volume per cent of alkanedithiols in the solution used to spin-cast films comprising a low-bandgap polymer and a fullerene derivative, the power-conversion efficiency of photovoltaic cells (air-mass 1.5 global conditions) is increased from 2.8% to 5.5% through altering the bulk heterojunction morphology. This discovery can potentially enable morphological control in bulk heterojunction materials where thermal annealing is either undesirable or ineffective.

3,178 citations


Journal ArticleDOI
TL;DR: This review looks at the unique property combination that characterizes phase-change materials, in particular the contrast between the amorphous and crystalline states, and the origin of the fast crystallization kinetics.
Abstract: Phase-change materials are some of the most promising materials for data-storage applications. They are already used in rewriteable optical data storage and offer great potential as an emerging non-volatile electronic memory. This review looks at the unique property combination that characterizes phase-change materials. The crystalline state often shows an octahedral-like atomic arrangement, frequently accompanied by pronounced lattice distortions and huge vacancy concentrations. This can be attributed to the chemical bonding in phase-change alloys, which is promoted by p-orbitals. From this insight, phase-change alloys with desired properties can be designed. This is demonstrated for the optical properties of phase-change alloys, in particular the contrast between the amorphous and crystalline states. The origin of the fast crystallization kinetics is also discussed.

2,985 citations


Journal ArticleDOI
TL;DR: The electrocatalytic trends established for extended surfaces are used to explain the activity pattern of Pt(3)M nanocatalysts as well as to provide a fundamental basis for the catalytic enhancement of cathode catalysts.
Abstract: One of the key objectives in fuel-cell technology is to improve and reduce Pt loading as the oxygen-reduction catalyst. Here, we show a fundamental relationship in electrocatalytic trends on Pt(3)M (M=Ni, Co, Fe, Ti, V) surfaces between the experimentally determined surface electronic structure (the d-band centre) and activity for the oxygen-reduction reaction. This relationship exhibits 'volcano-type' behaviour, where the maximum catalytic activity is governed by a balance between adsorption energies of reactive intermediates and surface coverage by spectator (blocking) species. The electrocatalytic trends established for extended surfaces are used to explain the activity pattern of Pt(3)M nanocatalysts as well as to provide a fundamental basis for the catalytic enhancement of cathode catalysts. By combining simulations with experiments in the quest for surfaces with desired activity, an advanced concept in nanoscale catalyst engineering has been developed.

2,774 citations


Journal ArticleDOI
TL;DR: This work argues for a conceptual framework for these new building blocks based on anisotropy attributes and discusses the prognosis for future progress in exploiting an isotropy for materials design and assembly.
Abstract: A revolution in novel nanoparticles and colloidal building blocks has been enabled by recent breakthroughs in particle synthesis These new particles are poised to become the ‘atoms’ and ‘molecules’ of tomorrow’s materials if they can be successfully assembled into useful structures Here, we discuss the recent progress made in the synthesis of nanocrystals and colloidal particles and draw analogies between these new particulate building blocks and better-studied molecules and supramolecular objects We argue for a conceptual framework for these new building blocks based on anisotropy attributes and discuss the prognosis for future progress in exploiting anisotropy for materials design and assembly

2,558 citations


Journal ArticleDOI
TL;DR: The use of nanoscale disorder is demonstrated to stimulate human mesenchymal stem cells (MSCs) to produce bone mineral in vitro, in the absence of osteogenic supplements, which has implications for cell therapies.
Abstract: A key tenet of bone tissue engineering is the development of scaffold materials that can stimulate stem cell differentiation in the absence of chemical treatment to become osteoblasts without compromising material properties. At present, conventional implant materials fail owing to encapsulation by soft tissue, rather than direct bone bonding. Here, we demonstrate the use of nanoscale disorder to stimulate human mesenchymal stem cells (MSCs) to produce bone mineral in vitro, in the absence of osteogenic supplements. This approach has similar efficiency to that of cells cultured with osteogenic media. In addition, the current studies show that topographically treated MSCs have a distinct differentiation profile compared with those treated with osteogenic media, which has implications for cell therapies.

