Energy dissipation of a contact line moving on a nanotopographical defect.

Understanding the origin of the dissipative mechanisms that control the dynamics of a contact line is a real challenge. In order to study the energy dissipation at the contact line when a moving meniscus encounters topographical defects, we developed atomic force microscopy (AFM) experiments using nanofibers with nanometer scale defects. These experiments realized with three liquids are performed in two AFM modes: the contact mode (C-AFM) is used to measure the energy associated with the contact angle hysteresis in the limit of a static situation, deduced from advancing and receding dipping experiments on an isolated defect; the frequency-modulation mode (FM-AFM) is performed at different amplitudes and then velocities to measure the energy dissipated as the contact line moves over the same defect. Strong dissipation peaks appear above a threshold amplitude characteristic of the liquid and the defect, which is determined by the width of the hysteresis measured in statics. Furthermore, the dissipation energy of the moving contact line measured in dynamics is equal to the hysteresis capillary energy whatever the amplitude and is therefore independent of the contact line velocity. These results point out that the defect contribution to dissipation energy of a moving contact line on real surfaces is only governed by the pinning-depinning energy with no contribution of viscous effects.

Influence of Surface-Active Substances and Substrates on the Wettability of Individual Aerosol Particles during Condensation by Environmental Scanning Electron Microscopy.

The formation of liquid cloud droplets from aerosol particles in the Earth atmosphere is still under debate particularly because of the difficulties to quantify the importance of bulk and surface effects in these processes. Recently, single-particle techniques have been developed to access experimental key parameters at the scale of individual particles. Environmental scanning electron microscopy (ESEM) has the advantage to provide in situ monitoring of the water uptake of individual microscopic particles deposited on solid substrates. In this work, ESEM was used to compare droplet growth on pure ammonium sulfate (NH4)2SO4 and mixed sodium dodecyl sulfate/ammonium sulfate (SDS/(NH4)2SO4) particles and to explore the role of experimental parameters, such as the hydrophobic-hydrophilic character of the substrate, on this growth. With hydrophilic substrates, the growth on pure salt particles was strongly anisotropic, but this anisotropy was suppressed by the presence of SDS. With hydrophobic substrates, it is the wetting behavior of the liquid droplet that is impacted by the presence of SDS. The wetting behavior of the pure (NH4)2SO4 solution on a hydrophobic surface shows a step-by-step mechanism that can be attributed to successive pinning-depinning phenomena at the triple-phase line frontier. Unlike the pure (NH4)2SO4 solution, the mixed SDS/(NH4)2SO4 solution did not show such a mechanism. Therefore, the hydrophobic-hydrophilic character of the substrate plays an important role in the stability and dynamics of the liquid droplets' nucleation by water vapor condensation. In particular, hydrophilic substrates are not suited for the investigation of the hygroscopic properties (deliquescence relative humidity (DRH) and hygroscopic growth factor (GF)) of particles. Using hydrophobic substrates, data show that the DRH of (NH4)2SO4 particles is measured within 3% accuracy on the RH and their GF could indicate a size-dependent effect in the micrometer range. The presence of SDS does not seem to modify the DRH and GF of (NH4)2SO4 particles. This study shows that the water uptake on deposited particles is a complex process but, once carefully taken into account, ESEM is a suitable technique to study them.

Wetting at the Nanoscale: Molecular Mobility Induced by Contact Line Forces.

In this paper, we study the interaction of a contact line with molecules physically adsorbed on a surface. We developed specific atomic force microscopy (AFM) experiments where a nanoneedle attached at the extremity of the cantilever is dipped in a liquid droplet. The motion of the contact line at the extremity of the meniscus formed depends on the presence of topographical and chemical defects at the surface of the nanoneedle. The analysis of the force measured by AFM based on a capillary model allows one to distinguish the effects of topographical and chemical defects and to monitor minute changes of surface properties. Using six different liquids and five tips, we show that the change of the surface properties of one nanoneedle results either from the adsorption of airborne molecules when the tip is left in the air or from their desorption by the moving contact line when the tip is repeatedly dipped in the liquid. The desorption rate is found to depend only on the number of dipping cycles and is not influenced by the velocity or the liquid properties. A model based on the estimation of capillary and adsorption energies confirms a capillary desorption mechanism in agreement with the experimental results. Finally, we demonstrate that three distinct desorption mechanisms may be at play. Interestingly, using a deliberate contamination with large hydrocarbon molecules, we show that the capillary desorption studied in this paper can be used to clean surfaces.

