Modification of AgNP-Decorated PET: A Promising Strategy for Preparation of AgNP-Filled Nuclear Pores in Polymer Membranes.

Polymer-based membranes represent an irreplaceable group of materials that can be applied in a wide range of key industrial areas, from packaging to high-end technologies. Increased selectivity to transport properties or the possibility of controlling membrane permeability by external stimuli represents a key issue in current material research. In this work, we present an unconventional approach with the introduction of silver nanoparticles (AgNPs) into membrane pores, by immobilising them onto the surface of polyethyleneterephthalate (PET) foil with subsequent physical modification by means of laser and plasma radiation prior to membrane preparation. Our results showed that the surface characteristics of AgNP-decorated PET (surface morphology, AgNP content, and depth profile) affected the distribution and concentration of AgNPs in subsequent ion-track membranes. We believe that the presented approach affecting the redistribution of AgNPs in the polymer volume may open up new possibilities for the preparation of metal nanoparticle-filled polymeric membranes. The presence of AgNPs on the pore walls can facilitate the grafting of stimuli-responsive molecules onto these active sites and may contribute to the development of intelligent membranes with controllable transport properties.

Microstructural modifications induced in Si+-implanted yttria-stabilised zirconia: a combined RBS-C, XRD and Raman investigation.

The structural differences in (100)-, (110)- and (111)-oriented cubic yttria-stabilised zirconia (YSZ) single crystals after implantation with 2 MeV Si+ ions at the fluences of 5 × 1015, 1 × 1016 and 5 × 1016 cm-2 were studied using Rutherford backscattering spectrometry in the channelling mode (RBS-C), X-ray diffraction (XRD) and Raman spectroscopy. The RBS-C results show that the damage accumulation in the 〈110〉 direction exhibits a lower level of disorder (<0.3) than the other orientations (<0.6) and it seems that the (110) crystallographic orientation is the most resistant to radiation damage. The experimental results from the RBS measurement were compared with the results from the XRD measurements. The XRD data were analysed using the standard two-beam dynamical X-ray diffraction theory and the pure isotropic strain was deduced from the fit for the fluence of 5 × 1015 cm-2. It was shown that the maximum value of the isotropic strain does not depend on the surface orientation. The increase in signal intensity at ∼689 cm-1 is probably related to an increase in implantation defects such as oxygen vacancies.

Compositional and Structural Modifications by Ion Beam in Graphene Oxide for Radiation Detection Studies.

In the present study, graphene oxide foils 10 µm thick have been irradiated in vacuum using same charge state (one charge state) ions, such as protons, helium and oxygen ions, at the same energies (3 MeV) and fluences (from 5 × 1011 ion/cm2 to 5 × 1014 ion/cm2). The structural changes generated by the ion energy deposition and investigated by X-ray diffraction have suggested the generation of new phases, as reduced GO, GO quantum dots and graphitic nanofibers, carbon nanotubes, amorphous carbon and stacked-cup carbon nanofibers. Further analyses, based on Rutherford Backscattering Spectrometry and Elastic Recoil Detection Analysis, have indicated a reduction of GO connected to the atomic number of implanted ions. The morphological changes in the ion irradiated GO foils have been monitored by Transmission Electron, Atomic Force and Scanning Electron microscopies. The present study aims to better structurally, compositionally and morphologically characterize the GO foils irradiated by different ions at the same conditions and at very low ion fluencies to validate the use of GO for radiation detection and propose it as a promising dosimeter. It has been observed that GO quantum dots are produced on the GO foil when it is irradiated by proton, helium and oxygen ions and their number increases with the atomic number of beam gaseous ion.

Synthesis of Porous Polydimethylsiloxane Gold Nanoparticles Composites by a Single Step Laser Ablation Process.

