A New Spin-Correlated Plasmon in Novel Highly Oriented Single-Crystalline Gold Quantum Dots.

A concept of spin plasmon, a collective mode of spin-density, in strongly correlated electron systems has been proposed since the 1930s. It is expected to bridge between spintronics and plasmonics by strongly confining the photon energy in the subwavelength scale within single magnetic-domain to enable further miniaturizing devices. However, spin plasmon in strongly correlated electron systems is yet to be realized. Herein, we present a new spin correlated-plasmon at room temperature in novel Mott-like insulating highly oriented single-crystalline gold quantum-dots (HOSG-QDs). Interestingly, the spin correlated-plasmon is tunable from the infrared to visible, accompanied by spectral weight transfer yielding a large quantum absorption midgap state, disappearance of low-energy Drude response, and transparency. Supported with theoretical calculations, it occurs due to an interplay of surprisingly strong electron-electron correlations, s-p hybridization and quantum confinement in the s band. The first demonstration of the high sensitivity of spin correlated-plasmon in surface-enhanced Raman spectroscopy is also presented.

High-resolution fast-tomography brain-imaging beamline at the Taiwan Photon Source.

The new Brain Imaging Beamline (BIB) of the Taiwan Photon Source (TPS) has been commissioned and opened to users. The BIB and in particular its endstation are designed to take advantage of bright unmonochromatized synchrotron X-rays and target fast 3D imaging, ∼1 ms exposure time plus very high ∼0.3 µm spatial resolution. A critical step in achieving the planned performances was the solution to the X-ray induced damaging problems of the detection system. High-energy photons were identified as their principal cause and were solved by combining tailored filters/attenuators and a high-energy cut-off mirror. This enabled the tomography acquisition throughput to reach >1 mm3 min-1, a critical performance for large-animal brain mapping and a vital mission of the beamline.

Gold nano-mesh synthesis by continuous-flow X-ray irradiation.

X-ray irradiation has been extensively used in recent years as a fabrication step for nanoparticles and nanoparticle systems. A variant of this technique, continuous-flow X-ray irradiation, has recently been developed, and offers three important advantages: precise control of the irradiation dose, elimination of convection effects in the precursor solution, and suitability for large-scale production. Here, the use of this method to fabricate Au nano-meshes of interest as transparent and flexible electrodes for optoelectronics is reported. The study includes extensive characterization of the synthesis parameters and of the product properties, with rather encouraging results.

Interactions between lasers and two-dimensional transition metal dichalcogenides.

The recent increasing research interest in two-dimensional (2D) layered materials has led to an explosion of in the discovery of novel physical and chemical phenomena in these materials. Among the 2D family, group-VI transition metal dichalcogenides (TMDs), such as represented by MoS2 and WSe2, are remarkable semiconductors with sizable energy band gaps, which make the TMDs promising building blocks for new generation optoelectronics. On the other hand, the specificity and tunability of the band gaps can generate particularly strong light-matter interactions between TMD crystals and specific photons, which can trigger complex and interesting phenomena such as photo-scattering, photo-excitation, photo-destruction, photo-physical modification, photochemical reaction and photo-oxidation. Herein, we provide an overview of the phenomena explained by various interactions between lasers and the 2D TMDs. Characterizations of the optical fundamentals of the TMDs via laser spectroscopies are reviewed. Subsequently, photoelectric conversion devices enabled by laser excitation and the functionality extension and performance improvement of the TMDs materials via laser modification are comprehensively summarized. Finally, we conclude the review by discussing the prospects for further development in this research area.

Fluorescence Concentric Triangles: A Case of Chemical Heterogeneity in WS2 Atomic Monolayer.

We report a novel optical property in WS2 monolayer. The monolayer naturally exhibits beautiful in-plane periodical and lateral homojunctions by way of alternate dark and bright band in the fluorescence images of these monolayers. The interface between different fluorescence species within the sample is distinct and sharp. This gives rise to intriguing concentric triangular fluorescence patterns in the monolayer. The novel optical property of this special WS2 monolayer is facilitated by chemical heterogeneity. The photoluminescence of the bright band is dominated by emissions from trion and biexciton while the emission from defect-bound exciton dominates the photoluminescence at the dark band. The discovery of such concentric fluorescence patterns represents a potentially new form of optoelectronic or photonic functionality.

Atomic healing of defects in transition metal dichalcogenides.

As-grown transition metal dichalcogenides are usually chalcogen deficient and therefore contain a high density of chalcogen vacancies, deep electron traps which can act as charged scattering centers, reducing the electron mobility. However, we show that chalcogen vacancies can be effectively passivated by oxygen, healing the electronic structure of the material. We proposed that this can be achieved by means of surface laser modification and demonstrate the efficiency of this processing technique, which can enhance the conductivity of monolayer WSe2 by ∼400 times and its photoconductivity by ∼150 times.

