Optimization of the plasmonic properties of titanium nitride films sputtered at room temperature through microstructure and thickness control.

A current approach to depositing highly plasmonic titanium nitride films using the magnetron sputtering technique assumes that the process is performed at temperatures high enough to ensure the atoms have sufficient diffusivities to form dense and highly crystalline films. In this work, we demonstrate that the plasmonic properties of TiN films can be efficiently tuned even without intentional substrate heating by influencing the details of the deposition process and entailed films' stoichiometry and microstructure. We also discuss the dependence of the deposition time/films' thickness on the optical properties, which is another degree of freedom in controlling the optical response of the refractory metal nitride films. The proposed strategy allows for robust and cost-effective production of large-scale substrates with good plasmonic properties in a CMOS technology-compatible process that can be further processed, e.g., structurized. All reported films are characterized by the maximal values of the plasmonic Figure of Merit (FoM = - ε1/ε2) ranging from 0.8 to 2.6, and the sample with the best plasmonic properties is characterized by FoM at 700 nm and 1550 nm that is equal 2.1 in both cases. These are outstanding results, considering the films' polycrystallinity and deposition at room temperature onto a non-matched substrate.

Sonochemical synthesis of SnS and SnS2 quantum dots from aqueous solutions, and their photo- and sonocatalytic activity.

Our study reports the ultrasound-assisted synthesis of SnS and SnS2 in the form of nanoparticles using aqueous solutions of respective tin chloride and thioacetamide varying sonication time. The presence of both compounds is confirmed by powder X-ray diffraction, energy-dispersive X-ray spectroscopy, as well as Raman and FT-IR spectroscopic techniques. The existence of nanoparticles is proven by powder X-ray diffraction investigation and by high resolution transmission electron microscopy observations. The size of nanocrystallites are in the range of 3-8 nm and 30 50 nm for SnS, and 1.5-10 nm for SnS2. X-ray photoelectron spectroscopy measurements, used to investigate the chemical state of tin and sulphur atoms on the surface of nanoparticles, reveal that they are typically covered with tin on the same oxidation degree as respective bulk compound. Values of optical bandgaps of synthesized nanoparticles, according to the Tauc method, were 2.31, 1.47 and 1.05 eV for SnS (60, 90 and 120 min long synthesis, respectively), and 2.81, 2.78 and 2.70 eV for SnS2 (60, 90 and 120 min long synthesis, respectively). Obtained nanoparticles were utilized as photo- and sonocatalysts in the process of degradation of model azo-dye molecules by UV-C light or ultrasound. Quantum dots of SnS2 obtained under sonication lasting 120 min were the best photocatalyst (66.9 % color removal), while quantum dots of SnS obtained under similar sonication time were the best sonocatalyst (85.2 % color removal).

Titanium Nitride as a Plasmonic Material from Near-Ultraviolet to Very-Long-Wavelength Infrared Range.

Titanium nitride is a well-known conductive ceramic material that has recently experienced resumed attention because of its plasmonic properties comparable to metallic gold and silver. Thus, TiN is an attractive alternative for modern and future photonic applications that require compatibility with the Complementary Metal-Oxide-Semiconductor (CMOS) technology or improved resistance to temperatures or radiation. This work demonstrates that polycrystalline TiNx films sputtered on silicon at room temperature can exhibit plasmonic properties continuously from 400 nm up to 30 µm. The films' composition, expressed as nitrogen to titanium ratio x and determined in the Secondary Ion Mass Spectroscopy (SIMS) experiment to be in the range of 0.84 to 1.21, is essential for optimizing the plasmonic properties. In the visible range, the dielectric function renders the interband optical transitions. For wavelengths longer than 800 nm, the optical properties of TiNx are well described by the Drude model modified by an additional Lorentz term, which has to be included for part of the samples. The ab initio calculations support the experimental results both in the visible and infra-red ranges; particularly, the existence of a very low energy optical transition is predicted. Some other minor features in the dielectric function observed for the longest wavelengths are suspected to be of phonon origin.

Facile and reproducible method of stabilizing [Formula: see text] phases confined in nanocrystallites embedded in amorphous matrix.

Bismuth sesquioxide ([Formula: see text]) draws much attention due to wide variety of phases in which it exists depending on the temperature. Among them, [Formula: see text] phase is specially interesting because of its high oxide ion conductivity and prospects of applications as an electrolyte in fuel cells. Unfortunately, it is stable only in a narrow temperature range ca. 730-830 [Formula: see text]C. Our group has developed a facile and reproducible two-stage method of stabilizing [Formula: see text] crystalline phases confined in nanocrystallites embedded in amorphous matrix. In the first stage, glassy materials were obtained by a routine melt-quenching method: pure [Formula: see text] powders were melted in porcelain crucibles and fast-cooled down to room temperature. In the second step, the materials were appropriately heat-treated to induce formation of crystallites of [Formula: see text], [Formula: see text] or [Formula: see text] [Formula: see text] phases confined in a glassy matrix, depending on the process conditions. It was found out that the vitrification of the initial [Formula: see text] and the subsequent nanocrystallization were unexpectedly possible due to the presence of some Al, and Si impurities from the crucibles. Systematic DTA, XRD, optical, Raman and SEM/EDS studies were carried out to investigate the influence of the syntheses processes and allowed us to determine conditions under which the particular phases appear and remain stable down to room temperature.

On the Superconductivity Suppression in Eu1-xPrxBa2Cu3O7-δ.

