The Effect of Nutrients on Subjective Accomplishment at Work: Results from a Health Survey and a Single-Arm Dietary Intervention Study.

In Japan, many workers are exposed to chronic stress, sleep deprivation, and nutritional imbalance. They tend still to go to work when ill, leading to decreased work performance and productivity, which has become a major social problem. We conducted a human entry study with the aim of finding a link between these two factors and proposing an optimized diet, believing that a review of diet may lead to an improvement in labor productivity. In this study, we used subjective accomplishment (SA) as a measure of productivity. First, we compared nutrient intake between groups with high and low SA using data from a health survey of 1564 healthy male and female adults. Significant differences were found in the intake of 13 nutrients in males and 15 nutrients in females, including potassium, vitamin A, insoluble fiber, and biotin. Recommended daily intake of these nutrients was determined from survey data. Next, we designed test meals containing sufficient amounts of 17 nutrients and conducted a single-arm intervention study (registration code UMIN000047054) in Kameyama City, Mie Prefecture, Japan. Healthy working adults (males and females aged 20-79 years) were recruited and supplied with test meals, which were eaten once a day 5 days a week for 8 weeks. SA was significantly higher and daytime sleepiness (DS) was significantly lower after lunch on workdays in younger participants (under 60 years) when they ate the test meals as breakfast or lunch. Our results suggest that SA and DS, which change daily, are strongly influenced by the meal eaten before work, and that taking the 17 nutrients may help prevent presenteeism and improve labor productivity.

Enhancing Up-Conversion Luminescence Using Dielectric Metasurfaces: Role of the Quality Factor of Resonance at a Pumping Wavelength.

Photonic applications of up-conversion luminescence (UCL) suffer from poor external quantum yield owing to a low absorption cross-section of UCL nanoparticles (UCNPs) doped with lanthanide ions. In this regard, plasmonic nanostructures have been proposed for enhancing UCL intensity through strong electromagnetic local-field enhancement; however, their intrinsic ohmic loss opens additional nonradiative decay channels. Herein, we demonstrate that dielectric metasurfaces can overcome this disadvantage. A periodic array of amorphous-silicon nanodisks serves as a metasurface on which a layer of UCNPs is self-assembled. Sharp resonances supported by the metasurface overlap the absorption wavelength (λ = 980 nm) of UCNPs to excite them, resulting in the enhancement of UCL intensity. We further sharpen the resonances through rapid thermal annealing (RTA) of the metasurface, crystallizing silicon to reduce intrinsic optical losses. By optimizing the RTA condition (at 1000 °C for 20 min in N2/H2 (3 vol %) atmosphere), the resonance quality factor improves from 17.2 to 32.9, accompanied by an increase in the enhancement factor of the UCL intensity from 86- to over 600-fold. Moreover, a reduction in the intrinsic optical losses mitigates the UCL thermal quenching under a high excitation density. These findings provide a strategy for increasing light-matter interactions in nanophotonic composite systems and promote UCNP applications.

Up-to-Five-Photon Upconversion from Near-Infrared to Ultraviolet Luminescence Coupled to Aluminum Plasmonic Lattices.

The incorporation of upconversion luminescence (UCL) materials into various plasmonic structures promotes light-matter interactions in nanophotonic systems. It has been experimentally demonstrated that UCL enhancement entailing two photons exhibits a quadratic dependence on the excitation intensity. However, in the field of plasmonics, there have not been sufficient studies on high-order multi-photon upconversion processes. We report up-to-five-photon UCL, wherein λ = 1550 nm near-infrared light is converted to 382 nm ultraviolet light, from core-inert shell nanoparticles coupled to aluminum plasmonic lattices. The five-photon UCL intensity of nanoparticles on the plasmonic lattice is over 800 times stronger than that on the flat glass. We demonstrate that the enhancement of UCL scales with the nth power of the local field enhancement for n-photon process. These findings give a strategy to obtain high-order multi-photon UPL with aluminum plasmonic nanostructures and can contribute to anti-counterfeiting application.

