AFM Manipulation of EGaIn Microdroplets to Generate Controlled, On-Demand Contacts on Molecular Self-Assembled Monolayers.

Liquid metal droplets, such as eutectic gallium-indium (EGaIn), are important in many research areas, such as soft electronics, catalysis, and energy storage. Droplet contact on solid surfaces is typically achieved without control over the applied force and without optimizing the wetting properties in different environments (e.g., in air or liquid), resulting in poorly defined contact areas. In this work, we demonstrate the direct manipulation of EGaIn microdroplets using an atomic force microscope (AFM) to generate repeated, on-demand making and breaking of contact on self-assembled monolayers (SAMs) of alkanethiols. The nanoscale positional control and feedback loop in an AFM allow us to control the contact force at the nanonewton level and, consequently, tune the droplet contact areas at the micrometer length scale in both air and ethanol. When submerged in ethanol, the droplets are highly nonwetting, resulting in hysteresis-free contact forces and minimal adhesion; as a result, we are able to create reproducible geometric contact areas of 0.8-4.5 µm2 with the alkanethiolate SAMs in ethanol. In contrast, there is a larger hysteresis in the contact forces and larger adhesion for the same EGaIn droplet in air, which reduced the control over the contact area (4-12 µm2). We demonstrate the usefulness of the technique and of the gained insights in EGaIn contact mechanics by making well-defined molecular tunneling junctions based on alkanethiolate SAMs with small geometric contact areas of between 4 and 12 µm2 in air, 1 to 2 orders of magnitude smaller than previously achieved.

Dielectric breakdown of 2D muscovite mica.

Localized electrical breakdown (BD) measurements are performed on 2D muscovite mica flakes of ~ 2 to 15 nm thickness using Conduction Atomic Force Microscopy (CAFM). To obtain robust BD data by CAFM, the probed locations are spaced sufficiently far apart (> 1 µm) to avoid mutual interference and the maximum current is set to a low value (< 1 nA) to ensure severe damage does not occur to the sample. The analyses reveals that 2D muscovite mica has high electrical breakdown strength (12 MV/cm or more) and low leakage current, comparable to 2D hexagonal boron nitride (h-BN) of similar thickness. However, a significant difference compared to h-BN is the very low current necessary to avoid catastrophic damage during the BD event, even for very thin (2-3 nm) flakes. Further, for mica the BD transient always appear to be very abrupt, and no progressive BD process was definitively observed. These marked differences between mica and h-BN are attributed to the poor thermal conductivity of mica.

Localized Probing of Dielectric Breakdown in Multilayer Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) has emerged as a promising 2D/layered dielectric owing to its successful integration with graphene and other 2D materials, although a coherent picture of the overall dielectric breakdown mechanism in h-BN is yet to emerge. Here, we have carried out a systematic study using conduction atomic force microscopy to provide insights into the process of defect generation and dielectric degradation in the progressive breakdown (PBD) and hard breakdown (HBD) stages in 2-5 nm thick chemical vapor deposition (CVD)-grown multilayer h-BN films. The PBD and HBD regimes show different behaviors. Under electrical stress in the PBD stage, defects are generated progressively in the h-BN, leading to a gradual reduction of the effective barrier resistance and continuous soft breakdowns (SBDs) of the dielectric material. Random telegraph noise nano-spectroscopy shows that low frequency noise becomes dominant after an SBD event due to the creation of additional defects around the percolation path. We also observe a wide variation in the current-voltage (I-V) breakdown plots in the PBD stage, giving rise to non-Weibull statistical distribution of the breakdown voltage. We attribute this observation to the significant thickness inhomogeneity in the CVD films. At HBD, h-BN materials are always physically removed from the film, leading to the formation of pits at the breakdown location. Interestingly, pit formation is also occasionally observed in the PBD stage under very low current compliances, suggesting that breakdown may proceed by a mixture of defect generation and material removal in h-BN CVD films.

Quantum mechanical rippling of a MoS2 monolayer controlled by interlayer bilayer coupling.

