Etched Ion Tracks Research Articles

Highly sensitive urea sensing with ion-irradiated polymer foils

Recently we prepared urea-sensors by attaching urease to the inner walls of etched ion tracks within thin polymer foil. Here, alternative track-based sensor configurations are examined where the enzyme remained in solution. The conductivities of systems consisting of two parallel irradiated polymer foils and confining different urea/urease mixtures in between were examined. The correlations between conductivity and urea concentration differed strongly for foils with unetched and etched tracks, which points at different sensing mechanisms – tentatively attributed to the adsorption of enzymatic reaction products on the latent track entrances and to the enhanced conductivity of reaction product-filled etched tracks, respectively. All examined systems enable in principle, urea sensing. They point at the possibility of sensor cascade construction for more sensitive or selective sensor systems.

Ion track-based urea sensing

A highly sensitive urea biosensor is described. We employed polymer foils which are thin, swift heavy ion-irradiated polycarbonate foils, followed by etching. The examined geometrical arrangement is of 1 foil, two compartments system. One electrode is placed in each compartment and a sinusoidal voltage is applied to the system. The enzyme urease is attached to the inner walls of the etched ion tracks in the foil, and one of the compartments is filled with urea solution of variable concentrations which can then interact with the enzyme, resulting in a change of track resistance. These results are compared with those obtained using a simple, non-confined urea/urease mixture. We report that this strategy, where the enzyme is bound to the etched track walls, is very efficient, as it demonstrates very high sensitivity. In this system, urea can be detected at a concentration as low as 1 × 10 −7 M. The sensor is, moreover, still active at a concentration of 1 M urea. The currents associated with each concentration differ by a factor of 10.

Microbioreactor design for 3‐D cell cultivation to create a pharmacological screening system

AbstractA biocompatible cell culture environment that enables continued existence of three dimensionally aggregated cells in a polycarbonate‐based scaffold structure was developed. A micro structured polymeric scaffold allows perfusion of cells due to a microporous structure generated by ion track etching and micro thermoforming. Biocompatibility and sterilizability was approved for the whole system. As oxygenation and mass transport within a closed system is most relevant for 3‐D cell culture, two approaches of pumping systems were tested. The human hepatocarcinoma cell line HepG2 was used to examine basic cytological parameters in response to the enviroment. Our data indicate that an actively perfused 3‐D cell culture induces a more differentiated phenotype in HepG2 cells than the 2‐D setup. Thus, our results provide further support to the theory that 3‐D‐cultivated cells display a non‐proliferative behavior. In this respect, 3‐D cultures resemble in vivo conditions more closely. Microreactors are widely applied for organic syntheses, but can also be used for screening applications in drug discovery and medical research. The bioreactor versions presented here were equipped with active fluidic components.

Effect of nanopore geometry on ion current rectification

We present the results of systematic studies of ion current rectification performed onartificial asymmetric nanopores with different geometries and dimensions. The nanoporesare fabricated by the ion track etching method using surfactant-doped alkaline solutions.By varying the alkali concentration in the etchant and the etching time, control over thepore profile and dimensions is achieved. The pore geometry is characterized in detail usingfield-emission scanning electron microscopy. The dependence of the ion current rectificationratio on the pore length, tip diameter, and the degree of pore taper is analysed. Theexperimental data are compared to the calculations based on the Poisson–Nernst–Planckequations. A strong effect of the tip geometry on the diode-like behaviour is confirmed.

Funnel-type etched ion tracks in polymers

It is shown that conical track etching is a much more complicated process than generally assumed. The choice of the corresponding parameters (i.e. the ratios of concentrations and diffusion coefficients of both etchant (e.g. NaOH) and stopping solutions (e.g. HCl) and the etching temperature) determines the ratio of polymer dissolution to etchant penetration. The latter value controls the counterplay of diffusion, etching, ionic conductivity, field emission and capacitive effects, which is decisive for both the final track shapes and their electronic properties. The stages of track evolution during etching under different conditions are outlined in detail. Both transparent conical nanopores and “funnel-type” tracks can be obtained, the latter consisting of a shorter cone and a residual latent track. Depending on the internal structure of that latent track segment, such funnel-type tracks either allow smooth transmission of the rectified currents or they emit unipolar current spikes. Not only the study of electronic properties of single ion tracks, but also of a multitude of tracks makes sense. Depending on the applied parameters, the individual track properties may either just add up, or new effects may be found that emerge from the interaction of the tracks among each other. This is preferentially the case for spike-emitting tracks, where effects such as phase-locked spike synchronization can be found as described by neural network theory.

