Dielectric and Ultrasonic Properties of PDMS/TiO2 Nanocomposites.

This work presents the dielectric and ultrasonic properties of polydimethylsiloxane (PDMS) nanocomposites filled with titanium dioxide nanoparticles. The dielectric study was performed over a very broad range of frequencies (20 Hz-3 THz). The dielectric permittivity was almost frequency-independent in all the composites at room temperature over the whole range of measurement frequencies, and the dielectric losses were very low under these conditions (less than 2). The dielectric permittivity strongly increases with the nanoparticle concentration according to the Maxwell-Garnet model. Therefore, the investigated composites are suitable for various flexible electronic applications, particularly in the microwave and terahertz frequency ranges. Dielectric dispersion and increased attenuation of ultrasonic waves were observed at lower temperatures (below 280 K) due to the relaxation of polymer molecules at the PDMS/TiO2 interface and in the polymer matrix. The relaxation time followed the Vogel-Vulcher law, while the freezing temperature increased with the titanium dioxide concentration due to interactions between the polymer molecules and nanoparticles. The significant hysteresis in the ultrasonic properties indicated that titanium dioxide acts as a crystallization center. This is confirmed by the correlation between the hysteresis in the ultrasonic properties and the structure of the composites. The small difference in the activation energy values obtained from the ultrasonic and dielectric investigations is related to the fact that the dielectric dispersion is slightly broader than the Debye-type dielectric dispersion.

Stable and Reusable Lace-like Black Silicon Nanostructures Coated with Nanometer-Thick Gold Films for SERS-Based Sensing.

We propose a simple, fast, and low-cost method for producing Au-coated black Si-based SERS-active substrates with a proven enhancement factor of 106. Room temperature reactive ion etching of silicon wafer followed by nanometer-thin gold sputtering allows the formation of a highly developed lace-type Si surface covered with homogeneously distributed gold islands. The mosaic structure of deposited gold allows the use of Au-uncovered Si domains for Raman peak intensity normalization. The fabricated SERS substrates have prominent uniformity (with less than 6% SERS signal variations over large areas, 100 × 100 µm2). It has been found that the storage of SERS-active substrates in an ambient environment reduces the SERS signal by less than 3% in 1 month and not more than 40% in 20 months. We showed that Au-coated black Si-based SERS-active substrates can be reused after oxygen plasma cleaning and developed relevant protocols for removing covalently bonded and electrostatically attached molecules. Experiments revealed that the Raman signal of 4-MBA molecules covalently bonded to the Au coating measured after the 10th cycle was just 4 times lower than that observed for the virgin substrate. A case study of the reusability of the black Si-based substrate was conducted for the subsequent detection of 10-5 M doxorubicin, a widely used anticancer drug, after the reuse cycle. The obtained SERS spectra of doxorubicin were highly reproducible. We demonstrated that the fabricated substrate permits not only qualitative but also quantitative monitoring of analytes and is suitable for the determination of concentrations of doxorubicin in the range of 10-9-10-4 M. Reusable, stable, reliable, durable, low-cost Au-coated black Si-based SERS-active substrates are promising tools for routine laboratory research in different areas of science and healthcare.

Piezoelectric Nanogenerators Based On BaTiO3/PDMS Composites for High-Frequency Applications.

A series of highly flexible and environmentally friendly composites based on polydimethylsiloxane (PDMS) filled with 200 nm size ferroelectric BaTiO3 (BTO) particles at different concentrations (from 7 to 23 vol %) have been fabricated by a simple dispersion method. The dielectric, piezoelectric, and ultrasonic properties have been studied. The ferroelectric state of BTO was confirmed by differential scanning calorimetry and ultrasonic spectroscopy. The addition of BTO into PDMS strongly affects the dielectric properties of the composites. At low temperatures close to 160 K, the PDMS matrix exhibits a dielectric anomaly related to a dynamic glass transition, which shifts to higher temperatures as the BTO content increases due to the strong interaction between polymer chains and nanoparticles. Ultrasonic measurements demonstrate the appearance of a piezoelectric voltage signal on a thin plate of the composite with the highest available filler concentration (23 vol %) under longitudinal stress applied by a 10 MHz ultrasonic wave. As a result, at room temperature, the detected signal is characterized by output voltage and specific stored energy values of 10 mV and 367.3 MeV/m2, respectively, followed by a further increase with cooling to 35 mV at 150 K. The proposed BTO/PDMS composite system is thus a potential candidate for nanogenerators, namely, a simple, flexible, and lead-free device converting high-frequency (10 MHz) mechanical vibrations into electrical voltage.

