Céline Nayral

Surface Chemistry of InP Quantum Dots: A Comprehensive Study

Advanced (1)H, (13)C, and (31)P solution and solid-state NMR studies combined with IR spectroscopy were used to probe, at the molecular scale, the composition and the surface chemistry of indium phosphide (InP) quantum dots (QDs) prepared via a non-coordinating solvent strategy. This nanomaterial can be described as a core-multishell object: an InP core, with a zinc blende bulk structure, is surrounded first by a partially oxidized surface shell, which is itself surrounded by an organic coating. This organic passivating layer is composed, in the first coordination sphere, of tightly bound palmitate ligands which display two different bonding modes. A second coordination sphere includes an unexpected dialkyl ketone and residual long-chain non-coordinating solvents (ODE and its isomers) which interact through weak intermolecular bonds with the alkyl chains of the carboxylate ligands. We show that this ketone is formed during the synthesis process via a decarboxylative coupling route and provides oxidative conditions which are responsible for the oxidation of the InP core surface. This phenomenon has a significant impact on the photoluminescence properties of the as-synthesized QDs and probably accounts for the failure of further growth of the InP core.

Synthesis of tin and tin oxide nanoparticles of low size dispersity for application in gas sensing.

Nanocomposite core-shell particles that consist of a Sn0 core surrounded by a thin layer of tin oxides have been prepared by thermolysis of [(Sn(NMe2)2)2] in anisole that contains small, controlled amounts of water. The particles were characterized by means of electronic microscopies (TEM, HRTEM, SEM), X-ray diffraction (XRD) studies, photoelectron spectroscopy (XPS), and Mossbauer spectroscopy. The TEM micrographs show spherical nanoparticles, the size and size distribution of which depends on the initial experimental conditions of temperature, time, water concentration, and tin precursor concentration. Nanoparticles of 19 nm median size and displaying a narrow size distribution have been obtained with excellent yield in the optimized conditions. HRTEM, XPS, XRD and Mossbauer studies indicate the composite nature of the particles that consist of a well-crystallized tin beta core of approximately equals 11 nm covered with a layer of approximately equals 4 nm of amorphous tin dioxide and which also contain quadratic tin monoxide crystallites. The thermal oxidation of this nanocomposite yields well-crystallized nanoparticles of SnO2* without coalescence or size change. XRD patterns show that the powder consists of a mixture of two phases: the tetragonal cassiterite phase, which is the most abundant, and an orthorhombic phase. In agreement with the small SnO2 particle size, the relative intensity of the adsorbed dioxygen peak observed on the XPS spectrum is remarkable, when compared with that observed in the case of larger SnO2 particles. This is consistent with electrical conductivity measurements, which demonstrate that this material is highly sensitive to the presence of a reducing gas such as carbon monoxide.

Synthesis and characterization of monodisperse zinc and zinc oxide nanoparticles from the organometallic precursor [Zn(C6H11)2]

Abstract Decomposition of the organometallic precursor [Zn(C6H11)2] in wet anisole leads to the formation of monodisperse spherical Zn particles of 6 nm mean diameter. High resolution electron microscopy (HRTEM) indicates the crystalline nature of these particles and photoelectron studies (XPS) are consistent with the presence of both zinc and zinc oxide. In the presence of polyvinylpyrolidone (PVP), the decomposition leads to well dispersed nanoparticles for which HRTEM studies evidenced the presence of hexagonal zinc (0) surrounded by a thin layer of hexagonal zinc oxide of wurtzite type. The thermal oxidation of these zinc nanoparticles yields well-crystallized nanoparticles of ZnO without coalescence or size change. An X-ray diffraction pattern shows that the powder consists of pure hexagonal wurtzite-type phase.

InP/ZnS Nanocrystals: Coupling NMR and XPS for Fine Surface and Interface Description

Advanced (1)H, (13)C, and (31)P solution- and solid-state NMR studies combined with XPS were used to probe, at the molecular scale, the composition (of the core, the shell, and the interface) and the surface chemistry of InP/ZnS core/shell quantum dots prepared via a non-coordinating solvent strategy. The interface between the mismatched InP and ZnS phases is composed of an amorphous mixed oxide phase incorporating InPO(x) (with x = 3 and predominantly 4), In(2)O(3), and InO(y)(OH)(3-2y) (y = 0, 1). Thanks to the analysis of the underlying reaction mechanisms, we demonstrate that the oxidation of the upper part of the InP core is the consequence of oxidative conditions brought by decarboxylative coupling reactions (ketonization). These reactions occur during both the core preparation and the coating process, but according to different mechanisms.

