Membrane-Based In Situ Mid-Infrared Spectroscopic Ellipsometry: A Study on the Membrane Affinity of Polylactide-co-glycolide Nanoparticulate Systems.

Mid-infrared (IR) ellipsometry of thin films and molecule layers at solid-liquid interfaces has been a challenge because of the absorption of light in water. It has been usually overcome by using configurations utilizing illumination through the solid substrate. However, the access to the solid-liquid interface in a broad spectral range is also challenging due to the limited transparency of most structural materials in the IR wavelength range. In this work, we propose a concept of a microfabricated analysis cell based on an IR-transparent Si membrane with advantages of a robust design, flexible adaptation to existing equipment, small volume, multiple-angle capabilities, broad wavelength range, and opportunities of multilayer applications for adjusted ranges of high sensitivity. The chamber was prepared by 3D micromachining technology utilizing deep reactive ion etching of a silicon-on-insulator wafer and bonded to a polydimethylsiloxane microfluidic injection system resulting in a cell volume of approximately 50 µL. The mechanical stability of the 2 and 5 µm-thick membranes was tested using different "backbone" reinforcement structures. It was proved that the 5 µm-thick membranes are stable at lateral cell sizes of 5 mm by 20 mm. The cell provides good intensity and adjustment capabilities on the stage of a commercial mid-IR ellipsometer. The membrane configuration also provides optical access to the sensing interfaces at a broad range of incident angles, which is a significant advantage in many potential sensing structure configurations, such as plasmonic, multilayer, 2D, or metamaterial applications.

Plasmon-enhanced two-channel in situ Kretschmann ellipsometry of protein adsorption, cellular adhesion and polyelectrolyte deposition on titania nanostructures.

Plasmon-enhanced in situ spectroscopic ellipsometry was realized using the Kretschmann geometry. A 10-µL flow cell was designed for multi-channel measurements using a semi-cylindrical lens. Dual-channel monitoring of the layer formation of different organic structures has been demonstrated on titania nanoparticle thin films supported by gold. Complex modeling capabilities as well as a sensitivity of ~40 pg/mm2 with a time resolution of 1 s was achieved. The surface adsorption was enhanced by the titania nanoparticles due to the larger specific surface and nanoroughness, which is consistent with our previous results on titanate nanotubes.

Large-area nanoengineering of graphene corrugations for visible-frequency graphene plasmons.

Quantum confinement of the charge carriers of graphene is an effective way to engineer its properties. This is commonly realized through physical edges that are associated with the deterioration of mobility and strong suppression of plasmon resonances. Here, we demonstrate a simple, large-area, edge-free nanostructuring technique, based on amplifying random nanoscale structural corrugations to a level where they efficiently confine charge carriers, without inducing significant inter-valley scattering. This soft confinement allows the low-loss lateral ultra-confinement of graphene plasmons, scaling up their resonance frequency from the native terahertz to the commercially relevant visible range. Visible graphene plasmons localized into nanocorrugations mediate much stronger light-matter interactions (Raman enhancement) than previously achieved with graphene, enabling the detection of specific molecules from femtomolar solutions or ambient air. Moreover, nanocorrugated graphene sheets also support propagating visible plasmon modes, as revealed by scanning near-field optical microscopy observation of their interference patterns.

A Rational Fabrication Method for Low Switching-Temperature VO2.

Due to its remarkable switching effect in electrical and optical properties, VO2 is a promising material for several applications. However, the stoichiometry control of multivalent vanadium oxides, especially with a rational deposition technique, is still challenging. Here, we propose and optimize a simple fabrication method for VO2 rich layers by the oxidation of metallic vanadium in atmospheric air. It was shown that a sufficiently broad annealing time window of 3.0-3.5 h can be obtained at an optimal oxidation temperature of 400 °C. The presence of VO2 was detected by selected area diffraction in a transmission electron microscope. According to the temperature dependent electrical measurements, the resistance contrast (R30 °C/R100 °C) varied between 44 and 68, whereas the optical switching was confirmed using in situ spectroscopic ellipsometric measurement by monitoring the complex refractive indices. The obtained phase transition temperature, both for the electrical resistance and for the ellipsometric angles, was found to be 49 ± 7 °C, i.e., significantly lower than that of the bulk VO2 of 68 ± 6 °C.

Optimization of Plasmonic Gold Nanoparticle Concentration in Green LED Light Active Dental Photopolymer.

