Hyunung Yu

In situ control of oxygen vacancies in TiO 2 by atomic layer deposition for resistive switching devices

Oxygen vacancies (V(O)) have profound effects on the physical and chemical performance of devices based on oxide materials. This is particularly true in the case of oxide-based resistive random access memories, in which memory switching operation under an external electrical stimulus is closely associated with the migration and ordering of the oxygen vacancies in the oxide material. In this paper, we report on a reliable approach to in situ control of the oxygen vacancies in TiOx films. Our strategy for tight control of the oxygen vacancy is based on the utilization of plasma-enhanced atomic layer deposition of titanium oxide under precisely regulated decomposition of the precursor molecules (titanium (IV) tetraisopropoxide, Ti[OCH(CH₃)₂]₄) by plasma-activated reactant mixture (N₂+O₂). From the various spectroscopic and microstructural analyses by using Rutherford backscattering spectrometry, x-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, confocal Raman spectroscopy, and spectroscopic ellipsometry, we found that the precursor decomposition power (R(F)) of plasma-activated reactant mixture determines not only the oxygen vacancy concentration but also the crystallinity of the resulting TiO(x) film: nanocrystalline anatase TiO(x) with fewer oxygen vacancies under high R(F), while amorphous TiOx with more oxygen vacancies under low RF. Enabled by our controlling capability over the oxygen vacancy concentration, we were able to thoroughly elucidate the effect of oxygen vacancies on the resistive switching behavior of TiO(x)-based memory capacitors (Pt/TiO(x)/Pt). The electrical conduction behavior at the high resistance state could be explained within the framework of the trap-controlled space-charge-limited conduction with two characteristic transition voltages. One is the voltage (V(SCL)) for the transition from Ohmic conduction to space-charge-limited conduction, and the other is the voltage (V(TFL)) for transition from space-charge-limited conduction to trap-filled-limited conduction. In this work, we have disclosed for the first time the dependence of these two characteristic transition voltages (i.e., V(SCL) and V(TFL)) on the oxygen vacancy concentration.

Thermal stability of multilayer graphene films synthesized by chemical vapor deposition and stained by metallic impurities

Thermal stability is an important property of graphene that requires thorough investigation. This study reports the thermal stability of graphene films synthesized by chemical vapor deposition (CVD) on catalytic nickel substrates in a reducing atmosphere. Electron microscopies, atomic force microscopy, and Raman spectroscopy, as well as electronic measurements, were used to determine that CVD-grown graphene films are stable up to 700 °C. At 800 °C, however, graphene films were etched by catalytic metal nanoparticles, and at 1000 °C many tortuous tubular structures were formed in the film and carbon nanotubes were formed at the film edges and at catalytic metal-contaminated sites. Furthermore, we applied our pristine and thermally treated graphene films as active channels in field-effect transistors and characterized their electrical properties. Our research shows that remnant catalytic metal impurities play a critical role in damaging graphene films at high temperatures in a reducing atmosphere: this damage should be considered in the quality control of large-area graphene films for high temperature applications.

Advanced porous gold nanofibers for highly efficient and stable molecular sensing platforms.

Porous gold nanofibers are fabricated through templated electrochemical routes in porous alumina membranes. Gold-silver alloy is electrochemically deposited in the nanocylinders of the porous alumina templates and then the silver phase is selectively dealloyed. The resulting nanofibers present a nanoporous network with a pore dimension of approximately 10 nm and notable surface-enhanced Raman scattering (SERS) efficiencies which are at least seven times higher than from the smooth solid gold nanofibers without porosity. The relative SERS enhancement on porous gold is directly proved by imaging with a Raman microscope for conjugated porous gold/solid gold single nanorods.

Super-resolution of fluorescence-free plasmonic nanoparticles using enhanced dark-field illumination based on wavelength-modulation

Super-resolution imaging of fluorescence-free plasmonic nanoparticles (NPs) was achieved using enhanced dark-field (EDF) illumination based on wavelength-modulation. Indistinguishable adjacent EDF images of 103-nm gold nanoparticles (GNPs), 40-nm gold nanorods (GNRs), and 80-nm silver nanoparticles (SNPs) were modulated at their wavelengths of specific localized surface plasmon scattering. The coordinates (x, y) of each NP were resolved by fitting their point spread functions with a two-dimensional Gaussian. The measured localization precisions of GNPs, GNRs, and SNPs were 2.5 nm, 5.0 nm, and 2.9 nm, respectively. From the resolved coordinates of NPs and the corresponding localization precisions, super-resolution images were reconstructed. Depending on the spontaneous polarization of GNR scattering, the orientation angle of GNRs in two-dimensions was resolved and provided more elaborate localization information. This novel fluorescence-free super-resolution method was applied to live HeLa cells to resolve NPs and provided remarkable sub-diffraction limit images.

Quantitative compositional profiling of conjugated quantum dots with single atomic layer depth resolution via time-of-flight medium-energy ion scattering spectroscopy.

