Sangmin An

Mechanical properties of the nanoscale molecular cluster of water meniscus by high-precision frequency modulation atomic force spectroscopy

The mechanical properties (viscoelasticity) of the nanoscale molecular cluster of water meniscus, spontaneously formed between a quartz tip (∼100 nm curvature) and a mica substrate were quantitatively studied. The theoretical and experimental investigation was performed on the basis of the quartz tuning fork-based frequency modulation-atomic force microscope system with a high vertical resolution (∼0.5 A). The proposed system is suitable apparatus for the dynamic force spectroscopy of nanoscopic materials with several advantages including high sensitivity, short response time, immunity to the electrical noise, and simple and intuitive interpretation of the results using the frequency shift.

Nanoneedle transistor-based sensors for the selective detection of intracellular calcium ions.

We developed a nanoneedle transistor-based sensor (NTS) for the selective detection of calcium ions inside a living cell. In this work, a single-walled carbon nanotube-based field effect transistor (swCNT-FET) was first fabricated at the end of a glass nanopipette and functionalized with Fluo-4-AM probe dye. The selective binding of calcium ions onto the dye molecules altered the charge state of the dye molecules, resulting in the change of the source-drain current of the swCNT-FET as well as the fluorescence intensity from the dye. We demonstrated the electrical and fluorescence detection of the concentration change of intracellular calcium ions inside a HeLa cell using the NTS.

Low-volume liquid delivery and nanolithography using a nanopipette combined with a quartz tuning fork-atomic force microscope

Electric-field-induced low-volume liquid ejection under ambient conditions was realized at a low bias potential of 12 V via a nanopipette (aperture diameter of 30 nm) combined with a non-contact, distance-regulated (within 10 nm) quartz tuning fork-atomic force microscope. A capillary-condensed water meniscus, spontaneously formed in the tip-substrate nanogap, reduces the ejection barrier by four orders of magnitude, facilitating nanoliquid ejection and subsequent liquid transport/dispersion onto the substrate without contact damage from the pipette. A study of nanofluidics through a free-standing liquid nanochannel and nanolithography was performed with this technique. This is an important breakthrough for various applications in controlled nanomaterial-delivery and selective deposition, such as multicolor nanopatterning and nano-inkjet devices.

Superwetting of TiO2 by light-induced water-layer growth via delocalized surface electrons

Significance TiO2, which is chemically stable, harmless, and inexpensive, has been widely used for industrial applications. Recently, TiO2-coated materials, exhibiting superwetting under sunlight, have been developed for environmental solutions. However, the mechanism responsible for superwetting of TiO2 is still in controversy despite many studies. We clarified its origin by performing tip-based in situ measurements of the growth dynamics of the photo-adsorbed water layers, as associated with delocalized surface electrons. Combined with molecular dynamics simulations, we provided conclusive clues that the “water wets water” process promotes water adsorption on the water layers, producing superwetting. Titania, which exhibits superwetting under light illumination, has been widely used as an ideal material for environmental solution such as self-cleaning, water–air purification, and antifogging. There have been various studies to understand such superhydrophilic conversion. The origin of superwetting has not been clarified in a unified mechanism yet, which requires direct experimental investigation of the dynamic processes of water-layer growth. We report in situ measurements of the growth rate and height of the photo-adsorbed water layers by tip-based dynamic force microscopy. For nanocrystalline anatase and rutile TiO2 we observe light-induced enhancement of the rate and height, which decrease after O2 annealing. The results lead us to confirm that the long-range attraction between water molecules and TiO2, which is mediated by delocalized electrons in the shallow traps associated with O2 vacancies, produces photo-adsorption of water on the surface. In addition, molecular dynamics simulations clearly show that such photo-adsorbed water is critical to the zero contact angle of a water droplet spreading on it. Therefore, we conclude that this “water wets water” mechanism acting on the photo-adsorbed water layers is responsible for the light-induced superwetting of TiO2. Similar mechanism may be applied for better understanding of the hydrophilic conversion of doped TiO2 or other photo-catalytic oxides.

Energy dissipation of nanoconfined hydration layer: Long-range hydration on the hydrophilic solid surface

The hydration water layer (HWL), a ubiquitous form of water on the hydrophilic surfaces, exhibits anomalous characteristics different from bulk water and plays an important role in interfacial interactions. Despite extensive studies on the mechanical properties of HWL, one still lacks holistic understanding of its energy dissipation, which is critical to characterization of viscoelastic materials as well as identification of nanoscale dissipation processes. Here we address energy dissipation of nanoconfined HWL between two atomically flat hydrophilic solid surfaces (area of ~120 nm2) by small amplitude-modulation, noncontact atomic force microscopy. Based on the viscoelastic hydration-force model, the average dissipation energy is ~1 eV at the tapping amplitude (~0.1 nm) of the tip. In particular, we determine the accurate HWL thickness of ~6 layers of water molecules, as similarly observed on biological surfaces. Such a long-range interaction of HWL should be considered in the nanoscale phenomena such as friction, collision and self-assembly.

Effective stiffness of qPlus sensor and quartz tuning fork.