Typically, polymeric composites containing nanoparticles are realized by incorporating pre-made nanoparticles into a polymer matrix by using blending solvent or by the reduction of metal salt dispersed in the polymeric matrix. Generally, the production of pre-made Au NPs occurs in liquids with two-step processes: producing the gold nanoparticles first and then adding them to the liquid polymer. A reproducible method to synthetize Au nanoparticles (NPs) into polydimethylsiloxane (PDMS) without any external reducing or stabilizing agent is a challenge. In this paper, a single-step method is proposed to synthetize nanoparticles (NPs) and at the same time to realize reproducible porous and bulk composites using laser ablation in liquid. With this single-step process, the gold nanoparticles are therefore produced directly in the liquid polymer. The optical properties of the suspensions of AuNPs in distilled water and in the curing agent have been analyzed by the UV-VIS spectroscopy, employed in the transmission mode, and compared with those of the pure curing agent. The electrical dc conductivity of the porous PDMS/Au NPs nanocomposites has been evaluated by the I-V characteristics. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis have monitored the composition and morphology of the so-obtained composites and the size of the fabricated Au nanoparticles. Atomic force microscopy (AFM) has been used to determine the roughness of the bulk PDMS and its Au NP composites.

Optomechanical Processing of Silver Colloids: New Generation of Nanoparticle-Polymer Composites with Bactericidal Effect.

The properties of materials at the nanoscale open up new methodologies for engineering prospective materials usable in high-end applications. The preparation of composite materials with a high content of an active component on their surface is one of the current challenges of materials engineering. This concept significantly increases the efficiency of heterogeneous processes moderated by the active component, typically in biological applications, catalysis, or drug delivery. Here we introduce a general approach, based on laser-induced optomechanical processing of silver colloids, for the preparation of polymer surfaces highly enriched with silver nanoparticles (AgNPs). As a result, the AgNPs are firmly immobilized in a thin surface layer without the use of any other chemical mediators. We have shown that our approach is applicable to a broad spectrum of polymer foils, regardless of whether they absorb laser light or not. However, if the laser radiation is absorbed, it is possible to transform smooth surface morphology of the polymer into a roughened one with a higher specific surface area. Analyses of the release of silver from the polymer surface together with antibacterial tests suggested that these materials could be suitable candidates in the fight against nosocomial infections and could inhibit the formation of biofilms with a long-term effect.

Graphene oxide layers modified by light energetic ions.

In this paper, the effect of light ion irradiation on graphene oxide foil structure and composition was studied. Due to the excellent properties of graphene based materials suitable for application in electronics, optoelectronics, micro-mechanics and space technologies, the interaction of energetic ions with graphene based structures is worth studying. From the fundamental point of view, it is also interesting to get information about graphene oxide structure modification and the possible functional properties after irradiation by energetic ions. The light ion irradiation of graphene oxide (GO) foil was performed using 2.5 MeV H+ and 5.1 MeV He2+ ions. The change in the elemental composition of the GO foils after ion irradiation was investigated using Rutherford Backscattering Spectrometry and Elastic Recoil Detection Analysis. The influence of ion irradiation was further studied by microscopy methods. The chemical composition and structural changes of the GO foil surface were characterized by spectroscopy techniques including XPS, FTIR and Raman spectroscopy. Although the results of ion beam analysis indicated no significant compositional changes in the bulk of GO foils connected to ion irradiation, XPS, ATR-FTIR and Raman spectroscopy revealed reduction and removal of oxygen functionalities on the surface of graphene oxide. This reduction leads to a surface resistivity decrease after ion irradiation dependent on the ion species, fluence and energy.

Erbium ion implantation into diamond - measurement and modelling of the crystal structure.

Diamond is proposed as an extraordinary material usable in interdisciplinary fields, especially in optics and photonics. In this contribution we focus on the doping of diamond with erbium as an optically active centre. In the theoretical part of the study based on DFT simulations we have developed two Er-doped diamond structural models with 0 to 4 carbon vacancies in the vicinity of the Er atom and performed geometry optimizations by the calculation of cohesive energies and defect formation energies. The theoretical results showed an excellent agreement between the calculated and experimental cohesive energies for the parent diamond. The highest values of cohesive energies and the lowest values of defect formation energies were obtained for models with erbium in the substitutional carbon position with 1 or 3 vacancies in the vicinity of the erbium atom. From the geometry optimization the structural model with 1 vacancy had an octahedral symmetry whereas the model with 3 vacancies had a coordination of 10 forming a trigonal structure with a hexagonal ring. In the experimental part, erbium doped diamond crystal samples were prepared by ion implantation of Er+ ions using ion implantation fluences ranging from 1 × 1014 ions per cm2 to 5 × 1015 ions per cm2. The experimental results revealed a high degree of diamond structural damage after the ion implantation process reaching up to 69% of disordered atoms in the samples. The prepared Er-doped diamond samples annealed at the temperatures of 400, 600 and 800 °C in a vacuum revealed clear luminescence, where the 〈110〉 cut sample has approximately 6-7 times higher luminescence intensity than the 〈001〉 cut sample with the same ion implantation fluence. The reported results are the first demonstration of the Er luminescence in the single crystal diamond structure for the near-infrared spectral region.