Multilayered Composites with Carbon Nanotubes for Electromagnetic Shielding Application.

Bulk polylactic acid (PLA)/multiwall carbon nanotube (MWCNT) composites were prepared and investigated in wide frequency ranges (20 Hz-1 MHz and 24-40 GHz). It was determined that the percolation threshold in bulk PLA/MWCNT composites is close to 0.2 vol.% MWCNT. However, the best microwave dielectric properties and absorption were observed in composites with 3.0-5.0 vol.% MWCNT. Therefore, for future investigations, we selected layered (laminate) polymeric structures with gradual changes in MWCNT concentration from 0.2 to 8.0 vol.% MWCNT. Two approaches to laminate structure designs were examined and compared: a five-layer composite and a nine-layer composite that included four pure PLA middle layers. The addition of MWCNT enhanced the elastic modulus by up to 1.4-fold and tensile strength by up to 1.2-fold, with the best performance achieved at 5.0 vol.% loading. High microwave shielding was observed for these layered PLA/MWCNT structures with a gradient change in MWCNT concentration (up to 26 dB in both transmission and absorption coefficients) in the broad frequency range (from 24 to 40 GHz). Obtained structures are highly anisotropic, and the absorption coefficient is 2-5 dB higher in the direction of MWCNT concentration increase; however, the transmission coefficient is the same in both directions. The properties of microwave absorption are mainly unaffected by the additional polymeric layers. The absorption of the layered structure is greater than the absorption of single-layer composites with an optimal MWCNT concentration of the same thickness. The proposed laminate structure design is promising in the field of efficient electromagnetic shielding.

Multiwavelength SERS of Magneto-Plasmonic Nanoparticles Obtained by Combined Laser Ablation and Solvothermal Methods.

The present study introduces a novel method for the synthesis of magneto-plasmonic nanoparticles (MPNPs) with enhanced functionality for surface-enhanced Raman scattering (SERS) applications. By employing pulsed laser ablation in liquid (PLAL) to synthesize plasmonic nanoparticles and wet chemistry to synthesize magnetic nanoparticles, we successfully fabricated chemically pure hybrid Fe3O4@Au and Fe3O4@Ag nanoparticles. We demonstrated a straightforward approach of an electrostatic attachment of the plasmonic and magnetic parts using positively charged polyethylenimine. The MPNPs displayed high SERS sensitivity and reproducibility, and the magnetic part allowed for the controlled separation of the nanoparticles from the reaction mixture, their subsequent concentration, and their precise deposition onto a specified surface area. Additionally, we fabricated alloy based MPNPs from AgxAu100-x (x = 50 and 80 wt %) targets with distinct localized surface plasmon resonance (LSPR) wavelengths. The compositions, morphologies, and optical properties of the nanoparticles were characterized by using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis spectroscopy, and multiwavelength Raman spectroscopy. A standard SERS marker, 4-mercaptobenzoic acid (4-MBA), validated the enhancement properties of the MPNPs and found an enhancement factor of 2 × 108 for the Fe3O4@Ag nanoparticles at 633 nm excitation. Lastly, we applied MPNP-enhanced Raman spectroscopy for the analysis of the biologically relevant molecule adenine and found a limit of detection of 10-7 M at 785 nm excitation. The integration of PLAL and wet chemical methods enabled the relatively fast and cost-effective production of MPNPs characterized by high SERS sensitivity and signal reproducibility that are required in various fields, including biomedicine, food safety, materials science, security, and defense.

Green Removal of DUV-Polarity-Modified PMMA for Wet Transfer of CVD Graphene.