Study of surface morphology of ferrofluid deposited etched ion tracks in dielectric layers

Abstract An AFM study is reported on swift heavy irradiated Si/SiO 2 substrates which have been etched by aqueous hydrofluoric acid solution leading to ion tracks in which ferrofluids have been deposited leading to t unable e lectronic m aterials with p ores in o xide on s ilicon (TEMPOS) structure. Two ferrofluids with different carrier fluids (aqueous and non-aqueous) have been deposited in the tracks. Atomic force microscopy has been used to study the empty as well as filled tracks. Since the ferrofluids contain iron oxide particles, there is a possibility of agglomeration of these particles inside and outside the tracks. Surface area and pore volume of the tracks have been measured by Brunauer-Emmett-Teller (BET) method. The track properties (empty and filled) as observed by AFM have been correlated with BET measurements.

Stroke Asymmetry of Tilted Superhydrophobic Ion Track Textures

The stroke asymmetry of contact angles of water drops on tilted hydrophobic textures is demonstrated, obtained by ion track etching followed by a hydrophobic treatment. Preliminary trends concerning the advancing and receding contact angles are established, each with and against stroke direction. In rough agreement with Cassie-Baxter theory, the cosines of these four contact angles depend linearly on the wetted area fraction. The etched tracks are randomly distributed on the surface of polycarbonate disks and inclined by 30 degrees with respect to the surface, whereby the aspect ratio of individual etched cones is larger than 10. The morphology of the resulting surface is characterized by randomly shaped flat tops overhanging on one side and gradually falling off on the other side. The area fraction of the supporting tops can be calculated from the number of impinging ions per unit area and the cross section of the etched ion tracks. The top layer of the texture consists of flat, horizontal, irregularly shaped tops supporting water drops in the Cassie-Baxter state. With increasing etching time, the texture becomes increasingly clefted. To fabricate the textures, we irradiated polycarbonate with 5 x 10(7) (80)Br(7+) ions/cm(2) of 30 MeV total energy (having a range of about 20 microm in polycarbonate) at a tilt angle of 30 degrees with respect to the sample surface and etched the latent ion tracks selectively. The textured surface is made hydrophobic by carbondifluoride radicals (CF(2)) resulting from the decay of octafluorocyclobutane, C(4)F(8), in a plasma reactor. The goal of the report is to show that the tilt orientation of a superhydrophobic surface leads to advancing and receding contact angles depending on the orientation with and against the stroke direction. In addition, a rotating movement is demonstrated qualitatively by floating a rotationally asymmetric disk on an ultrasonic bath, similarly treated after an irradiation with (1.2 +/- 0.4) x 10(7) (129)Xe(27+) ions/cm(2) of 8.3 MeV/nucleon at an angle of 45 degrees, whereby the superhydrophobic side of the disk points downward to the water of the ultrasonic bath.

Preparation of Microporous Membranes by Swift Heavy Ion Irradiation and Impedance Characterization