This article reports on the non-trivial suppression of superconductivity in the Eu1-xPrxBCO cuprates. As non-magnetic Eu3+ ions are replaced by Pr3+ carrying a magnetic moment, spin-related superconductivity loss can be expected. The research shows that the superconductivity disappearance for x > 0.4 results from depletion of the carriers and their localization. The above conclusion was drawn by low-temperature X-ray diffraction analysis showing increased characteristic phonon frequencies with Pr content. This mechanism should promote electron-phonon coupling, at least for acoustic phonons. However, the inverse phenomenon was detected. Namely, there is a gradual deterioration of the optical phonons responsible for vibration of the Cu-O bonds with Pr increasing, as evidenced by Raman spectroscopy. Furthermore, the results of X-ray absorption spectroscopy precisely showed the location of the carriers for Pr-rich specimens. Finally, a schematic diagram for Eu1-xPrxBCO is proposed to consolidate the presented research.

Sonochemical preparation of SnS and SnS2 nano- and micropowders and their characterization.

Sonochemical production of tin(II) and tin(IV) sulfides is investigated. Different conditions of syntheses are examined: used solvent (ethanol or ethylenediamine), source of tin (SnCl2 or SnCl4), the molar ratio of thioacetamide to the tin source, and time of sonication. The obtained powders are characterized by the X-ray diffraction method (PXRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), and the Tauc method. Raman and FT-IR measurements were performed for the obtained samples, which additionally confirmed the crystallinity and phase composition of the samples. The influence of experimental conditions on composition (is it SnS or SnS2), morphology, and on the bandgap of obtained products is elucidated. It was found that longer sonication times favor more crystalline product. Each of bandgaps is direct and most of them show typical values - c.a. 1.3 eV for SnS and 2.4 eV for SnS2. However, there are some exceptions. Synthesized powders show a variety of forms such as needles, flower-like, rods, random agglomerates (SnS2) and balls (SnS). Using ethanol as a solvent led to powders of SnS2 independently of which tin chloride is used. Sonochemistry in ethylenediamine is more diverse: this solvent protects Sn2+ cations from oxidation so mostly SnS is obtained, while SnCl4 does not produce powder of SnS2 but Sn(SO4)2 instead or, at a higher ratio of thioacetamide to SnCl4, green clear mixture.

Change in Conductive-Radiative Heat Transfer Mechanism Forced by Graphite Microfiller in Expanded Polystyrene Thermal Insulation-Experimental and Simulated Investigations.

This article introduces an innovative approach to the investigation of the conductive-radiative heat transfer mechanism in expanded polystyrene (EPS) thermal insulation at negligible convection. Closed-cell EPS foam (bulk density 14-17 kg·m-3) in the form of panels (of thickness 0.02-0.18 m) was tested with 1-15 µm graphite microparticles (GMP) at two different industrial concentrations (up to 4.3% of the EPS mass). A heat flow meter (HFM) was found to be precise enough to observe all thermal effects under study: the dependence of the total thermal conductivity on thickness, density, and GMP content, as well as the thermal resistance relative gain. An alternative explanation of the total thermal conductivity "thickness effect" is proposed. The conductive-radiative components of the total thermal conductivity were separated, by comparing measured (with and without Al-foil) and simulated (i.e., calculated based on data reported in the literature) results. This helps to elucidate why a small addition of GMP (below 4.3%) forces such an evident drop in total thermal conductivity, down to 0.03 W·m-1·K-1. As proposed, a physical cause is related to the change in mechanism of the heat transfer by conduction and radiation. The main accomplishment is discovering that the change forced by GMP in the polymer matrix thermal conduction may dominate the radiation change. Hence, the matrix conduction component change is considered to be the major cause of the observed drop in total thermal conductivity of EPS insulation. At the microscopic level of the molecules or chains (e.g., in polymers), significant differences observed in the intensity of Raman spectra and in the glass transition temperature increase on differential scanning calorimetry(DSC) thermograms, when comparing EPS foam with and without GMP, complementarily support the above statement. An additional practical achievement is finding the maximum thickness at which one may reduce the "grey" EPS insulating layer, with respect to "dotted" EPS at a required level of thermal resistance. In the case of the thickest (0.30 m) panels for a passive building, above 18% of thickness reduction is found to be possible.

Raman scattering studies on very thin layers of gallium sulfide (GaS) as a function of sample thickness and temperature.

Gallium sulfide is a semiconducting material with a layered structure and a characteristic low interlayer interaction. Because of weak van der Waals forces, GaS crystals are relatively easy to exfoliate to very thin layers. In this work nanometric-GaS layers were obtained by a micro-mechanical exfoliation process and were transferred to Si/SiO2 substrate. The thickness of these layers was estimated from AFM measurements. Raman spectra were collected for different layer thicknesses ranging from one layer to bulk crystal. An analytical function fitted to experimental data is proposed to determine layer thickness from Raman measurements. For the first time, the Raman position and the FWHM of the main Raman peaks were measured on very thin GaS layers as a function of temperature in the range from 80 to 470 K. The first order temperature coefficients of the A 1g Raman peaks were determined. Phonon decay due to anharmonic processes at temperatures above 300 K in layers of thickness below 4 nm was observed. Contribution of optical phonon scattering processes to thermal properties of very thin GaS layers is discussed.

Temperature-dependent nonlinear phonon shifts in a supported MoS2 monolayer.

We report Raman spectra measurements on a MoS(2) monolayer supported on SiO(2) as a function of temperature. Unlike in previous studies, the positions of the two main Raman modes, E(2g)(1) and A(1g) exhibited nonlinear temperature dependence. Temperature dependence of phonon shifts and widths is explained by optical phonon decay process into two acoustic phonons. On the basis of Raman measurements, local temperature change under laser heating power at different global temperatures is derived. Obtained results contribute to our understanding of the thermal properties of two-dimensional atomic crystals and can help to solve the problem of heat dissipation, which is crucial for use in the next generation of nanoelectronic devices.