To fabricate graphene-based high-frequency electronic and optoelectronic devices, there is a high demand for scalable low-contaminated graphene with high mobility. Graphene synthesized via chemical vapor deposition (CVD) on copper foil appears promising for this purpose, but residues from the polymethyl methacrylate (PMMA) layer, used for the wet transfer of CVD graphene, drastically affect the electrical properties of graphene. Here, we demonstrate a scalable and green PMMA removal technique that yields high-mobility graphene on the most common technologically relevant silicon (Si) substrate. As the first step, the polarity of the PMMA was modified under deep-UV irradiation at λ = 254 nm, due to the formation of ketones and aldehydes of higher polarity, which simplifies hydrogen bonding in the step of its dissolution. Modification of PMMA polarity was confirmed by UV and FTIR spectrometry and contact angle measurements. Consecutive dissolution of DUV-exposed PMMA in an environmentally friendly, binary, high-polarity mixture of isopropyl alcohol/water (more commonly alcohol/water) resulted in the rapid and complete removal of DUV-exposed polymers without the degradation of graphene properties, as low-energy exposure does not form free radicals, and thus the released graphene remained intact. The high quality of graphene after PMMA removal was confirmed by SEM, AFM, Raman spectrometry, and by contact and non-contact electrical conductivity measurements. The removal of PMMA from graphene was also performed via other common methods for comparison. The charge carrier mobility in graphene films was found to be up to 6900 cm2/(V·s), demonstrating a high potential of the proposed PMMA removal method in the scalable fabrication of high-performance electronic devices based on CVD graphene.

Phosphate Ceramics with Silver Nanoparticles for Electromagnetic Shielding Applications.

Ceramic composites with nanoparticles are intensively investigated due to their unique thermal, mechanic and electromagnetic properties. In this work, dielectric properties of phosphate ceramics with round silver nanoparticles of various sizes were studied in the wide frequency range of 20 Hz-40 GHz for microwave shielding applications. The percolation threshold in ceramics is close to 30 wt.% of Ag nanoparticles content and it is higher for bigger-sized nanoparticles. The microwave complex dielectric permittivity of ceramics above the percolation threshold is rather high (ε' = 10 and ε″ = 10 at 30 GHz for ceramics with 50 wt.% inclusions of 30-50 nm size, it corresponds to almost 61% absorption of 2 mm-thickness plate) therefore these ceramics are suitable for microwave shielding applications. Moreover, the microwave absorption is bigger for ceramics with a larger concentration of fillers. In addition, it was demonstrated that the electrical transport in ceramics is thermally activated above room temperature and the potential barrier is almost independent of the concentration of nanoparticles. At very low temperature, the electrical transport in ceramics can be related to electron tunneling.

Photoelectric Properties of Planar and Mesoporous Structured Perovskite Solar Cells.

The high efficiency of perovskite solar cells strongly depends on the quality of perovskite films and carrier extraction layers. Here, we present the results of an investigation of the photoelectric properties of solar cells based on perovskite films grown on compact and mesoporous titanium dioxide layers. Kinetics of charge carrier transport and their extraction in triple-cation perovskite solar cells were studied by using transient photovoltage and time-resolved photoluminescence decay measurements. X-ray diffraction analysis revealed that the crystallinity of the perovskite films grown on mesoporous titanium dioxide is better compared to the films grown on compact TiO2. Mesoporous structured perovskite solar cells are found to have higher power conversion efficiency mainly due to enlarged perovskite/mesoporous -TiO2 interfacial area and better crystallinity of their perovskite films.

Silicon Passivation by Ultrathin Hafnium Oxide Layer for Photoelectrochemical Applications.

Hafnium oxide (HfO2) films on silicon have the potential for application in photovoltaic devices. However, very little is known about the photoelectrochemical and protective properties of HfO2 films on Si. In this study, ultrathin films of HfO2 in the range of 15-70 nm were deposited on p-Si and Au substrates by atomic layer deposition (ALD). Grazing incidence X-ray diffraction (GI-XRD) identified the amorphous structure of the layers. Quartz crystal nanogravimetry (QCN) with Si and Au substrates indicated dynamics of electrolyte intake into the oxide film. No indications of oxide dissolution have been observed in acid (pH 3) and alkaline (pH 12) electrolytes. Mott-Schottky plots showed that the dark Si surface adjacent to the SiHfO2 interface is positively charged in an acid electrolyte and negatively charged in an alkaline electrolyte. The number of photoelectrons was determined to be much greater than the doping level of silicon. The cathodic photoactivity of the p-Si electrode protected by HfO2 films was studied with respect to the reaction of hydrogen reduction in acid and alkaline solutions. In acid solution, the film enhanced the reduction process when compared to that on the coating free electrode. The acceleration effect was explained in terms of prevention of silicon oxide formation, whose passivating capability is higher than that of hafnia films. In an alkaline electrolyte, an inhibition effect of the film was determined. Hafnia films protected Si from corrosion in this medium; however, at the same time, the film reduced electrode activity.

