Effects of Temperature and Humidity on Energy Dissipation between Human Corneocytes and Nanoasperity Sliding Contacts.

Human haptic perception relies on the ability of sensory receptors underneath the skin corneocyte layer to sense external load, where adhesion and friction play an essential role in nanoscale solid-solid contact. Energy dissipation present at the surface interface due to the change of separation distance during sliding contact was uncovered, but the energy dissipation of human finger skin cell-nanoprobe contact under humidity and temperature conditions has not been investigated yet. In this paper, the energy dissipation of skin corneocyte-nanoprobe interface under variation of both humidity, 0.05-80%RH, and temperature ranging from 25 to 40 °C is directly measured by atomic force microscopy (AFM). Analytical models of dissipation energy for this nanomaterial interface mechanism are developed, and the results are compared to the measured values. AFM measurements of dissipation energy reveal that the amount of dissipated energy caused by water meniscus stretching monotonically increases with humidity and temperature, resulting in adhesion and friction decreases. The purposed analytical model represents that dissipation energy trend.

Mechanistic model for quantifying the effect of impact force on mechanochemical reactivity.

Conventional mechanochemical synthetic tools, such as ball mills, offer no methodology to quantitatively link macroscale reaction parameters, such as shaking frequency or milling ball radius, to fundamental drivers of reactivity, namely the force vectors applied to the reactive molecules. As a result, although mechanochemistry has proven to be a valuable method to make a wide variety of products, the results are seldom reproduceable between reactors, difficult to rationally optimize, and hard to ascribe to a specific reaction pathway. Here we have developed a controlled force reactor, which is a mechanochemical ball mill reactor with integrated force measurement and control during each impact. We relate two macroscale reactor parameters-impact force and impact time-to thermodynamic and kinetic transition state theories of mechanochemistry utilizing continuum contact mechanics principles. We demonstrate force controlled particle fracture of NaCl to characterize particle size evolution during reactions, and force controlled reaction between anhydrous copper(II) chloride and (1, 10) phenanthroline. During the fracture of NaCl, we monitor the evolution of particle size as a function of impact force and find that particles quickly reach a particle size of ∼100 µm largely independent of impact force, and reach steady state 10-100× faster than reaction kinetics of typical mechanochemical reactions. We monitor the copper(II) chloride reactivity by measuring color change during reaction. Applying our transition state theory developed here to the reaction curves of copper(II) chloride and (1, 10) phenanthroline at multiple impact forces results in an activation energy barrier of 0.61 ± 0.07 eV, distinctly higher than barriers for hydrated metal salts and organic ligands and distinctly lower than the direct cleavage of the CuCl bond, indicating that the reaction may be mediated by the higher affinity of Fe in the stainless steel vessel to Cl. We further show that the results in the controlled force reactor match rudimentary estimations of impact force within a commercial ball mill reactor Retsch MM400. These results demonstrate the ability to quantitatively link macroscale reactor parameters to reaction properties, motivating further work to make mechanochemical synthesis quantitative, predictable, and fundamentally insightful.

Surface haptic rendering of virtual shapes through change in surface temperature.

Compared to relatively mature audio and video human-machine interfaces, providing accurate and immersive touch sensation remains a challenge owing to the substantial mechanical and neurophysical complexity of touch. Touch sensations during relative lateral motion between a skin-screen interface are largely dictated by interfacial friction, so controlling interfacial friction has the potential for realistic mimicry of surface texture, shape, and material composition. In this work, we show a large modulation of finger friction by locally changing surface temperature. Experiments showed that finger friction can be increased by ~50% with a surface temperature increase from 23° to 42°C, which was attributed to the temperature dependence of the viscoelasticity and the moisture level of human skin. Rendering virtual features, including zoning and bump(s), without thermal perception was further demonstrated with surface temperature modulation. This method of modulating finger friction has potential applications in gaming, virtual and augmented reality, and touchscreen human-machine interaction.

Evaluation of the Electrowetting Effect on the Interfacial Mechanics between Human Corneocytes and Nanoasperities.

