Ca2MnO3X (X = Cl, Br) Oxyhalides with 1-Dimensional Ferromagnetic Chains of Square-Planar S = 2 Mn3.

Mixed anion oxyhalides with the formula Ca2MnO3X (X = Cl, Br) are synthesized using solid-state reaction methods. These two materials crystallize in a novel structure type due to the small ionic radius of Ca and the strong Jahn-Teller effect of Mn3+. The resulting structure (space group Cmcm) contains one-dimensional chains of MnO4 square planes, with an angle of ∼120° between neighboring planes. At low temperatures, the two materials adopt magnetic arrangements, with ferromagnetic chains coupled antiferromagnetically. On applying a magnetic field, both materials experience spin-flop transitions.

In Situ Transmission Electron Microscopy Analysis of Copper-Germanium Nanowire Solid-State Reaction.

A promising approach of making high quality contacts on semiconductors is a silicidation (for silicon) or germanidation (for germanium) annealing process, where the metal enters the semiconductor and creates a low resistance intermetallic phase. In a nanowire, this process allows one to fabricate axial heterostructures with dimensions depending only on the control and understanding of the thermally induced solid-state reaction. In this work, we present the first observation of both germanium and copper diffusion in opposite directions during the solid-state reaction of Cu contacts on Ge nanowires using in situ Joule heating in a transmission electron microscope. The in situ observations allow us to follow the reaction in real time with nanometer spatial resolution. We follow the advancement of the reaction interface over time, which gives precious information on the kinetics of this reaction. We combine the kinetic study with ex situ characterization using model-based energy dispersive X-ray spectroscopy (EDX) indicating that both Ge and Cu diffuse at the surface of the created Cu3Ge segment and the reaction rate is limited by Ge surface diffusion at temperatures between 360 and 600 °C. During the reaction, germanide crystals typically protrude from the reacted NW part. However, their formation can be avoided using a shell around the initial Ge NW. Ha direct Joule heating experiments show slower reaction speeds indicating that the reaction can be initiated at lower temperatures. Moreover, they allow combining electrical measurements and heating in a single contacting scheme, rendering the Cu-Ge NW system promising for applications where very abrupt contacts and a perfectly controlled size of the semiconducting region is required. Clearly, in situ TEM is a powerful technique to better understand the reaction kinetics and mechanism of metal-semiconductor phase formation.

Microwave Synthesis and Up-Conversion Properties of SHG-Active α-(La, Er)(IO3)3 Nanocrystals.

Pure α-La(IO3)3 and α-La0.85Er0.15(IO3)3 nanocrystals were synthesized by a microwave-assisted hydrothermal method leading to a reaction yield of 87 ± 4%. Electron microscopy and dynamic light scattering characterizations provide evidence for the formation of nanocrystals with an average size of 45 ± 10 nm for α-La(IO3)3 and 55 ± 10 nm for α-La0.85Er0.15(IO3)3. When dispersed in ethylene glycol, the nanocrystal suspensions exhibit second-harmonic generation under near-infrared excitations at 800 and 980 nm whereas additional photoluminescence by up-conversion is simultaneously observed in the case of α-La0.85Er0.15(IO3)3 nanocrystals. Quantitative assessments of the second-harmonic generation efficiency from second-harmonic scattering experiments at 1064 nm result in relatively high ⟨ d⟩ coefficients measured at 8.2 ± 2.0 and 8.0 ± 2.0 pm V-1 for α-La(IO3)3 and α-La0.85Er0.15(IO3)3, respectively. The relative intensity between second-harmonic generation and photoluminescence is discussed following the excitation wavelength.

Dynamic light scattering unveils stochastic degradation in large-pore mesoporous silica nanoparticles.

Mesoporous Silica Nanoparticles (MSNs) have been increasingly investigated as versatile drug delivery carriers. A particular challenge for the systemic use of MSNs lies in the control of their degradation, which has not been fully understood until now. We implemented standard dynamic light scattering (DLS) experiments and introduced a novel DLS technique in a confocal volume to track the dynamics of large-pore MSN degradation in situ. This unique DLS technique, which involves a small observation volume, was chosen for its ability to count particle by particle during the degradation process, a method that has not been commonly used in nanoparticle research. The experiments were performed in different media compositions at low particle concentrations, below the silica solubility limit. MSNs with large conical pores were prepared and studied as they offer the possibility to incorporate and release large-sized biomolecules. Large-pore MSNs followed a singular degradation mechanism following a stochastic-like behavior, a finding that challenges the common idea that all nanoparticles (NPs) degrade similarly and homogeneously over time. We showed that some NPs are observed intact over a prolonged period while most other NPs have already vanished or been transformed into swollen NPs. Thus, a heterogeneous degradation process occurs, while the total concentration of NPs undergoes an exponential decay. These large conical pores MSNs will be utilized as reliable biomolecule nanocarriers by predicting the factors underlying the NP hydrolytic stability.

Hybrid CdSe/ZnS Quantum Dot-Gold Nanoparticle Composites Assembled by Click Chemistry: Toward Affordable and Efficient Redox Photocatalysts Working with Visible Light.