Microlandscaping of Au nanoparticles on few-layer MoS2 films for chemical sensing.

Surface modification or decoration of ultrathin MoS2 films with chemical moieties is appealing since nanointerfacing can functionalize MoS2 films with bonus potentials. In this work, a facile and effective method for microlandscaping of Au nanoparticles (NPs) on few-layer MoS2 films is developed. This approach first employs a focused laser beam to premodify the MoS2 films to achieve active surface domains with unbound sulfur. When the activated surface is subsequently immersed in AuCl3 solution, Au NPs are found to preferentially decorate onto the modified regions. As a result, Au NPs can be selectively and locally anchored onto designated regions on the MoS2 surface. With a scanning laser beam, microlandscapes comprising of Au NPs decorated on laser-defined micropatterns are constructed. By varying the laser power, reaction time and thickness of the MoS2 films, the size and density of the NPs can be controlled. The resulting hybrid materials are demonstrated as efficient Raman active surfaces for the detection of aromatic molecules with high sensitivity.

X-ray-induced Cu deposition and patterning on insulators at room temperature.

X-ray irradiation is shown to trigger the deposition of Cu from solution, at room temperature, on a wide variety of insulating substrates: glass, passivated Si, TiN/Ti/SiO2/Si and photoresists like PMMA and SU-8. The process is suitable for patterning and the products can be used as seeds for electroplating of thicker overlayers.

Suppression of dark current in germanium-tin on silicon p-i-n photodiode by a silicon surface passivation technique.

We demonstrate that a complementary metal-oxide-semiconductor (CMOS) compatible silicon (Si) surface passivation technique effectively suppress the dark current originating from the mesa sidewall of the Ge(0.95)Sn(0.05) on Si (Ge(0.95)Sn(0.05)/Si) p-i-n photodiode. Current-voltage (I-V) characteristics show that the sidewall surface passivation technique could reduce the surface leakage current density (Jsurf) of the photodiode by ~100 times. A low dark current density (Jdark) of 0.073 A/cm(2) at a bias voltage of -1 V is achieved, which is among the lowest reported values for Ge(1-x)Sn(x)/Si p-i-n photodiodes. Temperature-dependent I-V measurement is performed for the Si-passivated and non-passivated photodiodes, from which the activation energies of dark current are extracted to be 0.304 eV and 0.142 eV, respectively. In addition, the optical responsivity of the Ge(0.95)Sn(0.05)/Si p-i-n photodiodes to light signals with wavelengths ranging from 1510 nm to 1877 nm is reported.

Band-offsets scaling of low-index Ge/native-oxide heterostructures.

We investigate, through XPS and AFM, the pseudo layer-by-layer growth of Ge native oxide across Ge(001), (110) and (111) surfaces in ambient environment. More significantly, our study reveals a universal set of valence and conduction band offset (VBO and CBO) values observed for Ge(001), Ge(110), and Ge(111) surfaces as a function of Ge-oxide concentration. We find that the band offsets appear to be the same across these low-index Ge surfaces i.e., for Ge-oxide/Ge heterostructures with the same Ge-oxide overlayer concentration or thickness. In contrast, different oxidation rates for Ge(001), Ge(110), and Ge(111) surfaces were observed, where the oxidation rate is fastest for Ge(001), compared to Ge(110) and Ge(111). This can be attributed to the different number of unsatisfied Ge dangling bonds (2 vs 1) associated to the respective ideal Ge surface in forming Ge-oxide. Thus, at any given oxidation time, the oxide concentration or thickness for each type of low index Ge surface will be different. This in turn will lead to different band offset value observed for each type of Ge surface. More significantly, we show that while oxidation rates can differ from different Ge surface-types, the band offset values can be estimated simply based on the Ge-oxide concentration regardless of Ge surface type.

Enabling chlorophyll photo-response for in-line real-time noninvasive direct probing of the quality of palm-oil during mill process.

During the milling process of palm oil, the degree of palm fruit ripeness is a critical factor that affects the quality and quantity of the oil. As the palm fruit matures, its chlorophyll level decreases, and since chlorophyll in oil has undesirable effects on hydrogenation, bleachability, and oxidative degradation, it's important to monitor the chlorophyll content in palm oil during the milling process. This study investigated the use of light-induced chlorophyll fluorescence (LICF) for non-invasive and real-time monitoring of chlorophyll content in diluted crude palm oil (DCO) located at the dilution and oil classification point in palm oil mill. An LICF probe was installed at the secondary pipe connected to main DCO pipeline, and the system communicates with a computer located in a separate control room via a Wi-Fi connection. Continuous measurements were recorded with an integration time of 500 ms, averaging of 10, and a time interval of 1 min between each recording during the oil mill's operation. All data were stored on the computer and in the cloud. We collected 60 DCO samples and sent them to the laboratory for American Oil Chemists' Society (AOCS) measurement to compare with the LICF signal. The LICF method achieved a correlation coefficient of 0.88 with the AOCS measurements, and it also provided a direct, quantitative, and unbiased assessment of the fruit ripeness in the mill. By incorporating Internet of Things (IoT) sensors and cloud storage, this LICF system enables remote and real-time access to data for chemometrics analysis.