A large subset of haptic surfaces employs electroadhesion to modulate both adhesion and friction at a sliding finger interface. The current theory of electroadhesion assumes that the applied electric field pulls the skin into stronger contact, increasing friction by increasing the real contact area, yet it is unknown what role environmental moisture plays in the effect. This paper uses atomic force microscopy (AFM)to determine the effect of humidity on the adhesion and friction between the single nanoscale asperity and individual human finger corneocytes. An analytical model of the total effective load of the AFM tip is developed to explain the humidity-voltage dependence of nanoscale adhesion and friction at contacting asperities. The results show that the electrowetting effect at the interface at high humidity accounts for 35% of the adhesive force but less than 8% of the total friction, implying that the electrowetting effect can be enhanced by optimizing surface topography to promote the formation and rupture of liquid menisci.

Electrowetting: A Consideration in Electroadhesion.

With the commercialization of haptic devices, understanding behavior under various environmental conditions is crucial for product optimization and cost reduction. Specifically, for surface haptic devices, the dependence of the friction force and the electroadhesion effect on the environmental relative humidity and the finger hydration level can directly impact their design and performance. This article presents the influence of relative humidity on the finger-surface friction force and the electroadhesion performance. Mechanisms including changes to Young's modulus of skin, contact angle change and capillary force were analyzed separately with experimental and numerical methods. Through comparison of the calculated capillary force in this paper and the electroadhesion force calculated in published papers, it was found that electrowetting at high voltage could contribute up to 60% of the total friction force increase in electroadhesion. Therefore, in future design of surface haptic devices, the effect of electrowetting should be considered carefully.

The role of mechanical force on the kinetics and dynamics of electrochemical redox reactions on graphene.

Electrochemical reactions are a critical class of processes strongly influenced by atomic scale effects, where the relationships between local chemical composition, stress, strain, and reactivity are not well understood. Here we investigate the relationship between applied stress and reaction rates for the oxygen evolution reaction on multi-layered graphene using conductive atomic force microscopy. During the reaction, oxygen groups accumulate on the surface and the oxygenation rate increases with applied load. The results also show that the rate is not uniform across the surface, where local edges and defects are more reactive than the basal plane. The results presented here are interpreted in the context of transition state theory, where applied load over the reaction coordinate linearly modifies the energy landscape. This work motivates the general efficacy of atomic force microscopy as a tool to study relationships between local mechanical surface effects and electrochemical reactivity.

Measurement of nanoscale molten polymer droplet spreading using atomic force microscopy.

We present a technique for measuring molten polymer spreading dynamics with nanometer scale spatial resolution at elevated temperatures using atomic force microscopy (AFM). The experimental setup is used to measure the spreading dynamics of polystyrene droplets with 2 µm diameters at 115-175 °C on sapphire, silicon oxide, and mica. Custom image processing algorithms determine the droplet height, radius, volume, and contact angle of each AFM image over time to calculate the droplet spreading dynamics. The contact angle evolution follows a power law with time with experimentally determined values of -0.29 ± 0.01, -0.08 ± 0.02, and -0.21 ± 0.01 for sapphire, silicon oxide, and mica, respectively. The non-zero steady state contact angles result in a slower evolution of contact angle with time consistent with theories combining molecular kinetic and hydrodynamic models. Monitoring the cantilever phase provides additional information about the local mechanics of the droplet surface. We observe local crystallinity on the molten droplet surface, where crystalline structures appear to nucleate at the contact line and migrate toward the top of the droplet. Increasing the temperature from 115 °C to 175 °C reduced surface crystallinity from 35% to 12%, consistent with increasingly energetically favorable amorphous phase as the temperature approaches the melting temperature. This platform provides a way to measure spreading dynamics of extremely small volumes of heterogeneously complex fluids not possible through other means.

Nanopatterning of GeTe phase change films via heated-probe lithography.

