Photovoltaic and photothermal effects induced by visible laser radiation in atomic force microscopy probes.

Excitation of electrons into higher energy states in solid state materials can be induced by absorption of visible light, a physical process generally studied by optical absorption spectroscopy. A promising approach for improving the spatial resolution of optical absorption spectroscopy beyond the diffraction limit is the detection of photoinduced forces by an atomic force microscope operating under wavelength-dependent light irradiation. Here, we report on a combined photovoltaic/photothermal effect induced by the absorption of visible light by the microscope probes. By monitoring the photoinduced modifications of the oscillation of the probes, it is found that the oscillation phase-voltage parabolic signals display specific fingerprints which depend on light intensity and the nature of the materials composing the probes. In particular, a localized surface photovoltage (SPV) is evidenced at the tip apex of uncoated Si probes, while none is observed on Au-coated Si probes. The photothermal effects are distinguished from photovoltaic effects by specific shifts of the phase-voltage parabolas. The findings are relevant for the whole range of atomic force microscopy techniques making use of visible light as an additional means of local optical characterization.

Magnetic force fields of isolated small nanoparticle clusters.

The usage of magnetic nanoparticles (NPs) in applications necessitates a precise mastering of their properties at the single nanoparticle level. There has been a lot of progress in the understanding of the magnetic properties of NPs, but incomparably less when interparticle interactions govern the overall magnetic response. Here, we present a quantitative investigation of magnetic fields generated by small clusters of NPs assembled on a dielectric non-magnetic surface. Structures ranging from individual NPs to fifth-fold particulate clusters are investigated in their magnetization saturation state by magnetic force microscopy and numerical calculations. It is found that the magnetic stray field does not increase proportionally with the number of NPs in the cluster. Both measured and calculated magnetic force fields underline the great importance of the exact spatial arrangement of NPs, shedding light on the magnetic force field distribution of particulate clusters, which is relevant for the quantitative evaluation of their magnetization and perceptibly for many applications.

Photonic Excitation of a Micromechanical Cantilever in Electrostatic Fields.

We present a specific near-field configuration where an electrostatic force gradient is found to strongly enhance the optomechanical driving of an atomic force microscope cantilever sensor. It is shown that incident photons generate a photothermal effect that couples with electrostatic fields even at tip-surface separations as large as several wavelengths, dominating the cantilever dynamics. The effect is the result of resonant phenomena where the photothermal-induced parametric driving acts conjointly (or against, depending on electric field direction) with a photovoltage generation in the cantilever. The results are achieved experimentally in an atomic force microscope operating in vacuum and explained theoretically through numerical simulations of the equation of motion of the cantilever. Intrinsic electrostatic effects arising from the electronic work-function difference of tip and surface are also highlighted. The findings are readily relevant for other optomicromechanical systems where electrostatic force gradients can be implemented.

High-resolution manipulation of gold nanorods with an atomic force microscope.

The controlled manipulation and precise positioning of nanoparticles on surfaces is a critical requisite for studying interparticle interactions in various research fields including spintronics, plasmonics, and nanomagnetism. We present here a method where an atomic force microscope operating in vacuum is used to accurately rotate and displace CTAB-coated gold nanorods on silica surfaces. The method relies on operating an AFM in a bimodal way which includes both dynamic and contact modes. Moreover, the phase of the oscillating probe is used to monitor the nanoparticle trajectory, which amplitude variations are employed to evaluate the energy dissipation during manipulation. The nanoscale displacement modes involve nanorod in-plane rotation and sliding, but no rolling events. The transitions between these displacement modes depend on the angle between the scan axis direction and the nanorod long axis. The findings reveal the importance of mean tip-substrate distance and of oscillation amplitude of the tip. The role of substrate surface and of CTAB molecular bi-layer at nanorod surface is also discussed.

Interface bonding in silicon oxide nanocontacts: interaction potentials and force measurements.