2,249 citations


Journal ArticleDOI
TL;DR: The authors are starting to see a new paradigm where magnetization dynamics and charge currents act on each other in nanostructured artificial materials, allowing faster, low-energy operations: spin electronics is on its way.
Abstract: Electrons have a charge and a spin, but until recently these were considered separately. In classical electronics, charges are moved by electric fields to transmit information and are stored in a capacitor to save it. In magnetic recording, magnetic fields have been used to read or write the information stored on the magnetization, which 'measures' the local orientation of spins in ferromagnets. The picture started to change in 1988, when the discovery of giant magnetoresistance opened the way to efficient control of charge transport through magnetization. The recent expansion of hard-disk recording owes much to this development. We are starting to see a new paradigm where magnetization dynamics and charge currents act on each other in nanostructured artificial materials. Ultimately, 'spin currents' could even replace charge currents for the transfer and treatment of information, allowing faster, low-energy operations: spin electronics is on its way.

Journal ArticleDOI
TL;DR: It is shown that when graphene is epitaxially grown on SiC substrate, a gap of approximately 0.26 eV is produced and it is proposed that the origin of this gap is the breaking of sublattice symmetry owing to the graphene-substrate interaction.
Abstract: Graphene has shown great application potential as the hostmaterial for next-generation electronic devices. However, despite itsintriguing properties, one of the biggest hurdles for graphene to beuseful as an electronic material is the lack of an energy gap in itselectronic spectra. This, for example, prevents the use of graphene inmaking transistors. Although several proposals have been made to open agap in graphene's electronic spectra, they all require complexengineering of the graphene layer. Here, we show that when graphene isepitaxially grown on SiC substrate, a gap of ~;0.26 eV is produced. Thisgap decreases as the sample thickness increases and eventually approacheszero when the number of layers exceeds four. We propose that the originof this gap is the breaking of sublattice symmetry owing to thegraphene-substrate interaction. We believe that our results highlight apromising direction for band gap engineering of graphene.

Journal ArticleDOI
TL;DR: This review presents a brief summary of bottom-up and hybrid bottom- up/top-down strategies for nanoelectronics with an emphasis on memories based on the crossbar motif, including experimental demonstrations of key concepts such lithography-independent, chemically coded stochastic demultipluxers.
Abstract: Electronics obtained through the bottom-up approach of molecular-level control of material composition and structure may lead to devices and fabrication strategies not possible with top-down methods. This review presents a brief summary of bottom-up and hybrid bottom-up/top-down strategies for nanoelectronics with an emphasis on memories based on the crossbar motif. First, we will discuss representative electromechanical and resistance-change memory devices based on carbon nanotube and core-shell nanowire structures, respectively. These device structures show robust switching, promising performance metrics and the potential for terabit-scale density. Second, we will review architectures being developed for circuit-level integration, hybrid crossbar/CMOS circuits and array-based systems, including experimental demonstrations of key concepts such lithography-independent, chemically coded stochastic demultipluxers. Finally, bottom-up fabrication approaches, including the opportunity for assembly of three-dimensional, vertically integrated multifunctional circuits, will be critically discussed.

Journal ArticleDOI
TL;DR: A self-healing system capable of autonomously repairing repeated damage events via a three-dimensional microvascular network embedded in the substrate is reported, opening new avenues for continuous delivery of healing agents for self-repair as well as other active species for additional functionality.
Abstract: Self-healing polymers composed of microencapsulated healing agents exhibit remarkable mechanical performance and regenerative ability, but are limited to autonomic repair of a single damage event in a given location. Self-healing is triggered by crack-induced rupture of the embedded capsules; thus, once a localized region is depleted of healing agent, further repair is precluded. Re-mendable polymers can achieve multiple healing cycles, but require external intervention in the form of heat treatment and applied pressure. Here, we report a self-healing system capable of autonomously repairing repeated damage events. Our bio-inspired coating-substrate design delivers healing agent to cracks in a polymer coating via a three-dimensional microvascular network embedded in the substrate. Crack damage in the epoxy coating is healed repeatedly. This approach opens new avenues for continuous delivery of healing agents for self-repair as well as other active species for additional functionality.

Journal ArticleDOI
TL;DR: In this article, the authors show how magnetism can be induced at the interface between the otherwise non-magnetic insulating perovskites SrTiO3 and LaAlO3.
Abstract: The electronic reconstruction at the interface between two insulating oxides can give rise to a highly conductive interface. Here we show how, in analogy to this remarkable interfaceinduced conductivity, magnetism can be induced at the interface between the otherwise non-magnetic insulating perovskites SrTiO3 and LaAlO3. A large negative magnetoresistance of the interface is found, together with a logarithmic temperature dependence of the sheet resistance.At lowtemperatures, the sheet resistance reveals magnetic hysteresis.Magnetic ordering is a key issue in solid-state science and its underlying mechanisms are still the subject of intense research. In particular, the interplay between localized magnetic moments and the spin of itinerant conduction electrons in a solid gives rise to intriguingmany-body effects such as Ruderman–Kittel–Kasuya–Yosida interactions3, the Kondo effect4 and carrier-induced ferromagnetism in diluted magnetic semiconductors5. The conducting oxide interface now provides a versatile system to induce and manipulate magnetic moments in otherwise non-magnetic materials.

