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M P Pileni

Publications and source records attributed to M P Pileni.

At least 19 recordsLinked to original sources

Silver nanodisks: optical properties study using the discrete dipole approximation method.

The simulated optical properties of silver nanodisks are presented. The extinction, absorption, and scattering efficiencies are calculated using the discrete dipole approximation. The influence of the nanodisk size, truncature (snip), aspect ratio, and environment on the plasmon resonance bands is investigated. In particular, the dipolar and multipolar resonance peak positions have been related to the specific features of the nanodisk geometry. An interpretation of the origins of each multipolar mode is proposed for the first time taking into account this geometry.

Journal Article↗

Intrinsic vibrational coherence in face-centered cubic supra-crystals of silver nanocrystals: Raman scattering measurements.

The ordering of silver nanocrystals is tuned from amorphous aggregates to highly well-ordered, face-centered cubic supra-crystals, using various substrates and controlling their temperature to obtain this. Low-frequency Raman scattering, for the first time, demonstrates vibrational coherence in fcc supra-crystals of nanocrystals. This is shown by a narrowing of the peak corresponding to the quadrupolar modes of the nanocrystals. However, this is obtained when the supra-crystals are smaller than the excitation wavelength. When the supra-crystals are larger, the narrowing cannot be observed. Furthermore, for any size of the supra-crystals, a shift to low frequency of the Raman peak due to the Lorentz field effect is seen.

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Mesoscopic solid structures of 11-nm maghemite, gamma-Fe2O3, nanocrystals: experiment and theory.

Solid structures made of collapsed cylinders organized in hexagonal, stripes and wavy line-like structures are fabricated by slow evaporation of maghemite nanocrystals dispersed in hexane and subjected to an applied field perpendicular to the substrate. The sizes of the experimental structures are well described by a theory based on the minimization of the total free energy. Comparison between experiment and theory shows that the structures are explained by a labyrinthine instability enabled by a colloidal liquid-gas phase transition during the evaporation process. From the theoretical model and experimental data, it is concluded that the height determines the radius of the cylinders, whereas the phase ratio of the magnetic to the total volume and the field strength have little influence under the conditions studied here.

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Seven-nanometer hexagonal close packed cobalt nanocrystals for high-temperature magnetic applications through a novel annealing process.

Seven-nanometer cobalt nanocrystals are synthesized by colloidal chemistry. Gentle annealing induces a direct structural transition from a low crystalline state to the hexagonal close packed (hcp) phase without changing the size, size distribution, and the lauric acid passivating layer. The hcp structured nanocrystals can be easily redispersed in solvent for further application and processing. We found that the magnetization at saturation and the magnetic anisotropy are strongly modified through the annealing process. Monolayer self-assembly of the hcp cobalt nanocrystals is obtained, and due to the dipolar interaction, ferromagnetic behavior close to room temperature has been observed. This work demonstrates a novel approach for obtaining small size hcp structured cobalt magnetic nanocrystals for many technological applications.

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Optical properties of gold nanorods: DDA simulations supported by experiments.

Simulations of the absorption efficiency using the discrete dipole approximation (DDA) method and taking into account the real shape of gold nanorods are reported. A dominant surface plasma band corresponding to the longitudinal resonance is observed. Its maximum position lambda(max) shifts to the red as the aspect ratio increases. The transversal dipolar and multipolar mode wavelength positions are also discussed. These data are in good agreement with previous theoretical work based on classical electrostatic predictions and assuming that gold nanorods behave as ellipsoidal particles. From the experimental point of view, good agreement with the published data for gold nanorods is obtained.

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Vibrational coherence of self-organized silver nanocrystals in f.c.c. supra-crystals.

Fabrication of devices from inorganic nanocrystals normally requires that they are self-organized into ordered structures. It has now been demonstrated that nanocrystals are able to self-organize in a 'supra'-crystal with a face-centred cubic (f.c.c.) structure. The physical properties of nanocrystals self-organized into compact arrays are quite different from those of both isolated nanocrystals and the bulk phase. The collective optical and magnetic properties of these nanocrystal assemblies are governed mainly by dipolar interactions. Here, we show that nanocrystals vibrate coherently when they are self-organized in f.c.c. supra-crystals. Hence, a phase relation exists between the vibrations of all of the nanocrystals in a supra-crystal. This vibrational coherence can be observed by a substantial change of the quadrupolar low-frequency Raman scattering peak. Although a change in electronic transport properties has previously been observed on self-organization of silver nanocrystals, vibrational coherence represents the first intrinsic property of f.c.c. supra-crystals.

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Mesostructures of cobalt nanocrystals. 2. Mechanism.