The interface bonding between two silicon-oxide nanoscale surfaces has been studied as a function of atomic nature and size of contacting asperities. The binding forces obtained using various interaction potentials are compared with experimental force curves measured in vacuum with an atomic force microscope. In the limit of small nanocontacts (typically <103 nm2) measured with sensitive probes the bonding is found to be influenced by thermal-induced fluctuations. Using interface interactions described by Morse, embedded atom model, or Lennard-Jones potential within reaction rate theory, we investigate three bonding types of covalent and van der Waals nature. The comparison of numerical and experimental results reveals that a Lennard-Jones-like potential originating from van der Waals interactions captures the binding characteristics of dry silicon oxide nanocontacts, and likely of other nanoscale materials adsorbed on silicon oxide surfaces. The analyses reveal the importance of the dispersive surface energy and of the effective contact area which is altered by stretching speeds. The mean unbinding force is found to decrease as the contact spends time in the attractive regime. This contact weakening is featured by a negative aging coefficient which broadens and shifts the thermal-induced force distribution at low stretching speeds.

Nanoscale adhesion and sliding on biased semiconductors.

We present experimental and theoretical results on controlling nanoscale sliding friction and adhesion by electric fields on model contacts realized by bringing a conductive atomic force microscope tip into contact with the surface of a silicon-oxide/silicon wafer. We find that applying a bias voltage on silicon (or on the conductive tip) enables a noticeable control of the sliding forces. Two electrostatic interactions are identified as being relevant for the friction variation as a function of applied voltage. The first is a short-range electrostatic interaction between opposite charges localized at oxide-silicon/silicon and tip/silicon-oxide interfaces. This attractive interaction results from the high capacity of the oxide-semiconductor interface to change its charge density in response to a bias voltage. Various regimes of charging resulting from silicon electronic bands' alignment and deformation are evidenced. We mainly focused here on the strong charge accumulation and inversion domains. The second longer-range electrostatic interaction is between the voltage-induced bulk and surface charges of both tip and sample. This interaction decreases very slowly with the distance between tip and silicon surface, i.e. oxide thickness, and can be attractive or repulsive depending on voltage polarity. Our results demonstrate the possibility of controlling nanoscale friction/adhesion in nanoscale contacts involving semiconductors. These results are relevant for the operation of nanoscale devices or for on-surface nanomanipulation of metallic nanoparticles. We model the experimental results by adding an electrostatic energy contribution to the tip-surface binding energy, which translates into an increase or decrease of the normal force and ultimately of the sliding friction.

Stochastic stick-slip nanoscale friction on oxide surfaces.

The force needed to move a nanometer-scale contact on various oxide surfaces has been studied using an atomic force microscope and theoretical modeling. Force-distance traces unveil a stick-slip movement with erratic slip events separated by several nanometers. A linear scaling of friction force with normal load along with low pull-off forces reveals dispersive adhesive interactions at the interface. We model our findings by considering a variable Lennard-Jones-like interaction potential, which accounts for slip-induced variation of the effective contact area. The model explains the formation and fluctuation of stick-slip phases and provides guidelines for predicting transitions from stick-slip to continuous sliding on oxide surfaces.

Puckering stick-slip friction induced by a sliding nanoscale contact.

An atomic force microscope reveals that the sliding of a nanotip on a graphite surface occurs through a nanoscale stick-slip mechanism. The angle between the sliding direction and a stiff crystallographic axis determines the periodicity of the slip events defining domains of various friction properties. The experimental data are interpreted using the reaction rate theory, with the energy barrier driven by a local deformation of the surface and a thermally activated relaxation.

Tilt-induced ferromagnetic ordering in anisotropic molecular monolayers.

It is shown that orientational ordering of anisotropic organic molecules with permanent magnetic dipoles in a tilted film should result in a macroscopic magnetisation in the plane of the film. The important requirement here is that the molecules are strongly biaxial, and the corresponding biaxial orientational order parameter in the tilted phase is sufficiently large. The molecules should also be characterised by a reduced symmetry of the magnetic core compared with existing "single molecular magnets". Possible symmetry groups of the molecular magnetic core, which allow for the existence of nonzero average magnetic moment, are discussed in detail. The tilt-induced ferromagnetic ordering of such molecules may be determined by nonmagnetic intermolecular interactions including, for example, quadrupole-quadrupole electrostatic interaction or dispersion interaction between molecules of particular symmetry. Magnetic intermolecular interactions are not important here, and as a result the induced ferromagnetic state may be stable in any temperature range where the corresponding tilted film is stable. These general conclusions, which form a theoretical foundation for the existence of novel fluid low-dimensional magnetic materials, are based on symmetry arguments and are supported by a simple mean-field molecular model. We also discuss how such induced ferromagnetic ordering may be observed in Langmuir-Blodgett films which seem to be the best candidates for preparing these magnetic materials.