Collective plasmonic resonances enhance the photoluminescence of rare-earth nanocrystal films processed by ultrafast annealing.

Herein, we demonstrate that rapid thermal annealing allows achieving close-to-one photoluminescence quantum yield while preserving the transparency of rare-earth nanocrystal films, which further enables their integration with nanophotonics. The combination with periodic arrays of aluminum nanodisks that support collective plasmonic resonances leads to enhanced directional emission.

Unique octahedral rotation pattern in the oxygen-deficient Ruddlesden-Popper compound Gd3Ba2Fe4O12.

A novel Ruddlesden-Popper-related compound, Gd3Ba2Fe4O12, was discovered and its crystal structure was determined via single-crystal X-ray diffraction. The structure has an ordered structure of octahedra and pyramids along the c axis. Gd3Ba2Fe4O12 belongs to the tetragonal system P42/ncm, with a = 5.59040 (10) Šand c = 35.1899 (10) Å. The A-site ions in the Ruddlesden-Popper structure, i.e. Gd3+ and Ba2+, exhibit an ordering along the c axis. The perfect oxygen deficiency is accommodated at the GdO layers in the proper Ruddlesden-Popper structure. Using the bond-valence-sum method, the Fe ions in the FeO6 octahedra and FeO5 pyramids represent valence states of +3 and +2.5, respectively, demonstrating a two-dimensional charge disproportionation. The corner-sharing FeO6 octahedra and FeO5 pyramids are tilted in opposite directions, with the neighbours around one axis of the simple perovskite configuration, which, using Glazer's notation, can be represented as a-b0c0/b0a-c0. In the perovskite blocks, the facing FeO5 pyramids across the Gd layer rotate in the same sense, which is a unique rotation feature related to oxygen deficiency.

Evidence of the retardation effect on the plasmonic resonances of aluminum nanodisks in the symmetric/asymmetric environment.

A single metallic nanodisk is the simplest plasmonic nanostructure, but it is robust enough to generate a Fano resonance in the forward and backward scattering spectra by the increment of nanodisk height in the symmetric and asymmetric dielectric environment. Thanks to the phase retardation effect, the non-uniform distribution of electric field along the height of aluminum (Al) nanodisk generates the out-of-plane higher-order modes, which interfere with the dipolar mode and subsequently result in the Fano-lineshape scattering spectra. Meanwhile, the symmetry-breaking effect by the dielectric substrate and the increment of refractive index of the symmetric dielectric environment further accelerate the phase retardation effect and contribute to the appearance of out-of-plane modes. The experimental results on the periodic Al nanodisk arrays with different heights confirm the retardation-induced higher modes in the asymmetric and symmetric environment. The appearance of higher modes and blueshifted main dips in the transmission spectra prove the dominant role of out-of-plane higher modes on the plasmonic resonances of the taller Al nanodisk.

Broadband scattering by an aluminum nanoparticle array as a white pixel in commercial color printing applications.

Plasmonic color using metallic nanostructures has attracted considerable interest because of its subwavelength resolution and long sustainability. Significant efforts have been devoted to expanding the gamut of plasmonic color generation by tuning the composition, shape, and components in the primary pixel. In this study, we develop a novel and straightforward strategy for aluminum plasmonic color printing aimed at practical commercial applications. An array of aluminum nanodisks is designed for the broadband scattering of white pixels instead of the three primary colors. Examples presented include trademark and QR codes, which are common in the market of consumer advertising and item identification, that are encoded and fabricated in experiments with aluminum white color pixels to demonstrate feasibility. This simple and efficient strategy is compatible with cost-effective industrial fabrication methods, such as photolithography and nanoimprinting, and requires relatively simpler manufacturing procedures. Therefore, a new path is opened for the future with the extensive use of plasmonic color printing.