Localized photo-induced voltage with controlled polarity in single K enriched MoO3 nanobundle.

The photo-induced voltage in an individual K enriched MoO(3) nanobundle was studied with localized focused laser beam irradiation. Without an external bias voltage, a significant photo-induced voltage (36.5 mV) was produced in a single nanobundle under low laser power (2.2 mW). Remarkably, the amplitude and polarity of the voltage could be controlled by the location of the focused laser spot. Unlike the common photo-response that comes from metal-semiconductor junction or PN junction in hybrid nanomaterial, the observed photo-induced effect is from the nanobundle itself, attributed to the small band gap of the material.

The new X-ray/visible microscopy MAXWELL technique for fast three-dimensional nanoimaging with isotropic resolution.

Microscopy by Achromatic X-rays With Emission of Laminar Light (MAXWELL) is a new X-ray/visible technique with attractive characteristics including isotropic resolution in all directions, large-volume imaging and high throughput. An ultrathin, laminar X-ray beam produced by a Wolter type I mirror irradiates the sample stimulating the emission of visible light by scintillating nanoparticles, captured by an optical system. Three-dimensional (3D) images are obtained by scanning the specimen with respect to the laminar beam. We implemented and tested the technique with a high-brightness undulator at SPring-8, demonstrating its validity for a variety of specimens. This work was performed under the Synchrotrons for Neuroscience-an Asia-Pacific Strategic Enterprise (SYNAPSE) collaboration.

Nonvolatile rewritable memory effects in graphene oxide functionalized by conjugated polymer containing fluorene and carbazole units.

A new polymer, poly[{9,9-di(triphenylamine)fluorene}(9,9-dihexylfluorene)(4-aminophenylcarbazole)] (PFCz) was synthesized and used in a reaction with graphene oxide (GO) containing surface-bonded acyl chloride moieties to give a soluble GO-based polymer material GO-PFCz. A bistable electrical switching effect was observed in an electronic device in which the GO-PFCz film was sandwiched between indium-tin oxide (ITO) and Al electrodes. This device exhibited two accessible conductivity states, that is, a low-conductivity (OFF) state and a high-conductivity (ON) state, and can be switched to the ON state under a negative electrical sweep; it can also be reset to the initial OFF state by a reverse (positive) electrical sweep. The ON state is nonvolatile and can withstand a constant voltage stress of -1 V for 3 h and 10(8) read cycles at -1 V under ambient conditions. The nonvolatile nature of the ON state and the ability to write, read, and erase the electrical states, fulfill the functionality of a rewritable memory. The mechanism associated with the memory effects was elucidated from molecular simulation results and in-situ photoluminescence spectra of the GO-PFCz film under different electrical biases.

One-pot tuning of Au nucleation and growth: from nanoclusters to nanoparticles.

We describe a simple and effective method to obtain colloidal surface-functionalized Au nanoparticles. The method is primarily based on irradiation of a gold solution with high-flux X-rays from a synchrotron source in the presence of 11-mercaptoundecanoic acid (MUA). Extensive tests of the products demonstrated high colloidal density as well as excellent stability, shelf life, and biocompatibility. Specific tests with X-ray diffraction, UV-visible spectrometry, visible microscopy, Fourier transform infrared spectroscopy, dark-field visible-light scattering microscopy, and transmission electron microscopy demonstrated that MUA, being an effective surfactant, not only allows tunable size control of the nanoparticles, but also facilitates functionalization. The nanoparticle sizes were 6.45 ± 1.58, 1.83 ± 1.21, 1.52 ± 0.37 and 1.18 ± 0.26 nm with no MUA and with MUA-to-Au ratios of 1:2, 1:1, and 3:1. The MUA additionally enabled functionalization with l-glycine. We thus demonstrated flexibility in controlling the nanoparticle size over a large range with narrow size distribution.

Probing the photoresponse of individual Nb2O5 nanowires with global and localized laser beam irradiation.