Polyvinylalcohol Composite Filled with Carbon Dots Produced by Laser Ablation in Liquids.

Carbon dots (CDs), owing to their excellent photoluminescent features, have been extensively studied for physics preparation methods and for biomedical and optoelectronic device applications. The assessment of the applicability of CDs in the production of luminescent polymeric composites used in LEDs, displays, sensors, and wearable devices is being pursued. The present study reports on an original, environmentally friendly, and low-cost route for the production of carbon dots with an average size of 4 nm by laser ablation in liquid. Jointly, to prove the significance of the study for a wide range of applications, a free-standing flexible polyvinyl alcohol (PVA) composite containing photoluminescent carbon dots was manufactured. CDs were prepared using targets of porose charcoal with a density of 0.271 g/cm3 placed in phosphate-buffered saline (PBS) liquid solution and irradiated for 30 min by pulsed IR diode laser. The optical properties of the obtained suspension containing carbon dots were studied with UV-ViS and FTIR spectroscopies. The photoluminescence of the produced carbon dots was confirmed by the emission peak at 480 nm in the luminescence spectrum. A narrow luminescence band with a full width at half-maximum (FWHM) of less than 40 nm could be an asset in spectral emission analysis in different applications. Atomic force microscopy confirms the feasibility of manufacturing CDs in clean and biocompatible environments, paving the way for an easier and faster production route, crucial for their wider applicability.

Overview of Polyethylene Terephthalate Foils Patterned Using 10 MeV Carbon Ions for Realization of Micromembranes.

Polymer membranes are conventionally prepared using high-energy particles from radioactive decay or by the bombardment of hundreds of MeVs energy ions. In both circumstances, tracks of damage are produced by particles/ions passing through the polymer, and successively, the damaged material is removed by chemical etching to create narrow pores. This process ensures nanosized pore diameter but with random placement, leading to non-uniform local pore density and low membrane porosity, which is necessary to reduce the risk of their overlapping. The present study is focused on the use of polyethylene terephthalate (PET) foils irradiated by 10.0 MeV carbon ions, easily achievable with ordinary ion accelerators. The ion irradiation conditions and the chemical etching conditions were monitored to obtain customized pore locations without pore overlapping in PET. The quality, shape, and size of the pores generated in the micromembranes can have a large impact on their applicability. In this view, the Scanning Transmission Ion Microscopy coupled with a computer code created in our laboratory was implemented to acquire new visual and quantitative insights on fabricated membranes.

Mask-Assisted Deposition of Ti on Cyclic Olefin Copolymer Foil by Pulsed Laser Deposition.

Cyclic olefin copolymer (COC) is a novel type of thermoplastic polymer gaining the attention of the scientific community in electronic, optoelectronic, biomedicine and packaging applications. Despite the benefits in the use of COC such as undoubted optical transparency, chemical stability, a good water-vapor barrier and biocompatibility, its original hydrophobicity restricts its wider applicability and optimization of its performances. Presently, we report on the optical and morphological properties of the films of COC covered with Ti in selected areas. The layer of Ti on COC was deposited by pulsed lased deposition processing. The Ti/COC film was characterized by UV-Vis spectroscopy indicating that its transmittance in the visible region decreased by about 20% with respect to the pristine polymer. The quality of the deposited Ti was assessed with the morphology by scanning electron (SEM) and atomic force microscopies (AFM). The modification of the wettability was observed by the sessile drop method indicating a reduction of the native hydrophilicity.

Graphene Oxide and Polymer Humidity Micro-Sensors Prepared by Carbon Beam Writing.

