Katsutoshi Fukuda

Construction of highly ordered lamellar nanostructures through Langmuir-Blodgett deposition of molecularly thin titania nanosheets tens of micrometers wide and their excellent dielectric properties.

Exfoliated unilamellar titania nanosheets of Ti(0.87)O(2) with a lateral size of 10-30 microm were deposited layer-by-layer onto various substrates by Langmuir-Blodgett procedure to produce a highly ordered lamellar nanofilms. The nanosheets dispersed in an aqueous suspension containing quaternary ammonium ions as a supporting electrolyte floated spontaneously at the air/liquid interface, and they were successfully transferred onto the substrate after surface compression. Neat tiling of the nanosheets could be realized at an optimized surface pressure. The film thus obtained was exposed to UV light to turn the substrate surface hydrophilic, which was helpful for stable repetition of monolayer deposition. Layer-by-layer growth was confirmed by UV-visible absorption spectra, which showed progressive enhancement of an absorption band due to the nanosheet. Cross-sectional transmission electron microscopy images visualized the ultrathin film homogeneously deposited on the substrate surface and a lamellar fringe of the layer-by-layer assembled nanosheets was clearly resolved at a higher magnification. X-ray diffraction data on the films showed sharp basal reflections up to the seventh order, and Williamson-Hall analysis of the pattern indicated that the film was coherent across the total thickness with respect to X-ray and that the lattice strain was extremely small. In addition, the first basal reflection was accompanied by small satellite peaks, which are accounted for by the Laue interference function. All these features clearly indicate the formation of a highly ordered lamellar nanostructure of the titania nanosheets comparable to artificial lattice films produced via modern vapor-phase deposition processes. The obtained films showed superior dielectric and insulating properties as a reflection of the highly organized film nanoarchitecture.

Direct Observation of a Metastable Crystal Phase of LixFePO4 under Electrochemical Phase Transition

The phase transition between LiFePO4 and FePO4 during nonequilibrium battery operation was tracked in real time using time-resolved X-ray diffraction. In conjunction with increasing current density, a metastable crystal phase appears in addition to the thermodynamically stable LiFePO4 and FePO4 phases. The metastable phase gradually diminishes under open-circuit conditions following electrochemical cycling. We propose a phase transition path that passes through the metastable phase and posit the new phases role in decreasing the nucleation energy, accounting for the excellent rate capability of LiFePO4. This study is the first to report the measurement of a metastable crystal phase during the electrochemical phase transition of LixFePO4.

Exfoliated Nanosheet Crystallite of Cesium Tungstate with 2D Pyrochlore Structure: Synthesis, Characterization, and Photochromic Properties

Layered cesium tungstate, Cs(6+x)W(11)O(36), with two-dimensional (2D) pyrochlore structure was exfoliated into colloidal unilamellar sheets through a soft-chemical process. Interlayer Cs ions were replaced with protons by acid exchange, and quaternary ammonium ions were subsequently intercalated under optimized conditions. X-ray diffraction (XRD) measurements on gluelike sediment recovered from the colloidal suspension by centrifugation showed a broad pattern of a pronounced wavy profile, which closely matched the square of calculated structure factor for the single host layer. This indicates the total delamination of the layered tungstate into nanosheets of Cs(4)W(11)O(36)(2-). Microscopic observations by transmission electron microscopy and atomic force microscopy clearly revealed the formation of unilamellar crystallites with a very high 2D anisotropy, a thickness of only approximately 2 nm versus lateral size up to several micrometers. In-plane XRD analysis confirmed that the 2D pyrochlore structure was retained. The colloidal cesium tungstate nanosheet showed strong absorption of UV light with sharp onset, suggesting a semiconducting nature. Analysis of the absorption profile provided 3.6 eV as indirect band gap energy, which is 0.8 eV larger than that of the bulk layered precursor, probably due to size quantization. The nanosheet exhibited highly efficient photochromic properties, showing reversible color change upon UV irradiation.