Nanoscale corrugations are of great importance in determining the physical properties of two-dimensional crystals. However, the mechanical behavior of atomically thin films under strain is not fully understood. In this Letter, we show a layer-dependent mechanical response of molybdenum disulfide (MoS(2)) subject to atomistic-precision strain induced by 2H-bilayer island epitaxy. Dimensional crossover in the mechanical properties is evidenced by the formation of star-shaped nanoripple arrays in the first monolayer, while rippling instability is completely suppressed in the bilayer. Microscopic-level quantum mechanical simulations reveal that the nanoscale rippling is realized by the twisting of neighboring Mo-S bonds without modifying the chemical bond length, and thus invalidates the classical continuum mechanics. The formation of nanoripple arrays significantly changes the electronic and nanotribological properties of monolayer MoS(2). Our results suggest that quantum mechanical behavior is not unique for sp(2) bonding but general for atomic membranes under strain.

High-speed jetting and spray formation from bubble collapse.

A method to create impacting jets at the micrometer length scale by means of a collapsing cavitation bubble is presented. A focused shock wave from a lithotripter leads to the nucleation of a cavitation bubble below a hole of 25 µm diameter etched in a silicon plate. The plate is placed at an air-water interface. The expansion and collapse of the bubble leads to two separate jets--an initial slow jet of velocity ∼10 m/s and a later faster jet of velocity ∼50 m/s. The jets subsequently impact coaxially, resulting in a circular sheet of liquid in the plane perpendicular to their axis. The sheet is characterized by a ring of droplets at its rim and breaks up into a spray as the shock pressure is increased. The results demonstrate an approach to create a high-speed jet and fine spray on demand at the micrometer scale.

Dynamic interactions between microbubbles in water.

The interaction between moving bubbles, vapor voids in liquid, can arguably represent the simplest dynamical system in continuum mechanics as only a liquid and its vapor phase are involved. Surprisingly, and perhaps because of the ephemeral nature of bubbles, there has been no direct measurement of the time-dependent force between colliding bubbles which probes the effects of surface deformations and hydrodynamic flow on length scales down to nanometers. Using ultrasonically generated microbubbles (approximately 100 microm size) that have been accurately positioned in an atomic force microscope, we have made direct measurements of the force between two bubbles in water under controlled collision conditions that are similar to Brownian particles in solution. The experimental results together with detailed modeling reveal the nature of hydrodynamic boundary conditions at the air/water interface, the importance of the coupling of hydrodynamic flow, attractive van der Waals-Lifshitz forces, and bubble deformation in determining the conditions and mechanisms that lead to bubble coalescence. The observed behavior differs from intuitions gained from previous studies conducted using rigid particles. These direct force measurements reveal no specific ion effects at high ionic strengths or any special role of thermal fluctuations in film thickness in triggering the onset of bubble coalescence.

Particulate templates and ordered liquid bridge networks in evaporative lithography.

We investigate the properties of latex particle templates required to optimize the development of ordered liquid bridge networks in evaporative lithography. These networks are key precursors in the assembly of solutions of conducting nanoparticles into large, optically transparent, and conducting microwire networks on substrates (Vakarelski, I. U.; Chan, D. Y. C.; Nonoguchi, T.; Shinto, H.; Higashitani, K. Phys. Rev. Lett., 2009, 102, 058303). An appropriate combination of heat treatment and oxygen plasma etching of a close-packed latex particle monolayer is shown to create open-spaced particle templates which facilitates the formation of ordered fully connected liquid bridge networks that are critical to the formation of ordered microwire networks. Similar results can also be achieved if non-close-packed latex particle templates with square or honeycomb geometries are used. The present results have important implications for the development of the particulate templates to control the morphology of functional microwire networks by evaporative lithography.

Hydrodynamic boundary conditions and dynamic forces between bubbles and surfaces.

Dynamic forces between a 50 microm radius bubble driven towards and from a mica plate using an atomic force microscope in electrolyte and in surfactant exhibit different hydrodynamic boundary conditions at the bubble surface. In added surfactant, the forces are consistent with the no-slip boundary condition at the mica and bubble surfaces. With no surfactant, a new boundary condition that accounts for the transport of trace surface impurities explains variations of dynamic forces at different speeds and provides a direct connection between dynamic forces and surface transport effects at the air-water interface.

Effect of tip size on force measurement in atomic force microscopy.