In this study, novel flexible micro-scale humidity sensors were directly fabricated in graphene oxide (GO) and polyimide (PI) using ion beam writing without any further modifications, and then successfully tested in an atmospheric chamber. Two low fluences (3.75 × 1014 cm-2 and 5.625 × 1014 cm-2) of carbon ions with an energy of 5 MeV were used, and structural changes in the irradiated materials were expected. The shape and structure of prepared micro-sensors were studied using scanning electron microscopy (SEM). The structural and compositional changes in the irradiated area were characterized using micro-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Rutherford back-scattering spectroscopy (RBS), energy-dispersive X-ray spectroscopy (EDS), and elastic recoil detection analysis (ERDA) spectroscopy. The sensing performance was tested at a relative humidity (RH) ranging from 5% to 60%, where the electrical conductivity of PI varied by three orders of magnitude, and the electrical capacitance of GO varied in the order of pico-farads. In addition, the PI sensor has proven long-term sensing stability in air. We demonstrated a novel method of ion micro-beam writing to prepare flexible micro-sensors that function over a wide range of humidity and have good sensitivity and great potential for widespread applications.

Ion Lithography of Single Ions Irradiation for Spatially Regular Arrays of Pores in Membranes of Polyethylene Terephthalate.

Routinely, in membrane technology, the decay from radioactive particles or the bombardment of ions with MeV energy per nucleon have been employed for the production of narrow and long pores in membranes. Presently, the ion lithography is proposed to make the fabrication cost more affordable. It is prospective for the use of medium capacity accelerators making more feasible the fabrication of customized membranes. Thin polyethylene terephthalate foils have been patterned using 12 MeV O5+ ions and then processed to obtain good aspect ratio ion track pores in membranes. Pores of micrometric diameter with the following profiles were fabricated in the membranes: truncated cone, double conical, ideal cone, and cylindrical. Monitoring of the shape and size of pores has been attempted with a combination of Scanning Transmission Ion Microscope and a newly designed simulation program. This study is focused on the use of low-energy ions, accomplished in all laboratories, for the fabrication of membranes where the pores are not randomly traced and exhibit higher surface density and negligible overlapping than in membranes commonly manufactured. The good reproducibility and the ordered pore locations can be potentially utilized in applications such as microfluidics and organ-on-chip microsystems, where cells growing over porous substrates are used in simulation of biological barriers and transport processes.

Creation of Gold Nanoparticles in ZnO by Ion Implantation-DFT and Experimental Studies.

Three different crystallographic orientations of the wurtzite ZnO structure (labeled as c-plane, a-plane and m-plane) were implanted with Au+ ions using various energies and fluences to form gold nanoparticles (GNPs). The ion implantation process was followed by annealing at 600 °C in an oxygen atmosphere to decrease the number of unwanted defects and improve luminescence properties. With regard to our previous publications, the paper provides a summary of theoretical and experimental results, i.e., both DFT and FLUX simulations, as well as experimental results from TEM, HRTEM, RBS, RBS/C, Raman spectroscopy and photoluminescence. From the results, it follows that in the ZnO structure, implanted gold atoms are located in random interstitial positions -experimentally, the amount of interstitial gold atoms increased with increasing ion implantation fluence. During ion implantation and subsequent annealing, the metal clusters and nanoparticles with sizes from 2 to 20 nm were formed. The crystal structure of the resulting gold was not cubic (confirmed by diffraction patterns), but it had a hexagonal close-packed (hcp) arrangement. The ion implantation of gold leads to the creation of Zn and O interstitial defects and extended defects with distinct character in various crystallographic cuts of ZnO, where significant O-sublattice disordering occurred in m-plane ZnO.

Erbium Luminescence Centres in Single- and Nano-Crystalline Diamond-Effects of Ion Implantation Fluence and Thermal Annealing.

We present a fundamental study of the erbium luminescence centres in single- and nano-crystalline (NCD) diamonds. Both diamond forms were doped with Er using ion implantation with the energy of 190 keV at fluences up to 5 × 1015 ions·cm-2, followed by annealing at controllable temperature in Ar atmosphere or vacuum to enhance the near infrared photoluminescence. The Rutherford Backscattering Spectrometry showed that Er concentration maximum determined for NCD films is slightly shifted to the depth with respect to the Stopping and Range of Ions in Matter simulation. The number of the displaced atoms per depth slightly increased with the fluence, but in fact the maximum reached the fully disordered target even in the lowest ion fluence used. The post-implantation annealing at 800 °C in vacuum had a further beneficial effect on erbium luminescence intensity at around 1.5 µm, especially for the Er-doped NCD films, which contain a higher amount of grain boundaries than single-crystalline diamond.