A new modular, easy-to-synthesize photocatalyst was prepared by assembling colloidal CdSe/ZnS quantum dots (QD) and gold nanoparticles (AuNP) via their ligands thanks to copper-catalyzed azide to alkyne cycloaddition (CuAAC) click chemistry. The resulting composite (QD-AuNP) photocatalyst was tested with a benchmark photoredox system previously reported by our group, for which QD alone acted as a photocatalyst but with a modest quantum yield (QY = 0.06%) and turnover number (TON = 350 in 3 h) due to poor charge separation. After optimization, the QD-AuNP composites exhibited much improved photocatalytic performances: up to five times higher TON (2600 in 3 h) and up to 24 times faster reaction in the first 10 min of visible irradiation. Such an improvement is attributed to an efficient electron transfer from QD to AuNP in the photoexcited QD-AuNP composites, which ensures a much better charge separation than that in QD alone. This was confirmed by studying both (i) the quenching of the QD photoluminescence during the synthesis of the QD-AuNP composites and (ii) the blue shift of the AuNP plasmon absorption band due to the accumulation of up to 7400 electrons per AuNP in QD-AuNP composites under visible light irradiation in the presence of electron donors.

Three different Ge environments in a new Sr5CuGe9O24 phase synthesized at high pressure and high temperature.

In the framework of expanding the range of copper-based compounds in the pyroxene family, we have synthesized at high pressure and high temperature a powder containing a mixture of a new phase with stoichiometry Sr5CuGe9O24 having two identified impurity phases. Electron crystallography showed that the new phase crystallizes in the monoclinic space group P2/c, with unit-cell parameters a = 11.8 Å, b = 8.1 Å, c = 10.3 Šand ß = 101.3°. We applied the recently developed low-dose electron diffraction tomography method to solve the structure by direct methods. The obtained structure model contains all 9 independent cation positions and all 13 oxygen positions. A subsequent refinement against powder X-ray diffraction data ascertained the high quality of the structure solution, in particular, the unusual structural arrangement that there are three different environments for Ge in this phase.

Structure determination of La18W10O57.

We report the synthesis, structure determination, and structure analysis of La(18)W(10)O(57), which presents 52.65 WO(3) mol % in the binary system La(2)O(3)-WO(3) in place of the previous reported compound: La(14)W(8)O(45), 53.3 WO(3) mol %. The structure has been determined from synchrotron and laboratory X-ray, neutron, and electron diffraction data. This tungstate crystallizes in the non-centrosymmetric hexagonal space group (no. 190) P62c, with Z = 2, a = 9.0448(1) A, c = 32.6846(3) A, and a measured density of 7.28(3) g x cm(-3). The structure consists of [WO(6)] octahedra, isolated or sometimes sharing a face, and unusual tungsten [WO(6)] trigonal prisms. This compound presents a subcell c' = c/6 = 5.45 A. Polytypism has been observed concerning this compound. Transmission electronic microscopy, ionic conductivity, and thermal expansion have been explored.

Low-dose electron diffraction tomography (LD-EDT).

A new electron diffraction tomography method is presented that is aimed to enable high performance electron crystallography experiments on beam sensitive materials using a standard TEM without any special equipment. Low-dose electron diffraction tomography minimizes the electron dose necessary for obtaining data sets suitable for structure solution by irradiating the crystal exclusively during the acquisition of the diffraction patterns. The performance of the method is successfully tested on two model structures, a complex oxide Sr5CuGe9O24 and the beam sensitive metal-organic framework (MOF) of manganese formiate. Even when the limited lifetime of a beam sensitive material only allows obtaining a data set of rather low completeness, the data quality is high enough for the structures to be solved to a high precision. Low-dose electron diffraction tomography is easy to implement and doesn't require any special equipment or lengthy calibration processes, making it accessible to a large number of scientists.

A new solvothermal method for the synthesis of size-controlled YAG:Ce single-nanocrystals.

Ce3+-doped Y3Al5O12 (YAG:Ce) nanocrystals were synthesized by a unique solvothermal method, under sub-critical conditions. A home-made autoclave was used, operating in a larger pressure and temperature range than that with conventional commercial equipment and allowing direct in situ photoluminescence (PL) and X-ray absorption characterizations. The study of various synthesis conditions (pressure, temperature, precursor concentration, reaction time) allowed the best reaction conditions to be pinpointed to control YAG:Ce nanocrystal size, as well as crystal quality, and to get efficient optical properties. Without any post thermal treatment, we succeeded in obtaining well-crystallized YAG:Ce nanocrystals (30-200 nm), displaying typical PL properties of YAG:Ce with a maximal emission at 550 nm. The pristine 100 nm-sized YAG:Ce nanoparticles present an internal quantum yield of about 40 ± 5%. In situ X-ray absorption near edge spectroscopy demonstrates the presence of Ce4+ in nanocrystals elaborated at high temperature, resulting from the oxidation of Ce3+ during the crystallization process.

Topological metastability and oxide ionic conduction in La(2)-(x)Eu(x)Mo(2)O(9).

The effect of partial substitution, up to x = 0.4, of La by trivalent Eu on the phase stability, thermal expansion, and transport properties of La2Mo2O9 are investigated using temperature-controlled X-ray powder diffraction, differential thermal analysis, and complex impedance spectroscopy. At low europium content (x < or = 0.1), the alpha-beta phase transition is observed at a temperature dependent on the sample shaping (powder, pellet, etc.). At high europium content (x > or = 0.25), the samples remain cubic (beta phase), regardless of the shaping. In the intermediate range of europium content (x = 0.15, 0.2), the phase stability is highly sensitive to the thermal history and the sample shaping, with a double-reversed beta-alpha-beta transition suppressed by the shaping/sintering process. The influence of the amount of europium on the transport mechanisms and parameters is studied in both low- (Arrhenius) and high-temperature (Vogel-Tammann-Fulcher = VTF) regimes. If the effect of substitution is rather mild and monotonous within each transport regime and crystallographic phase, an abrupt change in the Arrhenius parameters between the alpha- and beta-type phases is observed.