Osmotic Effects in Track-Etched Nanopores.

Asymmetrically etched ion-track membranes attract great interest for both fundamental and technical reasons because of a large variety of applications. So far, conductometric measurements during track etching provide only limited information about the complicated asymmetric etching process. In this paper, monitoring of osmotic phenomena is used to elucidate the initial phase of nanopore formation. It is shown that strong alkaline solutions generate a considerable osmotic flow of water through newborn conical pores. The interplay between diffusion and convection in the pore channel results in a substantially nonlinear alkali concentration gradient and a rapid change in the pore geometry after breakthrough. Similar phenomena are observed in experiments with cylindrical track-etched pores of 15-30 nm in radius. A theoretical description of the diffusion-convection processes in the pores is provided.

Shedding light on the mechanism of asymmetric track etching: an interplay between latent track structure, etchant diffusion and osmotic flow.

The method of producing single track-etched conical nanopores has received considerable attention and found many applications in diverse fields such as biosensing, nanofluidics, information processing and others. The performance of an asymmetric nanopore is largely determined by its geometry, especially by the size and shape of its tip. In this paper we reconstruct the profiles of so-called conical pores fabricated by asymmetric chemical etching of ion tracks in polymer foil. Conductometric measurements during etching and field emission scanning electron microscopy examinations of the resulting pores were employed in order to determine the pore geometry. We demonstrate that the pore constriction geometry evolves through a variety of configurations with advancing time after breakthrough. While immediately after breakthrough the pore tips are trumpet-shaped, further etching is strongly affected by osmotic effects which eventually lead to bullet-shaped pore tips. We evidence that the osmotic flow appearing during asymmetric track etching has a determinative effect on pore formation. A convection-diffusion model is presented that semi-quantitatively explains the effect of osmotic processes under asymmetric track etching conditions. In addition, a phenomenon of reagent contaminant precipitation in nanopores is reported and discussed.

Accurate characterization of single track-etched, conical nanopores.

Single track-etched conical nanopores in polymer foils have attracted considerable attention in recent years due to their potential applications in biosensing, nanofluidics, information processing, and other fields. The performance of a nanopore critically depends on the size and shape of its narrowest, nanometer-sized region. In this paper, we reconstructed the profiles of both doubly-conical and conical pores, using an algorithm based on conductometric measurements performed in the course of etching, coupled with SEM data. We showed that pore constriction deviates from the conical shape, and the deviation depends on the energy loss of the particle that produced the track. Funnel-like profiles of tracks of four ions with different atomic numbers were derived from experimental data. The simulations, using a Poisson-Nernst-Planck model, demonstrated that the ion current rectification properties of the funnel-shaped asymmetrical pores significantly differ from those of conical ones if the tip radius of the pore is smaller than 10 nm. Upon subjecting to further etching, the pores gradually approach the "ideal" conical geometry, and the ion transport properties of these two pore configurations become almost indistinguishable.

Asymmetric ion track nanopores for sensor technology. Reconstruction of pore profile from conductometric measurements.

We reconstruct the profile of asymmetric ion track nanopores from an algorithm developed for conductometric measurements of symmetric nanopores. The validity of the reconstruction is supported by FESEM observations. Our analysis reveals that asymmetric pores fabricated by one-sided etching are funnel-like and not conical. The analysis provides the constriction diameter and the pore profile as a function of etching time. The reconstruction of the pore profile defines the starting conditions of asymmetric nanopores at breakthrough. The deviation from the conical shape is most pronounced at the pore tip. This critical zone dominates transport properties relevant to ion conductance, selectivity, current rectification, resistive pulse sensing and biosensors. The classical cone approximation used until now underestimates the tip diameter by a factor of two. As transport processes in nanopores depend in a highly nonlinear way on the constriction diameter the presented reconstruction must be taken into account when studying ionic and molecular transport processes in asymmetric pores.

Effect of nanopore geometry on ion current rectification.

We present the results of systematic studies of ion current rectification performed on artificial asymmetric nanopores with different geometries and dimensions. The nanopores are 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 the pore profile and dimensions is achieved. The pore geometry is characterized in detail using field-emission scanning electron microscopy. The dependence of the ion current rectification ratio on the pore length, tip diameter, and the degree of pore taper is analysed. The experimental data are compared to the calculations based on the Poisson-Nernst-Planck equations. A strong effect of the tip geometry on the diode-like behaviour is confirmed.

Ultrasound attenuation in cylindrical micro-pores: nondestructive porometry of ion-track membranes.

The propagation of ultrasonic waves in the cylindrical micro-pores (pore diam. 1 microm) of ion-track membranes (ITMs) is studied. This membrane fabrication technique provides unique possibilities to obtain cylindrical micro-pores with a very high degree of accuracy in pore shape, size, and orientation. Several ITMs were specially produced having the same pore diameter, orientation, and geometry, but different thickness. Porosity, pore diameter, and shape were determined using scanning electron microscopy, and then the coefficient of ultrasound transmission was measured using air coupling and spectral analysis. These experimental conditions permit us to eliminate the influence of the boundary conditions and to achieve a strong decoupling between the fluid filling the pores and the solid constituent of the membrane. Hence, the velocity and the attenuation coefficient for ultrasound propagation in the pores can be measured. These parameters are compared with the predictions made by conventional theories for sound propagation in porous media and in cylindrical channels. The conclusions of this work provide a better understanding of wave propagation in micro-pores and establish the basis of an ultrasonic porometry technique for ITMs.