Mesoscopic patterns of cobalt nanocrystals produced by applying a magnetic field perpendicular to the substrate during the deposition process are presented. These mesoscopic patterns markedly differ with the size distribution of the cobalt nanocrystals. Well-defined columns are produced when the size distribution of cobalt nanocrystals is low; conversely, the coalescence of columns with formations of labyrinths occurs for a large size distribution. A formation mechanism of these structures is proposed.

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Mesostructures of cobalt nanocrystals. 1. Experiment and theory.

Solid mesostructures made of cylinders are produced by the slow evaporation of cobalt nanocrystals dispersed in hexane and subjected to an applied field perpendicular to the substrate. Varying the initial nanocrystal concentration is found to be an efficient method for changing the pattern size. The experimental structures and the theoretical predictions based on the minimization of the total free energy are in good agreement. A comparison of experiment with theory allowed us to conclude that the mesostructures form as a result of a liquid-gas phase transition during the evaporation process. Within the theoretical model and the experimental data, it is concluded that the phase ratio of the magnetic to the total volume and the height of the cylinders govern the pattern geometry. In contrast, because of the saturation of the magnetization curve, the mesostructures are not influenced by the field strength.

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Silver nanodisks: size selection via centrifugation and optical properties.

Silver nanodisks, having two different sizes, and spherical particles are synthesized by soft chemistry. By using centrifugation, nanodisks are mainly selected. The experimental absorption spectra of these nanodisks with different sizes are compared to those simulated using the discrete dipole approximation method. For small nanodisk sizes, the nanodisk shape is neglected and the simulated spectra closest to the experiments are obtained by assuming a spheroidal particle. Conversely, for larger nanodisks, the precise geometries represented by snip and aspect ratio are needed for good agreement between experiments and simulations.

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Influence of short-range interactions on the mesoscopic organization of magnetic nanocrystals.

Magnetic fluids of 10-nm maghemite, gamma- Fe2 O3 , nanocrystals, subjected or not to an applied field parallel to the substrate, produce, after evaporation, mesoscopic structures. These differ markedly with the surface coating agent used to prevent particles from coalescence. Citrate ions and carboxylic acids with different chain lengths are employed as coating agents. The change in the mesoscopic structure is studied both experimentally and theoretically. The mesoscopic structures obtained by Brownian dynamics simulations are in good agreement with the experimental observations. In particular, the appearance of chainlike organizations in spite of the particles being weakly dipolar is explained by an interplay of van der Waals and magnetic dipolar interactions.

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Intrinsic behavior of face-centered-cubic supra-crystals of nanocrystals self-organized on mesoscopic scale.

We describe intrinsic behavior due to the high ordering of nanocrystals at the mesoscopic scale. The first example shows well-defined columns in the formation of cobalt nanocrystals when an applied magnetic field is applied during the evaporation process. Collective breathing properties between nanocrystals are demonstrated. In both cases, these features are observed when the nanocrystals are highly ordered in fcc supra-crystals.

Computer Simulation↗

Nonlinear theory of pattern formation in ferrofluid films at high field strengths.

When a magnetic field is applied to a thin layer of a suspension of magnetic nanoparticles (ferrofluid), the formation of labyrinthine and hexagonal patterns is observed. We introduce a theory to describe ferrofluid patterns at high field, where a nonlinear relationship between field and magnetization is expected. The computational difficulties due to the use of a nonlinear magnetization curve are solved by a reformulation of the magnetic energy equation. The evolution of the pattern size at intermediate and very high fields can be understood by an analysis of limiting cases of the magnetization curve. In particular, at a very high field the pattern size reaches a constant saturation value which has been recently confirmed by experiments. The field for the onset of a nonlinear behavior is shifted to higher field strength due to a demagnetization effect. This can partially explain the ability of linear approaches to reproduce experimental data even at a high field. Finally, the impact of the nonlinearity of the magnetization curve on the transition between hexagonal and labyrinthine patterns is discussed.

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Van der Waals versus dipolar forces controlling mesoscopic organizations of magnetic nanocrystals.

The structure, thermodynamics and dynamics in many physical and chemical systems are determined by interplay of short-range isotropic and long-range anisotropic forces. Magnetic nanoparticles dispersed in solution are ideal model systems to study this interplay, as they are subjected to both isotropic van der Waals and anisotropic dipolar forces. Here we show from experiment an abrupt transition of maghemite nanocrystal organization from chain-like to random structures when nanoparticle solutions are evaporated under a magnetic field. This is explained by brownian dynamics simulations in terms of a variation of the strength of van der Waals interactions with the particle contact distance, which is tuned by the length of the molecules coating the particles. The weak dipole-dipole interactions between the maghemite particles are usually not sufficient to result in the chain formation observed here. However, due to the van der Waals interactions, when the nanocrystal contact distance is short enough, clusters of nanocrystals are formed during the evaporation process. These clusters exhibit large dipole moments compared with a single particle, which explains the formation of chain-like structures. Conversely, when the nanocrystal contact distance is too long, no nanocrystal aggregation occurs, and a random distribution of maghemite nanocrystals is obtained.

