Metal-Dielectric-Graphene Hybrid Heterostructures with Enhanced Surface Plasmon Resonance Sensitivity Based on Amplitude and Phase Measurements

Metal-dielectric-graphene hybrid heterostructures based on oxides Al2O3, HfO2, and ZrO2 as well as on complementary metal–oxide–semiconductor compatible dielectric Si3N4 covering plasmonic metals Cu and Ag have been fabricated and studied. We show that the characteristics of these heterostructures are important for surface plasmon resonance biosensing (such as minimum reflectivity, sharp phase changes, resonance full width at half minimum and resonance sensitivity to refractive index unit (RIU) changes) can be significantly improved by adding dielectric/graphene layers. We demonstrate maximum plasmon resonance spectral sensitivity of more than 30,000 nm/RIU for Cu/Al2O3 (ZrO2, Si3N4), Ag/Si3N4 bilayers and Cu/dielectric/graphene three-layers for near-infrared wavelengths. The sensitivities of the fabricated heterostructures were ~ 5–8 times higher than those of bare Cu or Ag thin films. We also found that the width of the plasmon resonance reflectivity curves can be reduced by adding dielectric/graphene layers. An unexpected blueshift of the plasmon resonance spectral position was observed after covering noble metals with high-index dielectric/graphene heterostructures. We suggest that the observed blueshift and a large enhancement of surface plasmon resonance sensitivity in metal-dielectric-graphene hybrid heterostructures are produced by stationary surface dipoles which generate a strong electric field concentrated at the very thin top dielectric/graphene layer.

A Facile Route of Manufacturing of Silicon-Based Nanostructures with Tuned Plasmonic Properties

An environment-friendly method of pulsed laser ablation in liquids is successfully employed for structural modification of silicon nanoparticles leading to a considerable narrowing of their size distribution accompanied with a reduction of the mean size. Contamination-free conditions of synthesis ensure the chemical purity of formed nanostructures that may reduce toxicity issues. Such a laser-induced modification leads to the appearance of plasmonic properties in semiconductor-based nanomaterials. Their spectral position can easily be varied in the whole visible range. Combined in one nanoparticle properties of semiconductors and noble metals can strongly promote applications of composite laser-synthesized nanoparticles for biosensing (using their plasmonic-based surface-enhanced ability) and bioimaging (using their both optical and magnetic abilities) purposes.

Theoretical study of perovskite nanowires optical response to hydrogen halides vapor exposure

Highly sensitive detection of harmful to the human health and environment hydrogen halide vapors is one of the key problems for the chemical industry. The available electrochemical and optical sensors most often show no selectivity to different hydrogen halides and can be produced via costly high-tech fabrication. In contrast to them, CsPbBr3 perovskite nanowires (NWs) exhibiting laser generation are capable of selective and precise detecting for HCl and HI. Exposure of a single NW to these analytes results in an anion exchange that modifies the chemical composition of the NW and therefore invokes a small spectral shift of the laser peak. Herein we propose a theoretical model describing such an optical response. Taking into account that the anion exchange occurs at the surface of the NW and initiates the formation of a core-shell structure, we perform numerical estimation of the eigenmode spectral position for different thicknesses of the chlorine-and iodine-rich shell. Calculations reveal that even a 10 nm shell causes a noticeable spectral shift of 0.81 and 0.63 nm for eigenmode in CsPbBr3-CsPbCl3 and CsPbBr3-CsPbl3 core-shell NWs, respectively.

Second harmonic generation in hybrid GaP/Au nanocylinders

To date, nanoscale dielectric and plasmonic systems with a nonlinear response are of great interest to researchers. This is due to a wide range of their potential applications in nonlinear optical converters and optical communication systems. The fundamental problem of nanoscale frequency converters is the low efficiency of nonlinear optical generation. The reason for this is that the main mechanism for increasing the efficiency of nonlinear signal generation via phase matching is not available at scales smaller than the wavelength. Here, we experimentally investigate the generation of the second optical harmonic in hybrid GaP/Au nanoparticles resonantly enhanced with plasmonic and Mie resonances. Using dark-field spectroscopy, it is shown that nanoantennas support a series of optical resonances in the visible range, the spectral position of which is in good agreement with the numerical simulation. We measured the second harmonic generation spectrum, with sharp resonances which is in accordance with linear scattering. Finally, the dependence of the second harmonic optical signal on the polarization is measured.

Spectral tuning of diamond photonic crystal slabs by deposition of a thin layer with silicon vacancy centers

The controlled extraction of light from diamond optical color centers is essential for their practical prospective applications as single photon sources in quantum communications and as biomedical sensors in biosensing. Photonic crystal (PhC) structures can be employed to enhance the collection efficiency from these centers by directing the extracted light towards the detector. However, PhCs must be fabricated with nanoscale precision, which is extremely challenging to achieve for current materials and nanostructuring technologies. Imperfections inherently lead to spectral mismatch of the extraction (leaky) modes with color center emission lines. Here, we demonstrate a new and simple two-step method for fabricating diamond PhC slabs with leaky modes overlapping the emission line of the silicon vacancy (SiV) centers. In the first step, the PhC structure with leaky modes blue shifted from the SiV emission line is fabricated in a nanocrystalline diamond without SiV centers. A thin layer of SiV-rich diamond is then deposited over the PhC slab so that the spectral position of the PhC leaky modes is adjusted to the emission line of the SiV centers, thereby avoiding the need for nanoscale precision of the structuring method. An intensity enhancement of the zero-phonon line of the SiV centers by a factor of nine is achieved. The color centers in the thin surface layer are beneficial for sensing applications and their properties can also be further controlled by the diamond surface chemistry. The demonstrated PhC tuning method can also be easily adapted to other optical centers and photonic structures of different types in diamond and other materials.

