Local Symmetry Deviation from the Average Structure of MnAs Revealed by Pair Distribution Function.

MnAs is an interesting material due to its magnetocaloric properties, which can be utilized in magnetic refrigeration. However, despite major efforts, its magnetic refrigeration performances in the substituted forms could not be improved compared to the parent MnAs phase. Both small and big box modeling of the pair distribution function of MnAs for the local structure description and powder X-ray diffraction for the average structure reveal an inherent local orthorhombic distortion in the hexagonal structure of MnAs. As a result of this distortion, any modification to the hexagonal structure results in an orthorhombic structure and a weaker magnetocaloric performance. This study highlights the importance of studying local distortion in magnetic materials. This is achieved by combining X-ray absorption spectroscopy with total scattering X-ray diffraction.

X-ray and Neutron Diffraction Studies of SrTe2FeO6Cl, an Oxide Chloride with Rare Anion Ordering.

The oxychloride SrTe2FeO6Cl is obtained by high-temperature solid-state synthesis under inert conditions in closed reaction vessels. The compound crystallizes in a novel monoclinic crystal structure that is described in the space group P121/n1 (No. 14). The unit cell parameters, a = 10.2604(1) Å, b = 5.34556(5) Å, c = 26.6851(3) Å, and ß = 93.6853(4)°, and atomic parameters were determined from synchrotron diffraction data, starting from a model that was obtained from single-crystal X-ray diffraction data. The anion lattice exhibits a rare ordering of oxide and chloride ions: one-dimensional zig-zag ladders of chlorine (squarelike motif) are surrounded by an oxygen matrix. Two different iron sites coordinated solely to oxygen are present in the structure, one octahedral and one square pyramidal, both distorted. Similarly, two different strontium coordinations are present; the first homoleptic coordinated to eight oxygen atoms and the second heteroleptic coordinated to four oxygen and four chlorine atoms in a fac-like manner. The lone pair of Te(IV) is directed toward the larger chlorine atoms. Magnetic susceptibility measurements confirm that Fe is +3 (d5) in the high-spin electronic configuration, exhibiting an almost ideal spin-only moment, µeff = 5.65 µB Fe-1. The slightly negative Weiss constant (θCW = -39 K) suggests dominating antiparallel spin-to-spin coupling in the paramagnetic temperature range, agreeing with an observed long-range antiferromagnetic spin ordering below Néel temperature, TN ∼ 13 K, and a broad second order-like anomaly in the specific heat measurement data. Low-temperature neutron diffraction data reveal that the antiferromagnetic ordered phase is C-type, with a k-vector (1/2, 1/2, 0) and ordered moment of 4.14(7) µB. The spin structure can be described as antiferromagnetic ordered layers stacked along the a-axis, forming layers of squares that alternate along the c-axis.

Electrical response from nanocomposite PDMS-Ag NPs generated by in situ laser ablation in solution.

Laser ablation technique is employed in order to generate polydimethylsiloxane (PDMS)/Ag NPs in situ, starting from a silver target in a solution of PDMS prepolymer and toluene. The produced surfactant-free nanoparticles are characterized by high resolution transmission electron microscopy (HRTEM) and scanning TEM-high angle annular dark field (STEM-HAADF) imaging modes, showing the majority of them to be of the order of 4 nm in diameter with a small percentage of larger Ag-AgCl multidomain NPs, embedded into a PDMS matrix. Low concentrations of carbon onion-like nanoparticles or larger fibers are also formed in the toluene-PDMS prepolymer solution. In accordance with this, UV-vis spectra shows no peak from silver NPs; their small size and their coverage by the PDMS matrix suppresses the signal of surface plasmon absorption. Inductively coupled plasma measurements reveal that the concentration of silver in the polymer is characteristically low, ~0.001% by weight. The electrical properties of the PDMS nanocomposite films are modified, with current versus voltage (I-V) measurements showing a low current of up to a few tenths of a pA at 5 V. The surface resistivity of the films is found to be up to ~10(10) Ω/sq. Under pressure (e.g. stress) applied by a dynamic mechanical analyzer (DMA), the I-V measurements demonstrate the current decreasing during the elastic deformation, and increasing during the plastic deformation.

Improved photovoltaic performances by post-deposition acidic treatments on tetrapod shaped colloidal nanocrystal solids.

The ligand exchange reaction with pyridine is the standard procedure for the integration of colloidal semiconductor nanocrystals (NCs) in photovoltaic devices; however, for large sized and irregularly shaped branched NCs, such as CdSe@CdTe tetrapods, this procedure can lead to a considerable waste of materials and the aggregation of NCs in the colloidal solution, therefore resulting in the formation of an inhomogeneous film and low device performances. Here, we report on alternative post-deposition treatments with carboxylic acids on films of CdSe@CdTe tetrapod shaped NCs. This approach guarantees the removal of the insulating surfactant, necessary to obtain good charge transport among NCs, while preserving the film integrity. We perform a complete characterization of the nanocrystalline films treated with different carboxylic acids and demonstrate the successful integration of such films in photovoltaic devices, showing a doubled efficiency with respect to the standard ligand exchange procedure. Our approach represents a general route towards the development of NC based devices with improved performances and minimized waste of material.

Single electron tunneling in large scale nanojunction arrays with bisferrocene-nanoparticle hybrids.

We report on the fabrication and single electron tunneling behaviour of large scale arrays of nanogap electrodes bridged by bisferrocene-gold nanoparticle hybrids (BFc-AuNP). Coulomb staircase was observed in the low temperature current-voltage curves measured on the junctions with asymmetric tunnel barriers. On the other hand, junctions with symmetric tunneling barrier exhibited mere nonlinear current voltage characteristics without discrete staircase. The experimental results agreed well with simulations based on the orthodox theory. The junction resistance showed thermally activated conduction behaviour at higher temperature. The overall voltage and temperature dependent results show that the transport behaviour of the large arrays of single particle devices obtained by a facile optical lithography and chemical etching process corresponds with the behaviour of single particle devices fabricated by other techniques like e-beam lithography and mechanical breaking methods.

Toward Quantum-dot Cellular Automata units: thiolated-carbazole linked bisferrocenes.

Quantum-dot Cellular Automata (QCA) exploit quantum confinement, tunneling and electrostatic interaction for transistorless digital computing. Implementation at the molecular scale requires carefully tailored units which must obey several structural and functional constraints, ranging from the capability to confine charge efficiently on different 'quantum-dot centers'-in order to sharply encode the Boolean states-up to the possibility of having their state blanked out upon application of an external signal. In addition, the molecular units must preserve their geometry in the solid state, to interact electrostatically in a controlled way. Here, we present a novel class of organometallic molecules, 6-3,6-bis(1-ethylferrocen)-9H-carbazol-9-yl-6-hexan-1-thiols, which are engineered to satisfy all such crucial requirements at once, as confirmed by electrochemistry and scanning tunneling microscopy measurements, and first principles density functional calculations.