The crystallization of amorphous germanium telluride (GeTe) thin films is controlled with nanoscale resolution using the heat from a thermal AFM probe. The dramatic differences between the amorphous and crystalline GeTe phases yield embedded nanoscale features with strong topographic, electronic, and optical contrast. The flexibility of scanning probe lithography enables the width and depth of the features, as well as the extent of their crystallization, to be controlled by varying probe temperature and write speed. Together, these technologies suggest a new approach to nanoelectronic and opto-electronic device fabrication.

Driving Surface Chemistry at the Nanometer Scale Using Localized Heat and Stress.

Driving and measuring chemical reactions at the nanoscale is crucial for developing safer, more efficient, and environment-friendly reactors and for surface engineering. Quantitative understanding of surface chemical reactions in real operating environments is challenging due to resolution and environmental limitations of existing techniques. Here we report an atomic force microscope technique that can measure reaction kinetics driven at the nanoscale by multiphysical stimuli in an ambient environment. We demonstrate the technique by measuring local reduction of graphene oxide as a function of both temperature and force at the sliding contact. Kinetic parameters measured with this technique reveal alternative reaction pathways of graphene oxide reduction previously unexplored with bulk processing techniques. This technique can be extended to understand and precisely tailor the nanoscale surface chemistry of any two-dimensional material in response to a wide range of external, multiphysical stimuli.

Direct mechanochemical cleavage of functional groups from graphene.

Mechanical stress can drive chemical reactions and is unique in that the reaction product can depend on both the magnitude and the direction of the applied force. Indeed, this directionality can drive chemical reactions impossible through conventional means. However, unlike heat- or pressure-driven reactions, mechanical stress is rarely applied isometrically, obscuring how mechanical inputs relate to the force applied to the bond. Here we report an atomic force microscope technique that can measure mechanically induced bond scission on graphene in real time with sensitivity to atomic-scale interactions. Quantitative measurements of the stress-driven reaction dynamics show that the reaction rate depends both on the bond being broken and on the tip material. Oxygen cleaves from graphene more readily than fluorine, which in turn cleaves more readily than hydrogen. The technique may be extended to study the mechanochemistry of any arbitrary combination of tip material, chemical group and substrate.

Laser-induced nanoscale thermocapillary flow for purification of aligned arrays of single-walled carbon nanotubes.

Although aligned arrays of single-walled carbon nanotubes (SWNTs) have outstanding potential for use in broad classes of advanced semiconductor devices, the relatively large population of metallic SWNTs (m-SWNTs) that results from conventional growth techniques leads to significantly degraded performance. Recently reported methods based on thermocapillary effects that enable removal of m-SWNTs from such arrays offer exceptional levels of efficiency, but the procedures are cumbersome and require multiple processing steps. Here we present a simple, robust alternative that yields pristine arrays of purely semiconducting SWNTs (s-SWNTs) by use of irradiation with an infrared laser. Selective absorption by m-SWNTs coated with a thin organic film initiates nanoscale thermocapillary flows that lead to exposure only of the m-SWNTs. Reactive ion etching eliminates the m-SWNTs without damaging the s-SWNTs; removal of the film completes the purification. Systematic experimental studies and computational modeling of the thermal physics illuminates the essential aspects of this process. Demonstrations include use of arrays of s-SWNTs formed in this manner as semiconducting channel materials in statistically relevant numbers of transistors to achieve both high mobilities (>900 cm2 V(-1) s(-1)) and switching ratios (>10(4)). Statistical analysis indicates that the arrays contain at least 99.8% s-SWNTs and likely significantly higher.

Nanometer scale alignment of block-copolymer domains by means of a scanning probe tip.

Alignment of perpendicularly oriented lamellar block copolymer domains using an AFM tip is demonstrated. The AFM tip orients the domains through local shearing, resulting in domain alignment parallel to tip travel. AFM tips can also deposit block copolymer nanostructures on heated substrates with a variety of experimentally observed domain alignments.

Improved atomic force microscope infrared spectroscopy for rapid nanometer-scale chemical identification.