Spin glass transition of single-crystalline TmFe2O4- δ.

TmFe2O4 is one kind of multiferroic material in which equivalent amounts of Fe2+ and Fe3+ occupy a two-dimensional triangular lattice, leading to charge and spin frustrations. The spin frustration is expected to be increased as the fraction of Fe2+ (Fe3+) becomes larger than that of Fe3+ (Fe2+). We have grown single-crystalline TmFe2O4-δ with oxygen vacancies by using floating zone melting method and examined its magnetic properties. On cooling the compound, a long-range magnetic ordering develops around ∼240 K. With further cooling, a maximum of zero-field-cooled (ZFC) magnetization is observed at 186.2 K. The ac magnetic susceptibility obtained by ZFC process also manifests a maximum in its temperature dependence, and the variation of spin-freezing temperature with frequency of ac magnetic field is explainable in terms of the dynamic scaling law with the critical component of 8.68(8). This value suggests that the spin glass transition occurs at 186.2 K. The effect of external dc magnetic field on the irreversible transition temperature is coincident with the de Almeida-Thouless (AT) line. Aging-memory and rejuvenation effect is also observed below the spin-freezing temperature. These facts support the idea that TmFe2O4-δ undergoes spin glass transition below the ferrimagnetic transition temperature. In other words, TmFe2O4-δ can be regarded as a reentrance spin glass. It is thought that the oxygen vacancies bring about unequal number of Fe2+ and Fe3+ ions and thereby strengthen the magnetic frustration among the iron ions coupled with antiferromagnetic interactions, leading to the spin glass behavior.

Optical Responses of Localized and Extended Modes in a Mesoporous Layer on Plasmonic Array to Isopropanol Vapor.

Mesoporous silica features open and accessible pores that can intake substances from the outside. The combination of mesoporous silica with plasmonic nanostructures represents an interesting platform for an optical sensor based on the dependence of plasmonic modes on the refractive index of the medium in which metallic nanoparticles are embedded. However, so far only a limited number of plasmonic nanostructures are combined with mesoporous silica, including random dispersion of metallic nanoparticles and flat metallic thin films. In this study, we make a mesoporous silica layer on an aluminum nanocylinder array. Such plasmonic arrangements support both localized surface plasmon resonances (LSPRs) and extended modes which are the result of the hybridization of LSPRs and photonic modes extending into the mesoporous layer. We investigate in situ optical reflectance of this system under controlled pressure of isopropanol vapor. Upon exposure, the capillary condensation in the mesopores results in a gradual spectral shift of the reflectance. Our analysis demonstrates that such shifts depend largely on the nature of the modes; that is, the extended modes show larger shifts compared to localized ones. Our materials represent a useful platform for the field of environmental sensing.

Enhancing upconversion photoluminescence by plasmonic-photonic hybrid mode.

Upconversion photoluminescence (UCPL) of rare-earth ions has attracted much attention due to its potential application in cell labeling, anti-fake printing, display, solar cell and so forth. In spite of high internal quantum yield, they suffer from very low external quantum yield due to poor absorption cross-section of rare-earth ions. In the present work, to increase the absorption by rare earth ions, we place the emitter layer on a diffractive array of Al nanocylinders. The array is designed to trap the near infrared light in the emitter layer via excitation of the plasmonic-photonic hybrid mode, a collective resonance of localized surface plasmons in nanocylinders via diffractive coupling. The trapped near-infrared light is absorbed by the emitter, and consequently the intensity of UCPL increases. In sharp contrast to the pure localized surface plasmons which are bound to the surface, the hybridization with diffraction allows the mode to extend into the layer, and the enhancement up to 9 times is achieved for the layer with 5.7 µm thick. This result explicitly demonstrates that coupling the excitation light to plasmonic-photonic hybrid modes is a sensible strategy to enhance UCPL from a thick layer.

Enhanced absorption and photoluminescence from dye-containing thin polymer film on plasmonic array.