Ferric Compounds↗

Self assemblies of nanocrystals: preparation, collective properties and uses.

Self-organization of nanocrystals depends on the type of nanomaterial and the coating. With silver nanocrystals, the self-organization is partially perturbed by the latter. With cobalt nanocrystals, the size distribution and thus the self-organization is controlled by the amount of reducing agent added during the chemical reaction and not by the micellar solution. It is possible to make "supra" crystals of cobalt nanoparticles in a face centered cubic (fcc) structure. By applying, during the evaporation process, an external magnetic field to ferrite nanocrystals dispersed in solution, nanocrystal organizations markedly change with their coating. Hence tubes are obtained with nanocrystals coated with citrate ions whereas thick films are produced when the coating is replaced by dodecanoic acid. Collective magnetic properties due to the organization in tubes are observed with a behavior similar to that observed with nanowires. The use of nanocrystals as a mask to produce various patterns on silicon is described.

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Towards efficient methods for the study of pattern formation in ferrofluid films.

Hexagonal and labyrinthine patterns appear in thin ferrofluid films after application of a magnetic field perpendicular to the film. The pattern size and the stability of the hexagonal and labyrinthine structures can be predicted by free energy approaches. Several approximations are used in the literature to accelerate the calculation of the magnetic energy. They are usually based on the use of a uniform, average or constant magnetization. In the uniform approximation the magnetization at all points in the pattern is assumed to be equal to its value at the center of the stripes or cylinders in the labyrinthine or hexagonal patterns. Recent papers indicate that this approximation gives qualitatively wrong results. This is corroborated here by a comparison with accurate results. When a volume- averaged magnetization is used during the calculation of the demagnetization field, from which the magnetic energy is evaluated, the theoretical results are only slightly modified with respect to the accurate results. Thus, we can propose a new method which gives results in good agreement with the accurate values and accelerates the calculations by a factor of 1000. The influence of the approximations is explained by a study of the evolution of the demagnetization field in the patterns. This study indicates that the volume-averaged approximation might only be reliable for patterns with a homogeneously distributed magnetic fluid. Another approximation of a constant magnetization, which is widely used in the literature, assumes that the magnetization does not change during the pattern formation in contrast to the uniform and average approximations. A different way of computing the constant magnetization than that usually employed markedly improves the agreement with the accurate results. This is explained by the derivation of a direct relationship between the approximations of a constant and an average magnetization.

Biophysics↗

Electron-phonon scattering in metal clusters.

Electron-lattice energy exchanges are investigated in gold and silver nanoparticles with sizes ranging from 30 to 2.2 nm embedded in different environments. Femtosecond pump-probe experiments performed in the low-perturbation regime demonstrate a strong increase of the intrinsic electron-phonon interaction for nanoparticles smaller than 10 nm due to a confinement effect.

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Theoretical study of the field-induced pattern formation in magnetic liquids.

When a thin layer of magnetic fluid confined with an immiscible nonmagnetic liquid is subjected to a perpendicular field, the formation of hexagonal and labyrinthine patterns is observed experimentally. To develop a coherent theoretical description of this phenomenon, the free energy functionals of both types of magnetic structures are derived. Both energy functionals have the same form, which explains that the theoretical results found in this paper for hexagonal and labyrinthlike striped patterns are analogous. The size of the patterns is determined by minimizing the free energy. The influence of the method for computing the magnetic energy on the theoretical results is studied. An accurate computation of the magnetic energy proves important in predicting the experimental pattern size as a function of external field and of layer height. How the results change, when a constant magnetization is assumed during the pattern formation is also investigated. The transition between hexagonal and striped structures is studied by a comparison of their free energies. The ratio of the magnetic to the nonmagnetic liquid is found to be an important factor for the relative stability of the patterns. In agreement with experiments, striped structures are observed at large phase ratios, whereas at small phase ratios hexagonal patterns predominate.

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Supra-aggregates.

Mixtures of oil (isooctane), water, and a double-chained ionic surfactant, Cu(AOT)2 [copper(II) bis(2-ethylhexyl)sulfosuccinate] form equilibrium phases consisting of spontaneous emulsions thermodynamically stable systems. The experimental conditions are such that the head polar group of the surfactant is totally hydrated. The emulsion droplets are comprised of supra aggregates, lamellar spherulites in which interior and exterior are bicontinuous microemulsions. The microstructures and component ratios can be predicted from elementary considerations that require only the notion of local and global packing constraints. The phenomenon of supra aggregation, microphases within any topologically closed container, in equilibrium with an external phase, appears quite general. The results throw some light on the meaning of 'phase' in mesostructured fluids.

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