Gaspard Pardon

Modeling and simulation of electrostatically gated nanochannels

Today, despite the growing interest in nanofluidics, the descriptions of the many complex physical phenomena occurring at this scale remain scattered in the literature. Due to the additional complexity encountered when considering electrostatic nanofluidic gating, it is important to regroup several relevant theories and discuss them with regard to this application. In this work, we present a theoretical study of electrostatically gated phenomena and propose a model for the electrostatic gating of ion and molecular transport in nanochannels. In addition to the classical electrokinetic equations, that are reviewed in this work, several relevant phenomena are considered and combined to describe gating effects on nanofluidic properties more accurately. Dynamic surface charging is accounted for and is shown to be an essential element for electrostatic gating. The autoprotolysis of water is also considered to allow for accurate computing of the surface charge. Modifications of the Nernst-Planck equations are considered for more accurate computing of the concentration profiles at higher surface potentials by accounting for ion crowding near charge walls. The sensitivity of several parameters to the electric field and ion crowding is also studied. Each of these models is described separately before their implementation in a finite element model. The model is verified against previous experimental work. Finally, the model is used to simulate the tuning of the ionic current through the nanochannel via electrostatic gating. The influence of the additional models on these results is discussed. Guidelines for potentially better gating efficiencies are finally proposed.

Pt–Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al(2)O(3)) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al(2)O(3) layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al(2)O(3) using ALD.

Single-Step Imprinting of Femtoliter Microwell Arrays Allows Digital Bioassays with Attomolar Limit of Detection

Bead-based microwell array technology is growing as an ultrasensitive analysis tool as exemplified by the successful commercial applications from Illumina and Quanterix for nucleic acid analysis and ultrasensitive protein measurements, respectively. High-efficiency seeding of magnetic beads is key for these applications and is enhanced by hydrophilic-in-hydrophobic microwell arrays, which are unfortunately often expensive or labor-intensive to manufacture. Here, we demonstrate a new single-step manufacturing approach for imprinting cheap and disposable hydrophilic-in-hydrophobic microwell arrays suitable for digital bioassays. Imprinting of arrays with hydrophilic-in-hydrophobic microwells is made possible using an innovative surface energy replication approach by means of a hydrophobic thiol-ene polymer formulation. In this polymer, hydrophobic-moiety-containing monomers self-assemble at the hydrophobic surface of the imprinting stamp, which results in a hydrophobic replica surface after polymerization. After removing the stamp, microwells with hydrophobic walls and a hydrophilic bottom are obtained. We demonstrate that the hydrophilic-in-hydrophobic imprinted microwell arrays enable successful and efficient self-assembly of individual water droplets and seeding of magnetic beads with loading efficiencies up to 96%. We also demonstrate the suitability of the microwell arrays for the isolation and digital counting of single molecules achieving a limit of detection of 17.4 aM when performing a streptavidin-biotin binding assay as model system. Since this approach is up-scalable through reaction injection molding, we expect it will contribute substantially to the translation of ultrasensitive digital microwell array technology toward diagnostic applications.

Surface energy micropattern inheritance from mold to replica

We report a novel surface-energy patterning phenomenon, in which a novel polymer composition inherits the surface energy of the medium it is in contact with during polymerization. This surface property mimicking process occurs via spontaneous selective molecular alignment of hydrophilic and hydrophobic monomers mixed into an off-stoichiometry thiol-ene (OSTE) formulation. This single-step method for simultaneous structuring and surface energy micropatterning of polymer structures is potentially more robust and lower cost than state-of-the-art processes requiring post-processing surface modification steps. We further demonstrate the self-assembly of a liquid droplet array on the replicated polymer surfaces.

Electrostatic gating of ion and molecule transport through a nanochannel-array membrane

This work presents a predictive and todays most complete model for electrostatic gating of nanofluidic channels. The model is based on the classical mean field equations and accounts for the surface reactivity. The model is successfully verified against previously published experimental data [1]. The fabrication concept of a novel device is introduced and its predicted performances are discussed with the help of the presented model. A ∼40x performance improvement, in terms of tunability of the ionic conductivity in the nanochannel, in comparison to the result presented in [1], is expected.

Off-stoichiometry improves the photostructuring of thiol–enes through diffusion-induced monomer depletion

Thiol–enes are a group of alternating copolymers with highly ordered networks and are used in a wide range of applications. Here, “click” chemistry photostructuring in off-stoichiometric thiol–enes is shown to induce microscale polymeric compositional gradients due to species diffusion between non-illuminated and illuminated regions, creating two narrow zones with distinct compositions on either side of the photomask feature boundary: a densely cross-linked zone in the illuminated region and a zone with an unpolymerized highly off-stoichiometric monomer composition in the non-illuminated region. Using confocal Raman microscopy, it is here explained how species diffusion causes such intricate compositional gradients in the polymer and how off-stoichiometry results in improved image transfer accuracy in thiol–ene photostructuring. Furthermore, increasing the functional group off-stoichiometry and decreasing the photomask feature size is shown to amplify the induced gradients, which potentially leads to a new methodology for microstructuring.