In situ optical sub-wavelength thickness control of porous anodic aluminum oxide.

Porous anodic aluminum oxide (PAAO), sometimes referred to as nanoporous anodic alumina, serves as a cost-effective template for nanofabrication in many fields of science and engineering. However, production of ultrathin PAAO membranes with precise thickness in the optical sub-wavelength range remains challenging because of difficulties regarding process control at the initial stage of anodic oxidation. In this study, we demonstrate a technique for consistently manufacturing PAAO with the targeted thickness. An electrochemical cell with an optical window was designed for reflectance spectroscopy of PAAO during anodization. Real-time fitting of spectra to a transfer-matrix model enabled continuous monitoring of the thickness growth of the PAAO layer. Automation software was designed to terminate the anodization process at preset PAAO thickness values. While the concept was illustrated using the widely used method of anodization in a 0.3 M oxalic acid electrolyte with a 40 V potential, it can be readily customized for other protocols. PAAO layers with effective thickness below 300 nm could be produced with a few nanometers accuracy using single-crystal aluminum substrates. The results were confirmed using spectroscopic ellipsometry. The method for controlling the thickness during anodization eliminates the necessity of sample sectioning for electron microscopy and is particularly valuable for the small-scale production of PAAO-based functional optical coatings.

Characterization of Mechanical Oscillations in Bismuth Selenide Nanowires at Low Temperatures.

A single transistor preamplifier circuit was designed to facilitate electrical detection of mechanical oscillations in nanoelectromechanical systems (NEMSs) at low temperatures. The amplifier was integrated in the close vicinity of the nanowire inside the cryostat to minimize cabling load and interference. The function of the circuit was impedance conversion for current flow measurements in NEMSs with a high internal resistance. The circuit was tested to operate at temperatures as low as 5 K and demonstrated the ability to detect oscillations in double-clamped bismuth selenide nanowires upon excitation by a 0.1 MHz-10 MHz AC signal applied to a mechanically separated gate electrode. A strong resonance frequency dependency on temperature was observed. A relatively weak shift in the oscillation amplitude and resonance frequency was measured when a DC bias voltage was applied to the gate electrode at a constant temperature.

Low-Vacuum Catalyst-Free Physical Vapor Deposition and Magnetotransport Properties of Ultrathin Bi2Se3 Nanoribbons.

In this work, a simple catalyst-free physical vapor deposition method is optimized by adjusting source material pressure and evaporation time for the reliable obtaining of freestanding nanoribbons with thicknesses below 15 nm. The optimum synthesis temperature, time and pressure were determined for an increased yield of ultrathin Bi2Se3 nanoribbons with thicknesses of 8-15 nm. Physical and electrical characterization of the synthesized Bi2Se3 nanoribbons with thicknesses below 15 nm revealed no degradation of properties of the nanoribbons, as well as the absence of the contribution of trivial bulk charge carriers to the total conductance of the nanoribbons.

Humidity-dependent electrical performance of CuO nanowire networks studied by electrochemical impedance spectroscopy.

Electrochemical impedance spectroscopy was applied for studying copper oxide (CuO) nanowire networks assembled between metallic microelectrodes by dielectrophoresis. The influence of relative humidity (RH) on electrical characteristics of the CuO nanowire-based system was assessed by measurements of the impedance Z. A slight increase of Z with increasing RH at low humidity was followed by a three orders of magnitude decrease of Z at RH above 50-60%. The two opposite trends observed across the range of the examined RH of 5-97% can be caused by water chemisorption and physisorption at the nanowire interface, which suppress electronic transport inside the p-type semiconductor nanowire but enhance ionic transport in the water layers adsorbed on the nanowire surface. Possible physicochemical processes at the nanowire surface are discussed in line with equivalent circuit parameters obtained by fitting impedance spectra. The new investigation data can be useful to predict the behavior of nanostructured CuO in humid environments, which is favorable for advancing technology of nanowire-based systems suitable for sensor applications.

