Igor Iatsunskyi

Tuning of ZnO 1D nanostructures by atomic layer deposition and electrospinning for optical gas sensor applications

We explored for the first time the ability of a three-dimensional polyacrylonitrile/ZnO material-prepared by a combination of electrospinning and atomic layer deposition (ALD) as a new material with a large surface area-to enhance the performance of optical sensors for volatile organic compound (VOC) detection. The photoluminescence (PL) peak intensity of these one-dimensional nanostructures has been enhanced by a factor of 2000 compared to a flat Si substrate. In addition, a phase transition of the ZnO ALD coating from amorphous to crystalline has been observed due to the properties of a polyacrylonitrile nanofiber template: surface strain, roughness, and an increased number of nucleation sites in comparison with a flat Si substrate. The greatly improved PL performance of these nanostructured surfaces could produce exciting materials for implantation in VOC optical sensor applications.

Boron Nitride Nanoporous Membranes with High Surface Charge by Atomic Layer Deposition

In this work, we report the design and the fine-tuning of boron nitride single nanopore and nanoporous membranes by atomic layer deposition (ALD). First, we developed an ALD process based on the use of BBr3 and NH3 as precursors in order to synthesize BN thin films. The deposited films were characterized in terms of thickness, composition, and microstructure. Next, we used the newly developed process to grow BN films on anodic aluminum oxide nanoporous templates, demonstrating the conformality benefit of BN prepared by ALD, and its scalability for the manufacturing of membranes. For the first time, the ALD process was then used to tune the diameter of fabricated single transmembrane nanopores by adjusting the BN thickness and to enable studies of the fundamental aspects of ionic transport on a single nanopore. At pH = 7, we estimated a surface charge density of 0.16 C·m-2 without slip and 0.07 C·m-2 considering a reasonable slip length of 3 nm. Molecular dynamics simulations performed with experimental conditions confirmed the conductivities and the sign of surface charges measured. The high ion transport results obtained and the ability to fine-tune nanoporous membranes by such a scalable method pave the way toward applications such as ionic separation, energy harvesting, and ultrafiltration devices.

Analytical, thermodynamical and kinetic characteristics of photoluminescence immunosensor for the determination of Ochratoxin A

Ochratoxin A (OTA) is one of the most widespread and dangerous food contaminants. Therefore, rapid, label-free and precise detection of low OTA concentrations requires novel sensing elements with advanced bio-analytical properties. In the present paper we report photoluminescence (PL) based immunosensor for the detection of OTA. During the development of immunosensor photoluminescent ZnO nanorods (ZnO-NRs) were deposited on glass substrate. Then the ZnO-NRs were silanized and covalently modified by Protein-A (Glass/ZnO-NRs/Protein-A). The latest structure was modified by antibodies against OTA (Anti-OTA) in order to form OTA-selective layer (Glass/ZnO-NRs/Protein-A/Anti-OTA). In order to improve immunosensors selectivity the surface of Glass/ZnO-NRs/Protein-A/Anti-OTA was additionally blocked by BSA. Formed Glass/ZnO-NRs/Protein-A/BSA&Anti-OTA structures were integrated within portable fiber optic detection system, what is important for the development of low cost and portable immunosensors. The immunosensor has been tested in a wide range of OTA concentrations from 10-4ng/ml until 20ng/ml. Interaction isotherms were derived from analytical signals of immunosensor. Association constant and Gibbs free energy for the interaction of Glass/ZnO-NRs/Protein-A/Anti-OTA with OTA were calculated, analyzed and compared with some other related results. Sensitivity range and limit of detection were determined as 0.1-1ng/ml and 10-2ng/ml, respectively. Interaction kinetics of ZnO-NRs with OTA was evaluated. Response time of the immunosensor toward OTA was in the range of 500-800s. Some insights related to the mechanism of PL-signal generation are proposed and discussed.