Molecular Desorption by a Moving Contact Line.

The interaction of the contact line with topographical or chemical defects at the nanometer scale sets the macroscopic wetting properties of a liquid on a solid substrate. Based on specific atomic force microscopy (AFM) experiments, we demonstrate that molecules physically sorbed on a surface are removed by a dynamic contact line. The mechanism of molecules desorption is directly determined by the capillary force exerted at the contact line on the molecules. We also emphasize the potential of AFM to clearly decorrelate the effects of topographical and chemical defects and monitor, with a subsecond time resolution, the dynamics of molecules adsorption on a surface.

Spontaneous migration of cellular aggregates from giant keratocytes to running spheroids.

Despite extensive knowledge on the mechanisms that drive single-cell migration, those governing the migration of cell clusters, as occurring during embryonic development and cancer metastasis, remain poorly understood. Here, we investigate the collective migration of cell on adhesive gels with variable rigidity, using 3D cellular aggregates as a model system. After initial adhesion to the substrate, aggregates spread by expanding outward a cell monolayer, whose dynamics is optimal in a narrow range of rigidities. Fast expansion gives rise to the accumulation of mechanical tension that leads to the rupture of cell-cell contacts and the nucleation of holes within the monolayer, which becomes unstable and undergoes dewetting like a liquid film. This leads to a symmetry breaking and causes the entire aggregate to move as a single entity. Varying the substrate rigidity modulates the extent of dewetting and induces different modes of aggregate motion: "giant keratocytes," where the lamellipodium is a cell monolayer that expands at the front and retracts at the back; "penguins," characterized by bipedal locomotion; and "running spheroids," for nonspreading aggregates. We characterize these diverse modes of collective migration by quantifying the flows and forces that drive them, and we unveil the fundamental physical principles that govern these behaviors, which underscore the biological predisposition of living material to migrate, independent of length scale.

Nanoscale Wetting of Single Viruses.

The epidemic spread of many viral infections is mediated by the environmental conditions and influenced by the ambient humidity. Single virus particles have been mainly visualized by atomic force microscopy (AFM) in liquid conditions, where the effect of the relative humidity on virus topography and surface cannot be systematically assessed. In this work, we employed multi-frequency AFM, simultaneously with standard topography imaging, to study the nanoscale wetting of individual Tobacco Mosaic virions (TMV) from ambient relative humidity to water condensation (RH > 100%). We recorded amplitude and phase vs. distance curves (APD curves) on top of single virions at various RH and converted them into force vs. distance curves. The high sensitivity of multifrequency AFM to visualize condensed water and sub-micrometer droplets, filling gaps between individual TMV particles at RH > 100%, is demonstrated. Dynamic force spectroscopy allows detecting a thin water layer of thickness ~1 nm, adsorbed on the outer surface of single TMV particles at RH < 60%.

Long-range hydrodynamic forces in liquid FM-AFM.

We study the effects of hydrodynamic forces in frequency-modulation AFM experiments (FM-AFM) in liquid. We first establish the theoretical equations needed to derive the interaction stiffness k int and the damping ß int due to the hydrodynamic forces from the frequency shift and the excitation amplitude. We develop specific FM-AFM experiments to measure the variation of k int and ß int over a large range of distance in water up to 200 µm. Comparison between theory and experiments point out that the evolution of k int at short and long distance arises from unsteady hydrodynamic forces on the cantilever. On the other hand, ß int is small at long distance and diverges at short probe-surface distance, as predicted by the classical Reynolds sphere model.

Shape and Effective Spring Constant of Liquid Interfaces Probed at the Nanometer Scale: Finite Size Effects.

We investigate the shape and mechanical properties of liquid interfaces down to nanometer scale by atomic force microscopy (AFM) and scanning electron microscopy (SEM) combined with in situ micromanipulation techniques. In both cases, the interface is probed with a cylindrical nanofiber with radius R of the order of 25-100 nm. The effective spring constant of the nanomeniscus oscillated around its equilibrium position is determined by static and frequency-modulation (FM) AFM modes. In the case of an unbounded meniscus, we find that the effective spring constant k is proportional to the surface tension γ of the liquid through k = (0.51 ± 0.06)γ, regardless of the excitation frequency from quasi-static up to 450 kHz. A model based on the equilibrium shape of the meniscus reproduces well the experimental data. Electron microscopy allowed to visualize the meniscus profile around the fiber with a lateral resolution of the order of 10 nm and confirmed its catenary shape. The influence of a lateral confinement of the interface is also investigated. We showed that the lateral extension L of the meniscus influences the effective spring constant following a logarithmic evolution k ∼ 2πγ/ln(L/R) deduced from the model. This comprehensive study of liquid interface properties over more than 4 orders of magnitude in meniscus size shows that advanced FM-AFM and SEM techniques are promising tools for the investigation of mechanical properties of liquids down to nanometer scale.

