Analysis of the Dielectric Properties of Alkali-Free Aluminoborosilicate Glasses by Considering the Contributions of Electronic and Ionic Polarizabilities in the GHz Frequency Range.

Recently, the investigation of the dielectric properties of glasses in the GHz frequency range has attracted great interest for use in printed circuit boards (PCBs) as a reinforcing material in the application of high-speed 5G/6G communications. In particular, glasses with low dielectric properties are a prerequisite for high-frequency applications. In this study, the GHz dielectric properties of alkali-free aluminoborosilicate glasses without and with La2O3 were analyzed using the Clausius-Mossotti equation where both the electronic and ionic polarizabilities contribute to the dielectric constant. The dielectric polarizability (αD) and oxide ion polarizability (αO2-) were calculated from the measured dielectric constant (εGHz) at 1 GHz and the glass density. The dielectric constants (εopt) at the optical frequencies and electronic polarizabilities (αe) of the glasses were calculated from the refractive index measured at 633 nm and the glass density. The εGHz values were found to be significantly higher than the εopt values in both series of glasses, due to the ionic polarizability (αi), which contributes additionally to the εGHz. The lower dielectric constants of the La2O3-incoporated glasses than that of the reference glass without La2O3 may be due to the lower ionic polarizability originated from the incorporation of the high cation field strength of the La3+ ions.

Ultrahighly Sensitive Surface-Enhanced Raman Spectroscopy Film of Silver Nanoparticles Dispersed in Three Dimensions on a Thin Alumina Nanowire Framework.

To develop highly sensitive surface-enhanced Raman spectroscopy (SERS) films, various types of aggregated Ag nanowire (NW) and nanoparticle (NP) complex structures were fabricated using anodic aluminum oxide (AAO) templates and thermal evaporation. Aggregated AgNW structures with numerous tapered nanogaps were fabricated via Ag deposition on aggregated thin alumina nanowires of different lengths. AgNP complex structures were obtained by collapsing vertically aligned thin alumina nanowires 1 µm in length and depositing AgNPs on their tops and sides using surface tension during ethanol drying after functionalization. The Raman signal enhancement factors (EFs) of the samples were evaluated by comparing the SERS signal of the thiophenol (TP) self-assembled monolayer (SAM) on the nanostructures with the Raman signal of neat TP. EFs as high as ~2.3 × 107 were obtained for the optimized aggregated AgNW structure (NW length of 1 µm) and ~3.5 × 107 for the optimized AgNP complex structure. The large EF of the AgNP complex film is attributed mainly to the AgNPs dispersed in three dimensions on the sides of the thin alumina nanowires, strongly implying some important, relevant physics yet to be discovered and also a very promising nanostructure scheme for developing ultrahighly sensitive SERS films with EF > 108.

Reusable Wrinkled Nanoporous Silver Film Fabricated by Plasma Treatment for Surface-Enhanced Raman Scattering Applications.

A nanoporous silver film (npAgF), a promising structure for surface-enhanced Raman spectroscopy (SERS), can be fabricated by using successive O2 and Ar plasma treatments on a planar silver film. The common dealloying method for producing an npAgF involves annealing at high temperatures to produce an alloy film, as well as harsh etching using corrosive chemicals. By contrast, the plasma-based method can be applied directly to various functional substrates to produce more sophisticated npAgF structures. Herein, we report a facile fabrication method for a wrinkled npAgF (w-npAgF) for SERS applications using a thermally contractible polystyrene substrate. The w-npAgF had 3D wrinkles of the nanoporous structure and showed approximately 8 times higher SERS enhancement than did the flat npAgF. Moreover, the w-npAgF could be reused for multiple SERS measurements of different molecules by mild O2 and Ar plasma treatments after each use, in which the O2 plasma effectively removed the adsorbed organic molecules and the Ar plasma reduced silver oxide to pristine silver for subsequent SERS measurements. The wrinkled nanoporous structure was maintained after multiple mild plasma treatments for reuse. The simplicity of plasma-based fabrication and high sensitivity of w-npAgFs are promising features for the green production of low-cost and reusable 3D SERS substrates.

Early on-site detection of strawberry anthracnose using portable Raman spectroscopy.

We developed a method for the early on-site detection of strawberry anthracnose using a portable Raman system with multivariate statistical analysis algorithms. By using molecular markers based on Raman spectra, the proposed method can detect anthracnose in strawberry stems 3 days after exposure to Colletotrichum gloeosporioides. A fiber-optic probe was applied for the portable Raman system, and the acquisition time was 10 s. We found that the molecular markers were closely related to the following subjects: i) an increase in amide III and fatty acids of C. gloeosporioides invading strawberry stems (Raman bands at 1180-1310 cm-1) and ii) a decrease in metabolites in strawberry plants, such as phenolic compounds and terpenoids (Raman bands at 760, 800, and 1523 cm-1). We also found that the increased fluorescence background caused by various chromophores within the invading C. gloeosporioides could serve as a marker. A two-dimensional cluster plot obtained by principal component analysis (PCA) showed that the three groups (control, fungal infection, and pathogen) were distinguishable. The linear discriminant analysis (LDA)-based prediction algorithm could identify C. gloeosporioides infection with a posterior probability of over 40%, even when no symptoms were visible on the inoculated strawberry plants.