Thin films containing light emitters act as light-to-light converters that absorb the incident light and emit luminescence. This well-known phenomenon is photoluminescence (PL). When a photoluminescent film is notably thinner than the absorption length of emitters, it exhibits weak absorption of incident light. The absorption can be increased by depositing the thin film on a plasmonic array of metallic nanocylinders arranged with a specific periodicity. The array couples the incident light into the thin film, facilitating the plasmon-enhanced absorption by the emitters in the film. In this study, we demonstrate both experimentally and numerically the plasmon-enhanced absorption of a rhodamine 6G-containing film that is thinner than its absorption length using a periodic array of Al nanocylinders. The experimental results demonstrate that the spectrally integrated PL intensity is increased up to 3.78 times. In addition to enhanced absorption, the array is also found to diffract the PL into a direction determined by the periodicity, thereby facilitating the multiplied enhancement of PL. The combination of the two factors yields a PL intensity enhanced up to 10 times at a specific angle and wavelength. Numerical simulations combining the carrier kinetics with full-wave electromagnetics in the time-domain support the experimental observations.

Demonstration of temperature-plateau superheated liquid by photothermal conversion of plasmonic titanium nitride nanostructures.

A liquid can be heated up above its boiling point, known as superheating. In this metastable state, the liquid temperature keeps increasing as the liquid is being heated. In contrast, we experimentally demonstrate that the temperature of superheated water can be kept constant even at elevated heating power. Water heating is done by the photothermal conversion of plasmonic titanium nitride nanostructures on a sapphire substrate under the illumination of continuous wave laser irradiation. The temperature-constant superheating is also observed for ethylene glycol and 2-acetoxy-1-methoxypropane, and is attributed to the high thermal conductivity of the substrate. This unique superheating yet achieved by a simple method can be useful in optical trapping and various optical heating applications.

Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond: Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden-Popper Phases.

Hybrid improper ferroelectricity, which utilizes nonpolar but ubiquitous rotational/tilting distortions to create polarization, offers an attractive route to the discovery of new ferroelectric and multiferroic materials because its activity derives from geometric rather than electronic origins. Design approaches blending group theory and first principles can be utilized to explore the crystal symmetries of ferroelectric ground states, but in general, they do not make accurate predictions for some important parameters of ferroelectrics, such as Curie temperature ( TC). Here, we establish a predictive and quantitative relationship between TC and the Goldschmidt tolerance factor, t, by employing n = 2 Ruddlesden-Popper (RP) A3B2O7 as a prototypical example of hybrid improper ferroelectrics. The focus is placed on an RP system, (Sr1- xCa x)3Sn2O7 ( x = 0, 0.1, and 0.2), which allows for the investigation of the purely geometric (ionic size) effect on ferroelectric transitions, due to the absence of the second-order Jahn-Teller active (d0 and 6s2) cations that often lead to ferroelectric distortions through electronic mechanisms. We observe a ferroelectric-to-paraelectric transition with TC = 410 K for Sr3Sn2O7. We also find that the TC increases linearly up to 800 K upon increasing the Ca2+ content, i.e., upon decreasing the value of t. Remarkably, this linear relationship is applicable to the suite of all known A3B2O7 hybrid improper ferroelectrics, indicating that the  TC correlates with the simple crystal chemistry descriptor, t, based on the ionic size mismatch. This study provides a predictive guideline for estimating the TC of a given material, which would complement the convergent group-theoretical and first-principles design approach.

Collective plasmonic modes excited in Al nanocylinder arrays in the UV spectral region.