Layering transitions and Schlieren textures in Langmuir films of two organic radicals.

Two paramagnetic radicals have been investigated in terms of their film-forming properties at the air-water interface. Although the radicals failed to display any mesomorphic behavior in the bulk, they were found prone to built-up multilayer films on the Langmuir trough. The molecules seem to dimerize in the upper layers of the films that exhibit striking Schlieren textures when observed with Brewster angle microscopy. These Schlieren textures, together with the ability to form multilayers, indicate that the molecules came close to displaying smectic mesomorphism. A tentative model of the layers' structure is proposed, and a suggestion for synthesizing new molecules with actual mesomorphism is offered. The presented results show that the study of the behavior of molecules at the air-water interface can shed a new light on their behavior in the bulk and help in the design of new magnetic mesogens.

Smectic ordering in liquid-crystal-aerosil dispersions. I. X-ray scattering.

Comprehensive x-ray scattering studies have characterized the smectic ordering of octylcyanobiphenyl (8CB) confined in the hydrogen-bonded silica gels formed by aerosil dispersions. For all densities of aerosil and all measurement temperatures, the correlations remain short range, demonstrating that the disorder imposed by the gels destroys the nematic (N) to smectic-A (SmA) transition. The smectic correlation function contains two distinct contributions. The first has a form identical to that describing the critical thermal fluctuations in pure 8CB near the N-SmA transition, and this term displays a temperature dependence at high temperatures similar to that of the pure liquid crystal. The second term, which is negligible at high temperatures but dominates at low temperatures, has a shape given by the thermal term squared and describes the static fluctuations due to random fields induced by confinement in the gel. The correlation lengths appearing in the thermal and disorder terms are the same and show a strong variation with gel density at low temperatures. The temperature dependence of the amplitude of the static fluctuations further suggests that nematic susceptibility becomes suppressed with increasing quenched disorder. The results overall are well described by a mapping of the liquid-crystal-aerosil system onto a three-dimensional XY model in a random field with disorder strength varying linearly with the aerosil density.

Hydrogen-bonded silica gels dispersed in a smectic liquid crystal: a random field XY system.

The effect on the nematic to smectic-A transition in octylcyanobiphenyl (8CB) due to dispersions of hydrogen-bonded silica (aerosil) particles is characterized with high-resolution x-ray scattering. The particles form weak gels in 8CB creating a quenched disorder that replaces the transition with the growth of short-range smectic correlations. The correlations include thermal critical fluctuations that dominate at high temperatures and a second contribution that quantitatively matches the static fluctuations of a random field system and becomes important at low temperatures.

Amphiphilic diblock dendrimers: synthesis and incorporation in Langmuir and Langmuir-Blodgett films.

A new dendron with peripheral long alkyl chains and containing five C(60) units in the branching shell has been prepared and attached to a Fréchet-type dendron functionalized with ethylene glycol chains. The peripheral substitution of the resulting globular dendrimer with hydrophobic chains on one hemisphere and hydrophilic groups on the other provides the perfect hydrophobic/hydrophilic balance allowing the formation of stable Langmuir films. Furthermore, a perfect reversibility has been observed in successive compression/decompression cycles. The diblock structure of the dendrimer has been also crucial for the efficient transfer of the Langmuir films in order to obtain well-ordered multilayered Langmuir-Blodgett films. This approach appears particularly interesting since functional groups not well adapted for the preparation of Langmuir and Langmuir-Blodgett films such as fullerenes can be attached into the branching shell of the dendritic structure and, thus, efficiently incorporated in thin ordered films.