Synthesis and use of a novel SnO2 nanomaterial for gas sensing

Abstract Decomposition of the organometallic precursor [Sn(NMe 2 ) 2 ] 2 in a controlled water/anisol mixture leads to the formation of monodisperse nanocomposite particles of Sn/SnO x . Full oxidation of the particles into SnO 2 occurs at 600°C without size or morphology change. These particles can be deposited onto silicon nitride covered microelectronic platforms and used as sensitive layers of gas sensors. Doping of the sensors with palladium can be achieved either by co-decomposition of organometallic precursors (doping in volume) or by deposition of palladium on preformed SnO 2 nanoparticles (doping in surface). The doped sensors display an unusually high sensitivity for CO sensing.

Low-temperature FIR and submillimetre mass absorption coefficient of interstellar silicate dust analogues

Context. Cold dust grains are responsible for the far-infrared and submillimetre (FIR/submm) emission observed by Herschel and Planck. Their thermal emission is usually expressed as a modified black body law in which the FIR/submm dust opacity, or mass absorption coefficient (MAC), is described by the MAC at a given wavelength κλ0 and the temperature- and wavelength-independent emissivity spectral index β. However, numerous data from previous space and balloon-borne missions and recently from Herschel and Planck show that the dust emission is not well understood, as revealed for example by the observed anti-correlation of β with the grain temperature. Aims. The aim of this work is to measure the optical properties of interstellar dust analogues at low temperatures to give astronomers the necessary data for interpreting FIR/submm observations such as those from the Herschel and Planck satellites. Methods. We synthesised, via sol-gel methods, analogues of interstellar amorphous silicate grains, rich in Mg and Ca, and having stoichiometry of olivine and pyroxene. The samples are characterised by various techniques to determine their composition, size, amorphisation degree. All the amorphous samples are annealed at 1100 ◦ C to study the crystallised materials for comparison. We measured the MAC of all the samples in the 2–25 μm range at room temperature and in the 100–1000/1500 μm range for grain temperatures varying from 300 to 10 K. Results. The experimental results show that, for all the amorphous samples, the grain MAC decreases when the grain temperature decreases and that the local spectral index, β, defined as the slope of the MAC curve, is anti-correlated with the grain temperature. These variations, which are not observed in the crystallised samples, are related to the amorphous nature of the samples. In addition, the spectral shape of the MAC is complex and cannot be described by a single spectral index over the 100–1500 μm range. At short wavelengths (λ ≤ 500/700 μm), β is in the range 1.6–2.1 for all grain temperature and grain composition. However, at longer wavelengths (λ ≥ 500/700 μm), β ≤ 2 for samples with a pyroxene stoichiometry and β ≥ 2 for samples with an olivine stoichiometry. Conclusions. The dust properties in the FIR/submm domain and at low temperature are more complicated than expected. The simplifying asymptotic expression based on a single temperature- and wavelength-independent spectral index used by astronomers is not appropriate to describe the dust MAC, hence the dust emission, and may induce significant errors on the derived parameters, such as the dust mass and the dust physical and chemical properties. Instead, dust emission models should use the dust MAC as a function of wavelength and temperature.

Influence of a transverse static magnetic field on the magnetic hyperthermia properties and high-frequency hysteresis loops of ferromagnetic FeCo nanoparticles

The influence of a transverse static magnetic field on the magnetic hyperthermia properties is studied on a system of large-losses ferromagnetic FeCo nanoparticles. The simultaneous measurement of the high-frequency hysteresis loops and of the temperature rise provides an interesting insight into the losses and heating mechanisms. A static magnetic field of only 40 mT is enough to cancel the heating properties of the nanoparticles, a result reproduced using numerical simulations of hysteresis loops. These results cast doubt on the possibility to perform someday magnetic hyperthermia inside a magnetic resonance imaging setup.