Polypropylene (PP) microporous membranes were successfully prepared by swift heavy ion irradiation and track-etching. Polypropylene foils were irradiated with (197)Au ions of kinetic energy 11.4 MeV.u(-1) (total energy of 2245.8 MeV) and fluence 1x10(8) ions.cm(-2) at normal incidence. The damaged regions produced by the gold ions along the trajectories were etched in H(2)SO(4) and K(2)Cr(2)O(7) solutions leading to the formation of cylindrical pores in the membranes. The pore diameters of the PP microporous membranes increased from 380 to 1610 nm as the etching time increased from 5 to 30 min. The surface and cross-section morphologies of the porous membranes were characterized by scanning electron microscopy (SEM). The micropores in the membranes were found to be cylindrical in shape, homogeneous in distribution, and equal in size. Some mathematical relations of the porosity of the PP microporous membranes were established by analytic derivation. The microporous membranes were used in lithium-ion batteries to measure their properties as separators. The electrical conductivity of the porous membrane immersed in liquid electrolyte was found to be comparable to that of commercial separators by electrochemical impedance spectroscopy (EIS). The results showed that the porosity and electrical conductivity were dependent on the ion fluence and etching time. By adjusting these two factors, microporous membranes with good porosity and electrical conductivity were made that met the requirements for commercial use.

Superoleophobic Behavior Induced by Nanofeatures on Oleophilic Surfaces

The control of surface wetting properties to produce robust and strong hydrophobic and oleophobic effects on intrinsically oleophilic surfaces is at the heart of many technological applications. In this paper, we explore the conditions to observe such effects when the roughness of the substrate is of fractal nature and consists of nanofeatures obtained by the ion track etching technique. The wetting properties were investigated using eight different liquids with surface tensions gamma varying from 18 to 72 mN m(-1). While it is observed that all the tested oils readily wet the flat substrates, it is found that the contact angles are systematically exalted on the rough surfaces even for the liquids with very low surface tension. For liquids with gamma > or = 25 mN m(-1) an oleophobic behavior is clearly induced by the nanostructuration. For liquids with gamma < 25 mN m(-1), although the contact angle is enhanced on the nanorough surfaces, it conserves its oleophilic character (theta* lower than 90 degrees). Moreover, our experiments show that even in the case of hexane, liquid having the lowest surface tension, the homogeneous wetting (Wenzel state) is never reached. This high resistance to liquid impregnation is discussed within the framework of recent approaches explaining the wetting properties of superoleophobic surfaces.

Track PVB membrane based on irradiation with high energy protons

AbstractOne of the methods of polymeric material modification is based on the irradiation with accelerated ions. Chemical etching of ion tracks in polymers is a method which is widely used in the fabrication of micro/nano-structures with predetermined characteristics. For the present study polyvinyl butyral (PVB) porous membrane was prepared by track-etching technique. Commercially available PVB film was irradiated by 30 MeV energy protons to form latent tracks, and then etched chemically by potassium hydroxide (KOH) with the different normalities. The etching rate of PVB was related to the concentration of etching reagent, temperature and time. The porous size and shape were investigated by scanning electron microscope (SEM) after and before etching. Relationships in between the etching rate and the etching parameters were established from experimental data, and can be used to control the pore size of PVB track-etch membrane. The Pore sizes and their structures were evaluated by optical microscope (OM) and scanning electron microscope (SEM). The results have shown the micro/nano-pores formation in the PVB films. The physico-chemical properties of the irradiated samples were investigated and compared with the un-irradiated one using the FTIR and DSC and DTG systems, as well.

Metallic microwires obtained as replicas of etched ion tracks in polymer matrixes: Microscopy and emission properties

Specially prepared porous matrixes (with through and dead-end pores of cylindrical or conical forms) were used as the templates for making ensembles of microwires. The process of electrodeposition of metal (Cu) into these pores was investigated. AFM technique was used for studying the “composite material” (metal microwires embedded into the polymer matrix). It was shown that the combination of different modes of AFM (tapping with phase-contrast mode, contact with lateral force mode) makes it possible to detect metal in the polymer matrix. Additional spread resistance mode in the contact regime allowed to measure the electrical conductivity of a single wire. The ensembles of free-standing microwires (metallic replicas of the pores obtained after removing of the polymer matrix) were used as the substrates (for deposition of the probe) for ion emission in the mass-spectrometer. It was shown that the intensity of formed ion beam increases with increasing of power of the laser pulse and with increasing of the mass of the probe. The intensity of mass-spectra signal on the power of laser pulse has a threshold character with saturation accompanied with the appearance of dimer ions. At the same time this intensity decreases with the increasing of the surface density of wires. The effect of degradation of wires during the laser pulse irradiation was found.