Real-time ultrasensitive detection of ammonia gas using a compact CRDS spectrometer.

Trace-level ammonia gas in air was analyzed using a fiber-based compact cavity ring-down spectrometer (CRDS). For the compact spectrometer, a 20 cm linear cavity with two high reflectivity (>99.999%) mirrors was employed. The laser frequency was locked to the cavity resonance by using frequency shifted (160 MHz) optical feedback. For N H 3 detection, a strong absorption band at 1513.98 nm with an absorption cross section of 3.3⋅10-21 c m/m o l e c u l e was used. As a result, a detection sensitivity of ∼0.1p p b (3-σ) was achieved for N H 3 within 10 s.

Quantitative analysis of trace N2, Ar in O2 using glow discharge optical emission spectroscopy.

A trace level of N2 and Ar gases in O2 ambience were quantitatively analyzed for the first time by glow discharge optical emission spectroscopy. Microplasma was generated in a compact gas cell by a metal (Au) electrode pair of 1 mm diameter and ∼1 mm separation with the driving voltage of ∼0.9 kV and the current of ∼5 mA in ∼60 Torr. 358 and 813 nm optical emission bands were used for N2 and Ar detection, respectively. A spectroscopy fiber bundle having a circular input cross section of ∼700 µm in diameter and an output of 100 µm in width and 3 mm in height was employed to promote the signal collection efficiency while preserving high spectral resolution. As a result, the detection sensitivities <1 ppm (3 - σ) were attained for both N2 and Ar within 10 s. The detection accuracy was also promoted by correcting the N2 and Ar band signal intensities using the neighboring O emission band intensities, which led to detection errors <2% (3 - σ) for both N2 and Ar.

Surface conversion of ZnO nanorods to ZIF-8 to suppress surface defects for a visible-blind UV photodetector.

ZnO nanomaterials are promising building blocks for an efficient UV photodetector; however, their slow sensing behavior and undesired response to visible light, which are attributed to surface defects, such as oxygen or zinc vacancies, are challenges that remain to be addressed. Here, we transformed the ZnO nanorod surface into a zeolitic imidazolate framework-8 (ZIF-8) to eliminate ZnO surface defects. Vertical-type photodetectors were fabricated incorporating a Schottky junction at the ZIF-8/gold (Au) top electrode and could respond to UV light with a rapid response and recovery (1-2 s) and demonstrated a UV-to-visible rejection ratio in the order of 103, qualifying them as efficient visible-blind UV photodetectors. It is noteworthy that the ZIF-8 layer effectively separated the photogenerated electron-hole pairs, and thus reduced their recombination probability. The enhanced photodetector displayed excellent figures-of-merit: a responsivity of 291 A W-1 and a detectivity of 5.9 × 1013 cm Hz1/2 W-1 under illumination at 295 nm.

Strong polarization-dependent terahertz modulation of aligned Ag nanowires on Si substrate.

Optically tunable, strong polarization-dependent transmission of terahertz pulses through aligned Ag nanowires on a Si substrate is demonstrated. Terahertz pulses primarily pass through the Ag nanowires and the transmittance is weakly dependent on the angle between the direction of polarization of the terahertz pulse and the direction of nanowire alignment. However, the transmission of a terahertz pulse through optically excited materials strongly depends on the polarization direction. The extinction ratio increases as the power of the pumping laser increases. The enhanced polarization dependency is explained by the redistribution of photocarriers, which accelerates the sintering effect along the direction of alignment of the Ag nanowires. The photocarrier redistribution effect is examined by the enhancement of terahertz emission from the sample. Oblique metal nanowires on Si could be utilized for designing optically tunable terahertz polarization modulators.

Long-Standing Stability of Silver Nanorod Array Substrates Functionalized Using a Series of Thiols for a SERS-Based Sensing Application.

Silver nanorod (AgNR) array substrates were fabricated using an oblique angle thermal evaporation technique; their long-term stability, surface uniformity and reproducibility, which are primary requirements for their widespread realistic application and commercialization, were assessed using surface-enhanced Raman scattering (SERS) spectroscopy. The nanorod surfaces were functionalized using a series of organic thiols, which range from hydrophilic to hydrophobic, to mimic various conditions that often arise during detection of hydrophilic/phobic analytes in a realistic application field. A group of these functionalized substrates was stored in ambient laboratory atmosphere; another in light minimized, moisture-free vacuum; while another was stowed carefully and neatly in water to mimic realistic conditions. The effects of these storing conditions were studied. A surfactant was added to the water to maintain consistent surface wetting in the third group. SERS spectra of nanorod substrates prior to functionalization were also recorded to investigate the effect of adventitious carbonaceous contaminants. A meticulous systematic study on the reproducibility of SERS signals was carried out: spot-to-spot, substrate-to-substrate, batch-to-batch, day-to-day. The relative standard deviation (RSD) shown by the SERS signals acquired from various spots of a single substrate was less than 3%, which is very similar to the only account reported so far, in which RSD is reported as 2%. The wetting behavior of these thiol functionalized AgNR substrates are investigated using static contact angle measurements. The functionalized substrates have exhibited excellent long-standing stability over a period of six months when stored appropriately; hence, they are highly suitable for mass production towards realistic application.

