Chi Won Ahn

Large-Area Single-Layer MoSe2 and Its van der Waals Heterostructures

Layered structures of transition metal dichalcogenides stacked by van der Waals interactions are now attracting the attention of many researchers because they have fascinating electronic, optical, thermoelectric, and catalytic properties emerging at the monolayer limit. However, the commonly used methods for preparing monolayers have limitations of low yield and poor extendibility into large-area applications. Herein, we demonstrate the synthesis of large-area MoSe2 with high quality and uniformity by selenization of MoO3 via chemical vapor deposition on arbitrary substrates such as SiO2 and sapphire. The resultant monolayer was intrinsically doped, as evidenced by the formation of charged excitons under low-temperature photoluminescence analysis. A van der Waals heterostructure of MoSe2 on graphene was also demonstrated. Interestingly, the MoSe2/graphene heterostructures show strong quenching of the characteristic photoluminescence from MoSe2, indicating the rapid transfer of photogenerated charge carriers between MoSe2 and graphene. The development of highly controlled heterostructures of two-dimensional materials will further promote advances in the physics and chemistry of reduced dimensional systems and will provide novel applications in electronics and optoelectronics.

Chemical, thermal, and electric field induced unfolding of single protein molecules studied using nanopores.

Single-molecule experimental techniques have recently shown to be of significant interest for use in numerous applications in both the research laboratory and industrial settings. Although many single-molecule techniques exist, the nanopore platform is perhaps one of the more popular techniques due to its ability to act as a molecular sensor of biological macromolecules. For example, nanopores offer a unique, new method for probing various properties of proteins and can contribute to elucidating key biophysical information in conjunction with existing techniques. In the present study, various forms of bovine serum albumin (BSA) are detected including thermally refolded BSA, urea-denatured BSA, and multiple forms of BSA detected at elevated electric field strengths (with and without urea). We also provide excluded volume measurements for each of these states that normally are difficult to obtain due to unknown and unstable protein conformations.

Detection of long and short DNA using nanopores with graphitic polyhedral edges.

Graphene is a unique material with a thickness as low as a single atom, high in-plane conductivity and a robust lattice that is self-supporting over large length scales. Schematically, graphene is an ideal solid-state material for tuning the properties of a nanopore because self-supported sheets, ranging from single to multiple atomic layers, can create pores with near-arbitrary dimensions which can provide exquisite control of the electric field drop within the pore. In this study, we characterize the drilling kinetics of nanopores using a thermionic electron source and various electron beam fluxes to minimize secondary hole formation. Once established, we investigated the use of multilayer graphene to create highly tailored nanostructures including nanopores with graphite polyhedral crystals formed around the nanopore edge. Finally, we report on the translocation of double stranded and single stranded DNA through such graphene pores and show that the single stranded DNA translocates much slower allowing detection of extremely short fragments (25 nucleotides in length). Our findings suggest that the kinetic and controllable properties of graphene nanopores under sculpting conditions can be used to further enhance the detection of DNA analytes.

Preparation of graphene with few defects using expanded graphite and rose bengal

We report an easy exfoliation technique using expanded graphite and rose bengal that requires shorter sonication time compared to that of currently reported methods in order to produce an aqueous graphene dispersion and high-quality graphene sheets with few defects. This is a simple method for graphene preparation using expanded graphite and rose bengal (RB) with amphiphilic properties as a surfactant in a short reaction time. RB with a hydrophilic carboxyl group and a hydrophobic aromatic group helps to separate the expanded graphite (EG) layers and prevents reformation of the exfoliated graphene layersvia electrostatic repulsion. The obtained graphene flakes showed oxygenated sp3carbon on the sheet edge and consisted mostly of mono- and few-layer graphene with lateral dimensions of a few hundred nanometres. This method facilitates graphene preparation for various applications.

Recovery improvement of graphene-based gas sensors functionalized with nanoscale heterojunctions

We report a development of reduced graphene oxide (rGO)-based gas sensors with a practical recovery by facile functionalization with tin dioxide nanoclusters. Upon the introduction of UV illumination to this nanostructure, the reaction on surfaces of tin dioxide nanoclusters was activated and thereby the nanoscale heterojunction barriers between the rGO sheet and the nanoclusters were developed. This lowered the conductance to quickly recover, which was intensified as the cluster density has reached to the percolation threshold. However, after the formation of the cluster percolating network, the sensor response has totally changed into a deterioration of the sensitivity as well as the recovery.