Strategies towards advanced ion track-based biosensors

Three approaches towards ion track-based biosensors appear to be feasible. The development of the first one began a decade ago [Siwy, Z.; Trofin, L.; Kohl, P.; Baker, L.A.; Martin, C.R.; Trautmann, C. J. Am. Chem. Soc. 2005, 127, 5000–5001; Siwy, Z.S.; Harrell, C.C.; Heins, E.; Martin, C.R.; Schiedt, B.; Trautmann, C.; Trofin, L.; Polman, A. Presented at the 6th International Conference on Swift Heavy Ions in Matter, Aschaffenburg, Germany, May 28–31, 2005] and makes use of the concept that the presence of certain biomolecules within liquids can block the passage through narrow pores if being captured there, thus switching off the pore's electrical conductivity. The second, having been successfully tested half a year ago [Fink, D.; Klinkovich, I.; Bukelman, O.; Marks, R.S.; Fahrner, W.; Kiv, A.; Fuks, D.; Alfonta, L. Biosens. Bioelectron. 2009, 24, 2702–2706], is based on the accumulation of enzymatic reaction products within the confined volume of narrow etched ion tracks which modifies the pore's electrical conductivity. The third and most elegant, at present under development, will exploit the charge transfer from enzymes to semiconductors embedded within etched tracks, enabling the enzymes undergoing specific reactions with the biomolecules to be detected. These strategies can be realized either within carrier-free nanoporous polymeric membranes embedded in the corresponding bioliquids, or within contacted nanoporous insulating layers on semiconducting substrates, the so-called TEMPOS structures [Fink, D.; Petrov, A.; Hoppe, H.; Fahrner, W.R.; Papaleo, R.M.; Berdinsky, A.; Chandra, A.; Biswas, A.; Chadderton, L.T. Nucl. Instrum. Methods B 2004, 218, 355–361]. The latter have the advantage of exhibiting a number of peculiar electronic properties, such as the ability for logic and/or combination of input signals, tunable polarity, negative differential resistances, tunability by external parameters such as light, magnetic fields, etc. and self-pulsations, which should enable one to design intelligent autonomous biosensors. It also appears possible to let the enzymatic reactions take place on the surface of carbon nanotubes embedded within such TEMPOS structures. The advantages and disadvantages of all these approaches will be compared with each other, in respect to detection selectivity, sensitivity and accuracy, as well as sensor reproducibility, reusability and stability.

Nanodesign of superhydrophobic surfaces

When deposited on a hydrophobic rough surface, a small water drop looks like a small pearl. In this study we investigate the conditions to observe such a phenomenon when the roughness of the substrate, of fractal nature, consists of nanofeatures obtained by the ion track etching technique. The surface roughness was characterized by two parameters: the fractal dimension Df and the aspect ratio AR. Both were extracted from the analysis of atomic force microscopy images and were directly correlated with the etching time. Df is found in the interval of 2.46–2.69, while AR varies from 0.5 to ∼15. We show that for the highest Df values the water contact angles on these surfaces can exceed 150°, while the hysteresis—the difference between the advancing and receding contact angles—is reduced to 4–5°. Superhydrophobic surfaces can thus be obtained and this property seems well controlled by the fractal dimension, which is itself controlled by the ion track etching process. Furthermore, the experimental results are well described by the wetting theory, and it is shown that superhydrophobicity of these surfaces results from a single-scale roughness of nanometric size.