Atomic force microscope infrared spectroscopy (AFM-IR) can perform IR spectroscopic chemical identification with sub-100 nm spatial resolution, but is relatively slow due to its low signal-to-noise ratio (SNR). In AFM-IR, tunable IR laser light is incident upon a sample, which results in a rise in temperature and thermomechanical expansion of the sample. An AFM tip in contact with the sample senses this nanometer-scale photothermal expansion. The tip motion induces cantilever vibrations, which are measured either in terms of the peak-to-peak amplitude of time-domain data or the integrated magnitude of frequency-domain data. Using a continuous Morlet wavelet transform to the cantilever dynamic response, we show that the cantilever dynamics during AFM-IR vary as a function of both time and frequency. Based on the observed cantilever response, we tailor a time-frequency-domain filter to identify the region of highest vibrational energy. This approach can increase the SNR of the AFM cantilever signal, such that the throughput is increased 32-fold compared to state-of-the art procedures. We further demonstrate significant increases in AFM-IR imaging speed and chemical identification of nanometer-scale domains in polymer films.

Atomic force microscope infrared spectroscopy on 15 nm scale polymer nanostructures.

We measure the infrared spectra of polyethylene nanostructures of height 15 nm using atomic force microscope infrared spectroscopy (AFM-IR), which is about an order of magnitude improvement over state of the art. In AFM-IR, infrared light incident upon a sample induces photothermal expansion, which is measured by an AFM tip. The thermomechanical response of the sample-tip-cantilever system results in cantilever vibrations that vary in time and frequency. A time-frequency domain analysis of the cantilever vibration signal reveals how sample thermomechanical response and cantilever dynamics affect the AFM-IR signal. By appropriately filtering the cantilever vibration signal in both the time domain and the frequency domain, it is possible to measure infrared absorption spectra on polyethylene nanostructures as small as 15 nm.

Ultrananocrystalline diamond tip integrated onto a heated atomic force microscope cantilever.

We report a wear-resistant ultrananocrystalline (UNCD) diamond tip integrated onto a heated atomic force microscope (AFM) cantilever and UNCD tips integrated into arrays of heated AFM cantilevers. The UNCD tips are batch-fabricated and have apex radii of approximately 10 nm and heights up to 7 µm. The solid-state heater can reach temperatures above 600 °C and is also a resistive temperature sensor. The tips were shown to be wear resistant throughout 1.2 m of scanning on a single-crystal silicon grating at a force of 200 nN and a speed of 10 µm s(-1). Under the same conditions, a silicon tip was completely blunted. We demonstrate the use of these heated cantilevers for thermal imaging in both contact mode and intermittent contact mode, with a vertical imaging resolution of 1.9 nm. The potential application to nanolithography was also demonstrated, as the tip wrote hundreds of polyethylene nanostructures.

Nanometer-scale infrared spectroscopy of heterogeneous polymer nanostructures fabricated by tip-based nanofabrication.

There is a significant need for chemical identification and chemical imaging of nanofabricated structures and devices, especially for multiple materials integrated at the nanometer scale. Here we present nanofabrication, chemical identification, and nanometer-scale chemical imaging of polymer nanostructures with better than 100 nm spatial resolution. Polymer nanostructures of polyethylene, polystyrene, and poly(3-dodecylthiophene-2,5-diyl) were fabricated by tip-based nanofabrication. Nanometer-scale infrared measurements using atomic force microscopy infrared spectroscopy (AFM-IR) obtained quantitative chemical spectra of these nanostructures. We show chemical imaging of intersecting patterns of nanometer-scale polymer lines of different chemical compositions. The results indicate that for closely packed heterogeneous nanostructures, the spatial resolution of AFM-IR is not limited by nanometer-scale thermal diffusion, but is instead limited by the cantilever sensitivity and the signal-to-noise ratio of the AFM-IR system.

Nanometer-scale flow of molten polyethylene from a heated atomic force microscope tip.

