Donghoon Han

Electrochemical signal amplification for immunosensor based on 3D interdigitated array electrodes.

We devised an electrochemical redox cycling based on three-dimensional interdigitated array (3D IDA) electrodes for signal amplification to enhance the sensitivity of chip-based immunosensors. The 3D IDA consists of two closely spaced parallel indium tin oxide (ITO) electrodes that are positioned not only on the bottom but also the ceiling, facing each other along a microfluidic channel. We investigated the signal intensities from various geometric configurations: Open-2D IDA, Closed-2D IDA, and 3D IDA through electrochemical experiments and finite-element simulations. The 3D IDA among the four different systems exhibited the greatest signal amplification resulting from efficient redox cycling of electroactive species confined in the microchannel so that the faradaic current was augmented by a factor of ∼100. We exploited the enhanced sensitivity of the 3D IDA to build up a chronocoulometric immunosensing platform based on the sandwich enzyme-linked immunosorbent assay (ELISA) protocol. The mouse IgGs on the 3D IDA showed much lower detection limits than on the Closed-2D IDA. The detection limit for mouse IgG measured using the 3D IDA was ∼10 fg/mL, while it was ∼100 fg/mL for the Closed-2D IDA. Moreover, the proposed immunosensor system with the 3D IDA successfully worked for clinical analysis as shown by the sensitive detection of cardiac troponin I in human serum down to 100 fg/mL.

Surface Enhanced Raman Scattering on Non‐SERS Active Substrates and In Situ Electrochemical Study based on a Single Gold Microshell

A single gold microshell, which was elaborately fabricated to carry numerous hot spots on its own surface, enabled the acquisition of the SERS spectra from the molecules on non-SERS active substrates such as Si/SiO2, ITO, and glass. A self-assembled monolayer of 11-mercaptoundecanols on the gold microshell offered an easy and reliable way to electrically insulate from the underlying flat Pt electrode and accomplish in situ monitoring the electrochemical reaction with minimal interference.

Synthesis of copper nanoparticles by solid-state plasma-induced dewetting

Copper nanoparticles were prepared by the plasma treatment of Cu thin films without extra heating. The Cu nanoparticles were formed through a solid-state dewetting process at temperatures of less than 450 K. The particle sizes, from 10 to 80 nm, were controlled by changing the thickness of the Cu film; the particle size increased linearly with the film thickness. The Cu nanoparticles produced by plasma treatment showed an excellent size uniformity compared to those prepared by heat treatment. In the early stage of the dewetting of the Cu film, uniformly distributed holes nucleated, and the holes grew and coalesced until the Cu nanoparticles were formed. The low operating temperatures used contributed to the production of uniform Cu nanoparticles.

Electrochemistry at single molecule occupancy in nanopore-confined recessed ring-disk electrode arrays

Electrochemical reactions at nanoscale structures possess unique characteristics, e.g. fast mass transport, high signal-to-noise ratio at low concentration, and insignificant ohmic losses even at low electrolyte concentrations. These properties motivate the fabrication of high density, laterally ordered arrays of nanopores, embedding vertically stacked metal-insulator-metal electrode structures and exhibiting precisely controlled pore size and interpore spacing for use in redox cycling. These nanoscale recessed ring-disk electrode (RRDE) arrays exhibit current amplification factors, AFRC, as large as 55-fold with Ru(NH3)62/3+, indicative of capture efficiencies at the top and bottom electrodes, Φt,b, exceeding 99%. Finite element simulations performed to investigate the concentration distribution of redox species and to assess operating characteristics are in excellent agreement with experiment. AFRC increases as the pore diameter, at constant pore spacing, increases in the range 200-500 nm and as the pore spacing, at constant pore diameter, decreases in the range 1000-460 nm. Optimized nanoscale RRDE arrays exhibit a linear current response with concentration ranging from 0.1 μM to 10 mM and a small capacitive current with scan rate up to 100 V s-1. At the lowest concentrations, the average pore occupancy is 〈n〉 ∼ 0.13 molecule establishing productive electrochemical signals at occupancies at and below the single molecule level in these nanoscale RRDE arrays.

Addressable Direct-Write Nanoscale Filament Formation and Dissolution by Nanoparticle-Mediated Bipolar Electrochemistry

Nanoscale conductive filaments, usually associated with resistive memory or memristor technology, may also be used for chemical sensing and nanophotonic applications; however, realistic implementation of the technology requires precise knowledge of the conditions that control the formation and dissolution of filaments. Here we describe and characterize an addressable direct-write nanoelectrochemical approach to achieve repeatable formation/dissolution of Ag filaments across a ∼100 nm poly(ethylene oxide) (PEO) film containing either Ag+ alone or Ag+ together with 50 nm Ag-nanoparticles acting as bipolar electrodes. Using a conductive AFM tip, formation occurs when the PEO film is subjected to a forward bias, and dissolution occurs under reverse bias. Formation-dissolution kinetics were studied for three film compositions: Ag|PEO-Ag+, Ag|poly(ethylene glycol) monolayer-PEO-Ag+, and Ag|poly(ethylene glycol) monolayer-PEO-Ag+/Ag-nanoparticle. Statistical analysis shows that the distribution of formation times exhibits Gaussian behavior, and the fastest average initial formation time occurs for the Ag|PEO-Ag+ system. In contrast, formation in the presence of Ag nanoparticles likely proceeds by a noncontact bipolar electrochemical mechanism, exhibiting the slowest initial filament formation. Dissolution times are log-normal for all three systems, and repeated reformation of filaments from previously formed structures is characterized by rapid regrowth. The direct-write bipolar electrochemical deposition/dissolution strategy developed here presents an approach to reconfigurable, noncontact in situ wiring of nanoparticle arrays-thereby enabling applications where actively controlled connectivity of nanoparticle arrays is used to manipulate nanoelectronic and nanophotonic behavior. The system further allows for facile manipulation of experimental conditions while simultaneously characterizing surface conditions and filament formation/dissolution kinetics.

