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.

Control of the transition temperatures of metallomesogens by specific interface design: application to Mn12 single molecule magnets.

Reaction of the Single Molecule Magnet [Mn(12)O(12)(CH(3)CO(2))(16)(H(2)O)(4)] (Mn(12)) with mesogenic dendritic ligands Li (i = 4, 5) quantitatively yields functional clusters [Mn(12)O(12)(Li-H)(16)(H(2)O)(4)] (i = 4, 5) that self-organize into a thermotropic SmA-type liquid crystalline phase. The perturbation of the molecular interface by methylation of the terminal mesogenic cyanobiphenyl groups induces a significant decrease of the clearing temperature without affecting the magnetic properties and the supramolecular organization of the Mn(12)-based clusters.

Size-dependent properties of magnetic iron oxide nanocrystals.

The fine control of iron oxide nanocrystal sizes within the nanometre scale (diameters range from 2.5 to 14 nm) allows us to investigate accurately the size-dependence of their structural and magnetic properties. A study of the growth conditions of these nanocrystals obtained by thermal decomposition of an iron oleate precursor in high-boiling point solvents has been carried out. Both the type of solvent used and the ligand/precursor ratio have been systematically varied, and were found to be the key parameters to control the growth process. The lattice parameters of all the nanocrystals deduced from X-ray diffraction measurements are consistent with a structure of the type Fe3-xO4, i.e. intermediate between magnetite and maghemite, which evolves toward the maghemite structure for the smallest sizes (x=1/3). The evolution of the magnetic behavior with nanoparticle sizes emphasizes clearly the influence of the surface, especially on the saturation magnetization Ms and the magneto-crystalline anisotropy K. Dipolar interactions and thermal dependence have been also taken into account in the study on the nanoscale size-effect of magnetic properties.

Dendromesogens: liquid crystal organizations of poly(amidoamine) dendrimers versus starburst structures.

A new series of liquid crystalline poly(amidoamine) (PAMAM) dendrimers is described. These dendrimers are made by attaching to the 0-, 1-, 2-, 3-, and 4-generation of PAMAM-terminal promesogenic units that carry two decyloxy chains in the 3- and 4-positions of their peripheral aromatic ring. X-ray diffraction studies show that all the compounds display a hexagonal columnar mesophase. A high density of aliphatic chains imposes a curved interface with the promesogenic units that forces the molecules to adopt a radial conformation, and therefore, the columnar structure. A model for the supramolecular organization of the different generations within the columnar mesophase is proposed based on the variation of some of the structural parameters.