Journal ArticleDOI
TL;DR: It is found that ripples spontaneously appear owing to thermal fluctuations with a size distribution peaked around 80 A which is compatible with experimental findings and might be due to the multiplicity of chemical bonding in carbon.
Abstract: The stability of two-dimensional (2D) layers and membranes is the subject of a long-standing theoretical debate. According to the so-called Mermin–Wagner theorem1, long-wavelength fluctuations destroy the long-range order of 2D crystals. Similarly, 2D membranes embedded in a 3D space have a tendency to be crumpled2. These fluctuations can, however, be suppressed by anharmonic coupling between bending and stretching modes meaning that a 2D membrane can exist but will exhibit strong height fluctuations2,3,4. The discovery of graphene, the first truly 2D crystal5,6, and the recent experimental observation of ripples in suspended graphene7 make these issues especially important. Besides the academic interest, understanding the mechanisms of the stability of graphene is crucial for understanding electronic transport in this material that is attracting so much interest owing to its unusual Dirac spectrum and electronic properties8,9,10,11. We address the nature of these height fluctuations by means of atomistic Monte Carlo simulations based on a very accurate many-body interatomic potential for carbon12. We find that ripples spontaneously appear owing to thermal fluctuations with a size distribution peaked around 80 A which is compatible with experimental findings7 (50–100 A). This unexpected result might be due to the multiplicity of chemical bonding in carbon.

Journal ArticleDOI
TL;DR: It is shown that ABO fails in graphene, a zero-bandgap semiconductor that becomes a metal if the Fermi energy is tuned applying a gate voltage, Vg, which induces a stiffening of the Raman G peak that cannot be described within ABO.
Abstract: The adiabatic Born-Oppenheimer approximation (ABO) has been the standard ansatz to describe the interaction between electrons and nuclei since the early days of quantum mechanics. ABO assumes that the lighter electrons adjust adiabatically to the motion of the heavier nuclei, remaining at any time in their instantaneous ground state. ABO is well justified when the energy gap between ground and excited electronic states is larger than the energy scale of the nuclear motion. In metals, the gap is zero and phenomena beyond ABO (such as phonon-mediated superconductivity or phonon-induced renormalization of the electronic properties) occur. The use of ABO to describe lattice motion in metals is, therefore, questionable. In spite of this, ABO has proved effective for the accurate determination of chemical reactions, molecular dynamics and phonon frequencies in a wide range of metallic systems. Here, we show that ABO fails in graphene. Graphene, recently discovered in the free state, is a zero-bandgap semiconductor that becomes a metal if the Fermi energy is tuned applying a gate voltage, Vg. This induces a stiffening of the Raman G peak that cannot be described within ABO.

Journal ArticleDOI
TL;DR: Key aspects of the physics of this approach, which has some features in common with related but comparatively low-resolution techniques for graphic arts, are revealed through direct high-speed imaging of the droplet formation processes.
Abstract: Efforts to adapt and extend graphic arts printing techniques for demanding device applications in electronics, biotechnology and microelectromechanical systems have grown rapidly in recent years. Here, we describe the use of electrohydrodynamically induced fluid flows through fine microcapillary nozzles for jet printing of patterns and functional devices with submicrometre resolution. Key aspects of the physics of this approach, which has some features in common with related but comparatively low-resolution techniques for graphic arts, are revealed through direct high-speed imaging of the droplet formation processes. Printing of complex patterns of inks, ranging from insulating and conducting polymers, to solution suspensions of silicon nanoparticles and rods, to single-walled carbon nanotubes, using integrated computer-controlled printer systems illustrates some of the capabilities. High-resolution printed metal interconnects, electrodes and probing pads for representative circuit patterns and functional transistors with critical dimensions as small as 1 μm demonstrate potential applications in printed electronics.