An atomic force microscope (AFM) has been used to study solvation forces at the solid-liquid interface between highly oriented pyrolytic graphite (HOPG) and the liquids octamethylcyclotetrasiloxane (OMCTS), n-hexadecane (n-C16H34), and n-dodecanol (n-C11H23CH2OH). Oscillatory solvation forces (F) are observed for various measured tip radii (Rtip=15-100 nm). It is found that the normalized force data, F/Rtip, differ between AFM tips with a clear trend of decreasing F/Rtip with increasing Rtip.

Combinational application of surface plasmon resonance spectroscopy and quartz crystal microbalance for studying nuclear hormone receptor-response element interactions.

Conventional methodologies for studying protein-DNA complexes, such as electrophoretic mobility shift assays (EMSAs), lack the real-time sensitivity and precision to accurately characterize the complex dynamics of interactions between transcription factors and their binding sites. To better understand the interactions between estrogen receptor (ER) subtypes and the estrogen response elements (EREs), we employed surface plasmon resonance (SPR) spectroscopy and quartz crystal microbalance with dissipation measurement (QCM-D) and made the following observations: (1) base substitutions in ERE half-sites reduced binding affinity for both ERalpha and ERbeta, (2) ERalpha has a higher sequence specificity than ERbeta or there were more nonspecific interactions between ERbeta and control DNA, and (3) ERalpha bound ERE as dimers and ERbeta bound as tetramers. These findings highlight intrinsic differences in DNA-binding properties between receptor subtypes, which are not apparent based on the high degree of conservation (96% identity) in their DNA-binding domains and results from EMSA studies. With this study, we demonstrate the potential of utilizing SPR and QCM in combination for a comprehensive characterization of ER-DNA interactions, including sequence-dependent binding mechanisms and structural differences in ERalpha-DNA and ERbeta-DNA complexes.

Direct adsorption and monolayer self-assembly of acetyl-protected dithiols.

The alpha,omega-dithiols, with sulfur-containing groups at both ends of the molecules, can be used to bridge a metallic gap. Functional self-assembled monolayers (SAMs) of these dithiols must "stand up" on the surface and expose one thiol group for further reaction. However, both parallel and upright surface orientations and multilayer formation can occur for alpha,omega-dithiols. We find SAMs deposited directly from acetyl protected dithiols (i.e., with no de-protection step) overcome these problems. We present a systematic study of adsorption kinetics from in situ surface plasmon resonance spectroscopy, X-ray photoelectron spectroscopy, and secondary ion mass spectroscopy of alkane- and oligo(phenylene ethylnylene)-based alpha,omega-dithioacetates on gold.

Frequency interference between two mesa-shaped quartz crystal microbalances.

The multichannel quartz crystal microbalance (MQCM) is very attractive for biosensor applications. The principle of the MQCM design involves fabricating arrays of quartz microbalances on a single substrate, and it is important that the individual sensor performance is not influenced by the neighboring devices. Feasible ways to control the coupling of acoustical energy within a MQCM structure are to increase the difference in the resonance frequency between the electroded and unelectroded portions of the substrate; and a practical way to achieve this is to use mesa structures. In this paper, the frequency interference between two mesa-shaped quartz crystal microbalances is investigated using Mindlin's theory. The results show that even a very small mesa height (approximately 5% of the plate thickness) can greatly reduce the frequency interference and more effectively trap the acoustic energy. This allows for a broader design window and higher packing density for MQCM applications.

Quartz tuning fork biosensor.

The use of quartz tuning forks for biosensor applications is investigated. The basis of the sensor is to coat the tuning fork surfaces with specific biomolecules and measure subsequent mass loading from the selective binding of complementary analytes. Two experimental set-ups are evaluated, direct mechanical excitation and self-excitation. Mechanical excitation is achieved by mounting the fork on a piezoelectric plate and it is found that the change in oscillation amplitude on adsorption can be monitored to give the change in mass. However, a major drawback is that the sensitivity is determined by the Q-factor, which varies significantly between different sensors and different experimental arrangements. In self-excitation mode, tuning fork motion is activated and detected by placing the fork within a tuned circuit. Using self-excitation mode, anti-human IgG modified tuning forks can sense the binding of human IgG in the range of 5-100 microg ml(-1). The significance of this study is that quartz tuning forks are routinely made using standard microfabrication process, thus suggesting the possibility of facile microfabrication of arrays of quartz sensors.