Peter Lemmens

Approaching the ground state of the Kagomé antiferromagnet

Y0.5Ca0.5BaCo4O7 contains kagomé layers of Co ions, whose spins are strongly coupled, with a Curie-Weiss temperature of -2200 K. At low temperature, T=1.2 K, our diffuse neutron scattering study with polarization analysis reveals characteristic spin correlations close to a predicted two-dimensional coplanar ground state with staggered chirality. The absence of three-dimensional long-range antiferromagnetic order indicates negligible coupling between the kagomé layers. The scattering intensities are consistent with high spin S=3/2 states of Co2+ in the kagomé layers and low spin S=0 states for Co3+ ions on interlayer sites. Our observations agree with previous Monte Carlo simulations indicating a ground state of effectively short range, staggered chiral spin order.

Effect of HF concentration on physical and electronic properties of electrochemically formed nanoporous silicon

The most common fabrication technique of porous silicon (PS) is electrochemical etching of a crystalline silicon wafer in a hydrofluoric (HF) acid-based solution. The electrochemical process allows for precise control of the properties of PS such as thickness of the porous layer, porosity, and average pore diameter. The effect ofHF concentration in the used electrolyte on physical and electronic properties of PS was studied by visual color observation, measuring nitrogen sorption isotherm, field emission type scanning electron microscopy, Raman spectroscopy, and photoluminescence spectroscopy. It was found that with decrease in HF concentration, the pore diameter increased. The PS sample with large pore diameter, that is, smaller nanocrystalline size of Si between the pores, was found to lead to a pronounced photoluminescence peak. The systematic rise of photoluminescence peak with increase of pore diameter and porosity of PS was attributed to quantum confinement. The changes in nanocrystalline porous silicon were also clearly observed by an asymmetric broadening and shift of the optical silicon phonons in Raman spectra. The change in electronic properties of PS with pore diameter suggests possibilities of use of PS material as a template for fundamental physics as well as an opticalmaterial for technological applications.

Microscopic evidence of spin state order and spin state phase separation in layered cobaltites RBaCo2O5.5 with R=Y, Tb, Dy, and Ho.

We report muon-spin relaxation measurements on the magnetic structures of RBaCo2O(5.5) with R=Y, Tb, Dy, and Ho. Three different phases, one ferrimagnetic and two antiferromagnetic, are identified below 300 K. They consist of different ordered spin state arrangements of high-, intermediate-, and low-spin Co3+ of CoO6 octahedra. Phase separation into well separated regions with different spin state order is observed in the antiferromagnetic phases. The unusual strongly anisotropic magnetoresistance and its onset at the FM-AFM phase boundary is explained.

Perovskites and thin films—crystallography and chemistry

We discuss the crystallographic and chemical basis of the perovskite family (ABX(3)) of oxides that are used in different thin film applications. Starting with the original structure we extend our scope to several modifications. Basic parameters like the ionic radii, the tolerance factor, the occupation of the oxygen sublattice and their effect on the structural parameters will be mentioned together with examples of relationships between structural and physical properties in the bulk and at interfaces.

Microwave-assisted synthesis of porous Mn2O3 nanoballs as bifunctional electrocatalyst for oxygen reduction and evolution reaction

Technological hurdles that still prevent the commercialization of fuel cell technologies necessitate designing low-cost, efficient and non-precious metals. These could serve as alternatives to high-cost Pt-based materials. Herein, a facile and effective microwave-assisted route has been developed to synthesize structurally uniform and electrochemically active pure and transition metal-doped manganese oxide nanoballs (Mn2O3 NBs) for fuel cell applications. The average diameter of pure and doped Mn2O3 NBs was found to be ~610 nm and ~650 nm, respectively, as estimated using transmission electron microscopy (TEM). The nanoparticles possess a good degree of crystallinity as evident from the lattice fringes in high-resolution transmission electron microscopy (HRTEM). The cubic crystal phase was ascertained using X-ray diffraction (XRD). The energy dispersive spectroscopic (EDS) elemental mapping confirms the formation of copper-doped Mn2O3 NBs. The experimental parameter using trioctylphosphine oxide (TOPO) as the chelating agent to control the nanostructure growth has been adequately addressed using scanning electron microscopy (SEM). The solid NBs were formed by the self-assembly of very small Mn2O3 nanoparticles as evident from the SEM image. Moreover, the concentration of TOPO was found to be the key factor whose subtle variation can effectively control the size of the as-prepared Mn2O3 NBs. The cyclic voltammetry and galvanostatic charge/discharge studies demonstrated enhanced electrochemical performance for copper-doped Mn2O3 NBs which is supported by a 5.2 times higher electrochemically active surface area (EASA) in comparison with pure Mn2O3 NBs. Electrochemical investigations indicate that both pure and copper-doped Mn2O3 NBs exhibit a bifunctional catalytic activity toward the four-electron electrochemical reduction as well the evolution of oxygen in alkaline media. Copper doping in Mn2O3 NBs revealed its pronounced impact on the electrocatalytic activity with a high current density for the electrochemical oxygen reduction and evolution reaction. The synthetic approach provides a general platform for fabricating well-defined porous metal oxide nanostructures with prospective applications as low-cost catalysts for alkaline fuel cells.

