Abstract: The present work reports on the synthesis of fluorine doped Fe2O3 nanomaterials by a single-step plasma enhanced-chemical vapor deposition (PE-CVD) strategy. In particular, Fe(hfa)2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine) was used as molecular source for both Fe and F in Ar/O2 plasmas. The structure, morphology and chemical composition of the synthesized nanosystems were thoroughly analyzed by two-dimensional X-ray diffraction (XRD2), field emission-scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS) and transmission electron microscopy (TEM). A suitable choice of processing parameters enabled the selective formation of α-Fe2O3 nanomaterials, characterized by an homogeneous F doping, even at 100 °C. Interestingly, a simultaneous control of the system nanoscale organization and fluorine content could be achieved by varying the sole growth temperature. The tailored properties of the resulting materials can be favourably exploited for several technological applications, ranging from photocatalysis, to photoelectrochemical cells and gas sensing.

Abstract: Variations in local bond length and coordination in boron-doped nanocrystalline diamond (NCD) films have been studied through changes in the fine structure of boron and carbon K-edges in electron energy-loss spectra, acquired in a scanning transmission electron microscope. The presence of high concentrations of B in pristine diamond regions and enrichment of B at defects in single NCD grains is demonstrated. Local bond length variations are evidenced through an energy shift of the carbon 1s → σ* edge at B-rich defective regions within single diamond grains, indicating an expansion of the diamond bond length at sites with local high B content.

Abstract: This paper discusses the nucleation behaviour of the CoSi to CoSi2 transformation from cobalt silicide thin films grown by deposition at elevated substrate temperatures ranging from 375 °C to 600 °C. A combination of channelling, real-time Rutherford backscattering spectrometry, real-time x-ray diffraction, and transmission electron microscopy was used to investigate the effect of the deposition temperature on the subsequent formation temperature of CoSi2, its growth behaviour, and the epitaxial quality of the CoSi2 thus formed. The temperature at which deposition took place was observed to exert a significant and systematic influence on both the formation temperature of CoSi2 and its growth mechanism. CoSi films grown at the lowest temperatures were found to increase the CoSi2 nucleation temperature above that of CoSi2 grown by conventional solid phase reaction, whereas the higher deposition temperatures reduced the nucleation temperature significantly. In addition, a systematic change in growth mechanism of the subsequent CoSi2 growth occurs as a function of deposition temperature. First, the CoSi2 growth rate from films grown at the lower reactive deposition temperatures is substantially lower than that grown at higher reactive deposition temperatures, even though the onset of growth occurs at a higher temperature, Second, for deposition temperatures below 450 °C, the growth appears columnar, indicating nucleation controlled growth. Elevated deposition temperatures, on the other hand, render the CoSi2 formation process layer-by-layer which indicates enhanced nucleation of the CoSi2 and diffusion controlled growth. Our results further indicate that this observed trend is most likely related to stress and changes in microstructure introduced during reactive deposition of the CoSi film. The deposition temperature therefore provides a handle to tune the CoSi2 growth mechanism.

Abstract: The concept of resolution in high-resolution electron microscopy (HREM) is the power to resolve neighboring atoms. Since the resolution is related to the width of the point spread function of the microscope, it could in principle be determined from the image of a point object. However, in electron microscopy there are no ideal point objects. The smallest object is an individual atom. If the width of an atom is much smaller than the resolution of the microscope, this atom can still be considered as a point object. As the resolution of the microscope enters the sub-Å regime, information about the microscope is strongly entangled with the information about the atoms in HREM images. Therefore, we need to find an alternative method to determine the resolution in an object-independent way. In this work we propose to use the image wave of a crystalline object in zone axis orientation. Under this condition, the atoms of a column act as small lenses so that the electron beam channels through the atom column periodically. Because of this focusing, the image wave of the column can be much more peaked than the constituting atoms and can thus be a much more sensitive probe to measure the resolution. Our approach is to use the peakiness of the image wave of the atom column to determine the resolution. We will show that the resolution can be directly linked to the total curvature of the atom column wave. Moreover, we can then directly obtain the resolution of the microscope given that the contribution from the object is known, which is related to the bounding energy of the atom. The method is applied on an experimental CaTiO3 image wave.