A periodic array of plasmonic nanocylinders can sustain both surface plasmon polaritons (SPPs) and optical diffraction in the plane of the array. Thus the optical energy can be efficiently trapped in the plane of the array, providing a good platform for controlling light. Plasmonic arrays have been investigated in the visible range, while studies in the ultraviolet (UV) range have been limited due to material-related restrictions and higher precision required for optical diffraction in the UV compared to that in the visible range. In this study, we fabricated periodic arrays of Al nanocylinders with periods comparable to optical wavelengths in the UV for simultaneous excitation of both SPPs and optical diffraction in the UV spectral region. We deposited UV-absorbing and highly luminous dielectric films on the arrays, observed enhanced photoluminescence of the film under UV laser excitation, and demonstrated that such periodic arrays can trap the UV light energy. Our findings show that periodic arrays of Al nanocylinders are useful for controlling UV light.

Perovskite-Type InCoO3 with Low-Spin Co3+: Effect of In-O Covalency on Structural Stabilization in Comparison with Rare-Earth Series.

Perovskite rare-earth cobaltites ACoO3 (A = Sc, Y, La-Lu) have been of enduring interest for decades due to their unusual structural and physical properties associated with the spin-state transitions of low-spin Co3+ ions. Herein, we have synthesized a non-rare-earth perovskite cobaltite, InCoO3, at 15 GPa and 1400 °C and investigated its crystal structure and magnetic ground state. Under the same high-pressure and high-temperature conditions, we also prepared a perovskite-type ScCoO3 with an improved cation stoichiometry in comparison to that in a previous study, where synthesis at 6 GPa and 1297 °C yielded a perovskite cobaltite with cation mixing on the A-site, (Sc0.95Co0.05)CoO3. The two perovskite phases have nearly stoichiometric cation compositions, crystallizing in the orthorhombic Pnma space group. In the present investigation, comprehensive studies on newly developed and well-known Pnma ACoO3 perovskites (A = In, Sc, Y, Pr-Lu) show that InCoO3 does not fulfill the general evolution of crystal metrics with A-site cation size, indicating that InCoO3 and rare-earth counterparts have different chemistry for stabilizing the Pnma structures. Detailed structural analyses combined with first-principles calculations reveal that the origin of the anomaly for InCoO3 is ascribed to the A-site cation displacements that accompany octahedral tilts; despite the highly tilted CoO6 network, the In-O covalency makes In3+ ions reluctant to move from their ideal cubic-symmetry position, leading to less orthorhombic distortion than would be expected from electrostatic/ionic size mismatch effects. Magnetic studies demonstrate that InCoO3 and ScCoO3 are diamagnetic with a low-spin state of Co3+ below 300 K, in contrast to the case of (Sc0.95Co0.05)CoO3, where the high-spin Co3+ ions on the A-site generate a large paramagnetic moment. The present work extends the accessible composition range of the low-spin orthocobaltite series and thus should help to establish a more comprehensive understanding of the structure-property relation.

Giant Faraday Rotation through Ultrasmall Fe0n Clusters in Superparamagnetic FeO-SiO2 Vitreous Films.

Magnetooptical (MO) glasses and, in particular, Faraday rotators are becoming key components in lasers and optical information processing, light switching, coding, filtering, and sensing. The common design of such Faraday rotator materials follows a simple path: high Faraday rotation is achieved by maximizing the concentration of paramagnetic ion species in a given matrix material. However, this approach has reached its limits in terms of MO performance; hence, glass-based materials can presently not be used efficiently in thin film MO applications. Here, a novel strategy which overcomes this limitation is demonstrated. Using vitreous films of xFeO·(100 - x)SiO2, unusually large Faraday rotation has been obtained, beating the performance of any other glassy material by up to two orders of magnitude. It is shown that this is due to the incorporation of small, ferromagnetic clusters of atomic iron which are generated in line during laser deposition and rapid condensation of the thin film, generating superparamagnetism. The size of these clusters underbids the present record of metallic Fe incorporation and experimental verification in glass matrices.

Instability of spin glass phase in divalent iron phosphate glass under a magnetic field.