Impact of Cesium Concentration on Optoelectronic Properties of Metal Halide Perovskites.

Performance of a perovskite solar cell is largely influenced by the optoelectronic properties of metal halide perovskite films. Here we study the influence of cesium concentration on morphology, crystal structure, photoluminescence and optical properties of the triple cation perovskite film. Incorporation of small amount (x = 0.1) of cesium cations into Csx(MA0.17FA0.83)1−x Pb(I0.83Br0.17)3 leads to enhanced power conversion efficiency (PCE) of the solar cell resulting mainly from significant rise of the short-current density and the fill factor value. Further increase of Cs concentration (x > 0.1) decreases the film's phase purity, carrier lifetime and correspondingly reduces PCE of the solar cell. Higher concentration of Cs (x ≥ 0.2) causes phase segregation of the perovskite alongside with formation of Cs-rich regions impeding light absorption.

Nanostructured Manganite Films Grown by Pulsed Injection MOCVD: Tuning Low- and High-Field Magnetoresistive Properties for Sensors Applications.

The results of colossal magnetoresistance (CMR) properties of La0.83Sr0.17Mn1.21O3 (LSMO) films grown by pulsed injection MOCVD technique onto various substrates are presented. The films with thicknesses of 360 nm and 60 nm grown on AT-cut single crystal quartz, polycrystalline Al2O3, and amorphous Si/SiO2 substrates were nanostructured with column-shaped crystallites spread perpendicular to the film plane. It was found that morphology, microstructure, and magnetoresistive properties of the films strongly depend on the substrate used. The low-field MR at low temperatures (25 K) showed twice higher values (-31% at 0.7 T) for LSMO/quartz in comparison to films grown on the other substrates (-15%). This value is high in comparison to results published in literature for manganite films prepared without additional insulating oxides. The high-field MR measured up to 20 T at 80 K was also the highest for LSMO/quartz films (-56%) and demonstrated the highest sensitivity S = 0.28 V/T at B = 0.25 T (voltage supply 2.5 V), which is promising for magnetic sensor applications. It was demonstrated that Mn excess Mn/(La + Sr) = 1.21 increases the metal-insulator transition temperature of the films up to 285 K, allowing the increase in the operation temperature of magnetic sensors up to 363 K. These results allow us to fabricate CMR sensors with predetermined parameters in a wide range of magnetic fields and temperatures.

Gold Nanoparticles Generated Using the Nanosecond Laser Treatment of Multilayer Films and Their Use for SERS Applications.

Surface-enhanced Raman spectroscopy (SERS) substrates fabricated using a repeated laser treatment of thin gold films are demonstrated. The presented SERS substrates consist of the gold nanoparticles, whose density and size depend on the used film thickness and number of treated films. The larger number of the treated gold film layers increases the amount of larger nanoparticles (size >20 nm). However, a large number of small nanoparticles (5-20 nm) in all cases is also observed. The manufactured SERS substrates exhibit a high enhancement factor, which is in the range of 106. The enhancement factor can be increased by adding an additional Au coating on the top of nanoparticles generated from a single gold layer. The demonstrated laser-based fabrication approach of large-scale SERS substrates is simple, reliable, without the use of chemicals for the reduction and stabilization of nanoparticles, and cost-effective.

Platinum Nanoparticles Modified Copper/Titanium Electrodes as Electrocatalysts for Borohydride Oxidation.

In this study, sodium borohydride oxidation has been investigated on the platinum nanoparticles modified copper/titanium catalysts (PtNPsCu/Ti), which were fabricated by employing the electroless copper plating and galvanic displacement technique. ICP-OES, XRD, FESEM, and EDX have been used to characterize PtNPsCu/Ti catalysts' composition, structure, and surface morphology. The oxidation of sodium borohydride was examined on the PtNPsCu/Ti catalysts using cyclic voltammetry and chrono-techniques.