Abstract: The magnetic properties of manganite bilayers composed of G-type antiferromagnetic (AFM) SrMnO3 and double-exchange ferromagnetic (FM) La0.7Sr0.3MnO3 are studied. A spin-glass state is observed as a result of competing magnetic orders and spin frustration at the La0.7Sr0.3MnO3/SrMnO3 interface. The dependence of the irreversible temperature on the cooling magnetic field follows the Almeida-Thouless line. Although an ideal G-type AFM SrMnO3 is featured with a compensated spin configuration, the bilayers exhibit exchange bias below the spin glass freezing temperature, which is much lower than the Néel temperature of SMO, indicating that the exchange bias is strongly correlated with the spin glass state. The results indicate that the spin frustration that originates from the competition between the AFM super-exchange and the FM double-exchange interactions can induce a strong magnetic anisotropy at the La0.7Sr0.3MnO3/SrMnO3 interface.

Abstract: (La2/3Ca1/3MnO3)n/(BaTiO3)m (LCMOn/BTOm) superlattices on MgO and SrTiO3 substrates with different layer thicknesses (n = 10, 38, 40 and m = 5, 18, 20) have been grown by metal organic aerosol deposition (MAD) and have been fully characterized down to the atomic scale to study the interface characteristics. Scanning transmission electron microscopy combined with spatially resolved electron energy-loss spectroscopy provides clear evidence for the existence of atomically sharp interfaces in MAD grown films, which exhibit epitaxial growth conditions, a uniform normal strain, and a fully oxidized state. Below a critical layer thickness the LCMO structure is found to change from the bulk Pnma symmetry to a pseudocubic R3̅ c symmetry. An atomically flat interface reconstruction consisting of a single Ca-rich atomic layer is observed on the compressively strained BTO on LCMO interface, which is thought to partially neutralize the total charge from the alternating polar atomic layers in LCMO as well as relieving strain at the interface. No interface reconstruction is observed at the tensile strained LCMO on BTO interface.

Abstract: Investigating domain boundaries and their effects on the behaviour of materials automatically implies the need for detailed knowledge on the structural aspects of the atomic configurations at these interfaces. Not only in view of nearest neighbour interactions but also at a larger scale, often surpassing the unit cell, the boundaries can contain structural elements that do not exist in the bulk. In the present contribution, a number of special boundaries resulting from phase transformations or crystal growth and those recently investigated by advanced transmission electron microscopy techniques in different systems will be reviewed. These include macrotwins between microtwinned martensite plates in NiAl, austenite-single variant martensite habit planes in low hysteresis NiTiPd, nanotwins in non-textured nanostructured Pd and ferroelastic domain boundaries in CaTiO3. In all discussed cases these boundaries play an essential role in the properties of the respective materials.

Abstract: We demonstrate site-specific mapping of the oxygen coordination number for transition metals in complex oxides using atomically resolved electron energy-loss spectroscopy in an aberration-corrected scanning transmission electron microscope. Pb2Sr2Bi2Fe6O16 contains iron with a constant Fe3+ valency in both octahedral and tetragonal pyramidal coordination and is selected to demonstrate the principle of site-specific coordination mapping. Analysis of the site-specific Fe-L2,3 data reveals distinct variations in the fine structure that are attributed to Fe in a six-fold (octahedron) or five-fold (distorted tetragonal pyramid) oxygen coordination. Using these variations, atomic resolution coordination maps are generated that are in excellent agreement with simulations.

Abstract: It is demonstrated that glycogen as a biodegradable and inexpensive material coming from renewable resources can be used as a carrier for the construction of in vivo imaging nanoagents. The model system considered is composed of glycogen modified with gadolinium and fluorescent labels. Systematic studies of properties of these nanocarriers by a variety of physical methods and results of in vivo tests of biodegradability are reported. This represents, to the authors' best knowledge, the first such use of glycogen.

