Search

Scanning polarization force microscopy was used to study the topography, polarizability, and contact potential of cleaved NaCl(100) as a function of the relative humidity (RH) between <5% and 40%. In this humidity range there are reversible changes in surface potential and polarizability, while large scale modifications in step topography and irreversible ion redistribution occur above 40% RH. In dry conditions the surface contact potential was more negative near atomic steps than over flat terraces. As humidity was increased, changes were observed in the local polarizability of the steps due to ionic solvation, and the contact potential of the terraces became more negative. At 40% RH surface-potential differences between steps and terraces could no longer be detected. These results are interpreted in terms of preferential anion solvation, initially localized near steps, and later spreading over the entire surface. [ABSTRACT FROM AUTHOR]

NaCl hillocks have been grown on the NaCl(100) monocrystalline surface by simply making the tip of an atomic force microscope cantilever interact with the surface. A quantitative discussion about the hillock dissolution process as well as physical stability of these ionic surfaces has been made. Molecular dynamics simulations helped us to interpret the experimental data. An explanation for the hillock formation and dissolution phenomena is also discussed. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

All surfaces exposed to ambient conditions are covered by a thin film of water. Other than at high humidity conditions, i.e., relative humidity higher than 80%, those water films have nanoscale thickness. Nevertheless, even the thinnest film can profoundly affect the physical and chemical properties of the substrate. Information on the structure of these water films can be obtained from spectroscopic techniques based on photons, but these usually have poor lateral resolution. When information with nanometer resolution in the three dimensions is needed, for example for surfaces showing heterogeneity in water affinity at the nanoscale, Atomic Force Microscopy (AFM) is the preferred tool since it can provide such resolution while being operated in ambient conditions. A complication in the interpretation of the data arises when using AFM, however, since, in most cases, direct interaction between a solid probe and a solid surface occurs. This induces strong perturbations of the liquid by the probe that should be controlled or avoided. The aim of this review is to provide an overview of different AFM methods developed to overcome this problem, measuring different interactions between the AFM probe and the water films, and to discuss the type of information about the water film that can be obtained from these interactions. [ABSTRACT FROM AUTHOR]

Scanning electron microscopy (SEM) is a powerful imaging technique able to obtain astonishing images of the micro- and the nano-world. Unfortunately, the technique has been limited to vacuum conditions for many years. In the last decades, the ability to introduce water vapor into the SEM chamber and still collect the electrons by the detector, combined with the temperature control of the sample, has enabled the study of ice at nanoscale. Astounding images of hexagonal ice crystals suddenly became real. Since these first images were produced, several studies have been focusing their interest on using SEM to study ice nucleation, morphology, thaw, etc. In this paper, we want to review the different investigations devoted to this goal that have been conducted in recent years in the literature and the kind of information, beyond images, that was obtained. We focus our attention on studies trying to clarify the mechanisms of ice nucleation and those devoted to the study of ice dynamics. We also discuss these findings to elucidate the present and future of SEM applied to this field. [ABSTRACT FROM AUTHOR]

Abstract: Thanks to the ability of an AFM to topographically image a surface and to apply forces perpendicular to it we have studied the case of nanometer-scale beakers, formed by dewetting of a dissolution of an organic material with its solvent, filled with water. The confinement of such water nanodroplets (WNDs) allows their imaging and the exploration of their mechanical behavior. Surprisingly to a certain extent, the WNDs mechanical response can be approximated by a hookean spring exhibiting force constants, closely related to the surface tension, significantly larger than the well-known value of 0.073Nm−1. We ascribe the larger values to the nanometric length scale involved. [Copyright &y& Elsevier]

Water becomes ordered in the form of hexagonal ice at room temperature under controlled humidity conditions upon confinement in the nanometer range between protective graphene sheets and crystalline (111) surfaces with hexagonal symmetry of the alkali earth fluoride BaF2. Interfacial water/substrate pseudoepitaxy turns out to be a critical parameter since ice is only formed when the lattice mismatch is small, an observation based on the absence of ice on (111) surfaces of isostructural CaF2 [ABSTRACT FROM AUTHOR]

Ambient amplitude modulation atomic force microscopy (AM AFM) is one of the most broadly used techniques as it is versatile and can provide measurements of single nanostructures routinely. Nevertheless, the technique typically measures an apparent height of nanostructures that does not coincide with the true height. Here, we carry out an exhaustive study of the several possibilities that arise in the presence and in the absence of adsorbed water layers when measuring the height of nanostructures. A method to control whether water layers are perturbed and whether intermittent mechanical contact occurs is provided. We show that the predicted range of apparent heights in the several interaction regimes is as large as the experimental values that are routinely obtained. In one extreme the apparent height might be larger than the true height even when sample deformation occurs. In the other, height reversal might occur even when sample deformation is much smaller than the loss of height. A main mechanism leading to such a broad range of measurements is identified in terms of the presence of water layers and the long range character of the resulting forces. In short, due to these long range effects, the gap in separation in the two amplitude branches, i.e., the attractive and the repulsive regimes, might be an order of magnitude larger in the presence of water than in its absence. [ABSTRACT FROM AUTHOR]