Positive and Negative Changes in the Electrical Conductance Related to Hybrid Filler Distribution Gradient in Composite Flexible Thermoelectric Films Subjected to Bending.

P-type multiwalled carbon nanotubes (MWCNTs), as well as heterostructures fabricated by direct deposition of inorganic thermoelectric materials as antimony and bismuth chalcogenides on MWCNT networks are known as perspective materials for application in flexible thermoelectric polymer-based composites. In this work, the electrical response of three types of Sb2Te3-MWCNT heterostructures-based flexible films-free standing on a flexible substrate, encapsulated in polydimethylsiloxane (PDMS), and mixed in polyvinyl alcohol (PVA) is studied in comparison with the flexible films prepared by the same methods using bare MWCNTs. The electrical conductance of these films when each side of it was subsequently subjected to compressive and tensile stress during the film bending down to a 3 mm radius is investigated in relation to the distribution gradient of Sb2Te3-MWCNT heterostructures or bare MWCNTs within the film. It is found that all investigated Sb2Te3-MWCNT films exhibit a reversible increase in the conductance in response to the compressive stress of the film side with the highest filler concentration and its decrease in response to the tensile stress. In contrast, free-standing and encapsulated bare MWCNT networks with uniform distribution of nanotubes showed a decrease in the conductance irrelevant to the bending direction. In turn, the samples with the gradient distribution of the MWCNTs, prepared by mixing the MWCNTs with PVA, revealed behavior that is similar to the Sb2Te3-MWCNT heterostructures-based films. The analysis of the processes impacting the changes in the conductance of the Sb2Te3-MWCNT heterostructures and bare MWCNTs is performed. The proposed in this work bending method can be applied for the control of the uniformity of distribution of components in heterostructures and fillers in polymer-based composites.

Electrochemical Immunosensor for the Determination of Antibodies against Prostate-Specific Antigen Based on ZnO Nanostructures.

In this study, ZnO nanostructures with different types of morphologies and particle sizes were evaluated and applied for the development of an immunosensor. The first material was composed of spherical, polydisperse nanostructures with a particle size in the range of 10-160 nm. The second was made up of more compact rod-like spherical nanostructures with the diameter of these rods in the range of 50-400 nm, and approximately 98% of the particles were in the range of 20-70 nm. The last sample of ZnO was made up of rod-shaped particles with a diameter of 10-80 nm. These ZnO nanostructures were mixed with Nafion solution and drop-casted onto screen-printed carbon electrodes (SPCE), followed by a further immobilization of the prostate-specific antigen (PSA). The affinity interaction of PSA with monoclonal antibodies against PSA (anti-PSA) was evaluated using the differential pulse voltammetry technique. The limit of detection and limit of quantification of anti-PSA were determined as 1.35 nM and 4.08 nM for compact rod-shaped spherical ZnO nanostructures, and 2.36 nM and 7.15 nM for rod-shaped ZnO nanostructures, respectively.

p-Type PVA/MWCNT-Sb2Te3 Composites for Application in Different Types of Flexible Thermoelectric Generators in Combination with n-Type PVA/MWCNT-Bi2Se3 Composites.

This work is devoted to the fabrication of p-type polyvinyl alcohol (PVA)-based flexible thermoelectric composites using multiwall carbon nanotubes-antimony telluride (MWCNT-Sb2Te3) hybrid filler, the study of the thermoelectrical and mechanical properties of these composites, and the application of these composites in two types (planar and radial) of thermoelectric generators (TEG) in combination with the previously reported PVA/MWCNT-Bi2Se3 flexible thermoelectric composites. While the power factors of PVA/MWCNT-Sb2Te3 and PVA/MWCNT-Bi2Se3 composites with 15 wt.% filler were found to be similar, the PVA/MWCNT-Sb2Te3 composite with 25 wt.% filler showed a ~2 times higher power factor in comparison with the PVA/MWCNT-Bi2Se3 composites with 30 wt.% filler, which is attributed to its reduced electrical resistivity. In addition, developed PVA/MWCNT-Sb2Te3 composites showed a superior mechanical, electrical, and thermoelectric stability during 100 consequent bending cycles down to a 3 mm radius, with insignificant fluctuations of the resistance within 0.01% of the initial resistance value of the not bent sample. Demonstrated for the first time, 2-leg TEGs composed from p-type PVA/MWCNT-Sb2Te3 and n-type PVA/MWCNT-Bi2Se3 composites showed a stable performance under different external loads and showed their potential for applications involving low temperature gradients and power requirements in the range of nW.