Journal ArticleDOI
TL;DR: This work has used highly faceted cubic Pt seeds to direct the epitaxial overgrowth of a secondary metal, and demonstrates this concept with lattice-matched Pd to produce conformal shape-controlled core-shell particles, and then extends it to lattices-mismatched Au to give anisotropic growth.
Abstract: Morphological control of nanocrystals has become increasingly important, as many of their physical and chemical properties are highly shape dependent. Nanocrystal shape control for both single- and multiple-material systems, however, remains empirical and challenging. New methods need to be explored for the rational synthetic design of heterostructures with controlled morphology. Overgrowth of a different material on well-faceted seeds, for example, allows for the use of the defined seed morphology to control nucleation and growth of the secondary structure. Here, we have used highly faceted cubic Pt seeds to direct the epitaxial overgrowth of a secondary metal. We demonstrate this concept with lattice-matched Pd to produce conformal shape-controlled core-shell particles, and then extend it to lattice-mismatched Au to give anisotropic growth. Seeding with faceted nanocrystals may have significant potential towards the development of shape-controlled heterostructures with defined interfaces.

Journal ArticleDOI
TL;DR: The demonstration of a four-state resistive memory element in a tunnel junction with multiferroic barriers represents a major step in this direction.
Abstract: Multiferroics might hold the future for the ultimate memory device. The demonstration of a four-state resistive memory element in a tunnel junction with multiferroic barriers represents a major step in this direction.

Journal ArticleDOI
TL;DR: This work shows that films of La (0.1)Bi(0.9)MnO(3) (LBMO) are ferromagnetic and ferroelectric, and retain both ferroic properties down to a thickness of 2 nm, and represents an advance over the original four-state memory concept based on multiferroics.
Abstract: Multiferroics are singular materials that can exhibit simultaneously electric and magnetic orders. Some are ferroelectric and ferromagnetic and provide the opportunity to encode information in electric polarization and magnetization to obtain four logic states. However, such materials are rare and schemes allowing a simple electrical readout of these states have not been demonstrated in the same device. Here, we show that films of La0.1Bi0.9MnO3 (LBMO) are ferromagnetic and ferroelectric, and retain both ferroic properties down to a thickness of 2 nm. We have integrated such ultrathin multiferroic films as barriers in spin-filter-type tunnel junctions that exploit the magnetic and ferroelectric degrees of freedom of LBMO. Whereas ferromagnetism permits read operations reminiscent of magnetic random access memories (MRAM), the electrical switching evokes a ferroelectric RAM write operation. Significantly, our device does not require the destructive ferroelectric readout, and therefore represents an advance over the original four-state memory concept based on multiferroics.

Journal ArticleDOI
TL;DR: This work presents a scalable and parallel process for transferring hundreds of pre-aligned silicon nanowires onto plastic to yield highly ordered films for low-power sensor chips, and uses SiO2 surface chemistries to construct a 'nano-electronic nose' library.
Abstract: The development of a robust method for integrating high-performance semiconductors on flexible plastics could enable exciting avenues in fundamental research and novel applications. One area of vital relevance is chemical and biological sensing, which if implemented on biocompatible substrates, could yield breakthroughs in implantable or wearable monitoring systems. Semiconducting nanowires (and nanotubes) are particularly sensitive chemical sensors because of their high surface-to-volume ratios. Here, we present a scalable and parallel process for transferring hundreds of pre-aligned silicon nanowires onto plastic to yield highly ordered films for low-power sensor chips. The nanowires are excellent field-effect transistors, and, as sensors, exhibit parts-per-billion sensitivity to NO2, a hazardous pollutant. We also use SiO2 surface chemistries to construct a ‘nano-electronic nose’ library, which can distinguish acetone and hexane vapours via distributed responses. The excellent sensing performance coupled with bendable plastic could open up opportunities in portable, wearable or even implantable sensors.

Journal ArticleDOI
TL;DR: This review surveys recent advances in the rapidly evolving area of irradiation effects in nanostructured materials, with particular emphasis on carbon systems because of their technological importance and the unique ability of graphitic networks to reconstruct under irradiation.
Abstract: Irradiating solids with energetic particles is usually thought to introduce disorder, normally an undesirable phenomenon. But recent experiments on electron or ion irradiation of various nanostructures demonstrate that it can have beneficial effects and that electron or ion beams may be used to tailor the structure and properties of nanosystems with high precision. Moreover, in many cases irradiation can lead to self-organization or self-assembly in nanostructures. In this review we survey recent advances in the rapidly evolving area of irradiation effects in nanostructured materials, with particular emphasis on carbon systems because of their technological importance and the unique ability of graphitic networks to reconstruct under irradiation. We dwell not only on the physics behind irradiation of nanostructures but also on the technical applicability of irradiation for nanoengineering of carbon and other systems.