Hydrophilic and size-controlled graphene nanopores for protein detection

This paper describes a general approach for transferring clean single-layer graphene onto silicon nitride nanopore devices and the use of the electron beam of a transmission electron microscope (TEM) to drill size-controlled nanopores in freely suspended graphene. Besides nanopore drilling, we also used the TEM to heal and completely close the unwanted secondary holes formed by electron beam damage during the drilling process. We demonstrate electron beam assisted shrinking of irregularly shaped 40-60 nm pores down to 2 nm, exhibiting an exquisite control of graphene nanopore diameter. Our fabrication workflow also rendered graphene nanopores hydrophilic, allowing easy wetting and use of the pores for studying protein translocation and protein-protein interaction with a high signal to noise ratio.

Electrical property measurements of metallized flagella-templated silica nanotube networks

We present an improvement in the electrical properties of silica nanotubes by coating metal nanoparticles on their surfaces. The silica nanotubes are formed from bacterial flagella bio-templates having a tubular structure. Successive depositions of metal nanoparticles on the silica nanotubes are performed through easily functionalized silica surfaces. The results show uniform metal nanoparticle sizes and a high surface area coverage. By incorporating gold, palladium and iron oxide nanoparticles, the metallized silica nanotubes gain electrical properties with the potential to create unique nanoelectronic materials. In this study, the metallized silica nanotubes with network structures are aligned and their electrical behaviors are investigated in both dry and wet conditions. The metallized silica nanotubes are found to be electrically conductive along the network structures. The current-voltage characteristics show remarkably improved electrical conductivities depending on the type of metal nanoparticle loading and nanotube network concentration.

Surface plasmon resonance enhanced photoconductivity in Cu nanoparticle films.

We describe an all-electrical plasmon detection based on the near field coupling between plasmons and percolating electrons. It is the technique to electrically detect the local field enhancement from randomly distributed Cu nanoparticles coupled to a plasmon resonance. In addition, we revealed that plasmon-sensitivity is maximized at the percolation threshold, the minimum Cu particle surface coverage which can make the percolation path through the particles. Our detectors have a simple structure for easy fabrication and a high level of sensitivity to plasmon resonance.

Multiple consecutive recapture of rigid nanoparticles using a solid-state nanopore sensor

Solid‐state nanopore sensors have been used to measure the size of a nanoparticle by applying a resistive pulse sensing technique. Previously, the size distribution of the population pool could be investigated utilizing data from a single translocation, however, the accuracy of the distribution is limited due to the lack of repeated data. In this study, we characterized polystyrene nanobeads utilizing single particle recapture techniques, which provide a better statistical estimate of the size distribution than that of single sampling techniques. The pulses and translocation times of two different sized nanobeads (80 nm and 125 nm in diameter) were acquired repeatedly as nanobeads were recaptured multiple times using an automated system controlled by custom‐built scripts. The drift‐diffusion equation was solved to find good estimates for the configuration parameters of the recapture system. The results of the experiment indicated enhancement of measurement precision and accuracy as nanobeads were recaptured multiple times. Reciprocity of the recapture and capacitive effects in solid state nanopores are discussed. Our findings suggest that solid‐state nanopores and an automated recapture system can also be applied to soft nanoparticles, such as liposomes, exosomes, or viruses, to analyze their mechanical properties in single‐particle resolution.

Substrate Dependent Ad-Atom Migration on Graphene and the Impact on Electron-Beam Sculpting Functional Nanopores

The use of atomically thin graphene for molecular sensing has attracted tremendous attention over the years and, in some instances, could displace the use of classical thin films. For nanopore sensing, graphene must be suspended over an aperture so that a single pore can be formed in the free-standing region. Nanopores are typically drilled using an electron beam (e-beam) which is tightly focused until a desired pore size is obtained. E-beam sculpting of graphene however is not just dependent on the ability to displace atoms but also the ability to hinder the migration of ad-atoms on the surface of graphene. Using relatively lower e-beam fluxes from a thermionic electron source, the C-atom knockout rate seems to be comparable to the rate of carbon ad-atom attraction and accumulation at the e-beam/graphene interface (i.e., Rknockout ≈ Raccumulation). Working at this unique regime has allowed the study of carbon ad-atom migration as well as the influence of various substrate materials on e-beam sculpting of graphene. We also show that this information was pivotal to fabricating functional graphene nanopores for studying DNA with increased spatial resolution which is attributed to atomically thin membranes.