Design of Boron Nitride/Gelatin Electrospun Nanofibers for Bone Tissue Engineering

Gelatin is a biodegradable biopolymer obtained by collagen denaturation, which shows poor mechanical properties. Hence, improving its mechanical properties is very essential toward the fabrication of efficient nontoxic material for biomedical applications. For this aim, various methods are employed using external fillers such as ceramics or bioglass. In this report, we introduce boron nitride (BN)-reinforced gelatin as a new class of two-dimensional biocompatible nanomaterials. The effect of the nanofiller on the mechanical behavior is analyzed. BN is efficiently exfoliated using the biopolymer gelatin as shown through Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). The exfoliated BN reinforces gelatin electrospun fibers, which results in an increase in the Youngs modulus. The Electrospun Mats (ESM) are stable after the glutaraldehyde cross-linking, and the fibrous morphology is preserved. The cross-linked gelatin/BN ESM is highly bioactive in forming bonelike hydroxyapatite as shown by scanning electron microscopy. Due to their enhanced mineralization ability, the cross-linked ESM have been tested on human bone cells (HOS osteosarcoma cell line). The cell attachment, proliferation, and biocompatibility results show that the ESM are nontoxic and biodegradable. The analysis of osteoblast gene expression and the measurement of alkaline phosphatase activity confirm that these materials are suitable for bone tissue engineering.

Gold coated porous silicon nanocomposite as a substrate for photoluminescence-based immunosensor suitable for the determination of Aflatoxin B1

A rapid and low cost photoluminescence (PL) immunosensor for the determination of low concentrations of Aflatoxin B1 (AFB1) has been developed. This immunosensor was based on porous silicon (PSi) covered by thin gold layer (Au) and modified by antibodies against AFB1 (anti-AFB1). PSi layer was formed on silicon substrate, then the surface of PSi was covered by 30nm layer of gold (PSi/Au) using electrochemical and chemical deposition methods and in such ways PSi/Au(El.) and PSi/Au(Chem.) structures were formed, respectively. In order to find PSi/Au the most efficiently suitable for PL-based sensor design, structure several different PSi/Au(El.) and PSi/Au(Chem.) structures were designed while using different conditions for electrochemical or chemical deposition of gold layer. It was shown that during the formation of PSi/Au structure crystalline Au nanoparticles uniformly coated the surface of the PSi pores. PL spectroscopy of PSi/Au nanocomposites was performed at room temperature and it showed a wide emission band centered at 700nm. Protein A was covalently immobilized on the surface of PSi/Au(El.) and PSi/Au(Chem.) forming PSi/Au(El.)/Protein-A and PSi/Au(Chem.)/Protein-A structures, respectively. In the next step PSi/Au(El.)/Protein-A and PSi/Au(Chem.)/Protein-A structures were modified by anti-AFB1 and in such way a structures (PSi/Au(El.)/Protein-A/anti-AFB1 and PSi/Au(Chem.)/Protein-A/anti-AFB1) sensitive towards AFB1 were designed. The PSi/Au(El.)/Protein-A/anti-AFB1- and PSi/Au(Chem.)/Protein-A/anti-AFB1-based immunosensors were tested in a wide range of AFB1 concentrations from 0.001 upon 100ng/ml. Interaction of AFB1 with PSi/Au(El.)/Protein-A/anti-AFB1- and PSi/Au(Chem.)/Protein-A/anti-AFB1-based structures resulted PL quenching. The highest sensitivity towards AFB1 was determined for PSi/Au(El.)/Protein-A/anti-AFB1-based immunosensor and it was in the range of 0.01-10ng/ml. The applicability of PSi/Au-based structures as new substrates suitable for PL-based immunosensors is discussed.

Enhancement of optical and mechanical properties of Si nanopillars by ALD TiO2 coating

The mechanical and optical properties of Si and TiO2–Si nanopillars (NPl) were investigated. Mesoporous silicon NPl arrays were fabricated by metal-assisted chemical etching and nanosphere lithography, and then pillars were covered by TiO2 using the atomic layer deposition technique. We performed scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, reflectance, photoluminescence (PL) spectroscopy and nanoindentation to characterize the as-prepared and annealed TiO2–Si NPl. The main structural and mechanical parameters of TiO2–Si NPl (grain size, strain, critical load, elastic recovery and Youngs module) were calculated. Reflectance and PL spectroscopy were used to study the impact of morphology on optical properties of TiO2–Si NPl before and after annealing. It was established that the nanostructures of TiO2 penetrated inside the porous matrix of Si pillar improve the mechanical properties of TiO2–Si NPl. The results of nanoindentation study have shown that Youngs modulus of annealed TiO2–Si NPl is about three times higher than for the pure Si NPl.