Solid-state SiO2 nano-gears AFM tip manipulation on HOPG.

On a native graphite surface, 15 nm-thick solid-state nanogears are nanofabricated with a 30 nm outer diameter and six teeth. The nanogears are manipulated one at a time by the tip of an atomic force microscope using the sample stage displacements for the manipulation and recording of the corresponding manipulation signals. For step heights below 3.0 nm, nanogears are manipulated up and down native graphite surface step edges. In the absence of a central shaft per nanogear, gearing between nanogears is limited to a few 1/12 turns for six teeth. When the graphite step is higher than 3 nm, a rack-and-pinion mechanism was constructed along the edge with a 90 nm nanogear pinion.

The condensation of water on adsorbed viruses.

The wetting and dewetting behavior of biological nanostructures and to a greater degree single molecules is not well-known even though their contact with water is the basis for all biology. Here, we show that environmental electron microscopy (EM) can be applied as a means of imaging the condensation of water onto viruses. We captured the formation of submicrometer water droplets and filaments on single viral particles by environmental EM and by environmental transmission EM. The condensate structures are compatible with capillary condensation between adsorbed virus particles and with known droplet shapes on patterned surfaces. Our results confirm that such droplets exist down to <50 nm. The viruses preserved their shape after a condensation/evaporation cycle as expected from their stability in air and water. Moreover we developed procedures that overcome problems of beam damage and of resolving structures with a low atomic number.

Integration of plant viruses in electron beam lithography nanostructures.

Tobacco mosaic virus (TMV) is the textbook example of a virus, and also of a self-assembling nanoscale structure. This tubular RNA/protein architecture has also found applications as biotemplate for the synthesis of nanomaterials such as wires, as tubes, or as nanoparticle assemblies. Although TMV is, being a biological structure, quite resilient to environmental conditions (temperature, chemicals), it cannot be processed in electron beam lithography (eBL) fabrication, which is the most important and most versatile method of nanoscale structuring. Here we present adjusted eBL-compatible processes that allow the incorporation of TMV in nanostructures made of positive and negative tone eBL resists. The key steps are covering TMV by polymer resists, which are only heated to 50 °C, and development (selective dissolution) in carefully selected organic solvents. We demonstrate the post-lithography biochemical functionality of TMV by selective immunocoating of the viral particles, and the use of immobilized TMV as direct immunosensor. Our modified eBL process should be applicable to incorporate a wide range of sensitive materials in nanofabrication schemes.

New probes based on carbon nano-cones for scanning probe microscopies.

All-graphenic carbon morphologies grown on individual carbon nanotubes (CNTs) consisting of short-fiber segments bearing sharp micro-/nano-cones at both ends were mounted as new probes for scanning probe microscopies (SPM). Three mounting procedures were tested, two based on focused ion and/or electron beam processes operated in scanning electron microscopes, and another based on an irradiation-free procedure under an optical microscope. The benefits and drawbacks of all the methods are described in details. The extent to which the structural integrity of the carbon material of the cones was affected by each of the mounting processes was also investigated using Raman spectroscopy and high-resolution transmission electron microscopy. The carbon cones were found to be sensitive to both ion and electron irradiation to an unusual extent with respect to structurally-close nano-objects such as multi-wall CNTs. This was assumed to be due to the occurrence of a large number of free graphene-edges at the cone surface. The suitability of such carbon cones as SPM probes is demonstrated, the characteristics of which make them potentially superior to Si-, diamond-, or CNT-probes.

Contact angle hysteresis at the nanometer scale.

Using atomic force microscopy with nonconventional carbon tips, the pinning of a liquid contact line on individual nanometric defects was studied. This mechanism is responsible for the occurrence of the contact angle hysteresis. The presence of weak defects which do not contribute to the hysteresis is evidenced for the first time. The dissipated energy associated with strong defects is also measured down to values in the range of kT, which correspond to defect sizes in the order of 1 nm.

Capillary forces during liquid nanodispensing.