Investigation of initial stage of chemical etching of ion tracks in polycarbonate

Chemical track etching and the growth of nanochannels in ion-irradiated polycarbonate foils were investigated by loss of weight measurements and IR-spectroscopy. The data provided by both methods are in good agreement and allow us to shed light on the early stage of pore formation including times where the breakthrough of the pores has not yet occurred. Clear evidence is shown that the pore growth as a function of etching time depends on the irradiation fluence. For fixed etching parameters, foils containing 7 × 10 9 tracks/cm 2 exhibit much smaller pores than samples with 2 × 10 8 tracks/cm 2. This effect is independent of the etching temperature and appears for irradiations with Pb ions as well as for Ca–ion tracks sensitized by UV exposure. Model calculations for different etching times and fluences show that the data for low track densities can be fitted quite well by describing the radial etching rate by the track etch rate changing into the bulk etch rate with a Gaussian-shaped transition.

Templates for engineered nano-objects for use in microwave, electronic devices and biomedical sensing application

Nanoporous templates have been developed and fabricated employing technology based on heavy ion bombardment and track etching of polymer films or polymer layers deposited on substrates; an alternative and unique tool based on the adaptation of an atomic force microscopy has been also developed to elaborate nanotemplates with pores of ultra-small dimensions down to a few nanometers. Different types of nano-objects elaborated using these templates have been further characterized regarding their specific properties: spin dependent phenomena in magnetic nano-objects (GMR, TMR, spin filtering, magneto-Coulomb effect, spin transfer torque phenomena), microwave properties of ferromagnetic nanowires arrays, optical properties of confined emitting polymer and biomedical applications of magnetic (Ni) and Ni/Au composite nanowires. Potential application of magnetic nanowire arrays has been also considered in sensor for automotive contact-less positioning system.

Tuning the Characteristics of Electrochemically Fabricated Gold Nanowires

We have developed different electrochemical procedures for the production of gold nanowires with variable and controllable crystallographic and morphological properties using etched ion track templates. The texture of the nanowires is tuned by the variation of the electrodeposition parameters. Potentiostatic plating at low overvoltage provides strongly (110) textured wires for diameters below 100 nm. With the increase in diameter above 100 nm, this texture decreases and the signal from ({111} planes becomes more pronounced. Under reverse pulse deposition conditions, (100) textured wires are generated. The growth mechanism is discussed in detail in terms of the surface energy minimum principle. In addition, wires are shaped in a reliable way from cylindrical to conical geometry by engineering the pore structure in the template.

Nanostructures of Si/SiO2/metal systems with tracks of fast heavy ions

Structures based on the SiO2/n-Si and SiO2/p-Si systems, with nanopores in silicon dioxide layers filled with Cu and Ni nanoparticles, have been prepared and investigated using the fast heavy ion technology, which includes irradiation with 197Au26+ ions, chemical etching of ion tracks, and subpotential electrochemical deposition. The selectivity of filling nanopores with metals and cluster character of their formation in tracks is shown.

Nanoporous SiO2/Si thin layers produced by ion track etching: Dependence on the ion energy and criterion for etchability

Vitreous SiO2 thin films thermally grown onto Si wafers were bombarded by Au ions with energies from 0.005 to 11.1 MeV/u and by ions at constant velocity (0.1 MeV/u A197u, T130e, A75s, S32, and F19). Subsequent chemical etching produced conical holes in the films with apertures from a few tens to ∼150 nm. The diameter and the cone angle of the holes were determined as a function of energy loss of the ions. Preferential track etching requires a critical electronic stopping power Seth∼2 keV/nm, independent of the value of the nuclear stopping. However, homogeneous etching, characterized by small cone opening angles and narrow distributions of pore sizes and associated with a continuous trail of critical damage, is only reached for Se&amp;gt;4 keV/nm. The evolution of the etched-track dimensions as a function of specific energy (or electronic stopping force) can be described by the inelastic thermal spike model, assuming that the etchable track results from the quenching of a zone which contains sufficient energy for melting. The model correctly predicts the threshold for the appearance of track etching Seth if the radius of the molten region has at least 1.6 nm. Homogeneous etching comes out only for latent track radii larger than 3 nm.