In ambient conditions, nanometric water layers form on hydrophilic surfaces covering them and significantly changing their properties and characteristics. Here we report the excitation of subharmonics in amplitude modulation atomic force microscopy induced by intermittent water contacts. Our simulations show that there are several regimes of operation depending on whether there is perturbation of water layers. Single period orbitals, where subharmonics are never induced, follow only when the tip is either in permanent contact with the water layers or in pure noncontact where the water layers are never perturbed. When the water layers are perturbed subharmonic excitation increases with decreasing oscillation amplitude. We derive an analytical expression which establishes whether water perturbations compromise harmonic motion and show that the predictions are in agreement with numerical simulations. Empirical validation of our interpretation is provided by the observation of a range of values for apparent height of water layers when subharmonic excitation is predicted. [ABSTRACT FROM AUTHOR]

Abstract The structure and growth of water films on surfaces is reviewed, starting from single molecules to two-dimensional wetting layers, and liquid interfaces. This progression follows the increase in temperature and vapor pressure from a few degrees Kelvin in ultra-high vacuum, where Scanning Tunneling and Atomic Force Microscopies (STM and AFM) provide crystallographic information at the molecular level, to ambient conditions where surface sensitive spectroscopic techniques provide electronic structure information. We show how single molecules bind to metal and non-metal surfaces, their diffusion and aggregation. We examine how water molecules can be manipulated by the STM tip via excitation of vibrational and electronic modes, which trigger molecular diffusion and dissociation. We review also the adsorption and structure of water on non-metal substrates including mica, alkali halides, and others under ambient humid conditions. We finally discuss recent progress in the exploration of the molecular level structure of solid-liquid interfaces, which impact our fundamental understanding of corrosion and electrochemical processes. [ABSTRACT FROM AUTHOR]

Measuring the level of hydrophilicity of heterogeneous surfaces and the true height of water layers that form on them in hydrated conditions has a myriad of applications in a wide range of scientific and technological fields. Here, we describe a true non-contact mode of operation of atomic force microscopy in ambient conditions and a method to establish the source of apparent height. A dependency of the measured water height on operational parameters is identified with water perturbations due to uncontrolled modes of imaging where intermittent contact with the water layer, or even the surface, might occur. In this paper we show how to (1) determine when the water is being perturbed and (2) distinguish between four different interaction regimes. Each of the four types of interaction produces measurements ranging from fractions of the true height in one extreme to values which are as large as four times the real height in the other. We show the dependence of apparent height on the interaction regime both theoretically and empirically. The agreement between theory and experiment on a BaF2(111) sample displaying wet and un-wet regions validates our results. [ABSTRACT FROM AUTHOR]

Since the inception of the atomic force microscope (AFM), dynamic methods (dynamic atomic force microscopy) have been very fruitful by establishing methods to quantify dissipative and conservative forces in the nanoscale and by providing a means to apply gentle forces to the samples with high resolution. Here, we discuss developments that cover over a decade of our work on energy dissipation, phase contrast, and the extraction of relevant material properties from observables. We describe the attempts to recover material properties via one-dimensional amplitude and phase curves from force models and explore the evolution of these methods in terms of force reconstruction, fits of experimental measurements, and the more recent advances in multifrequency AFM. We further discuss open questions and key possible paths to advance the field. [ABSTRACT FROM AUTHOR]

Here, we show that the well-known hydrophobic leucine (Leu) zipper motif (also known as the coiled-coil or Leu scissors motif), typically found in proteins, can be used as a source of inspiration in coordination polymers built from Leu-containing dipeptides or tripeptides. We demonstrate that this motif can be extended to form Velcro-like layers of Leu, and that the hydrophobicity of these layers is transferred to coordination polymers, thereby enabling the development of a new type of hydrophobic materials. [ABSTRACT FROM AUTHOR]

Materials with surfaces that can be switched from high/superhydrophobicity to superhydrophilicity are useful for myriad applications. Herein, we report a metal-organic framework (MOF) assembled from ZnII ions, 1,4-benzenedicarboxylate, and a hydrophobic carborane-based linker. The MOF crystal-surface can be switched between hydrophobic and superhydrophilic through a chemical treatment to remove some of the building blocks. [ABSTRACT FROM AUTHOR]

Materials with surfaces that can be switched from high/superhydrophobicity to superhydrophilicity are useful for myriad applications. Herein, we report a metal-organic framework (MOF) assembled from ZnII ions, 1,4-benzenedicarboxylate, and a hydrophobic carborane-based linker. The MOF crystal-surface can be switched between hydrophobic and superhydrophilic through a chemical treatment to remove some of the building blocks. [ABSTRACT FROM AUTHOR]