We present a comprehensive study of the capillary force measured during the liquid nanodispensing of attoliter droplets with an atomic force microscope tip. Due to the presence of a nanochannel drilled at the tip apex and connected to a reservoir droplet deposited on the cantilever, we observe a large variety of force curves during the deposition process. We propose a numerical method which accounts for most of the experimental observations. In particular, we clearly demonstrate the influence of the nanochannel diameter. This study leads to a better understanding of the mechanisms of liquid transfer from the tip to the surface and also provides a real time monitoring of the dispensing. Besides these applications, the method we use, which can handle a large variety of conditions and also complex geometries, may find a wide range of applications.

Evaporation of femtoliter sessile droplets monitored with nanomechanical mass sensors.

We present a time-resolved study of the evaporation in air of minuscule sessile droplets deposited by nanodispensing techniques. Highly sensitive nanomechanical resonators are designed to monitor in time the mass variation of evaporating liquid droplets. The precision of the measurement setup enables the study of droplets with diameters in the 1 mum range, which correspond to volumes of femtoliters and smaller, 9 orders of magnitude smaller than most of presently published data. Experimental data are compared with macroscopic models.

Wettability of partially suspended graphene.

The dependence of the wettability of graphene on the nature of the underlying substrate remains only partially understood. Here, we systematically investigate the role of liquid-substrate interactions on the wettability of graphene by varying the area fraction of suspended graphene from 0 to 95% by means of nanotextured substrates. We find that completely suspended graphene exhibits the highest water contact angle (85° ± 5°) compared to partially suspended or supported graphene, regardless of the hydrophobicity (hydrophilicity) of the substrate. Further, 80% of the long-range water-substrate interactions are screened by the graphene monolayer, the wettability of which is primarily determined by short-range graphene-liquid interactions. By its well-defined chemical and geometrical properties, supported graphene therefore provides a model system to elucidate the relative contribution of short and long range interactions to the macroscopic contact angle.

Direct patterning of nanoparticles and biomolecules by liquid nanodispensing.

We report on the localized deposition of nanoparticles and proteins, nano-objects commonly used in many nanodevices, by the liquid nanodispensing (NADIS) technique which consists in depositing droplets of a solution through a nanochannel drilled at the apex of an AFM tip. We demonstrate that the size of spots can be adjusted from microns down to sub-50 nm by tuning the channel diameter, independently of the chemical nature of the solute. In the case of nanoparticles, we demonstrated the ultimate limit of the method and showed that large arrays of single (or pairs of) nanoparticles can be reproducibly deposited. We further explored the possibility to deposit different visible fluorescent proteins using NADIS without loss of protein function. The intrinsic fluorescence of these proteins is characteristic of their structural integrity; the retention of fluorescence after NADIS deposition demonstrates that the proteins are intact and functional. This study demonstrates that NADIS can be a viable alternative to other scanning probe lithography techniques since it combines high resolution direct writing of nanoparticles or biomolecules with the versatility of liquid lithography techniques.

Electrical detection of individual magnetic nanoparticles encapsulated in carbon nanotubes.

We report on low-temperature electrical transport measurements of single-walled carbon nanotubes (SWNTs) filled in their inner core with one-dimensional cobalt nanoparticles. The electrical transport properties of the hybrid devices are strongly sensitive to the magnetization reversal of isolated magnetic nanoparticles, resulting in strong hysteretic variations of the magnetoconductance. The magnetic anisotropy of a one-dimensional encapsulated cobalt nanoparticle is investigated, establishing an unusually strong dominating contribution of magnetic surface anisotropy.

Control of droplet size in liquid nanodispensing.

In this Letter, the phenomena and parameters governing the nanoscale dispensing of liquid through an apertured atomic force microscope probe milled by focused ion beam lithography are characterized in detail. We show that the size of deposited droplets can be reproducibly defined by controlling the aperture size on the probe and the surface energies of both tip outer wall and substrate surface. On the basis of these findings, tips with aperture diameter as small as 35 nm enabled the deposition of regular arrays of nanodroplets with diameter down to 70 nm on an alkylamine-modified surface. The fine control of droplet volumes down to a few tens of zeptoliters (10(-21)L) provides a unique tool for creating devices and probing the fundamentals of wetting at the nanometer scale.

Pinning of a contact line on nanometric steps during the dewetting of a terraced substrate.

We study the dewetting of polystyrene films on an alumina surface. We show that the morphology of dewetting holes is drastically modified by the nanometric steps on the surface. Nevertheless, below a critical step height of the order of the polymer chain dimension, the contact line is not anymore sensitive to the defects. This method thus gives an estimation of the limit of validity of macroscopic descriptions of wetting when going down to molecular dimensions.