Morphological and SERS Properties of Silver Nanorod Array Films Fabricated by Oblique Thermal Evaporation at Various Substrate Temperatures.

Aligned silver nanorod (AgNR) array films were fabricated by oblique thermal evaporation. The substrate temperature during evaporation was varied from 10 to 100 °C using a home-built water cooling system. Deposition angle and substrate temperature were found to be the most important parameters for the morphology of fabricated films. Especially, it was found that there exists a critical temperature at ~90 °C for the formation of the AgNR array. The highest enhancement factor of the surface-enhanced Raman scattering (SERS), observed in the Ag films coated with benzenethiol monolayer, was ~6 × 10(7). Hot spots, excited in narrow gaps between nanorods, were attributed to the huge enhancement factor by our finite-difference time-domain (FDTD) simulation reflecting the real morphology.

Label-free imaging and quantitative chemical analysis of Alzheimer's disease brain samples with multimodal multiphoton nonlinear optical microspectroscopy.

We developed multimodal multiphoton microspectroscopy using a small-diameter probe with gradient-index lenses and applied it to unstained Alzheimer's disease (AD) brain samples. Our system maintained the image quality and spatial resolution of images obtained using an objective lens of similar numerical aperture. Multicolor images of AD brain samples were obtained simultaneously by integrating two-photon excited fluorescence and second-harmonic generation on a coherent anti-Stokes Raman scattering (CARS) microendoscope platform. Measurements of two hippocampal regions, the cornus ammonis-1 and dentate gyrus, revealed more lipids, amyloid fibers, and collagen in the AD samples than in the normal samples. Normal and AD brains were clearly distinguished by a large spectral difference and quantitative analysis of the CH mode using CARS microendoscope spectroscopy. We expect this system to be an important diagnosis tool in AD research

Ultimate sensing resolution of water temperature by remote Raman spectroscopy.

The limit of sensing resolution of water temperature by remote Raman spectroscopy was investigated experimentally. A remote Raman spectrometer, which employed a telescope of 20 cm in pupil size and the second harmonic generation (SHG) of a Q-switched Nd:YAG laser, was used for the measurement. By analyzing the broad O-H stretching Raman band located near 3500 cm⁻¹, a parameter which is in second-order polynomial relation with water temperature from 13°C to 50°C could be obtained. The resolution of our remote Raman temperature sensor was better than ±0.2°C with measurement time shorter than 10 s. The influence of the Raman signal's signal-to-noise ratio on the resolution and salinity effect on the accuracy of temperature sensing were also investigated.

Rapid diagnosis of liver fibrosis using multimodal multiphoton nonlinear optical microspectroscopy imaging.

A multimodal multiphoton nonlinear optical (NLO) microspectroscopy imaging system was developed using a femtosecond laser and a photonic crystal fiber. Coherent anti-Stokes Raman scattering (CARS) microspectroscopy was combined with two-photon excitation fluorescence and second-harmonic generation microscopy in one platform and the system was applied to diagnose liver fibrosis. Normal and liver fibrosis tissues were clearly distinguished with the great difference from CARS spectra as well as multimodal multiphoton NLO images. We expect the system to be a rapid diagnosis tool for liver fibrosis at tissue level with label-free imaging of significant biochemical components.

All-optical image switching in a double-Λ system.

The coherent control of optical images has garnered attention because all information embedded in optical images is expected to be controlled in a parallel way. One of the most important control processes is switch for information delivery. We experimentally demonstrated phase-controlled optical image switching in a double-Λ system where the transmission of the image through a medium was switched. Two independent laser sources were adopted for a double-Λ system such that images inscribed in two weak probe light beams were incoherent with each other. Arbitrary phase was added to the optical images to show that switching could be accomplished just with the relative phase difference between the probe pixels.

Application of pulsed buffer gas jets for the signal enhancement of laser-induced breakdown spectroscopy.

We report a new simple method for the signal enhancement of laser-induced breakdown spectroscopy using a pulsed buffer gas jet. The signal is enhanced up to more than 10 fold by using argon gas jets, which are injected through a pulsed nozzle onto the sample area to be analyzed. By synchronizing the buffer gas pulse with the laser pulse and optimizing the spatial arrangements between the gas jet and the sample surface, we have successfully exploited the useful properties of the buffer gas in open atmosphere. The signal-enhancement mechanism in our buffer gas jet has been discussed. Also, applications to various samples (metal, glass, and paper) have been demonstrated.

Observation of a high Raman gain induced by a pulsed pump laser in a Lambda system of three fine-structure levels.

We have observed a high Raman gain in a quasi-stationary state realized by a single strong-pulsed-pump laser. The Raman gain, originating from the population inversion in the dressed state picture, was as large as 1700% in a Lambda system of three fine-structure levels of atomic samarium, corresponding to a gain cross section comparable with the linear absorption cross section for the same transition.