Synthesis of Nanosheet Crystallites of Ruthenate with an α-NaFeO2-Related Structure and Its Electrochemical Supercapacitor Property

Unilamellar crystallites of conductive ruthenium oxide having a thickness of about 1 nm were obtained via elemental exfoliation of a protonic layered ruthenate, H(0.2)RuO(2).0.5H(2)O, with an alpha-NaFeO(2)-related crystal structure. The obtained RuO(2) nanosheets possessed a well-defined crystalline structure with a hexagonal symmetry, reflecting the crystal structure of the parent material. The restacked RuO(2) nanosheets exhibited a high pseudocapacitance of approximately 700 F g(-1) in an acidic electrolyte, which is almost double the value of the nonexfoliated layered protonated ruthenate.

Titanoniobate and niobate nanosheet photocatalysts: superior photoinduced hydrophilicity and enhanced thermal stability of unilamellar Nb3O8 nanosheet

Unique photocatalysts based on novel two-dimensional (2D) oxide nanosheets have been synthesized and their photochemical activity has been examined. Monolayer films of titanoniobate and niobate (TiNbO5, Ti2NbO7, Ti5NbO14, and Nb3O8) nanosheets, synthesized by exfoliating layered oxide precursors through a soft-chemical procedure, were fabricated on quartz glass substrate via a sequential adsorption method. All the nanosheet films exhibited good photoinduced hydrophilicity, while their oxidation activity was very low. This behavior can be regarded as inherent features of nanosheet-type photocatalysts having molecularly thin 2D anisotropy. Such ultrathin flexible structures are advantageous for facilitating photo-driven surface wettability change. Especially, the hydrophilic conversion property of Nb3O8 nanosheet was highly efficient, showing activity that was at least one order of magnitude superior to that of the widely used photocatalyst film of polycrystalline anatase TiO2. Moreover, the monolayer film of Nb3O8 nanosheet was found to have enhanced thermal stability and chemical resistance, particularly against diffusion of sodium ions at elevated temperature: Nb3O8 nanosheet film heated on sodium-rich glass (soda-lime glass) substrate maintained excellent hydrophilic conversion activity, whereas Ti0.87O2 nanosheet as well as anatase (TiO2) based photocatalysts was virtually deactivated. These features are a great advantage of Nb3O8 nanosheet photocatalysts for developing the practical super-hydrophilic applications where post-annealing is indispensable.

All-Nanosheet Ultrathin Capacitors Assembled Layer-by-Layer via Solution-Based Processes

All-nanosheet ultrathin capacitors of Ru0.95O20.2-/Ca2Nb3O10-/Ru0.95O20.2- were successfully assembled through facile room-temperature solution-based processes. As a bottom electrode, conductive Ru0.95O20.2- nanosheets were first assembled on a quartz glass substrate through a sequential adsorption process with polycations. On top of the Ru0.95O20.2- nanosheet film, Ca2Nb3O10- nanosheets were deposited by the Langmuir-Blodgett technique to serve as a dielectric layer. Deposition parameters were optimized for each process to construct a densely packed multilayer structure. The multilayer buildup process was monitored by various characterizations such as atomic force microscopy (AFM), ultraviolet-visible absorption spectra, and X-ray diffraction data, which provided compelling evidence for regular growth of Ru0.95O20.2- and Ca2Nb3O10- nanosheet films with the designed multilayer structures. Finally, an array of circular films (50 μm ϕ) of Ru0.95O20.2- nanosheets was fabricated as top electrodes on the as-deposited nanosheet films by combining the standard photolithography and sequential adsorption processes. Microscopic observations by AFM and cross-sectional transmission electron microscopy, as well as nanoscopic elemental analysis, visualized the sandwich metal-insulator-metal structure of Ru0.95O20.2-/Ca2Nb3O10-/Ru0.95O20.2- with a total thickness less than 30 nm. Electrical measurements indicate that the system really works as an ultrathin capacitor, achieving a capacitance density of ∼27.5 μF cm(-2), which is far superior to currently available commercial capacitor devices. This work demonstrates the great potential of functional oxide nanosheets as components for nanoelectronics, thus contributing to the development of next-generation high-performance electronic devices.