Journal ArticleDOI
TL;DR: The present approach using a 2DEG provides a new route to realize practical thermoelectric materials without the use of toxic heavy elements and enhances the Seebeck coefficient without reducing the electrical conductivity.
Abstract: Enhancement of the Seebeck coefficient (S ) without reducing the electrical conductivity (sigma) is essential to realize practical thermoelectric materials exhibiting a dimensionless figure of merit (ZT=S2 x sigma x T x kappa-1) exceeding 2, where T is the absolute temperature and kappa is the thermal conductivity. Here, we demonstrate that a high-density two-dimensional electron gas (2DEG) confined within a unit cell layer thickness in SrTiO(3) yields unusually large |S|, approximately five times larger than that of SrTiO(3) bulks, while maintaining a high sigma2DEG. In the best case, we observe |S|=850 microV K-1 and sigma2DEG=1.4 x 10(3) S cm-1. In addition, by using the kappa of bulk single-crystal SrTiO(3) at room temperature, we estimate ZT approximately 2.4 for the 2DEG, corresponding to ZT approximately 0.24 for a complete device having the 2DEG as the active region. The present approach using a 2DEG provides a new route to realize practical thermoelectric materials without the use of toxic heavy elements.

Journal ArticleDOI
TL;DR: A striking enhancement of the catalytic activity of Rh particles confined inside nanotubes for the conversion of CO and H2 to ethanol within carbon and other nanotube systems is reported.
Abstract: Carbon nanotubes (CNTs) have well-defined hollow interiors and exhibit unusual mechanical and thermal stability as well as electron conductivity1. This opens intriguing possibilities to introduce other matter into the cavities2,3,4,5, which may lead to nanocomposite materials with interesting properties or behaviour different from the bulk6,7,8. Here, we report a striking enhancement of the catalytic activity of Rh particles confined inside nanotubes for the conversion of CO and H2 to ethanol. The overall formation rate of ethanol (30.0 mol mol−1Rh h−1) inside the nanotubes exceeds that on the outside of the nanotubes by more than an order of magnitude, although the latter is much more accessible. Such an effect with synergetic confinement has not been observed before in catalysis involving CNTs. We believe that our discovery may be of a quite general nature and could apply to many other processes. It is anticipated that this will motivate theoretical and experimental studies to further the fundamental understanding of the host–guest interaction within carbon and other nanotube systems.

Journal ArticleDOI
TL;DR: A sodium/lithium iron phosphate, A(2)FePO(4)F (A=Na, Li), that could serve as a cathode in either Li-ion or Na-ion cells and possesses facile two-dimensional pathways for Li+ transport, and the structural changes on reduction-oxidation are minimal.
Abstract: In the search for new positive-electrode materials for lithium-ion batteries, recent research has focused on nanostructured lithium transition-metal phosphates that exhibit desirable properties such as high energy storage capacity combined with electrochemical stability1,2. Only one member of this class—the olivine LiFePO4 (ref. 3)—has risen to prominence so far, owing to its other characteristics, which include low cost, low environmental impact and safety. These are critical for large-capacity systems such as plug-in hybrid electric vehicles. Nonetheless, olivine has some inherent shortcomings, including one-dimensional lithium-ion transport and a two-phase redox reaction that together limit the mobility of the phase boundary4,5,6,7. Thus, nanocrystallites are key to enable fast rate behaviour8,9. It has also been suggested that the long-term economic viability of large-scale Li-ion energy storage systems could be ultimately limited by global lithium reserves, although this remains speculative at present. (Current proven world reserves should be sufficient for the hybrid electric vehicle market, although plug-in hybrid electric vehicle and electric vehicle expansion would put considerable strain on resources and hence cost effectiveness.) Here, we report on a sodium/lithium iron phosphate, A2FePO4F (A=Na, Li), that could serve as a cathode in either Li-ion or Na-ion cells. Furthermore, it possesses facile two-dimensional pathways for Li+ transport, and the structural changes on reduction–oxidation are minimal. This results in a volume change of only 3.7% that—unlike the olivine—contributes to the absence of distinct two-phase behaviour during redox, and a reversible capacity that is 85% of theoretical.