Optimization of Colloidal Gold Nanoparticles on Porous Anodic Aluminum Oxide Substrates for Refractometric Sensing.

A new composite metal-insulator-metal (MIM) system consisting of exceptionally dense non-close-packed (NCP) arrays of gold or silver nanoparticles, porous anodic aluminum oxide (PAAO), and bulk aluminum substrate interacts strongly with visible light and may become a very useful component for optical applications. The proposed MIM structure can be synthesized using accessible lithography-free chemical and physical processes (anodization and capillary force assisted colloidal particle deposition) that are suitable for the low-cost production of specialized devices. Here, we present a systematic study to determine the essential MIM structure parameters (nanoparticle size and PAAO layer thickness) for localized surface plasmon resonance (LSPR) refractometric sensing. A performance comparison was done by recording the spectra of scattered light upon angled illumination in media with different refractive indices. A clear advantage for maximizing the signal to background ratio was observed in the case of 60 and 80 nm Au nanoparticles with a PAAO thickness in a narrow range between 300 and 375 nm. Sensitivity exceeding a 200 nm peak wavelength shift per refractive index unit was found for 60 nm Au nanoparticles on approximately 500-nm-thick PAAO. The experimental observations were supported by finite-difference time-domain (FDTD) simulations.

Distribution of Iron Nanoparticles in Arrays of Vertically Aligned Carbon Nanotubes Grown by Chemical Vapor Deposition.

Arrays of aligned carbon nanotubes (CNTs) are anisotropic nanomaterials possessing a high length-to-diameter aspect ratio, channels passing through the array, and mechanical strength along with flexibility. The arrays are produced in one step using aerosol-assisted catalytic chemical vapor deposition (CCVD), where a mixture of carbon and metal sources is fed into the hot zone of the reactor. Metal nanoparticles catalyze the growth of CNTs and, during synthesis, are partially captured into the internal cavity of CNTs. In this work, we considered various stages of multi-walled CNT (MWCNT) growth on silicon substrates from a ferrocene-toluene mixture and estimated the amount of iron in the array. The study showed that although the mixture of precursors supplies evenly to the reactor, the iron content in the upper part of the array is lower and increases toward the substrate. The size of carbon-encapsulated iron-based nanoparticles is 20-30 nm, and, according to X-ray diffraction data, most of them are iron carbide Fe3C. The reasons for the gradient distribution of iron nanoparticles in MWCNT arrays were considered, and the possibilities of controlling their distribution were evaluated.

Nanometric Moiré Stripes on the Surface of Bi2Se3 Topological Insulator.

Mismatch between adjacent atomic layers in low-dimensional materials, generating moiré patterns, has recently emerged as a suitable method to tune electronic properties by inducing strong electron correlations and generating novel phenomena. Beyond graphene, van der Waals structures such as three-dimensional (3D) topological insulators (TIs) appear as ideal candidates for the study of these phenomena due to the weak coupling between layers. Here we discover and investigate the origin of 1D moiré stripes on the surface of Bi2Se3 TI thin films and nanobelts. Scanning tunneling microscopy and high-resolution transmission electron microscopy reveal a unidirectional strained top layer, in the range 14-25%, with respect to the relaxed bulk structure, which cannot be ascribed to the mismatch with the substrate lattice but rather to strain induced by a specific growth mechanism. The 1D stripes are characterized by a spatial modulation of the local density of states, which is strongly enhanced compared to the bulk system. Density functional theory calculations confirm the experimental findings, showing that the TI surface Dirac cone is preserved in the 1D moiré stripes, as expected from the topology, though with a heavily renormalized Fermi velocity that also changes between the top and valley of the stripes. The strongly enhanced density of surface states in the TI 1D moiré superstructure can be instrumental in promoting strong correlations in the topological surface states, which can be responsible for surface magnetism and topological superconductivity.