Tantalum oxide nanomesh as self-standing one nanometre thick electrolyte

Tantalum oxide (TaO3) nanosheets coated on the surface of a LiCoO2 cathode decrease its interfacial resistance in a solid-state battery by two orders of magnitude. Since the interfacial resistance is rate-determining in the solid-state system, the interfacial structure of the nanosheet is anticipated to pave the way for realising high-performance solid-state lithium batteries. The reduction in the interfacial resistance also strongly suggests that the TaO3 nanosheet is a self-standing solid electrolyte layer with an ultimate thinness of 1 nm. It has a wide band gap and a mesh structure with openings that are almost the same in size as the lithium ion, which prevents electronic conduction and allows the penetration of lithium ions, respectively.

Conductivity of ruthenate nanosheets prepared via electrostatic self-assembly: characterization of isolated single nanosheet crystallite to mono- and multilayer electrodes.

Ultrathin films composed of ruthenate nanosheets (RuO(2)ns) were fabricated via electrostatic self-assembly of unilamellar RuO(2)ns crystallites derived by total exfoliation of an ion-exchangeable layered ruthenate. Ultrathin films with submonolayer to monolayer RuO(2)ns coverage and multilayered RuO(2)ns thin films were prepared by controlled electrostatic self-assembly and layer-by-layer deposition using a cationic copolymer as the counterion. Electrical properties of a single RuO(2)ns crystallite were successfully measured by means of scanning probe microscopy. The sheet resistance of an isolated single RuO(2)ns crystallite was 12 kΩ sq(-1). Self-assembled submonolayer films behaved as a continuous conducting film for coverage above 70%, which was discussed based on a two-dimensional percolation model. Low sheet resistance was attained for multilayered films with values less than 1 kΩ sq(-1). Interestingly, the grain boundary resistance between nanosheets seems to contribute only slightly to the sheet resistance of self-assembled films.

Photochromogenic Nanosheet Crystallites of Tungstate with a 2D Bronze Structure

Layered rubidium tungstate, Rb(4)W(11)O(35), with a two-dimensional (2D) bronze-type tunnel structure was successfully delaminated into colloidal nanosheets via a soft-chemical process involving acid exchange and subsequent intercalation of tetrabutylammonium ions. Characterizations by transmission electron microscopy and atomic force microscopy confirmed the formation of unilamellar 2D nanosheet crystallites with a unique thickness of ∼3 nm and an average lateral size of 400 nm. The obtained nanosheets exhibited reversible color change upon UV-light excitation via an optical band gap of 3.5 eV. The ultimate 2D aspect ratio favorable for an adsorption of charge-compensating cations to trapped electrons working as a color center is presumably responsible for highly efficient photochromic behavior. Its coloration mainly consists of a broad band at a wavelength of 1800 nm and longer, which is much different from that of the common tungstate nanomaterials. Thus, the chromogenic nanosheet obtained in this study features the intense UV absorption and optically switchable visible-to-IR absorption, which may be useful for window applications such as cutoff filters and heat-absorbing films.

High Thermal Robustness of Molecularly Thin Perovskite Nanosheets and Implications for Superior Dielectric Properties

A systematic study has been conducted to examine the thermal stability of layer-by-layer assembled films of perovskite-type nanosheets, (Ca2Nb3O10(-))n (n = 1-10), which exhibit superior dielectric and insulating properties. In-plane and out-of-plane X-ray diffraction data as well as observations by atomic force microscopy and transmission electron microscopy indicated the high thermal robustness of the nanosheet films. In a monolayer film with an extremely small thickness of ∼2 nm, the nanosheet was stable up to 800 °C, the temperature above which segregation into CaNb2O6 and Ca2Nb2O7 began. The critical temperature moderately decreased as the film thickness, or the number of nanosheet layers, increased, and reached 700 °C for seven- and 10-layer films, which is comparable to the phase transformation temperature for a bulk phase of the protonic layered oxide of HCa2Nb3O10·1.5H2O as a precursor of the nanosheet. This thermal stabilization of perovskite-type nanosheets should be associated with restricted nucleation and crystal growth peculiar to such ultrathin 2D bound systems. The stable high-k dielectric response (εr = 210) and highly insulating nature (J < 10(-7) A cm(-2)) remained substantially unchanged even after the nanosheet film was annealed up to 600 °C. This study demonstrates the high thermal stability of 2D perovskite-type niobate nanosheets in terms of structure and dielectric properties, which suggests promising potential for future high-k devices operable over a wide temperature range.