Garment capture from a photograph

This paper presents a new method which can create the virtual garment from a single photograph of a real garment put on to the mannequin. In solving this problem, we obtain the insight from the pattern drafting theory in the clothing field. We abstract the drafting process into a computer module, which takes the garment type and primary body sizes then produces the draft as the output. Then the problem is reduced to find out the garment type and primary body sizes. We find that information by analyzing the silhouette of the garment with respect to the mannequin. The method works robustly and produces practically usable virtual clothes that can be used for the graphical coordination. Copyright

Voltage‐Gated Nanoparticle Transport and Collisions in Attoliter‐Volume Nanopore Electrode Arrays

Single nanoparticle analysis can reveal how particle-to-particle heterogeneity affects ensemble properties derived from traditional bulk measurements. High-bandwidth, low noise electrochemical measurements are needed to examine the fast heterogeneous electron-transfer behavior of single nanoparticles with sufficient fidelity to resolve the behavior of individual nanoparticles. Herein, nanopore electrode arrays (NEAs) are fabricated in which each pore supports two vertically spaced, individually addressable electrodes. The top ring electrode serves as a particle gate to control the transport of silver nanoparticles (AgNPs) within individual attoliter volume NEAs nanopores, as shown by redox collisions of AgNPs collisions at the bottom disk electrode. The AgNP-nanoporeis system has wide-ranging technological applications as well as fundamental interest, since the transport of AgNPs within the NEA mimics the transport of ions through cell membranes via voltage-gated ion channels. A voltage threshold is observed above which AgNPs are able to access the bottom electrode of the NEAs, i.e., a minimum potential at the gate electrode is required to switch between few and many observed collision events on the collector electrode. It is further shown that this threshold voltage is strongly dependent on the applied voltage at both electrodes as well as the size of AgNPs, as shown both experimentally and through finite-element modeling. Overall, this study provides a precise method of monitoring nanoparticle transport and in situ redox reactions within nanoconfined spaces at the single particle level.

Direct‐Write Formation and Dissolution of Silver Nanofilaments in Ionic Liquid‐Polymer Electrolyte Composites

Materials with reconfigurable optical properties are candidates for applications such as optical cloaking and wearable sensors. One approach to fabricate these materials is to use external fields to form and dissolve nanoscale conductive channels in well-defined locations within a polymer. In this study, conductive atomic force microscopy is used to electrochemically form and dissolve nanoscale conductive filaments at spatially distinct points in a polyethylene glycol diacrylate (PEGDA)-based electrolyte blended with varying amounts of ionic liquid (IL) and silver salt. The fastest filament formation and dissolution times are detected in a PEGDA/IL composite that has the largest modulus (several GPa) and the highest polymer crystal fraction. This is unexpected because filament formation and dissolution events are controlled by ion transport, which is typically faster within amorphous regions where polymer mobility is high. Filament kinetics in primarily amorphous and crystalline regions are measured, and two different mechanisms are observed. The formation time distributions show a power-law dependence in the crystalline regions, attributable to hopping-based ion transport, while amorphous regions show a normal distribution. The results indicate that the timescale of filament formation/dissolution is determined by local structure, and suggest that structure could be used to tune the optical properties of the film.

Asymmetric Nafion-Coated Nanopore Electrode Arrays as Redox-Cycling-Based Electrochemical Diodes

Inspired by the functioning of cellular ion channels, pore-based structures with nanoscale openings have been fabricated and integrated into ionic circuits, for example, ionic diodes and transistors, for signal processing and detection. In these systems, the nonlinear current responses arise either because asymmetric nanopore geometries break the symmetry of the ion distribution, creating unequal surface charge across the nanopore, or by coupling unidirectional electron transfer within a nanopore electrode. Here we develop a high-performance redox-cycling-based electrochemical diode by coating an asymmetric ion-exchange membrane, that is, Nafion, on the top surface of a nanopore electrode array (Nafion@NEA), in which each pore in the array exhibits one or more annular electrodes. Nafion@NEAs exhibit highly sensitive and charge-selective electroanalytical measurements due to efficient redox-cycling reaction, the permselectivity of Nafion, and the strong confinement of redox species in the nanopore array. In addition, the top electrode of dual-electrode Nafion@NEAs can serve as a voltage-controlled switch to gate ion transport within the nanopore. Thus Nafion@NEAs can be operated as a diode by switching voltages applied to the top and bottom electrodes of the NEA, leading to a large rectification ratio, fast response times, and simplified circuitry without the need for external electrodes. By taking advantage of closely spaced and individually addressable electrodes, the redox-cycling electrochemical diode has the potential for application to large-scale production and electrochemically controlled circuit operations, which go well beyond conventional electronic diodes or transistors.