Novel transport phenomena through nanopores are expected to emerge as their diameters approach subnanometer scales. However, it has been challenging to explore such a regime experimentally. Here, this study reports on polymer subnanometer pores exhibiting unique selective ionic transport. 12 μm long, parallel oriented polymer nanopores are fabricated in polyethylene terephthalate (PET) films by irradiation with GeV heavy ions and subsequent 3 h exposure to UV radiation. These nanopores show ionic transport selectivity spanning more than 6 orders of magnitude: the order of the transport rate is Li+>Na+>K+>Cs+>>Mg2+>Ca2+>Ba2+, and heavy metal ions such as Cd2+ and anions are blocked. The transport can be switched off with a sharp transition by decreasing the pH value of the electrolyte. Structural measurements and molecular dynamics simulations suggest that the ionic transport is attributed to negatively charged nanopores with pore radii of ≈0.3 nm, and the selectivity is associated with the dehydration effect.
The cylindrical nanoscale density variations resulting from the interaction of 185 MeV and 2.2 GeV Au ions with 1.0 μm thick amorphous SiN :H and SiO :H layers are determined using small angle x-ray scattering measurements. The resulting density profiles resembles an under-dense core surrounded by an over-dense shell with a smooth transition between the two regions, consistent with molecular-dynamics simulations. For amorphous SiN :H, the density variations show a radius of 4.2 nm with a relative density change three times larger than the value determined for amorphous SiO :H, with a radius of 5.5 nm. Complementary infrared spectroscopy measurements exhibit a damage cross-section comparable to the core dimensions. The morphology of the density variations results from freezing in the local viscous flow arising from the non-uniform temperature profile in the radial direction of the ion path. The concomitant drop in viscosity mediated by the thermal conductivity appears to be the main driving force rather than the presence of a density anomaly.
We present experimental evidence for the formation of ion tracks in amorphous Si induced by swift heavy-ion irradiation. An underlying core-shell structure consistent with remnants of a high-density liquid structure was revealed by small-angle x-ray scattering and molecular dynamics simulations. Ion track dimensions differ for as-implanted and relaxed Si as attributed to different microstructures and melting temperatures. The identification and characterization of ion tracks in amorphous Si yields new insight into mechanisms of damage formation due to swift heavy-ion irradiation in amorphous semiconductors.
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