Determination of lithium in human serum by isotope dilution atomic absorption spectrometry

The therapeutic dose of lithium (Li) compounds, which are widely used for the treatment of psychiatric and hematologic disorders, is close to its toxic level; therefore, drug monitoring protocols are mandatory. Herein, we propose a fast, simple, and low-cost analytical procedure for the traceable determination of Li concentration in human serum, based on the monitoring of the Li isotope dilution through the partially resolved isotope shift in its electronic transition around 670.80 nm using a commercially available high-resolution continuum source graphite furnace atomic absorption spectrometer. With this technique, serum samples only require acidic digestion before analysis. The procedure requires three measurements—an enriched 6Li spike, a mixture of a certified standard solution and spike, and a mixture of the sample and spike with a nominal 7Li/6Li ratio of 0.82. Lanthanum has been used as an internal spectral standard for wavelength correction. The spectra are described as the linear superposition of the contributions of the respective isotopes, each consisting of a spin-orbit doublet, which can be expressed as Gaussian components with constant spectral position and width and different relative intensity, reflecting the isotope ratio in the sample. Both the spectral constants and the correlation between isotope ratio and relative band intensity have been experimentally obtained using commercially available materials enriched with Li isotopes. The Li characteristic mass (mc) obtained corresponds to 0.6 pg. The procedure has been validated using five human serum certified reference materials. The results are metrologically comparable and compatible to the certified values. The measurement uncertainties are comparable to those obtained by the more complex and expensive technique, isotope dilution mass spectrometry. Graphical abstract

Density Functional Theory Study of the Solvent Effects on Electronic Transition Energies of Porphyrins

We have calculated the solvent effects on the ground state and the lowest triplet state absorption spectra of meso-tetraphenylporphyrin (TPP), meso-tetrakis(p-sulfonatophenyl)porphyrin (TSPP) and their diprotonated forms (H4TPP and H4TSPP) in thirty-nine different solvent using time-dependent-DFT density functional theory (TD-DFT) coupled with CPCM method. The results of the calculations show that the Q-bands and Soret-bands (or B-bands) in the absorption spectra of these compounds substantially change as function of solvent dielectric constant (ε) up to 20.493 (acetone), but become stabile in high polar solvents with dielectric constants ε > 20. The relative shifts in the B-bands are more significant than that in the Q-bands. The magnitude of the shifts in the spectral position of the Q and B bands are in the following order: H4TSPP > H4TPP > TPP > TSPP for the B-bands and H4TSPP > H4TPP > TSPP > TPP for the Q-bands. We also have determined that the energy-gaps between the B/Q-bands and their nearest triplet states are also solvent dependent for ε < ~ 20.493.

Charge Density-Versus Time-Controlled Pulse Anodization in the Production of PAA-Based DBRs for MIR Spectral Region

A robust and reliable method for fabricating porous anodic alumina (PAA)-based distributed Bragg reflectors (DBRs), operating in mid-infrared (MIR) spectral region, is presented. The method relies on application of high (UH) and low (UL) voltage pulse sequence repeated in cycles. PAA-based DBR consists of alternating high-(dH) and low-porosity (dL) layers translated directly into periodically varied refractive index. Two anodization modes were used: time- and charge density-controlled mode. The former generated dH + dL pairs with non-uniform thickness (∆d) and effective refractive index (∆neff). It is supposed, that owing to a compensation effect between the ∆d and ∆neff, the photonic stopbands (PSBs) were symmetrical and intensive (transmittance close to zero). Under the charge density-controlled mode dH + dL pairs of uniform thickness were formed. However, the remaining ∆neff provided an asymmetrical broadening of PSBs. Furthermore, it is demonstrated that the spectral position of the PSBs can be precisely tuned in the 3500–5500 nm range by changing duration of voltage pulses, the amount of charge passing under subsequent UH and UL pulses, and by pore broadening after the electrochemical synthesis. The material can be considered to be used as one-dimensional transparent photonic crystal heat mirrors for solar thermal applications.

Concordance of the spectral properties of dorsal wing scales with the phylogeographic structure of European male Polyommatus icarus butterflies

The males of more than 80% of the Lycaenidae species belonging to the tribe Polyommatini exhibit structural coloration on their dorsal wing surfaces. These colors have a role in reinforcement in prezygotic reproductive isolation. The species-specific colors are produced by the cellular self-assembly of chitin/air nanocomposites. The spectral position of the reflectance maximum of such photonic nanoarchitectures depends on the nanoscale geometric dimensions of the elements building up the nanostructure. Previous work showed that the coloration of male Polyommatus icarus butterflies in the Western and Eastern Palearctic exhibits a characteristic spectral difference (20 nm). We investigated the coloration and the de novo developed DNA microsatellites of 80 P. icarus specimens from Europe from four sampling locations, spanning a distance of 1621 km. Remarkably good concordance was found between the spectral properties of the blue sexual signaling color (coincident within 5 nm) and the population genetic structure as revealed by 10 microsatellites for the P. icarus species.

A method to detect the content of substance in solution by using spectral position information of photonic crystal

Photonic crystal is a dielectric structure arranged according to certain rules, and its excellent electromagnetic wave characteristics can be used to manufacture a lot of kinds of photonic crystal devices. In this paper, a defect is introduced into the photonic crystal, and the transfer matrix method is used to study the relationship between the liquid concentration and the peak value of the liquid transmission at the electromagnetic wave length when the defect is a mixture of ethanol and glycol. The results show that by observing and measuring the position of the peak transmittance of the mixed liquid, the substance content of the liquid mixture, that is, the concentration, can be inferred. The accuracy of this method is compared with the experimental results, which shows that this method has high accuracy. This method is simple and easy to operate. This result opens up a new direction for the application of photonic crystals.