Photoresponse of isolated Nb(2)O(5) nanowires (NW) padded with platinum (Pt) at both ends were studied with global irradiation by a laser beam and localized irradiation using a focused laser beam. Global laser irradiation on individual NW in ambient and vacuum conditions revealed photocurrent contributions with different time characteristics (rapid and slowly varying components) arising from defect level excitations, thermal heating effect, surface states and NW-Pt contacts. With a spot size of < 1 µm, localized irradiation highlighted the fact that the measured photocurrent in this single NW device (with and without applied bias) depended sensitively on the photoresponse at the NW-Pt contacts. At applied bias, unidirectional photocurrent was observed and higher photocurrent was achieved with localized laser irradiation at reverse-biased NW-Pt contacts. At zero bias, the opposite polarity of photocurrents was detected when the two NW-Pt contacts were subjected to focused laser beam irradiation. A reduced Schottky barrier/width resulting from an increase in charge carriers and thermoelectric effects arising from the localized thermal heating due to focused laser beam irradiation were proposed as the mechanisms dictating the photocurrent at the NW-Pt interface. Comparison of photocurrents generated upon global and localized laser irradiation showed that the main contribution to the photocurrent was largely due to the photoresponse of the NW-Pt contacts.

Vibrational frequencies in Car-Parrinello molecular dynamics.

Car-Parrinello molecular dynamics (CPMD) are widely used to investigate the dynamical properties of molecular systems. An important issue in such applications is the dependence of dynamical quantities such as molecular vibrational frequencies upon the fictitious orbital mass µ. Although it is known that the correct Born-Oppenheimer dynamics are recovered at zero µ, it is not clear how these dynamical quantities are to be rigorously extracted from CPMD calculations. Our work addresses this issue for vibrational frequencies. We show that when the system is sufficiently close to the ground state the calculated ionic vibrational frequencies are ω(M) = ω(0M)[1 -C(µ/M)] for small µ/M, where ω(0M) is the Born-Oppenheimer ionic frequency, M the ionic mass, and C a constant that depends upon the ion-orbital coupling force constants. Our analysis also provides a quantitative understanding of the orbital oscillation amplitudes, leading to a relationship between the adiabaticity of a system and the ion-orbital coupling constants. In particular, we show that there is a significant systematic dependence of calculated vibrational frequencies upon how close the CPMD trajectory is to the Born-Oppenheimer surface. We verify our analytical results with numerical simulations for N(2), Sn(2), and H/Si(100)-(2×1).

Growth dynamics and kinetics of monolayer and multilayer graphene on a 6H-SiC(0001) substrate.

Using Scanning Tunnelling Microscopy (STM), the transformation from the commonly known carbon-rich (6√3×6√3)R30° reconstructed surface to graphene on the 6H-SiC(0001) substrate is systematically investigated with the aid of adsorbing cobalt (Co) which acts as a tracer to map the evolution of these surfaces. The formation of graphene is observed to begin from the step-edges as Si desorption occurs and the growth process continues akin to that of a step flow growth mode. Analysis of the surface step-height evolution at various stages of graphitization shows that as the initial (6√3×6√3)R30° surface converts to form graphene, three Si-C bilayers beneath collapse to regenerate a C-rich structure which also has a (6√3×6√3)R30° periodicity at the interface between graphene and the SiC bulk. Based on these observations, a structural mechanism for the growth of mono- and multilayer graphene is proposed. In addition, we also examine the rate at which the initial (6√3×6√3)R30° surface coverts to graphene as a function of time and temperature. Kinetic analysis of the growth process reveals that the transformation occurs with an activation energy of 3.0 ± 0.4 eV, a value close to the breaking of a Si-C bond.

Impact of Electrical Conductivity on the Electrochemical Performances of Layered Structure Lithium Trivanadate (LiV3-x M x O8, M= Zn/Co/Fe/Sn/Ti/Zr/Nb/Mo, x = 0.01-0.1) as Cathode Materials for Energy Storage.

Pristine trivanadate (LiV3O8) and doped lithium trivanadate (LiV3-x M x O8, M = Zn/Co/Fe/Sn/Ti/Zr/Nb/Mo, x = 0.01/0.05/0.1 M) compounds were prepared by a simple reflux method in the presence of the polymer, Pluronic P123, as the chelating agent. For comparison, pristine LiV3O8 alone was also prepared in the absence of the chelating agent. The Rietveld-refined X-ray diffraction patterns shows all compounds to exist in the layered monoclinic LiV3O8 phase belonging to the space group of P21/m. Scanning electron microscopy analysis shows the particles to exhibit layers of submicron-sized particles. The electrochemical performances of the coin cells were compared at a current density of 30 mA/g in the voltage window of 2-4 V. The cells made with compounds LiV2.99Zr0.01O8 and LiV2.95Sn0.05O8 show a high discharge capacity of 245 ± 5 mA h/g, with an excellent stability of 98% at the end of the 50th cycle. The second cycle discharge capacity of 398 mA h/g was obtained for the compound LiV2.99Fe0.01O8, and its capacity retention was found to be 58% after 50 cycles. The electrochemical performances of the cells were correlated with the electrical properties and the changes in the structural parameters of the compounds.