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.

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.

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.

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.

Interface-Driven Strain in Heavy Ion-Irradiated Zr/Nb Nanoscale Metallic Multilayers: Validation of Distortion Modeling via Local Strain Mapping.

Nanolayered metallic alloys are promising materials for nuclear applications thanks to their resistance to radiation damage. Here, we investigate the effect of ion (C, Si, and Cu) irradiation at room temperature with different fluences into sputtered Zr/Nb metallic multilayer films with periods 27 nm (thin) and 96 nm (thick). After irradiation, while a high strain in the entire thin nanoscale metallic multilayer (NMM) is observed, a quite small strain in the entire thick NMM is established. This difference is further analyzed by a semianalytical model, and the reasons behind it are revealed, which are also validated by local strain mapping. Both methods show that within a thick layer, two opposite distortions occur, making the overall strain small, whereas in a thin layer, all the atomic planes are affected by the interface and are subjected to only a single type of distortion (Nb─tension and Zr─compression). In both thin and thick NMMs, with increasing damage, the strain around the interface increases, resulting in a release of the elastic energy at the interface (decrease in the lattice mismatch), and the radiation-induced transition of the Zr/Nb interfaces from incoherent to partially coherent occurs. Density functional theory simulations decipher that the inequality of point defect diffusion flux from the inner to the interface-affected region is responsible for the presence of opposite distortions within a layer. Technologically, based on this work, we estimated that Zr/Nb55 with thicknesses around Zr = 24 nm and Nb = 31 nm is the most promising multilayer system with the high radiation damage resistance and minimum swelling for nuclear applications.

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.

Performance and application of heavy ion nuclear microbeam facility at the Nuclear Physics Institute in Rez, Czech Republic.

The Tandetron Laboratory of the Nuclear Physics Institute of the Czech Academy of Sciences is equipped with five beam lines associated with a 3 MV tandem electrostatic accelerator model 4130 MC from High Voltage Engineering Europa B.V. This accelerator is coupled with two duoplasmatron sources and a single sputter ion source and provides ions from hydrogen to gold. One of these lines is a nuclear microbeam facility, utilizing ion beams of micro- and sub-micro sizes for materials research by use of particle induced x-ray emission spectroscopy, particle induced gamma emission, Rutherford back-scattering spectroscopy, and scanning transmission ion microscopy methods as well as for ion beam writing. The major advantage of the presented microprobe is a possibility of 3D structure creation not only in polymer materials using light ions but also in other materials such as glass, ceramics, etc. by use of heavy ions. The focusing system allows focusing of charged particles with a maximum rigidity of 11 MeV amu/q2. The usual resolution in high and low current modes is 2 × 3 µm2 for a 100 pA and 0.3 × 0.5 µm2 for the 2000 ions/s of 2 MeV protons, respectively. A detailed facility description is given in the paper. The applications of focused beams of heavy ions as well as examples of light ions utilizing are also presented in the article.

Comparison of PM2.5 chemical composition and sources at a rural background site in Central Europe between 1993/1994/1995 and 2009/2010: Effect of legislative regulations and economic transformation on the air quality.

From December 1993 to January 1995 and from October 2009 to October 2010, a total of 320 and 365 daily samples of the PM2.5 were collected at a rural background site (National Atmospheric Observatory Kosetice) in Central Europe. The PM2.5 samples were analyzed for 29 and 26 elements respectively by Particle-Induced X-ray Emission (PIXE) and water-soluble inorganic ions by Ion Chromatography (IC) in 2009/2010. The Positive Matrix Factorization (PMF) was applied to the chemical composition of PM2.5 to determine its sources. The decreasing trends of almost all elements concentrations, especially the metals regulated by the EU Directive (2004/107/EC) are evident. The annual median ratios indicate a decrease in concentrations of the PM2.5 elements. The slight increase of K concentrations and Spearman's rank correlation coefficient rs 0.09 K/Se points to a rise in residential wood combustion. The S concentrations are nearly comparable (higher mean in 2009/2010, while the annual median ratio is under 1). The five major source types in the mid-1990s were ascribed to brown coal combustion, oil combustion, sea salt and dust - long-range transport, re-suspended dust and black coal combustion. The industrial combustion of brown and/or black coal (rs 0.75 Se/As, rs 0.57 Ga/Ge and rs 0.20 As/Zn) and oil (rs 0.72 V/Ni) of the regional origin dominated. In the 1990s, the potential source regions were the border area of Czech Republic, German and Poland (brown coal), the Moravia-Silesia region at the Czech-Polish border (black coal), and Slovakia, Austria, Hungary, and the Balkans (oil). In 2009/2010, the apportioned sources were sulfate, residential heating, nitrate, industry, re-suspended dust, and sea salt and dust - long-range transport. The secondary sulfate from coal combustion and residential biomass burning (rs 0.96, K/K+) of local origin dominated. The declining trend of the elemental concentrations and change in the source pattern of the regional background PM2.5 in Central Europe between the mid-1990s and 2009/10 reflects the economic transformation and impact of stricter legislation in Central Europe.