High Electrocatalytic Response of a Mechanically Enhanced NbC Nanocomposite Electrode Toward Hydrogen Evolution Reaction

Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin-film electrodes of metal carbides are a promising alternative due to their reduced price and similar catalytic properties. However, most of the studied structures neglect long-lasting chemical and structural stability, focusing only on electrochemical efficiency. Herein we report on a new approach to easily deposit and control the micro/nanostructure of thin-film electrodes based on niobium carbide (NbC) and their electrocatalytic response. We will show that, by improving the mechanical properties of the NbC electrodes, microstructure and mechanical resilience can be obtained while maintaining high electrocatalytic response. We also address the influence of other parameters such as conductivity and chemical composition on the overall performance of the thin-film electrodes. Finally, we show that nanocomposite NbC electrodes are promising candidates toward HER and, furthermore, that the methodology presented here is suitable to produce other transition-metal carbides with improved catalytic and mechanical properties.

Synthesis, structure, EPR studies and up-conversion luminescence of ZnO:Er3+–Yb3+@Gd2O3 nanostructures

ZnO:Er3+–Yb3+@Gd2O3 nanostructures were obtained by “wet” chemistry methods – the sol–gel technique for the preparation of ZnO and ZnO:Er3+–Yb3+ nanoparticles (NPs), and the seed deposition method for obtaining Gd2O3. The crystal structure, morphology, phase and elemental composition, resonant microwave absorption of rare earth ions, point defects in the ZnO:Er3+–Yb3+@Gd2O3 crystal structure and up-conversion luminescence were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR) spectroscopy, and optical spectroscopy. The crystallization temperature (600 °C) of the Gd2O3 phase on the ZnO surface was found. As-obtained ZnO:Er3+–Yb3+ NPs (with size ∼7 nm) are highly crystalline and monodispersed. ZnO:Er3+–Yb3+ NPs annealing at 900 °C leads to the formation of highly polydispersed ZnO:Er3+–Yb3+ NPs, covered by a Gd2O3 shell. The process of the incorporation of the rare earth ions into the ZnO structure, as well as the effect of Gd2O3 content on the morphology and visible up-conversion (UC) luminescence in ZnO:Er3+–Yb3+ matrices were studied.

Raman spectroscopy of nanostructured silicon fabricated by metal-assisted chemical etching

In this work, we present a detailed experimental Raman investigation of nanostructured silicon films prepared by metalassisted chemical etching with different nanocrystal sizes and structures. Interpretation of observed one and two-phonon Raman peaks are presented. First-order Raman peak has a small redshift and broadening. This phenomenon is analyzed in the framework of the phonon confinement model. Second-order Raman peaks were found to be shifted and broadened in comparison to those in the bulk silicon. The peak shift and broadening of two-phonon Raman scattering relates to phonon confinement and disorder. A broad Raman peak between 900-1100 cm-1 corresponds to superposition of three transverse optical phonons ~2TO (X), 2TO (W) and 2TO (L). Influence of excitation wavelength on intensity redistribution of two-phonon Raman scattering components (2TO) is demonstrated and preliminary theoretical explanation of this observation is presented.

Mechanical properties of boron nitride thin films prepared by atomic layer deposition

Due to their wide bandgap, boron nitride (BN) thin films are the focus of interest for their potential applications in microelectronic devices. The reliability of these devices is essential and is directly linked to the mechanical properties of the films used for their fabrication. Herein, an atomic layer deposition (ALD) process based on sequential pulses of BBr3 and NH3 at 750 °C is used in order to prepare BN thin films. We report the main physicochemical properties of the films using various analytical methods. We also performed nanoindentation experiments in order to determine the elastic modulus and the hardness. Next, we annealed the films at 1000 and 1350 °C in order to gain understanding on the relation between the annealing temperature, the microstructure obtained and the resulting mechanical properties. Although the hardness of the films presents similar values of 5 ± 1 GPa for all temperatures, it has been found that the elastic modulus increases up to 150 ± 9 GPa when applying an annealing treatment of 1350 °C, which represents a 37% improvement compared to the initial film prepared at 750 °C.