We investigate the nanometer-scale flow of molten polyethylene from a heated atomic force microscope (AFM) cantilever tip during thermal dip-pen nanolithography (tDPN). Polymer nanostructures were written for cantilever tip temperatures and substrate temperatures controlled over the range 100-260 °C and while the tip was either moving with speed 0.5-2.0 µm s(-1) or stationary and heated for 0.1-100 s. We find that polymer flow depends on surface capillary forces and not on shear between tip and substrate. The polymer mass flow rate is sensitive to the temperature-dependent polymer viscosity. The polymer flow is governed by thermal Marangoni forces and non-equilibrium wetting dynamics caused by a solidification front within the feature.

Controlling nanoscale friction through the competition between capillary adsorption and thermally activated sliding.

We demonstrate measurement and control of nanoscale single-asperity friction by using cantilever probes featuring an in situ solid-state heater in contact with silicon oxide substrates. The heater temperature was varied between 25 and 790 °C. By using a low thermal conductivity sample, silicon oxide, we are able to vary tip temperatures over a broad range from 25 ± 2 to 255 ± 25 °C. In ambient atmosphere with ∼30% relative humidity, the control of friction forces was achieved through the formation of a capillary bridge whose characteristics exhibit a strong dependence on temperature and sliding speed. The capillary condensation is observed to be a thermally activated process, such that heating in ambient air caused friction to increase due to the capillary bridge nucleating and growing. Above tip temperatures of ∼100 ± 10 °C, friction decreased drastically, which we attribute to controllably evaporating water from the contact at the nanoscale. In contrast, in a dry nitrogen atmosphere, friction was not affected appreciably by temperature changes. In the presence of a capillary, friction decreases at higher sliding speeds due to disruption of the capillary; otherwise, friction increases in accordance with the predictions of a thermally assisted sliding model. In ambient atmospheres, the rate of increase of friction with sliding speed at room temperature is sufficiently strong that the friction force changes from being smaller than the response at 76 ± 8 °C to being larger. Thus, an appropriate change in temperature can cause friction to increase at one sliding speed, while it decreases at another speed.

Local nanoscale heating modulates single-asperity friction.

We demonstrate measurement and control of single-asperity friction by using cantilever probes featuring an in situ solid-state heater. The heater temperature was varied between 25 and 650 °C (tip temperatures from 25 ± 2 to 120 ± 20 °C). Heating caused friction to increase by a factor of 4 in air at ∼ 30% relative humidity, but in dry nitrogen friction decreased by ∼ 40%. Higher velocity reduced friction in ambient with no effect in dry nitrogen. These trends are attributed to thermally assisted formation of capillary bridges between the tip and substrate in air, and thermally assisted sliding in dry nitrogen. Real-time friction measurements while modulating the tip temperature revealed an energy barrier for capillary condensation of 0.40 ± 0.04 eV but with slower kinetics compared to isothermal measurements that we attribute to the distinct thermal environment that occurs when heating in real time. Controlling the presence of this nanoscale capillary and the associated control of friction and adhesion offers new opportunities for tip-based nanomanufacturing.

Wear-resistant diamond nanoprobe tips with integrated silicon heater for tip-based nanomanufacturing.

We report exceptional nanoscale wear and fouling resistance of ultrananocrystalline diamond (UNCD) tips integrated with doped silicon atomic force microscope (AFM) cantilevers. The resistively heated probe can reach temperatures above 600 degrees C. The batch fabrication process produces UNCD tips with radii as small as 15 nm, with average radius 50 nm across the entire wafer. Wear tests were performed on substrates of quartz, silicon carbide, silicon, or UNCD. Tips were scanned for more than 1 m at a scan speed of 25 mum s(-1) at temperatures ranging from 25 to 400 degrees C under loads up to 200 nN. Under these conditions, silicon tips are partially or completely destroyed, while the UNCD tips exhibit little or no wear, no signs of delamination, and exceptional fouling resistance. We demonstrate nanomanufacturing of more than 5000 polymer nanostructures with no deterioration in the tip.