Magnetotransport Studies of Encapsulated Topological Insulator Bi2Se3 Nanoribbons.

The majority of proposed exotic applications employing 3D topological insulators require high-quality materials with reduced dimensions. Catalyst-free, PVD-grown Bi2Se3 nanoribbons are particularly promising for these applications due to the extraordinarily high mobility of their surface Dirac states, and low bulk carrier densities. However, these materials are prone to the formation of surface accumulation layers; therefore, the implementation of surface encapsulation layers and the choice of appropriate dielectrics for building gate-tunable devices are important. In this work, all-around ZnO-encapsulated nanoribbons are investigated. Gate-dependent magnetotransport measurements show improved charge transport characteristics as reduced nanoribbon/substrate interface carrier densities compared to the values obtained for the as-grown nanoribbons on SiO2 substrates.

Flexible N-Type Thermoelectric Composites Based on Non-Conductive Polymer with Innovative Bi2Se3-CNT Hybrid Nanostructured Filler.

This research is devoted to the fabrication of polyvinyl alcohol (PVOH) based n-type thermoelectric composites with innovative hybrid bismuth selenide-multiwalled carbon nanotube (Bi2Se3-MWCNT) fillers for application in flexible thermoelectric devices. Hybrid fillers were synthesized by direct deposition of Bi2Se3 on multiwalled carbon nanotubes using a physical vapor deposition method, thus ensuring direct electrical contact between the carbon nanotubes and Bi2Se3. The Seebeck coefficient of prepared PVOH/Bi2Se3-MWCNT composites was found to be comparable with that for the Bi2Se3 thin films, reaching -100 µV·K-1 for the composite with 30 wt.% filler, and fluctuations of the resistance of these composites did not exceed 1% during 100 repetitive bending cycles down to 10 mm radius, indicating the good mechanical durability of these composites and proving their high potential for application in flexible thermoelectrics. In addition, other properties of the fabricated composites that are important for the use of polymer-based materials such as thermal stability, storage modulus and linear coefficient of thermal expansion were found to be improved in comparison with the neat PVOH.

High-Yield Growth and Tunable Morphology of Bi2Se3 Nanoribbons Synthesized on Thermally Dewetted Au.

The yield and morphology (length, width, thickness) of stoichiometric Bi2Se3 nanoribbons grown by physical vapor deposition is studied as a function of the diameters and areal number density of the Au catalyst nanoparticles of mean diameters 8-150 nm formed by dewetting Au layers of thicknesses 1.5-16 nm. The highest yield of the Bi2Se3 nanoribbons is reached when synthesized on dewetted 3 nm thick Au layer (mean diameter of Au nanoparticles ~10 nm) and exceeds the nanoribbon yield obtained in catalyst-free synthesis by almost 50 times. The mean lengths and thicknesses of the Bi2Se3 nanoribbons are directly proportional to the mean diameters of Au catalyst nanoparticles. In contrast, the mean widths of the Bi2Se3 nanoribbons do not show a direct correlation with the Au nanoparticle size as they depend on the contribution ratio of two main growth mechanisms-catalyst-free and vapor-liquid-solid deposition. The Bi2Se3 nanoribbon growth mechanisms in relation to the Au catalyst nanoparticle size and areal number density are discussed. Determined charge transport characteristics confirm the high quality of the synthesized Bi2Se3 nanoribbons, which, together with the high yield and tunable morphology, makes these suitable for application in a variety of nanoscale devices.

Fabrication of an Extremely Cheap Poly(3,4-ethylenedioxythiophene) Modified Pencil Lead Electrode for Effective Hydroquinone Sensing.