Quartz tuning forks (QTFs) have been extensively employed in scanning probe microscopy. For quantitative measurement of the interaction in nanoscale using QTF as a force sensor, we first measured the effective stiffness of qPlus sensors as well as QTFs and then compared the results with the cantilever beam theory that has been widely used to estimate the stiffness. Comparing with the stiffness and the resonance frequency in our measurement, we found that those calculated based on the beam theory are considerably overestimated. For consistent analysis of experimental and theoretical results, we present the formula to calculate the stiffness of qPlus sensor or QTF, based on the resonance frequency. We also demonstrated that the effective stiffness of QTF is twice that of qPlus sensor, which agrees with the recently suggested model. Our study demonstrates the use of QTF for quantitative measurement of interaction force at the nanoscale in scanning probe microscopy.

Quartz tuning fork-based frequency modulation atomic force spectroscopy and microscopy with all digital phase-locked loop

We present a platform for the quartz tuning fork (QTF)-based, frequency modulation atomic force microscopy (FM-AFM) system for quantitative study of the mechanical or topographical properties of nanoscale materials, such as the nano-sized water bridge formed between the quartz tip (~100 nm curvature) and the mica substrate. A thermally stable, all digital phase-locked loop is used to detect the small frequency shift of the QTF signal resulting from the nanomaterial-mediated interactions. The proposed and demonstrated novel FM-AFM technique provides high experimental sensitivity in the measurement of the viscoelastic forces associated with the confined nano-water meniscus, short response time, and insensitivity to amplitude noise, which are essential for precision dynamic force spectroscopy and microscopy.

Nanopipette combined with quartz tuning fork-atomic force microscope for force spectroscopy/microscopy and liquid delivery-based nanofabrication

This paper introduces a nanopipette combined with a quartz tuning fork-atomic force microscope system (nanopipette/QTF-AFM), and describes experimental and theoretical investigations of the nanoscale materials used. The system offers several advantages over conventional cantilever-based AFM and QTF-AFM systems, including simple control of the quality factor based on the contact position of the QTF, easy variation of the effective tip diameter, electrical detection, on-demand delivery and patterning of various solutions, and in situ surface characterization after patterning. This tool enables nanoscale liquid delivery and nanofabrication processes without damaging the apex of the tip in various environments, and also offers force spectroscopy and microscopy capabilities.

Position-resolved Surface Characterization and Nanofabrication Using an Optical Microscope Combined with a Nanopipette/Quartz Tuning Fork Atomic Force Microscope

In this work, we introduce position-resolved surface characterization and nanofabrication using an optical microscope (OM) combined with a nanopipette-based quartz tuning fork atomic force microscope (nanopipette/QTF-AFM) system. This system is used to accurately determine substrate position and nanoscale phenomena under ambient conditions. Solutions consisting of 5 nm Au nanoparticles, nanowires, and polydimethylsiloxane (PDMS) are deposited onto the substrate through the nano/microaperture of a pulled pipette. Nano/microscale patterning is performed using a nanopipette/QTF-AFM, while position is resolved by monitoring the substrate with a custom OM. With this tool, one can perform surface characterization (force spectroscopy/microscopy) using the quartz tuning fork (QTF) sensor. Nanofabrication is achieved by accurately positioning target materials on the surface, and on-demand delivery and patterning of various solutions for molecular architecture.

Bifurcation-enhanced ultrahigh sensitivity of a buckled cantilever

Significance This work brings together the fields of nonlinear dynamics and precision measurement, aiming to develop a highly sensitive nonlinear mechanical force sensor. We use dynamic force spectroscopy of the buckled cantilever tip in an ambient condition, which allows sensitive detection of the noise-induced flipping near the bifurcation point. Key parameters, such as the fluctuation enhancement and the activation barrier of the buckling-to-flipping transition, lead to realization of the bifurcation-enhanced sensor. We contiguously observe the buckling–flipping dynamic transition of the softened tip resulting from the competition between fluctuation and bifurcation, providing the in situ continuous sensing of the mechanical vibrations. This work not only furthers our understanding of nonlinear dynamics at the nanoscale, but also is a stepping stone toward the highly sensitive mechanical sensor. Buckling, first introduced by Euler in 1744 [Euler L (1744) Opera Omnia I 24:231], a sudden mechanical sideways deflection of a structural member under compressive stress, represents a bifurcation in the solution to the equations of static equilibrium. Although it has been investigated in diverse research areas, such a common nonlinear phenomenon may be useful to devise a unique mechanical sensor that addresses the still-challenging features, such as the enhanced sensitivity and polarization-dependent detection capability. We demonstrate the bifurcation-enhanced sensitive measurement of mechanical vibrations using the nonlinear buckled cantilever tip in ambient conditions. The cantilever, initially buckled with its tip pinned, flips its buckling near the bifurcation point (BP), where the buckled tip becomes softened. The enhanced mechanical sensitivity results from the increasing fluctuations, unlike the typical linear sensors, which facilitate the noise-induced buckling-to-flipping transition of the softened cantilever. This allows the in situ continuous or repeated single-shot detection of the surface acoustic waves of different polarizations without any noticeable wear of the tip. We obtained the sensitivity above 106 V(m/s)−1, a 1,000-fold enhancement over the conventional seismometers. Our results lead to development of mechanical sensors of high sensitivity, reproducibility, and durability, which may be applied to detect, e.g., the directional surface waves on the laboratory as well as the geological scale.