0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 Phosphate Composites: Dielectric and Ferroelectric Properties.

Composite materials with 83 wt.% of the 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 distributed in phosphate-bonded ceramics were prepared at three different pressures. A phosphate matrix comprises a mixture of an aluminum phosphate binder and melted periclase, MgO. All samples demonstrate a homogeneous distribution of the ferroelectric perovskite phase and are thermally stable up to 900 K. At higher temperatures, the pyrochlore cubic phase forms. It has been found that the density of the composites non-monotonously depends on the pressure. The dielectric permittivity and losses substantially increase with the density of the samples. The fabricated composites demonstrate diffused ferroelectric-paraelectric transition and prominent piezoelectric properties.

Terahertz Photoconductivity Spectra of Electrodeposited Thin Bi Films.

Electron dynamics in the polycrystalline bismuth films were investigated by measuring emitted terahertz (THz) radiation pulses after their photoexcitation by tunable wavelength femtosecond duration optical pulses. Bi films were grown on metallic Au, Pt, and Ag substrates by the electrodeposition method with the Triton X-100 electrolyte additive, which allowed us to obtain more uniform films with consistent grain sizes on any substrate. It was shown that THz pulses are generated due to the spatial separation of photoexcited electrons and holes diffusing from the illuminated surface at different rates. The THz photoconductivity spectra analysis has led to a conclusion that the thermalization of more mobile carriers (electrons) is dominated by the carrier-carrier scattering rather than by their interaction with the lattice.

Dielectric Relaxation Spectroscopy and Synergy Effects in Epoxy/MWCNT/Ni@C Composites.

The dielectric/electric properties of the Ni@C (carbon-coated Ni)/epoxy composites and Ni@C/MWCNTs (multi-walled carbon nanotubes)/epoxy composites loaded with fixed MWCNTs amount just below the percolation threshold (0.09 vol.%) and Ni@C at different concentrations up to 1 vol.% were investigated in broad frequency (20 Hz-40 GHz) and temperature (30 K-500 K) regions. In composites with the only Ni@C nanoparticles, the electrical percolation threshold was determined between 10 and 15 vol.%. Above the percolation threshold the dielectric permittivity (ε') and the electrical conductivity (σ) of the composites loaded with Ni@C only are high enough, i.e., ε' = 105 and σ = 0.6 S/m at 100 Hz for composites with 30 vol.% Ni@C, to be used for electromagnetic shielding applications. The annealing to 500 K was proved to be an effective and simple tool to decrease the percolation threshold in epoxy/Ni@C composites. For hybrid composites series an optimal concentration of Ni@C (0.2 vol.%) was determined, leading to the conductivity absolute values several orders of magnitude higher than that of a composite filled with MWCNTs only. The synergy effects of using both fillers have been discussed. Below room temperature the electrical transport is mainly governed by epoxy resin compression in all composites, while the electron tunnelling was observed only in hybrid composites below 200 K. At higher temperatures (above 400 K), in addition to the nanoparticles redistribution effects, the electrical conductivity of epoxy resin makes a significant contribution to the total composite conductivity. The dielectric relaxation spectroscopy allows estimating the nanoparticles distributions in polymer matrix and could be used as the non-destructive and fast alternate to microscopy techniques for general polymer composite fabrication control.

Surface-Enhanced Raman Spectroscopy of Organic Molecules and Living Cells with Gold-Plated Black Silicon.

Black silicon (bSi) refers to an etched silicon surface comprising arrays of microcones that effectively suppress reflection from UV to near-infrared (NIR) while simultaneously enhancing the scattering and absorption of light. This makes bSi covered with a nm-thin layer of plasmonic metal, i.e., gold, an attractive substrate material for sensing of bio-macromolecules and living cells using surface-enhanced Raman spectroscopy (SERS). The performed Raman measurements accompanied with finite element numerical simulation and density functional theory analysis revealed that at the 785 nm excitation wavelength, the SERS enhancement factor of the bSi/Au substrate is as high as 108 due to a combination of electromagnetic and chemical mechanisms. This finding makes the SERS-active bSi/Au substrate suitable for detecting trace amounts of organic molecules. We demonstrate the outstanding performance of this substrate by highly sensitive and specific detection of a small organic molecule of 4-mercaptobenzoic acid and living C6 rat glioma cell nucleic acids/proteins/lipids. Specifically, the bSi/Au SERS-active substrate offers a unique opportunity to investigate the living cells' malignant transformation using characteristic protein disulfide Raman bands as a marker. Our findings evidence that bSi/Au provides a pathway to the highly sensitive and selective, scalable, and low-cost substrate for lab-on-a-chip SERS biosensors that can be integrated into silicon-based photonics devices.