Hydroquinone (HQ) is one of the major deleterious metabolites of benzene in the human body, which has been implicated to cause various human diseases. In order to fabricate a feasible sensor for the accurate detection of HQ, we attempted to electrochemically modify a piece of common 2B pencil lead (PL) with the conductive poly(3,4-ethylenedioxythiophene) or PEDOT film to construct a PEDOT/PL electrode. We then examined the performance of PEDOT/PL in the detection of hydroquinone with different voltammetry methods. Our results have demonstrated that PEDOT film was able to dramatically enhance the electrochemical response of pencil lead electrode to hydroquinone and exhibited a good linear correlation between anodic peak current and the concentration of hydroquinone by either cyclic voltammetry or linear sweep voltammetry. The influences of PEDOT film thickness, sample pH, voltammetry scan rate, and possible chemical interferences on the measurement of hydroquinone have been discussed. The PEDOT film was further characterized by SEM with EDS and FTIR spectrum, as well as for stability with multiple measurements. Our results have demonstrated that the PEDOT modified PL electrode could be an attractive option to easily fabricate an economical sensor and provide an accurate and stable approach to monitoring various chemicals and biomolecules.

Fabrication and Characterization of Double- and Single-Clamped CuO Nanowire Based Nanoelectromechanical Switches.

Electrostatically actuated nanoelectromechanical (NEM) switches hold promise for operation with sharply defined ON/OFF states, high ON/OFF current ratio, low OFF state power consumption, and a compact design. The present challenge for the development of nanoelectromechanical system (NEMS) technology is fabrication of single nanowire based NEM switches. In this work, we demonstrate the first application of CuO nanowires as NEM switch active elements. We develop bottom-up and top-down approaches for NEM switch fabrication, such as CuO nanowire synthesis, lithography, etching, dielectrophoretic alignment of nanowires on electrodes, and nanomanipulations for building devices that are suitable for scalable production. Theoretical modelling finds the device geometry that is necessary for volatile switching. The modelling results are validated by constructing gateless double-clamped and single-clamped devices on-chip that show robust and repeatable switching. The proposed design and fabrication route enable the scalable integration of bottom-up synthesized nanowires in NEMS.

Size Distribution, Mechanical and Electrical Properties of CuO Nanowires Grown by Modified Thermal Oxidation Methods.

Size distribution, Young's moduli and electrical resistivity are investigated for CuO nanowires synthesized by different thermal oxidation methods. Oxidation in dry and wet air were applied for synthesis both with and without an external electrical field. An increased yield of high aspect ratio nanowires with diameters below 100 nm is achieved by combining applied electric field and growth conditions with additional water vapour at the first stage of synthesis. Young's moduli determined from resonance and bending experiments show similar diameter dependencies and increase above 200 GPa for nanowires with diameters narrower than 50 nm. The nanowires synthesized by simple thermal oxidation possess electrical resistivities about one order of magnitude lower than the nanowires synthesized by electric field assisted approach in wet air. The high aspect ratio, mechanical strength and robust electrical properties suggest CuO nanowires as promising candidates for NEMS actuators.

Surface structure promoted high-yield growth and magnetotransport properties of Bi2Se3 nanoribbons.

In the present work, a catalyst-free physical vapour deposition method is used to synthesize high yield of Bi2Se3 nanoribbons. By replacing standard glass or quartz substrates with aluminium covered with ultrathin porous anodized aluminium oxide (AAO), the number of synthesized nanoribbons per unit area can be increased by 20-100 times. The mechanisms of formation and yield of the nanoribbons synthesized on AAO substrates having different arrangement and size of pores are analysed and discussed. It is shown that the yield and average length of the nanoribbons can base tuned by adjustment of the synthesis parameters. Analysis of magnetotransport measurements for the individual Bi2Se3 nanoribbons transferred on a Si/SiO2 substrate show the presence of three different populations of charge carriers, originating from the Dirac surface states, bulk carriers and carriers from a trivial 2DEG from an accumulation layer at the Bi2Se3 nanoribbon interface with the substrate.

Surface Lattice Resonances in Self-Assembled Arrays of Monodisperse Ag Cuboctahedra.

