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.

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.

Aims. We propose a new description of astronomical dust emission in the spectral region from the far-infrared to millimeter wavelengths. Methods. Unlike previous classical models, this description explicitly incorporates the effect of the disordered internal structure of amorphous dust grains. Our model is based on results from solid state physics used to interpret laboratory data. The model takes into account the effect of absorption by disordered charge distribution, as well as the effect of absorption by localized two level systems. Results. We review constraints on the various free parameters of the model from theory and laboratory experimental data. We show that, for realistic values of the free parameters, the shape of the emission spectrum will exhibit very broad structures whose shape will change in a non trivial way with the temperature of dust grains. The spectral shape also depends upon the parameters describing the internal structure of the grains. This opens new perspectives for identifying the nature of astronomical dust from the observed shape of the FIR/mm emission spectrum. A companion paper will provide an explicit comparison of the model with astronomical data.

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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 κ λ 0 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.

Indium phosphide colloidal quantum dots (QDs) are emerging as an efficient cadmium-free alternative for optoelectronic applications. Recently, syntheses based on easy-to-implement aminophosphine precursors have been developed. We show by solid-state nuclear magnetic resonance spectroscopy that this new approach allows oxide-free indium phosphide core or core/shell quantum dots to be made. Importantly, the oxide-free core/shell interface does not help in achieving higher luminescence efficiencies. We demonstrate that in the case of InP/ZnS and InP/ZnSe QDs, a more pronounced oxidation concurs with a higher photoluminescence efficiency. This study suggests that a II–VI shell on a III–V core generates an interface prone to defects. The most efficient InP/ZnS or InP/ZnSe QDs are therefore made with an oxide buffer layer between the core and the shell: it passivates these interface defects but also results in a somewhat broader emission line width.

30] Note the reversal of the hydrophilic±hydrophobic character of the two surface regions on going from operation 2 to operation 4 (Fig. 2).[31] a) [32] The role of atmospheric humidity in this tip-induced surface oxidation (by analogy with previously reported processes of scanning-probe anodization [26,33]) remains to be elucidated.[35] As suggested by the spectroscopic data and additional chemical derivatization experiments, NTS eo generated in this manner appears to be the enolate of a hydroxy carbonyl (ketone/aldehyde) species. Examples of some related enolic carbonyls may be found in a) S. ForsØn, M.

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.