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The investigation of electrochemical processes at the interface of two immiscible electrolyte solutions (ITIES) is of great interest for sensing applications, and serves as a surrogate to the study of biological transport phenomena, e.g. ion channels. Alongside e-beam lithography, focused ion beam (FIB) milling is an attractive method to prototype and fabricate nanopore arrays that support nanoITIES. Within this contribution, we explore the capability of FIB/scanning electron microscopy (SEM) tomography to visualize the actual pore structure and interfaces at silica-modified nanoporous membranes. The nanopores were also characterized by atomic force microscopy (AFM) using ultra-sharp AFM probes to determine the pore diameter, and using scanning transmission electron microscopy (STEM) and energy dispersive X-ray (EDX) spectroscopy, providing additional information on the elemental composition of deposits within the pores. Si-rich particles could be identified within the pores as well as at the orifice that had faced the organic electrolyte solution during electrochemical deposition. The prospects of the used techniques for investigating the interface at or within FIB-milled nanopores will be discussed.

The direct experimental characterization of diffusion processes at nanoscale remains a challenge that could help elucidate processes in biology, medicine and technology. In this report, two experimental approaches were employed to visualize ion diffusion profiles at the orifices of nanopores (radius (ra) of 86 ± 6 nm) in array format: (1) electrochemically assisted formation of silica deposits based on surfactant ion transfer across nanointerfaces between two immiscible electrolyte solutions (nanoITIES); (2) combined atomic force - scanning electrochemical microscopy (AFM-SECM) imaging of topography and redox species diffusion through the nanopores. The nature of the diffusion zones formed around the pores is directly related to the interpore distance within the array. Nanopore arrays with different ratios of pore center-to-center separation (rc) to pore radius (ra) were fabricated by focused ion beam (FIB) milling of silicon nitride (SiN) membranes, with 100 pores in a hexagonal arrangement. The ion diffusion profiles determined by the two visualization methods indicated the formation of overlapped or independent diffusion profiles at nanopore arrays with rc/ra ratios of 21 ± 2 and 91 ± 7, respectively. In particular, the silica deposition method resulted in formation of a single deposit encompassing the complete array with closer nanopore arrangement, whereas individual silica deposits were formed around each nanopore within the more widely spaced array. The methods reveal direct experimental evidence of diffusion zones at nanopore arrays and provide practical illustration that the pore-pore separation within such arrays has a significant impact on diffusional transport as the pore size is reduced to the nanoscale. These approaches to nanoscale diffusion zone visualization open up possibilities for better understanding of molecular transport processes within miniaturized systems.

In this work, independent radial diffusion at arrayed nanointerfaces between two immiscible electrolyte solutions (nanoITIES) was achieved. The arrays were formed at nanopores fabricated by focused ion beam milling of silicon nitride (SiN) membranes, enabling the reproducible and systematic design of five arrays with different ratios of pore center-to-center distance (rc) to pore radius (ra). Voltammetry across water–1,6-dichlorohexane nanoITIES formed at these arrays was examined by the interfacial transfer of tetrapropylammonium ions. The diffusion-limited ion-transfer current increased with the ratio rc/ra, reaching a plateau for rc/ra ≥ 56, which was equivalent to the theoretical current for radial diffusion to an array of independent nanoITIES. As a result, mass transport to the nanoITIES arrays was greatly enhanced due to the decreased overlap of diffusion zones at adjacent nanoITIES, allowing each interface in the array to behave independently. When the rc/ra ratio increased from 13 to 56, the analytical performance parameters of sensitivity and limit of detection were improved from 0.50 (±0.02) A M–1 to 0.76 (±0.02) A M–1 and from 0.101 (±0.003) μM to 0.072 (±0.002) μM, respectively. These results provide an experimental basis for the design of arrayed nanointerfaces for electrochemical sensing.

The electrochemical behaviour of single and arrayed nanoscale interfaces between two immiscible electrolyte solutions (single and array nanoITIES) is presented. The interfaces were formed at nanopores fabricated through the focused ion beam (FIB) milling of silicon nitride (SiN) membranes by using nanopores with approximately 30–80 nm radii and with pore-to-pore separations to pore radius ratios in the range of 16–32. Electrochemistry was performed through the interfacial transfer of tetrapropylammonium (TPrA+) across single and array nanoITIES between water and 1,6-dichlorohexane. The ion-transfer limiting current at the single nanoITIES was in excellent agreement with the current predicted by using an inlaid disc interface model. At nanoITIES arrays, experimental currents were lower than predicted for an array of inlaid interfaces, which is attributed to overlapped diffusion zones. As a result, FIB milling offers an attractive strategy to form nanoITIES for diverse investigations.

Conductive polymers, and in particular polypyrrole, are frequently used as biomimetic interfaces facilitating growth and/or differentiation of cells and tissues. Hence, studying forces and local interactions between such polymer interfaces and cells at the nanoscale is of particular interest. Frequently, such force interactions are not directly accessible with high spatial resolution. Consequently, we have developed nanoscopic polypyrrole electrodes, which are integrated in AFM-SECM probes. Bifunctional AFM-SECM probes were modified via ion beam-induced deposition resulting in pyramidal conductive Pt-C composite electrodes. These nanoscopic electrodes then enabled localized polypyrrole deposition, thus resulting in polymer-modified AFM probes with a well-defined geometry. Furthermore, such probes may be reversibly switched from an insulating to a conductive state. In addition, the hydrophilicity of such polymer tips is dependent on the dopant, and hence, on the oxidation state. Force studies applying different tip potentials were performed at plasma-treated glass surfaces providing localized information on the associated force interactions, which are dependent on the applied potential and the dopant.

Conductive polymers, and in particular polypyrrole, are frequently used as biomimetic interfaces facilitating growth and/or differentiation of cells and tissues. Hence, studying forces and local interactions between such polymer interfaces and cells at the nanoscale is of particular interest. Frequently, such force interactions are not directly accessible with high spatial resolution. Consequently, we have developed nanoscopic polypyrrole electrodes, which are integrated in AFM-SECM probes. Bifunctional AFM-SECM probes were modified via ion beam-induced deposition resulting in pyramidal conductive Pt-C composite electrodes. These nanoscopic electrodes then enabled localized polypyrrole deposition, thus resulting in polymer-modified AFM probes with a well-defined geometry. Furthermore, such probes may be reversibly switched from an insulating to a conductive state. In addition, the hydrophilicity of such polymer tips is dependent on the dopant, and hence, on the oxidation state. Force studies applying different tip potentials were performed at plasma-treated glass surfaces providing localized information on the associated force interactions, which are dependent on the applied potential and the dopant.

Conductive polymers, and in particular polypyrrole, are frequently used as biomimetic interfaces facilitating growth and/or differentiation of cells and tissues. Hence, studying forces and local interactions between such polymer interfaces and cells at the nanoscale is of particular interest. Frequently, such force interactions are not directly accessible with high spatial resolution. Consequently, we have developed nanoscopic polypyrrole electrodes, which are integrated in AFM-SECM probes. Bifunctional AFM-SECM probes were modified via ion beam-induced deposition resulting in pyramidal conductive Pt-C composite electrodes. These nanoscopic electrodes then enabled localized polypyrrole deposition, thus resulting in polymer-modified AFM probes with a well-defined geometry. Furthermore, such probes may be reversibly switched from an insulating to a conductive state. In addition, the hydrophilicity of such polymer tips is dependent on the dopant, and hence, on the oxidation state. Force studies applying different tip potentials were performed at plasma-treated glass surfaces providing localized information on the associated force interactions, which are dependent on the applied potential and the dopant.

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