Plasmonic metal nanoparticles arranged in periodic arrays can generate surface lattice plasmon resonances (SLRs) with high Q-factors. These collective resonances are interesting because the associated electromagnetic field is delocalized throughout the plane of the array, enabling applications such as biosensing and nanolasing. In most cases such periodic nanostructures are created via top-down nanofabrication processes. Here we describe a capillary-force-assisted particle assembly method (CAPA) to assemble monodisperse single-crystal colloidal Ag cuboctahedra into nearly defect-free >1 cm2 hexagonal lattices. These arrays are large enough to be measured with conventional ultraviolet-visible spectroscopy, which revealed an extinction peak with a Q-factor of 30 at orthogonal illumination and up to 80 at oblique illumination angles. We explain how the experimental extinction changes with different light polarizations and angles of incidence, and compare the evolution of the peaks with computational models based on the coupled dipole approximation and the finite element method. These arrays can support high Q-factors even when exposed to air, because of the high aspect ratio of the single-crystal nanoparticles. The observation of SLRs in a self-assembled system demonstrates that a high level of long-range positional control can be achieved at the single-particle level.

Investigating the mechanical properties of GeSn nanowires.

Germanium tin (GeSn) has been proposed as a promising material for electronic and optical applications due to the formation of a direct band-gap at a Sn content >7 at%. Furthermore, the ability to manipulate the properties of GeSn at the nanoscale will further permit the realisation of advanced mechanical devices. Here we report for the first time the mechanical properties of GeSn nanowires (7.1-9.7 at% Sn) and assess their suitability as nanoelectromechanical (NEM) switches. Electron microscopy analysis showed the nanowires to be single crystalline, with surfaces covered by a thin native amorphous oxide layer. Mechanical resonance and bending tests at different boundary conditions were used to obtain size-dependent Young's moduli and to relate the mechanical characteristics of the alloy nanowires to geometry and Sn incorporation. The mechanical properties of the GeSn nanowires make them highly promising for applications in next generation NEM devices.

Zinc oxide nanorod based immunosensing platform for the determination of human leukemic cells.

Zinc oxide (ZnO) based nanostructures owing unique physical properties - high photoluminescence, biocompatibility and other characteristics, therefore, they attract attention as building blocks suitable for biosensor development. In this research as a target we have used human leukemic cell line IM9 (IM9). IM9 was derived from the patient with a multiple myeloma and expressed cluster of differentiation proteins СD19 on the surface of 85-95% here investigated cancer cells. As a control sample healthy human's peripheral blood mononuclear cells (PBMC) were used and the expression of CD19 protein was found only in 5-9% of these cells. Two types of antibodies labeled by fluorescein isothiocyanate (FITC) were used for the labeling of human leukemic cells: FITC-conjugated mouse antibodies against Human CD19 protein (anti-CD19-FITC*) and FITC-conjugated mouse antibodies against Human IgG1 protein (anti-IgG1-FITC*). In order to demonstrate the applicability of zinc oxide nanorods (ZnO-NRs) based platforms three types of ZnO-NRs-based structures were investigated: (i) ZnO-NRs modified by anti-CD19-FITC*; (ii) ZnO-NRs modified by IM9 cells, which were pre-incubated with anti-CD19-FITC*; (iii) ZnO-NRs modified by PBMC cells, which were pre-incubated with anti-CD19-FITC*. It was demonstrated that IM9 cells after specific interaction with anti-CD19-FITC* bind to ZnO-NRs (ZnO-NRs/IM9 +anti-CD19-FITC*) and photoluminescence based signal significantly increase in comparison with that observed in control samples, which contained PBMC cells incubated with anti-CD19-FITC* (ZnO-NRs/PBMC+anti-CD19-FITC*). The photoluminescence results are in good correlation with the data obtained by flow cytometry. This study illustrate that ZnO-NRs exhibit a photoluminescence signal suitable for the determination of anti-CD19-FITC* labeled IM9 cell line at concentrations - from 10 till 500 cells adsorbed per 1 mm2 of ZnO-NRs platform.