Deformation Localization in Molecular Layers Constrained between Self-Assembled Au Nanoparticles.

The localized deformation of molecular monolayers constrained between the spherical surfaces of Au nanoparticles is studied by means of molecular dynamics simulations. Alkyl or polyethylene glycol long-chain molecules were homogeneously distributed over the curved Au surface, pushed against each other by repeated cycles of force relaxation and constant-volume equilibration at temperatures increasing from 50 to 300 K before being slowly quenched to near-zero temperature. Plots of minimum configurational energy can be obtained as a function of the nanoparticle distance, according to different directions of approach; therefore, such simulations describe a range of deformations, from perfectly uniaxial compression to a combination of compression and shear. Despite the relative rigidity of molecular backbones, the deformation is always found to be localized at the interface between the opposing molecular monolayers. We find that shorter ligands can be more densely packed on the surface but do no interdigitate upon compression; they respond to the applied force by bending and twisting, thus changing their conformation while remaining disjointed. On the contrary, longer ligands attain lower surface densities and can interprenetrate when the nanoparticles are compressed against each other; such molecules remain rather straight and benefit from the increased overlap to maximize the adhesion by dispersion forces. The apparent Young's and shear moduli of a dense nanostructure, composed of a triangular arrangement of identical MUDA-decorated Au nanoparticles, are found to be smaller than estimates indirectly deduced by atomic-force experiments but quite close to previous computer simulations of molecular monolayers on flat surfaces and of bulk nanoparticle assemblies.

Enhancing photocurrent transient spectroscopy by electromagnetic modeling.

The shape and duration of photocurrent transients generated by a photoconductive switch depend on both the intrinsic response of the active material and the geometry of the transmission line structure. The present electromagnetic model decouples both shape forming contributions. In contrast to previously published work, it accounts for the particular operating mode of transient spectroscopy. The objective is to increase the time resolution by two approaches, by optimizing structural response and by deconvolving it from experimental data. The switch structure is represented by an effective transimpedance onto which the active material acts as current generator. As proof of concept, the response of a standard microstrip switch is modeled and deconvolved from experimental data acquired in GaAs, yielding a single exponential material response and hence supporting the validity of the approach. Beyond compensating for the response deterioration by the structure, switch architectures can be a priori optimized with respect to frequency response. As an example, it is shown that a microstrip gap that can be deposited on materials incompatible with standard lithography reduces pulse broadening by an order of magnitude if it is provided with transitions to coplanar access lines.

Note: Quantitative (artifact-free) surface potential measurements using Kelvin force microscopy.

The measurement of local surface potentials by Kelvin force microscopy (KFM) can be sensitive to external perturbations which lead to artifacts such as strong dependences of experimental results (typically in a ∼1 V range) with KFM internal parameters (cantilever excitation frequency and/or the projection phase of the KFM feedback-loop). We analyze and demonstrate a correction of such effects on a KFM implementation in ambient air. Artifact-free KFM measurements, i.e., truly quantitative surface potential measurements, are obtained with a ∼30 mV accuracy.

Dynamic behavior of amplitude detection Kelvin force microscopy in ultrahigh vacuum.

The acquisition rate of all scanning probe imaging techniques with feedback control is limited by the dynamic response of the control loops. Performance criteria are the control loop bandwidth and the output signal noise power spectral density. Depending on the acceptable noise level, it may be necessary to reduce the sampling frequency below the bandwidth of the control loop. In this work, the frequency response of a vacuum Kelvin force microscope with amplitude detection (AM-KFM) using a digital signal processing (DSP) controller is characterized and optimized. Then, the main noise source and its impact on the output signal is identified. A discussion follows on how the system design can be optimized with respect to output noise. Furthermore, the interaction between Kelvin and distance control loop is studied, confirming the beneficial effect of KFM on topography artefact reduction in the frequency domain. The experimental procedure described here can be generalized to other systems and allows to locate the performance limitations.

Kelvin force microscopy at the second cantilever resonance: an out-of-vacuum crosstalk compensation setup.

We investigate the gap-voltage control loop in a Kelvin force microscopy setup with simultaneous non-contact topography imaging. The Kelvin controller electrostatically excites the second resonance of the cantilever at about 6.3 times the first resonance frequency and adjusts the DC component of the gap voltage to cancel the oscillation amplitude at this frequency, while the non-contact topography imaging is based on a frequency control loop that maintains a constant frequency of the mechanically excited first resonance of the cantilever by adjusting the tip-sample separation. Due to the self-excitation of the first resonance in our setup, it has to be considered that the electrostatic excitation at the second resonance frequency is applied to a closed feedback loop and cannot be considered as a simple superposition to the oscillation at the first resonance frequency. In particular, special care has to be taken about internal capacitive crosstalk between the tip bias and the cantilever deflection output signal. It is shown that such a coupling cannot be corrected by subtraction of a constant offset at the demodulator output since the crosstalk is sent into the self-excitation loop and is multiplied by the closed loop transfer function. We present a circuit that actively compensates, outside the vacuum environment, the internal crosstalk by adding to the deflection output a dephased fraction of the electrostatic excitation signal.

Probing nanoscale dipole-dipole interactions by electric force microscopy.

We address the issue of dipole-dipole interaction measurements at the nanometer scale. Electric dipoles with tunable effective momentum in the range 10(3)-10(4) D are generated by charge injection in single silicon nanoparticles on a conductive substrate and probed by a spectroscopic electric force microscopy analysis. Weak dipole-dipole force gradients are measured and identified from their quadratic momentum dependence. The results suggest that dipolar interactions associated with atomic-scale charge displacements or molecules can be probed by noncontact atomic force microscopy.

Near-field optics on silicon-electrolyte junctions.

A technique allowing near-field photocurrent (PC) mapping of silicon surfaces in contact with an electrolyte is presented. The illumination source is an optical fibre tip with a 100-nm aperture. A shear force detection system controls the tip-sample distance while scanning the tip across the silicon-electrolyte interface. Topographic and PC images on SiO2/Si mesas both show 300 nm resolution. It is shown that this PC contrast is induced by the tip-topography interaction and hence the PC resolution is limited by the resolution of the topography. Indeed, PC mapping on topography-less patterned porous-silicon/silicon samples shows that the lateral resolution is only limited by the aperture size which is of the order of 100 nm.