Abstract: Three-dimensional covalent organic frameworks (COFs) have been demonstrated as a new class of templates for nanoparticles. Photodecomposition of the [Pd(eta 3-C3H5)(eta 5-C5H5)]@COF-102 inclusion compound (synthesized by a gas-phase infiltration method) led to the formation of the Pd@COF-102 hybrid material. Advanced electron microscopy techniques (including high-angle annular dark-field scanning transmission electron microscopy and electron tomography) along with other conventional characterization techniques unambiguously showed that highly monodisperse Pd nanoparticles ((2.4 +/- 0.5) nm) were evenly distributed inside the COF-102 framework. The Pd@COF-102 hybrid material is a rare example of a metal-nanoparticle-loaded porous crystalline material with a very narrow size distribution without any larger agglomerates even at high loadings (30 wt %). Two samples with moderate Pd content (3.5 and 9.5 wt %) were used to study the hydrogen storage properties of the metal-decorated COF surface. The uptakes at room temperature from these samples were higher than those of similar systems such as Pd@metalorganic frameworks (MOFs). The studies show that the H2 capacities were enhanced by a factor of 2-3 through Pd impregnation on COF-102 at room temperature and 20 bar. This remarkable enhancement is not just due to Pd hydride formation and can be mainly ascribed to hydrogenation of residual organic compounds, such as bicyclopentadiene. The significantly higher reversible hydrogen storage capacity that comes from decomposed products of the employed organometallic Pd precursor suggests that this discovery may be relevant to the discussion of the spillover phenomenon in metal/MOFs and related systems.

Abstract: Porous solids with organized multiple porosity are of scientific and technological importance for broadening the application range from traditional areas of catalysis and adsorption/separation to drug release and biomedical imaging. Synthesis of crystalline porous materials offering a network of uniform micro- and mesopores remains a major scientific challenge. One strategy is based on variation of synthesis parameters of microporous networks, such as, for example, zeolites or metal organic frameworks (MOFs). Here, we show the rational development of an hierarchical variant of the microporous cubic Cu-3(BTC)(2) (BTC = 1,3,5-benzenetricarboxylate) HKUST-1 MOF having strictly repetitive S inn wide mesopores separated by uniform microporous walls in a single crystal structure. This new material coined COK-15 (COK = Centrum voor Oppervlaktechemie en Katalyse) was synthesized via a dual-templating approach. Stability was enhanced by Keggin type phosphotungstate (HPW) systematically occluded in the cavities constituting the walls between the mesopores.

Abstract: The treatment of sp2 carbon materials, including micrographite, nanographite, HOPG, onion-like-carbon, and single-walled carbon nanotubes, in a 3:1 sulfuric to nitric acid mixture produced photoluminescent reaction solutions. These colloidal, aqueous solutions appeared photoluminescently stable under a UV lamp and ranged in color from red to blue. The photoluminescent wavelength shifted to shorter wavelength with increasing reaction time or increasing reaction temperature. Raman spectroscopy showed evidence of defect structures in graphitic residue, and transmission electron microscopy showed unusual structures present in the supernatant including graphitic balls.

Abstract: Nanocrystalline ZnO doped with Ag-nanoclusters has been synthesized by a salt solid state reaction. Three overlapping broad emission bands due to the Ag nanoclusters have been detected at about 570, 750 and 900 nm. These emission bands are excited by an energy transfer from the exciton state of the ZnO host when pumped in the wavelength range from 250 to 400 nm. The 900 nm emission band shows characteristic orbital splitting into three components pointing out that the anisotropic crystalline wurtzite host of ZnO is responsible for this feature. Heat-treatment and temperature dependence studies confirm the origin of these emission bands. An energy level diagram for the emission process and a model for Ag nanoclusters sites are suggested. The emission of nanocrystalline ZnO doped with Ag nanoclusters may be applied for white light generation, displays driven by UV light, down-convertors for solar cells and luminescent lamps.

Abstract: Stearate@Cu/ZnO nanocomposite particles with molar ratios of ZnO ∶ Cu = 2 and 5 are synthesized by reduction of the metalorganic Cu precursor [Cu{(OCH(CH3)CH2N(CH3)2)}2] in the presence of stearate@ZnO nanoparticles. In the case of ZnO ∶ Cu = 5, high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) combined with electron-energy-loss-spectroscopy (EELS) as well as attenuated total reflection Fourier transform infrared (ATR-IR) spectroscopy are used to localize the small amount of Cu deposited on the surface of 35 nm sized stearate@ZnO particles. For ZnO ∶ Cu = 2, the microstructure of the nanocomposites after catalytic activity testing is characterized by HAADF-STEM techniques. This reveals the construction of large Cu nanoparticles (2050 nm) decorated by small ZnO nanoparticles (35 nm). The catalytic activity of both composites for the synthesis of methanol from syn gas is evaluated.