The spin glass behaviour of 50FeO · 50P2O5 (in mol%) glass has been examined under finite magnetic fields. The Sherrington-Kirkpatrick (SK) model, i.e. the mean field theory, is unsuitable for the interpretation of the frequency dependence of the ac magnetic susceptibility observed under an external field of 0.1 T; the critical exponent derived from the SK model is unphysically large. On the other hand, the droplet model explains well the frequency and field dependence of the spin-freezing temperature and the exponent of the thermally activated process is within the range defined by the droplet model. The results indicate that the spin glass phase of the 50FeO · 50P2O5 glass is unstable against magnetic fields.

ZnTaO2N: Stabilized High-Temperature LiNbO3-type Structure.

By using a high-pressure reaction, we prepared a new oxynitride ZnTaO2N that crystallizes in a centrosymmetric (R3̅c) high-temperature LiNbO3-type structure (HTLN-type). The stabilization of the HTLN-type structure down to low temperatures (at least 20 K) makes it possible to investigate not only the stability of this phase, but also the phase transition to a noncentrosymmetric (R3c) LiNbO3-type structure (LN-type) which is yet to be clarified. Synchrotron and neutron diffraction studies in combination with transmission electron microscopy show that Zn is located at a disordered 12c site instead of 6a, implying an order-disorder mechanism of the phase transition. It is found that the closed d-shell of Zn2+, as well as the high-valent Ta5+ ion, is responsible for the stabilization of the HTLN-type structure, affording a novel quasitriangular ZnO2N coordination. Interestingly, only 3% Zn substitution for MnTaO2N induces a phase transition from LN- to HTLN-type structure, implying the proximity in energy between the two structural types, which is supported by the first-principles calculations.

Topochemical Nitridation with Anion Vacancy-Assisted N(3-)/O(2-) Exchange.

We present how the introduction of anion vacancies in oxyhydrides enables a route to access new oxynitrides, by conducting ammonolysis of perovskite oxyhydride EuTiO3-xHx (x ∼ 0.18). At 400 °C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi(3.82+)O2.82H0.18, leading to the N(3-)/H(-)-exchanged product EuTi(4+)O2.82N0.12□0.06. When the ammonolysis temperature was increased up to 800 °C, we observed a further nitridation involving N(3-)/O(2-) exchange, yielding a fully oxidized Eu(3+)Ti(4+)O2N with the GdFeO3-type distortion (Pnma) as a metastable phase, instead of pyrochlore structure. Interestingly, the same reactions using the oxide EuTiO3 proceeded through a 1:1 exchange of N(3-) with O(2-) only above 600 °C and resulted in incomplete nitridation to EuTiO2.25N0.75, indicating that anion vacancies created during the initial nitridation process of EuTiO2.82H0.18 play a crucial role in promoting anion (N(3-)/O(2-)) exchange at high temperatures. Hence, by using (hydride-induced) anion-deficient precursors, we should be able to expand the accessible anion composition of perovskite oxynitrides.

Plasmonic arrays of titanium nitride nanoparticles fabricated from epitaxial thin films.

We have fabricated two-dimensional periodic arrays of titanium nitride (TiN) nanoparticles from epitaxial thin films. The thin films of TiN, deposited on sapphire and single crystalline magnesium oxide substrates by a pulsed laser deposition, are metallic and show reasonably small optical loss in the visible and near infrared regions. The thin films prepared were structured to the arrays of nanoparticles with the pitch of 400 nm by the combination of nanoimprint lithography and reactive ion etching. Optical transmission indicates that the arrays support the collective plasmonic modes, where the localized surface plasmon polaritons in TiN nanoparticles are radiatively coupled through diffraction. Numerical simulation visualizes the intense fields accumulated both in the nanoparticles and in between the particles, confirming that the collective mode originates from the simultaneous excitation of localized surface plasmon polaritons and diffraction. This study experimentally verified that the processing of TiN thin films with the nanoimprint lithography and reactive ion etching is a powerful and versatile way of preparing plasmonic nanostructures.