Chemical preparation of graphene materials results in extensive unintentional doping with heteroatoms and metals.

Chemical synthesis of graphene relies on the usage of various chemical reagents. The initial synthesis step, in which graphite is oxidized to graphite oxide, is achieved by a combination of chemical oxidants and acids. A subsequent chemical reduction step eliminates/reduces most oxygen functionalities to yield graphene. We demonstrate here that these chemical treatments significantly contaminate graphene with heteroatoms/metals, depending on the procedures followed. Contaminations with heteroatoms (N, B, Cl, S) or metals (Mn, Al) were present at relatively high concentrations (up to 3 at%), with their chemical states dependent on the procedures. Such unintentional contaminations (unwanted doping) during chemical synthesis are rarely anticipated and reported, although the heteroatoms/metals may alter the electronic and catalytic properties of graphene. In fact, the levels of unintentionally introduced contaminants on graphene are often higher than typical levels found on intentionally doped graphene. Our findings are important for scientists applying chemical methods to prepare graphene.

Carboranedithiols: building blocks for self-assembled monolayers on copper surfaces.

Two different positional isomers of 1,2-dicarba-closo-dodecaboranedithiols, 1,2-(HS)(2)-1,2-C(2)B(10)H(10) (1) and 9,12-(HS)(2)-1,2-C(2)B(10)H(10) (2), have been investigated as cluster building blocks for self-assembled monolayers (SAMs) on copper surfaces. These two isomers represent a convenient system in which the attachment of SH groups at different positions on the skeleton affects their acidic character and thus also determines their reactivity with a copper surface. Isomer 1 exhibited etching of polycrystalline Cu films, and a detailed investigation of the experimental conditions showed that both the acidic character of SH groups and the presence of oxygen at the copper surface play crucial roles in how the surface reaction proceeds: whether toward a self-assembled monolayer or toward copper film etching. We found that each positional isomer requires completely different conditions for the preparation of a SAM on copper surfaces. Optimized conditions for the former isomer required the exposure of a freshly prepared Cu surface to vapor of 1 in vacuum, which avoided the presence of oxygen and moisture. Adsorption from a dichloromethane solution afforded a sparsely covered Cu(0) surface; isomer 1 effectively removes the surface copper(I) oxide, forming a soluble product, but apparently binds only weakly to the clean Cu(0) surface. In contrast, adsorption of the latter, less volatile isomer proceeded better from a dichloromethane solution than from the vapor phase. Isomer 2 was even able to densely cover the copper surface cleaned up by the dichloromethane solution of 1. Both isomers exhibited high capacity to remove oxygen atoms from the surface copper(I) oxide that forms immediately after the exposure of freshly prepared copper films to ambient atmosphere. Isomer 2 showed suppression of Cu film oxidation. A number of methods including X-ray photoelectron spectroscopy (XPS), X-ray Rutherford back scattering (RBS), proton-induced X-ray emission (PIXE) analysis, atomic force microscopy (AFM), cyclic voltammetry, and contact angle measurements were used to investigate the experimental conditions for the preparation of SAMs of both positional isomers on copper surfaces and to shed light on the interaction between these molecules and a polycrystalline copper surface.