Enhanced Charge Separation and FRET at Heterojunctions between Semiconductor Nanoparticles and Conducting Polymer Nanofibers for Efficient Solar Light Harvesting

Energy harvesting from solar light employing nanostructured materials offer an economic way to resolve energy and environmental issues. We have developed an efficient light harvesting heterostructure based on poly(diphenylbutadiyne) (PDPB) nanofibers and ZnO nanoparticles (NPs) via a solution phase synthetic route. ZnO NPs (~20 nm) were homogeneously loaded onto the PDPB nanofibers as evident from several analytical and spectroscopic techniques. The photoinduced electron transfer from PDPB nanofibers to ZnO NPs has been confirmed by steady state and picosecond-resolved photoluminescence studies. The co-sensitization for multiple photon harvesting (with different energies) at the heterojunction has been achieved via a systematic extension of conjugation from monomeric to polymeric diphenyl butadiyne moiety in the proximity of the ZnO NPs. On the other hand, energy transfer from the surface defects of ZnO NPs (~5 nm) to PDPB nanofibers through Förster Resonance Energy Transfer (FRET) confirms the close proximity with molecular resolution. The manifestation of efficient charge separation has been realized with ~5 fold increase in photocatalytic degradation of organic pollutants in comparison to polymer nanofibers counterpart under visible light irradiation. Our results provide a novel approach for the development of nanoheterojunctions for efficient light harvesting which will be helpful in designing future solar devices.

Tuning the pore wall morphology of mesoporous silicon from branchy to smooth, tubular by chemical treatment

The effect of chemical treatment on physical and chemical properties, i.e., pore diameter, porosity, specific surface area, and chemical bonding of electrochemically formed mesoporous silicon were investigated by using of nitrogen sorption isotherm, scanning electron microscopy, and Fourier transform infrared spectroscopy. The adsorption isotherms measurements show the general behavior found for the porous materials, but at the same time, they exhibit clear differences following different chemical treatments of porous layer. It was clearly observed from Fourier transform infrared spectroscopy that the chemical environment of porous silicon wall changes significantly after chemical treatment. In scanning electron microscopy images, we see that the rough dendritic structure of the pore walls is modified to smooth tubular pore wall structure on chemical treatment. The changes in nanocrystalline porous silicon were also clearly observed by an asymmetric broadening and shift of the optical silicon phonons in R...

Nano surface engineering of Mn2O3 for potential light-harvesting application

Manganese oxides are well known applied materials including their use as efficient catalysts for various environmental applications. Multiple oxidation states and their change due to various experimental conditions are concluded to be responsible for their multifaceted functionality. Here we demonstrate that the interaction of a small organic ligand with one of the oxide varieties induces completely new optical properties and functionalities (photocatalysis). We have synthesized Mn2O3 microspheres via a hydrothermal route and characterized them using scanning electron microscopy (SEM), X-ray diffraction (XRD) and elemental mapping (EDAX). When the microspheres are allowed to interact with the biologically important small ligand citrate, nanometer-sized surface functionalized Mn2O3 (NPs) are formed. Raman and Fourier transformed infrared spectroscopy confirm the covalent attachment of the citrate ligand to the dangling bond of Mn at the material surface. While cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) analysis confirm multiple surface charge states after the citrate functionalization of the Mn2O3 NPs, new optical properties of the surface engineered nanomaterials in terms of absorption and emission emerge consequently. The engineered material offers a novel photocatalytic functionality to the model water contaminant methylene blue (MB). The effect of doping other metal ions including Fe3+ and Cu2+ on the optical and catalytic properties is also investigated. In order to prepare a prototype for potential environmental application of water decontamination, we have synthesized and duly functionalized the material on the extended surface of a stainless steel metal mesh (size 2 cm × 1.5 cm, pore size 150 μm × 200 μm). We demonstrate that the functionalized mesh always works as a “physical” filter of suspended particulates. However, it works as a “chemical” filter (photocatalyst) for the potential water soluble contaminant (MB) in the presence of solar light.

Lattice and electronic anomalies of CaFe 2 As 2 studied by Raman spectroscopy

FIG. 1: Raman spectra in (xx) and (xu) polarization at 4 and290 K, respectively. The solid lines denote the (xu) polariza-tion where the incident light is parallel to the x axis and thescattered light is unpolarized. For the (xx) polarization, theincident and scattered light is polarized parallel to the x axis.

Single Crystal Growth and Effect of Doping on Structural, Transport and Magnetic Properties of A1−xKxFe2As2 (A = Ba, Sr)

We demonstrate the preparation of large, free standing iron pnictide single crystals with a size up to 20 x 10 x 1 mm3 using solvents in zirconia crucibles under argon atmosphere. Transport and magnetic properties are investigated to study the effect of potassium doping on the structural and superconducting property of the compounds. The spin density wave (SDW) anomaly at Ts ~138 K in BaFe2As2 single crystals from self-flux shifts to Ts ~85 K due to Sn solvent growth. We show direct evidence for an incorporation of Sn on the Fe site. The electrical resistivity data show a sharp superconducting transition temperature Tc~38.5 K for the single crystal of Ba0.68K0.32Fe2As2. A nearly 100% shielding fraction and bulk nature of the superconductivity for the single crystal were confirmed by magnetic susceptibility data. A sharp transition Tc~25 K occurred for the single crystal of Sr0.85K0.15Fe2As2. There is direct evidence for a coexistence of the SDW and superconductivity in the low doping regime of Sr1-xKxFe2As2 single crystals. Structural implications of the doping effects as well as the coexistence of the two order parameters are discussed.