Microfabrication of Chip-sized Scaffolds for Three-dimensional Cell cultivation

Using microfabrication technologies is a prerequisite to create scaffolds of reproducible geometry and constant quality for three-dimensional cell cultivation. These technologies offer a wide spectrum of advantages not only for manufacturing but also for different applications. The size and shape of formed cell clusters can be influenced by the exact and reproducible architecture of the microfabricated scaffold and, therefore, the diffusion path length of nutrients and gases can be controlled.1 This is unquestionably a useful tool to prevent apoptosis and necrosis of cells due to an insufficient nutrient and gas supply or removal of cellular metabolites. Our polymer chip, called CellChip, has the outer dimensions of 2 x 2 cm with a central microstructured area. This area is subdivided into an array of up to 1156 microcontainers with a typical dimension of 300 m edge length for the cubic design (cp- or cf-chip) or of 300 m diameter and depth for the round design (r-chip).2 So far, hot embossing or micro injection moulding (in combination with subsequent laborious machining of the parts) was used for the fabrication of the microstructured chips. Basically, micro injection moulding is one of the only polymer based replication techniques that, up to now, is capable for mass production of polymer microstructures.3 However, both techniques have certain unwanted limitations due to the processing of a viscous polymer melt with the generation of very thin walls or integrated through holes. In case of the CellChip, thin bottom layers are necessary to perforate the polymer and provide small pores of defined size to supply cells with culture medium e.g. by microfluidic perfusion of the containers. In order to overcome these limitations and to reduce the manufacturing costs we have developed a new microtechnical approach on the basis of a down-scaled thermoforming process. For the manufacturing of highly porous and thin walled polymer chips, we use a combination of heavy ion irradiation, microthermoforming and track etching. In this so called "SMART" process (Substrate Modification And Replication by Thermoforming) thin polymer films are irradiated with energetic heavy projectiles of several hundred MeV introducing so-called "latent tracks" Subsequently, the film in a rubber elastic state is formed into three dimensional parts without modifying or annealing the tracks. After the forming process, selective chemical etching finally converts the tracks into cylindrical pores of adjustable diameter.

Revelation of nuclear tracks and dislocations: A Monte Carlo simulation of mineral etching

A simple atomistic Monte Carlo simulation suggests that there are up to four stages in the evolution of an etch pit in the (0 0 1)-surface of an idealised regular lattice. During the first stage, the etch pit is an inverted pyramid; its horizontal and vertical dimensions increase at a constant rate; the apparent horizontal ( v h) and vertical ( v d) growth rates are faster than during all subsequent stages but nevertheless less than the step retreat rate ( v s) on account of surface etching ( v v). The pyramid apex is truncated in the second stage; it is thereafter bounded by an expanding bottom plane and shrinking lateral walls; this is accompanied by a gradual decrease of v h; v d drops to a negative value indicating a slow decrease of the etch-pit depth; the bottom plane acquires a concave-up curvature; the outward curvature of the walls, initiated during the first stage, increases. During the third stage the etch pit consists of a single concave-up bottom plane; v h and v d decrease at declining rates; consecutive etch-pit profiles are scalable in the horizontal direction. The hypothetical fourth stage is inferred but not documented by the simulations; it sets in when v h is reduced to zero; unless this corresponds to an as yet unidentified steady-state condition, the etch pit from here on forth shrinks until it eventually disappears altogether. The sole cause for this succession is the process of stochastic rounding of confined steps and faces. The triangular footprint of recoil-track, fission-track, ion-track and dislocation etch pits in trioctahedral mica and its compliance with the monoclinic symmetries implies that the relevant periodic bond chains are O–Mg/Fe–O chains in the octahedral layer. The size distribution of etched recoil tracks is due to (1) depth variations resulting from the size distribution of the latent tracks, (2) the random truncation of the surface tracks, (3) the variable rate of etch-pit enlargement and (4) the fact that new tracks are exposed at the surface due to surface etching. The greater size of dislocation, fission-track and ion-track etch pits is due to their greater extent below the surface. The increase of the number of etched tracks with etching time due to bulk etching is non-linear because the bulk etch rate v v is not constant. The evolution of etch-pit shape with continued etching can also cause loss of tracks due to observation effects related to loss of contrast.