New generation of magnetic and luminescent nanoparticles for in vivo real-time imaging

A new generation of optimized contrast agents is emerging, based on metallic nanoparticles (NPs) and semiconductor nanocrystals for, respectively, magnetic resonance imaging (MRI) and near-infrared (NIR) fluorescent imaging techniques. Compared with established contrast agents, such as iron oxide NPs or organic dyes, these NPs benefit from several advantages: their magnetic and optical properties can be tuned through size, shape and composition engineering, their efficiency can exceed by several orders of magnitude that of contrast agents clinically used, their surface can be modified to incorporate specific targeting agents and antifolding polymers to increase blood circulation time and tumour recognition, and they can possibly be integrated in complex architecture to yield multi-modal imaging agents. In this review, we will report the materials of choice based on the understanding of the basic physics of NIR and MRI techniques and their corresponding syntheses as NPs. Surface engineering, water transfer and specific targeting will be highlighted prior to their first use for in vivo real-time imaging. Highly efficient NPs that are safer and target specific are likely to enter clinical application in a near future.

Silica nanoparticles grown and stabilized in organic nonalcoholic media.

This work features an alternative approach to the well-documented preparation of silica nanoparticles in protic media. We present here the one-pot synthesis of silica nanoparticles of adjustable size (between 18 and 174 nm), prepared and stabilized in organic nonalcoholic solvents. This novel route is based on hydrolysis and condensation of tetraethoxysilane, using water as reactant and different primary amines (butylamine, octylamine, dodecylamine, hexadecylamine) as catalysts in tetrahydrofuran or dimethoxyethane. The growth rate can be finely adjusted, and the first stages of the formation are observed by transmission electronic microscopy, revealing a silicated network in which the silica particles are formed and then released in solution. The amine plays not only a catalyst role but is also implied, as well as the solvent, in the stabilization process and the size control of the particles. A detailed NMR study demonstrates a core-shell structure in which the silica core is surrounded by a layer of alkylammonium ions together with solvent.

Organometallic approach for platinum and palladium doping of tin and tin oxide nanoparticles: structural characterisation and gas sensor investigations

Platinum and palladium surface doped tin nanoparticles have been obtained by decomposition of [Pt2(dba)3] and [Pd(dba)2] organometallic precursors, respectively, in a colloidal suspension of tin/tin oxide core–shell nanoparticles of uniform size (≈13 nm), in anisole under 1 bar of carbon monoxide at room temperature. The particles can be isolated as pure solids and present effective doping ratios [Pt]/[Sn] and [Pd]/[Sn] of 2.5 and 3.1%, respectively. These nanomaterials have been characterized by means of transmission electron and high-resolution transmission electron microscopies (TEM and HRTEM), Energy Dispersive X-ray spectroscopy (EDX), photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (EXAFS and XANES). The TEM micrographs show spherical nanoparticles whose size and size distribution are essentially similar to those of the initial Sn/SnOx material. HRTEM, EDX, XPS and X-ray absorption spectroscopy (XAS) studies at the Pd and/or Sn-K edge show the conservation of the composite nature of the particles that consist of a tin(0) core covered with a layer of tin oxides on which the doping element is deposited under the form of crystalline metallic platelets of size near 2 nm. The thermal oxidation of these Pt- or Pd-doped tin materials yields nanoparticles of crystallized SnO2 covered with crystallites of Pt or Pd oxides, as demonstrated by XRD, XPS and XAS experiments, without coalescence or size change. In the oxidised Pd-doped material, EXAFS analysis combined with HRTEM, point towards the formation of two main Pd disordered oxide phases: a rather pure oxopalladate Pd3.5O4-type phase at the surface of the particle and a mixed Pd/Sn phase having a PdO structure-type at the interface Pd oxide/Sn oxide. The thermal oxidation process can be easily achieved onto the silicon platform of a micro-machined device after integration of the Pt- or Pd-doped Sn/SnOx colloidal suspension by drop deposition. The first electrical measurements indicate remarkable behaviours of the as-obtained microsensors when exposed to traces of carbon monoxide. In addition to the expected large increase of sensitivity of the doped relatively to the undoped sensitive layer measured in humid atmosphere, a surprising and unprecedented inversion of sensitivity from undoped to Pt- and Pd-doped sensors has been observed in dry atmosphere.