Journal ArticleDOI
TL;DR: This study measures the composition and solid density of the principal binding reaction product of cement hydration, calcium-silicate-hydrate (C-S-H) gel, one of the most complex of all gels, and quantifies a nanoscale calcium hydroxide phase that coexists with C- S-H gel.
Abstract: Although Portland cement concrete is the world’s most widely used manufactured material, basic questions persist regarding its internal structure and water content, and their effect on concrete behaviour. Here, for the first time without recourse to drying methods, we measure the composition and solid density of the principal binding reaction product of cement hydration, calcium–silicate–hydrate (C–S–H) gel, one of the most complex of all gels. We also quantify a nanoscale calcium hydroxide phase that coexists with C–S–H gel. By combining small-angle neutron and X-ray scattering data, and by exploiting the hydrogen/deuterium neutron isotope effect both in water and methanol, we determine the mean formula and mass density of the nanoscale C–S–H gel particles in hydrating cement. We show that the formula, (CaO)1.7(SiO2)(H2O)1.80, and density, 2.604 Mg m−3, differ from previous values for C–S–H gel, associated with specific drying conditions. Whereas previous studies have classified water within C–S–H gel by how tightly it is bound, in this study we classify water by its location—with implications for defining the chemically active (C–S–H) surface area within cement, and for predicting concrete properties.

Journal ArticleDOI
TL;DR: A comparatively low-loss, three-dimensional, all-semiconductor metamaterial that exhibits negative refraction for all incidence angles in the long-wave infrared region and requires only an anisotropic dielectric function with a single resonance is demonstrated.
Abstract: An optical metamaterial is a composite in which subwavelength features, rather than the constituent materials, control the macroscopic electromagnetic properties of the material. Recently, properly designed metamaterials have garnered much interest because of their unusual interaction with electromagnetic waves. Whereas nature seems to have limits on the type of materials that exist, newly invented metamaterials are not bound by such constraints. These newly accessible electromagnetic properties make these materials an excellent platform for demonstrating unusual optical phenomena and unique applications such as subwavelength imaging and planar lens design. 'Negative-index materials', as first proposed, required the permittivity, epsilon, and permeability, mu, to be simultaneously less than zero, but such materials face limitations. Here, we demonstrate a comparatively low-loss, three-dimensional, all-semiconductor metamaterial that exhibits negative refraction for all incidence angles in the long-wave infrared region and requires only an anisotropic dielectric function with a single resonance. Using reflection and transmission measurements and a comprehensive model of the material, we demonstrate that our material exhibits negative refraction. This is furthermore confirmed through a straightforward beam optics experiment. This work will influence future metamaterial designs and their incorporation into optical semiconductor devices.

Journal ArticleDOI
TL;DR: In this paper, the authors proposed an approach to the self-assembly of anisotropic nanoparticles by using the strategies that are established for the selfassembly of block copolymers.
Abstract: Organized arrays of anisotropic nanoparticles show electronic and optical properties that originate from the coupling of shape-dependent properties of the individual nanorods. The organization of nanorods in a controllable and predictable way provides a route to the fabrication of new materials and functional devices. So far, significant progress has been achieved in the self-assembly of nanorod arrays, yet the realization of a range of different structures requires changing the surface chemistry of the nanoparticles. We organized metal nanorods in structures with varying geometries by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polymer chains at both ends. The self-assembly was tuneable and reversible and it was achieved solely by changing the solvent quality for the constituent blocks. This approach provides a new route to the organization of anisotropic nanoparticles by using the strategies that are established for the self-assembly of block copolymers.

Journal ArticleDOI
TL;DR: A bimodal microporous twofold interpenetrating network is designed and synthesized, showing the first case of controlled sorption properties in flexible porous frameworks.
Abstract: Introducing a functional part into open-framework materials that tunes the pore size/shape and overall porous activity will open new routes in framework engineering and in the fabrication of new materials. We have designed and synthesized a bimodal microporous twofold interpenetrating network {[Ni(bpe)2(N(CN)2)](N(CN)2)(5H2O)}n (1), with two types of channel for anionic N(CN)2- (dicyanamide) and neutral water molecules, respectively. The dehydrated framework provides a dual function of specific anion exchange of free N(CN)2- for the smaller N3- anions and selective gas sorption. The N3-exchanged framework leads to a dislocation of the mutual positions of the two interpenetrating frameworks, resulting in an increase in the effective pore size in one of the counterparts of the channels and a higher accommodation of adsorbate than in the as-synthesized framework (1), showing the first case of controlled sorption properties in flexible porous frameworks.