Definitive Insight into the Graphite Oxide Reduction Mechanism by Deuterium Labeling.

The reduction of graphite oxide is one of the most important reactions in the production of graphene in gram quantities. The mechanisms of these widely used reactions are poorly understood. The mechanism of the chemical reduction of two different graphite oxides prepared by the chlorate (Hofmann method) and permanganate methods (Hummers method) has been investigated. Three different reduction agents, lithium tetrahydridoaluminate, sodium tetrahydridoborate, and lithium tetrahydridoborate, as well as their deuterated counterparts, were used for the reduction of graphite oxide. Reduced graphite oxides were analyzed by scanning electron microscopy, energy-dispersive spectroscopy, elemental combustion analysis, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy, and simultaneous thermal analysis. The concentration of boron incorporated into graphene was measured by prompt gamma activation analysis. Rutherford back-scattering spectroscopy and elastic recoil detection analysis were used for the determination of the elemental composition, including deuterium concentration, as evidence of CH bond formation.

Gold nanolayer and nanocluster coatings induced by heat treatment and evaporation technique.

The paper is focused on the preparation and surface characterization of gold coatings and nanostructures deposited on glass substrate. Different approaches for the layer preparation were applied. The gold was deposited on the glass with (i) room temperature, (ii) glass heated to 300°C, and (iii) the room temperature-deposited glass which was consequently annealed to 300°C. The sheet resistance and concentration of free carriers were determined by the van der Pauw method. Surface morphology was characterized using an atomic force microscopy. The optical properties of gold nanostructures were measured by UV-vis spectroscopy. The evaporation technique combined with simultaneous heating of the glass leads to change of the sheet resistance, surface roughness, and optical properties of gold nanostructures. The electrically continuous layers are formed for significantly higher thickness (18 nm), if the substrate is heated during evaporation process. The annealing process influences both the structure and optical properties of gold nanostructures. The elevated temperature of glass during evaporation amplifies the peak of plasmon resonance in the structures, the surface morphology being significantly altered.

Early stages of growth of gold layers sputter deposited on glass and silicon substrates.

Extremely thin gold layers were sputter deposited on glass and silicon substrates, and their thickness and morphology were studied by Rutherford backscattering (RBS) and atomic force microscopy (AFM) methods. The deposited layers change from discontinuous to continuous ones for longer deposition times. While the deposition rate on the silicon substrate is constant, nearly independent on the layer thickness, the rate on the glass substrate increases with increasing layer thickness. The observed dependence can be explained by a simple kinetic model, taking into account different sticking probabilities of gold atoms on a bare glass substrate and regions with gold coverage. Detailed analysis of the shape of the RBS gold signal shows that in the initial stages of the deposition, the gold layers on the glass substrate consist of gold islands with significantly different thicknesses. These findings were confirmed by AFM measurements, too. Gold coverage of the silicon substrate is rather homogeneous, consisting of tiny gold grains, but a pronounced worm-like structure is formed for the layer thickness at electrical continuity threshold. On the glass substrate, the gold clusters of different sizes are clearly observed. For later deposition stages, a clear tendency of the gold atoms to aggregate into larger clusters of approximately the same size is observed. At later deposition stages, gold clusters of up to 100 nm in diameter are formed.

A novel method for biopolymer surface nanostructuring by platinum deposition and subsequent thermal annealing.

A novel procedure for biopolymer surface nanostructuring with defined surface roughness and pattern dimension is presented. The surface properties of sputtered platinum layers on the biocompatible polymer poly(l-lactic acid) (PLLA) are presented. The influence of thermal treatment on surface morphology and electrical resistance and Pt distribution in ca. 100 nm of altered surface is described. The thickness, roughness and morphology of Pt structures were determined by atomic force microscopy. Surface sheet resistance was studied by a two-point technique. It was the sequence of Pt layer sputtering followed by thermal treatment that dramatically changed the structure of the PLLA's surface. Depending on the Pt thickness, the ripple-like and worm-like patterns appeared on the surface for thinner and thicker Pt layers, respectively. Electrokinetic analysis confirmed the Pt coverage of PLLA and the slightly different behaviour of non-annealed and annealed surfaces. The amount and distribution of platinum on the PLLA is significantly altered by thermal annealing.