The equilibrium state of graphene surfaces exposed to ambient conditions is of significant importance for applications from electronics to anti-corrosion layers and from a fundamental perspective. The environmental exposure influences macroscopic properties of the graphene surface, as recent studies on wettability reported. However, these studies are controversial for two reasons: firstly, time dependency of graphene wettability complicates comparison of results from different groups. Secondly it’s inherently difficult to understand the underlying physical phenomena by means of macroscopic measurements alone. Here we study the evolution of the wettability of graphene monolayers on copper by exposing samples to controlled ambient conditions. Static contact angle measurements reveal that the graphene undergoes a transition in its wettability from slightly hydrophilic to hydrophobic over timescales of the order of hours. To gain further insight, we apply Fourier transform infrared spectroscopy and a recently developed dynamic atomic force microscopy-based force spectroscopy to probe the sample surface at the nanoscale. This novel nanoscopic approach allows us to demonstrate that the transition in wettability of graphene is induced by the adsorption of water molecules from the environment in combination with hydrocarbon contamination. Furthermore, our nanoscale observations challenge the wetting transparency theory of graphene after exposure to the environment. [ABSTRACT FROM AUTHOR]

Highlights: [•] Self-assembled monolayers are formed on mica surface exposed to stearic acid vapors. [•] Monolayer structures are always defective keeping the surface hydrophilic. [•] Multilayer coatings form three-dimensional bilayer bulk-like structures. [•] Hydrophobic coatings are obtained only from a multilayer coverage. [Copyright &y& Elsevier]

Neurotransmitters are stored in synaptic vesicles, where they have been assumed to be in free solution. Here we report that in Torpedo synaptic vesicles, only 5% of the total acetylcholine (ACh) or ATP content is free, and that the rest is adsorbed to an intravesicular proteoglycan matrix. This matrix, which controls ACh and ATP release by an ion-exchange mechanism, behaves like a smart gel. That is, it releases neurotransmitter and changes its volume when challenged with small ionic concentration change. Immunodetection analysis revealed that the synaptic vesicle proteoglycan SV2 is the core of the intravesicular matrix and is responsible for immobilization and release of ACh and ATP. We suggest that in the early steps of vesicle fusion, this internal matrix regulates the availability of free diffusible ACh and ATP, and thus serves to modulate the quantity of transmitter released. [ABSTRACT FROM AUTHOR]

[Display omitted] • Surface composition of BaTiO 3 thin films is analyzed by XPS upon atmosphere exposure. • Over time down polarized surfaces are more active for oxidation and more hydrophilic. • High energy component in Ba 3d 5/2 spectra is related to barium peroxide (BaO 2). • O 2 annealing of BaTiO 3 films fosters oxidation of Ba sites and production of BaO 2. • Chemically assisted polarization switching from up to down state is observed. Dissociation and adsorption of water on ferroelectric oxide surfaces play important role in the processes of screening and switching dynamics of ferroelectric polarization, as well as in catalytic processes which can be additionally coupled with light, temperature or vibration stimuli. In this work, we present XPS study of ferroelectric BaTiO 3 thin films and determine the entanglement between surface chemistry, polarization direction and stability, by observing changes upon time exposure to environmental conditions, heating in O 2 atmosphere and irradiation in vacuum. We devote special attention to Ba 3d spectral region and identify two different oxidation states of O atoms in the compounds of Ba. While this second specie was generally attributed to Ba in surface compounds where it has different oxygen coordination than in the bulk, based on the XPS results of oxygen annealed thin films, we demonstrate that this so far neglected component, corresponds to barium peroxide (BaO 2) and identify it as important active specie for the study of screening mechanisms closely related with catalytic activity present in this ferroelectric material. Finally, we report on chemically assisted polarization switching in thin films induced by heating in vacuum or exposure to X-Ray radiation due to the formation of positive surface electric field created by oxygen or electron vacancies, respectively. [ABSTRACT FROM AUTHOR]

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%. [ABSTRACT FROM AUTHOR]

The fabrication of the photoanode of the n-type CuWO4 nanorod arrays was successfully carried out through electrochemical deposition using anodic aluminum oxide (AAO) control templates and for the first time produced distinct gaps between the nanorod arrays. The effectiveness and efficiency of the resulting deposition was shown by the performance of the photoelectrochemical (PEC) procedure with a current density of 1.02 mA cm−2 with irradiation using standard AM 1.5G solar simulator and electron changed radiation of 0.72% with a bias potential of 0.71 V (vs. Ag/AgCl). The gap between each nanorod indicated an optimization of the electrolyte penetration on the interface, which resulted in the expansion of the current density as much as 0.5 × 1024 cm−3 with a flat band potential of 0.14 V vs. Ag/AgCl and also a peak quantum efficiency of wavelength 410 nm. Thus, also indicating the gaps between the nanorod arrays is a promising structure to optimize the performance of the PEC water splitting procedure as a sustainable energy source. [ABSTRACT FROM AUTHOR]