Macro-, Micro- and Nano-Roughness of Carbon-Based Interface with the Living Cells: Towards a Versatile Bio-Sensing Platform.

Integration of living cells with nonbiological surfaces (substrates) of sensors, scaffolds, and implants implies severe restrictions on the interface quality and properties, which broadly cover all elements of the interaction between the living and artificial systems (materials, surface modifications, drug-eluting coatings, etc.). Substrate materials must support cellular viability, preserve sterility, and at the same time allow real-time analysis and control of cellular activity. We have compared new substrates based on graphene and pyrolytic carbon (PyC) for the cultivation of living cells. These are PyC films of nanometer thickness deposited on SiO2 and black silicon and graphene nanowall films composed of graphene flakes oriented perpendicular to the Si substrate. The structure, morphology, and interface properties of these substrates are analyzed in terms of their biocompatibility. The PyC demonstrates interface biocompatibility, promising for controlling cell proliferation and directional intercellular contact formation while as-grown graphene walls possess high hydrophobicity and poor biocompatibility. By performing experiments with C6 glioma cells we discovered that PyC is a cell-friendly coating that can be used without poly-l-lysine or other biopolymers for controlling cell adhesion. Thus, the opportunity to easily control the physical/chemical properties and nanotopography makes the PyC films a perfect candidate for the development of biosensors and 3D bioscaffolds.

Low Resistance TiO2/p-Si Heterojunction for Tandem Solar Cells.

Niobium-doped titanium dioxide (Ti1-xNbxO2) films were grown on p-type Si substrates at low temperature (170 °C) using an atomic layer deposition technique. The as-deposited films were amorphous and showed low electrical conductivity. The films became electrically well-conducting and crystallized into the an anatase structure upon reductive post-deposition annealing at 600 °C in an H2 atmosphere for 30 min. It was shown that the Ti0.72Nb0.28O2/p+-Si heterojunction fabricated on low resistivity silicon (10-3 Ω cm) had linear current-voltage characteristic with a specific contact resistivity as low as 23 mΩ·cm2. As the resistance dependence on temperature revealed, the current across the Ti0.72Nb0.28O2/p+-Si heterojunction was mainly determined by the band-to-band charge carrier tunneling through the junction.

Dielectric Relaxation in the Hybrid Epoxy/MWCNT/MnFe2O4 Composites.

The electrical properties of epoxy/MWCNT (multi-walled carbon nanotubes)/MnFe2O4 hybrid composites loaded with MWCNTs (below, 0.09 vol.%, and above, 0.58 vol.%, percolation threshold) and varying concentrations of MnFe2O4 up to 10 vol.% were studied in a wide frequency range (20 Hz-40 GHz) at different temperatures (20 K-500 K). At low frequencies, the dielectric permittivity and the electrical conductivity of composites with fixed amounts of MWCNT are strongly dependent on MnFe2O4 content. For MWCNT concentrations above the percolation threshold (i.e., 0.58 vol.%), the electrical conductivity highly decreases with the increase of the MnFe2O4 fraction. In contrast, for the epoxy/MWCNT just below the onset of electrical conductivity (0.09 vol.% of MWCNTs), there exists an optimal concentration of MnFe2O4 inclusions (i.e., 0.025 vol.%), leading to a dramatic increase of the electrical conductivity by three orders of magnitude. The electrical transport in composites is mainly governed by electron tunneling at lower temperatures (below 200 K), and it is highly impacted by the matrix conductivity at higher temperatures (above 400 K). The electrical properties were discussed in terms of the Maxwell-Wagner relaxation and distributions of relaxation times. A non-invasive platform based on dielectric relaxation spectroscopy was proposed for enhancing the synergetic effect coursed by using multiple nanoinclusions in polymer composites just below the percolation threshold.