Gold nanoparticles (AuNPs) display surface plasmon resonance (SPR) as a result of their irradiation at a targeted light frequency. SPR also results in heat production that increases the temperature of the surrounding environment, affecting polymerization. The aim was to investigate the SPR effect of AuNPs on a dimethacrylate-based photopolymer system. The tested composites were designed to overlap the illumination required for the polymerization and the plasmon effect. The 5 nm-sized dodecanethiol capped AuNPs were applied in different concentrations in the matrix that were irradiated with green light (λ = 532 nm), where the Irgacure 784 photoinitiator also absorbs the light. The plasmonic effect was investigated for the refractive index change by surface plasmon resonance imaging (SPRi) supplemented by ellipsometry. Moreover, optical transmission and transmission electron micrographs (TEM), diametral tensile stress (DTS), and confocal Raman spectroscopy was performed to determine the degree of conversion (DC) at 1.0, 1.4, and 2.0 mW/cm2 light intensities. It was found that the optimal conditions were at 0.0208 wt% AuNPs concentration and 1.4 mW/cm2 light intensity at which the refractive index change, DTS, and DC data were all maximal. The study confirmed that AuNPs are applicable to improve the polymerization efficiency of dental composite resin.

Flagellin-based electrochemical sensing layer for arsenic detection in water.

Regular monitoring of arsenic concentrations in water sources is essential due to the severe health effects. Our goal was to develop a rapidly responding, sensitive and stable sensing layer for the detection of arsenic. We have designed flagellin-based arsenic binding proteins capable of forming stable filament structures with high surface binding site densities. The D3 domain of Salmonella typhimurium flagellin was replaced with an arsenic-binding peptide motif of different bacterial ArsR transcriptional repressor factors. We have shown that the fusion proteins developed retain their polymerization ability and have thermal stability similar to that of wild-type filament. The strong arsenic binding capacity of the monomeric proteins was confirmed by isothermal titration calorimetry (ITC), and dissociation constants (Kd) of a few hundred nM were obtained for all three variants. As-binding fibers were immobilized on the surface of a gold electrode and used as a working electrode in cyclic voltammetry (CV) experiments to detect inorganic arsenic near the maximum allowable concentration (MAC) level. Based on these results, it can be concluded that the stable arsenic-binding flagellin variant can be used as a rapidly responding, sensitive, but simple sensing layer in a field device for the MAC-level detection of arsenic in natural waters.

Micro-combinatorial sampling of the optical properties of hydrogenated amorphous [Formula: see text] for the entire range of compositions towards a database for optoelectronics.

The optical parameters of hydrogenated amorphous a-[Formula: see text]:H layers were measured with focused beam mapping ellipsometry for photon energies from 0.7 to 6.5 eV. The applied single-sample micro-combinatorial technique enables the preparation of a-[Formula: see text]:H with full range composition spread. Linearly variable composition profile was revealed along the 20 mm long gradient part of the sample by Rutherford backscattering spectrometry and elastic recoil detection analysis. The Cody-Lorentz approach was identified as the best method to describe the optical dispersion of the alloy. The effect of incorporated H on the optical absorption is explained by the lowering of the density of localized states in the mobility gap. It is shown that in the low-dispersion near infrared range the refractive index of the a-[Formula: see text] alloy can be comprehended as a linear combination of the optical parameters of the components. The micro-combinatorial sample preparation with mapping ellipsometry is not only suitable for the fabrication of samples with controlled lateral distribution of the concentrations, but also opens new prospects in creating databases of compounds for optical and optoelectonic applications.

Sensing Layer for Ni Detection in Water Created by Immobilization of Bioengineered Flagellar Nanotubes on Gold Surfaces.

The environmental monitoring of Ni is targeted at a threshold limit value of 0.34 µM, as set by the World Health Organization. This sensitivity target can usually only be met by time-consuming and expensive laboratory measurements. There is a need for inexpensive, field-applicable methods, even if they are only used for signaling the necessity of a more accurate laboratory investigation. In this work, bioengineered, protein-based sensing layers were developed for Ni detection in water. Two bacterial Ni-binding flagellin variants were fabricated using genetic engineering, and their applicability as Ni-sensitive biochip coatings was tested. Nanotubes of mutant flagellins were built by in vitro polymerization. A large surface density of the nanotubes on the sensor surface was achieved by covalent immobilization chemistry based on a dithiobis(succimidyl propionate) cross-linking method. The formation and density of the sensing layer was monitored and verified by spectroscopic ellipsometry and atomic force microscopy. Cyclic voltammetry (CV) measurements revealed a Ni sensitivity below 1 µM. It was also shown that, even after two months of storage, the used sensors can be regenerated and reused by rinsing in a 10 mM solution of ethylenediaminetetraacetic acid at room temperature.