We report the quantitative compositional profiling of 3-5 nm CdSe/ZnS quantum dots (QDs) conjugated with a perfluorooctanethiol (PFOT) layer using the newly developed time-of-flight (TOF) medium-energy ion scattering (MEIS) spectroscopy with single atomic layer resolution. The collection efficiency of TOF-MEIS is 3 orders of magnitude higher than that of conventional MEIS, enabling the analysis of nanostructured materials with minimized ion beam damage and without ion neutralization problems. The spectra were analyzed using PowerMEIS ion scattering simulation software to allow a wide acceptance angle. Thus, the composition and core-shell structure of the CdSe cores and ZnS shells were determined with a 3% composition uncertainty and a 0.2-nm depth resolution. The number of conjugated PFOT molecules per QD was also quantified. The size and composition of the QDs were consistent with those obtained from high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. We suggest TOF-MEIS as a nanoanalysis technique to successfully elucidate the core-shell and conjugated layer structures of QDs, which is critical for the practical application of QDs in various nano- and biotechnologies.

Selective fluorescent-free detection of biomolecules on nanobiochips by wavelength dependent-enhanced dark field illumination

Individual silver nanoparticle-conjugated target protein (cTnI) molecules on gold-nanopatterned chip were selectively detected by wavelength dependent-enhanced dark field illumination. Using specific nanoparticles with unique sizes and materials, the immunotargeted nanoparticle on the chips was detected at the single-molecule level by monitoring changes in the plasmonic resonance based on wavelength dependence.

Bimodal porous gold opals for molecular sensing

We have fabricated bimodal porous gold skeletons by double-templating routes using poly(styrene) colloidal opals as templates. The fabricated gold skeletons show a bimodal pore-size distribution, with small pores within spheres and large pores between spheres. The templated bimodal porous gold skeletons were applied in Raman scattering experiments to study sensing efficiency for probe molecules. We found that the bimodal porous gold skeletons showed obvious enhancement of Raman scattering signals versus that of the unimodal porous gold which only has interstitial pores of several hundred nanometers.

Selective and Direct Immobilization of Cysteinyl Biomolecules by Electrochemical Cleavage of Azo Linkage

Controlled orientation and reserved activity of biomolecules, when site-selectively immobilized in a highly integrated manner on a minimal time scale, are crucial in designing biosensors for the multiplex detection. Here, we describe a novel method for the orientation-controlled immobilization of biomolecules based on site-selective electrochemical activation of p-hydroxyazobenzene self-assembled monolayer (SAM) followed by one-step coupling of cysteinyl biomolecules. The p-aminophenol, a product of reductive cleavage of p-hydroxyazobenzene, was subsequently oxidized to yield p-quinoneimine which then conjugated with cysteinyl biomolecules through 1,4-Michael addition, thus obviating additional linker agents and the related time consumption. Using this method, we selectively activated the electrode surface and immobilized laminin peptide IKVAV, a neurite promoting motif. When we cultured hippocampal neurons on the electrode, the extended neurites were found only within the electrochemically activated area. Hence, the proposed method represents a new promising platform for the patterning of functional peptides, active proteins, and live cells.

Molecular switching fluorescence based high sensitive detection of label-free C-reactive protein on biochip

A novel detection technique on biochip for the quantification of label-free C-reactive protein (CRP) based on molecular switching of fluorescence (MSF) is demonstrated by total internal reflection fluorescence microscopy. It alters fluorescence intensity of fluoreseinamine isomer 1 (FAI) upon binding with its specific ligand, O-phosphorylethanolamine (PEA). In the MSF-based detection, FAI was used as an ink, printed on a 3-glycidoxypropyl-trimethoxysilane (GPTS)-coated glass coverslip. With the addition of GPTS conjugated PEA solution to the FAI-printed coverslip, the fluorescence intensity was remarkably decreased. Addition of CRP increased fluorescence intensity linearly in the range of 800 aM to 500 fM (R=0.997). The MSF-based biochip assay for the estimation of CRP in human sera showed ∼200 times increased detection sensitivity in less than a third of the time to obtain results using a conventional enzyme-linked immunosorbent assay. This biochip detection is a promising new technique for the quantification of CRP molecules from trace amounts of clinical samples.

Enhanced detection sensitivity of carcinoembryonic antigen on a plasmonic nanoimmunosensor by transmission grating-based total internal reflection scattering microscopy

Carcinoembryonic antigen (CEA) is a glycoprotein associated with colorectal carcinomas and is commonly used as a clinical tumor marker. Enhanced detection sensitivity for the assay of CEA molecules was achieved on a plasmonic nanoimmunosensor by wavelength-dependent transmission grating (TG)-based total internal reflection scattering microscopy (TIRSM). The plasmonic nanoparticles were placed in an evanescent field layer on a glass nanoimmunosensor that produced evanescent wave scattering by the total internal reflection of light from two lasers. The light scattered by target protein (CEA)-bound 20-nm silver nanoparticles (plasmonic nanoprobes) was collected and spectrally isolated in first-order spectral images (n=+1) by a TG (70 grooves/mm). The combination of evanescent wave scattering and TG ​significantly enhanced the detection sensitivity and selectivity due to the minimized spectroscopic interference and background noise. The TG-TIRSM method detected the CEA molecules at concentrations down to 19.75zM with a wide linear dynamic range of 19.75zM-39.50nM (correlation coefficient, R=0.9903), which was 45 to 1.25×109 times lower than the detection limits and 2×105 to 2×1011 times wider than the dynamic ranges of previous assay methods. In particular, by simply changing the antibody of the target molecule, this technique can be used to detect various disease-related protein biomarkers directly in human biological samples at the single-molecule level.