Strain and size combined effects on the GaN band structure: VEELS and DFT study.

A nanoscale study of combined strain/size effects has been performed using monochromated valence electron energy-loss spectroscopy and density functional theory (DFT) calculations to locally explore the valence and conduction bands of a strained 2 nm GaN quantum well inserted between two fully relaxed AlN thick layers. Two main electronic transitions from the valence to the conduction band were experimentally detected and interpreted. The first transition was shown to be a collective oscillation (or plasmon), which was significantly blue-shifted in energy mainly due to the widening of the valence-band top-part. The second, however, had a single-particle character, that is: Ga-3d → Ga-4p, and was weakly affected by strain and size. In addition, our DFT calculations showed that strain and size can be adjusted separately to tune the GaN band-gap energy.

Inline electron holography and VEELS for the measurement of strain in ternary and quaternary (In,Al,Ga)N alloyed thin films and its effect on bandgap energy.

We present the use of (1) dark-field inline electron holography for measuring the structural strain, and indirectly obtaining the composition, in a wurtzite, 4-nm-thick InAlGaN epilayer on a AlN/GaN/AlN/GaN multinano-layer heterosystem, and (2) valence electron energy-loss spectroscopy to study the bandgap value of five different, also hexagonal, 20-50-nm-thick InAlGaN layers. The measured strain values were almost identical to the ones obtained by other techniques for similarly grown materials. We found that the biaxial strain in the III-N alloys lowers the bandgap energy as compared to the value calculated with different known expressions and bowing parameters for unstrained layers. By contrast, calculated and experimental values agreed in the case of lattice-matched (almost unstrained) heterostructures.

Microemulsions as reaction media for the synthesis of Pt nanoparticles.

For the synthesis of Pt nanoparticles we used water-in-oil droplet microemulsions as templates. The focus was on the correlation between the size of the microemulsion droplets and that of the resulting Pt particles. To study this correlation in a systematic way, all particles were synthesized at the water emulsification failure boundaries where the microemulsion droplets are spherical and where their size can easily be tuned by the amount of added water. The metallic particles were synthesized by mixing two microemulsions one of which contains the metal salt H(2)PtCl(6) and the other the reducing agent NaBH(4). The size and structure of the microemulsion droplets was studied via small-angle X-ray scattering, while the Pt particles were characterized by high-resolution transmission electron microscopy in combination with energy-dispersive X-ray spectroscopy and selected area electron diffraction. The clear correlation between droplet and particle size was further supported by accompanying Monte Carlo simulations.

Electron microscopy of polyoxometalate ions on graphene by electrospray ion beam deposition.

Aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) has enabled atomically resolved imaging of molecules adsorbed on low-dimensional materials like carbon nanotubes, graphene oxide and few-layer-graphene. However, conventional methods for depositing molecules onto such supports lack selectivity and specificity. Here, we describe the chemically selective preparation and deposition of molecules-like polyoxometalate (POM) anions [PW12O40]3- using electrospray ion-beam deposition (ES-IBD) along with high-resolution TEM imaging. This approach provides access to sub-monolayer coatings of intact molecules on freestanding graphene, which enables their atomically resolved ex situ characterization by low-voltage AC-HRTEM. The capability to tune the deposition parameters in either soft or reactive landing mode, combined with the well-defined high-vacuum deposition conditions, renders the ES-IBD based method advantageous over alternative methods such as drop-casting. Furthermore, it might be expanded towards depositing and imaging large and nonvolatile molecules with complex structures.

High-temperature superconductivity at the lanthanum cuprate/lanthanum-strontium nickelate interface.

The utilization of interface effects in epitaxial systems at the nanoscale has emerged as a very powerful approach for engineering functional properties of oxides. Here we present a novel structure fabricated by a state-of-the-art oxide molecular beam epitaxy method and consisting of lanthanum cuprate and strontium (Sr)-doped lanthanum nickelate, in which interfacial high-temperature superconductivity (Tc up to 40 K) occurs at the contact between the two phases. In such a system, we are able to tune the superconducting properties simply by changing the structural parameters. By employing electron spectroscopy and microscopy combined with dedicated conductivity measurements, we show that decoupling occurs between the electronic charge carrier and the cation (Sr) concentration profiles at the interface and that a hole accumulation layer forms, which dictates the resulting superconducting properties. Such effects are rationalized in the light of a generalized space-charge theory for oxide systems that takes account of both ionic and electronic redistribution effects.

High-temperature superconductivity in space-charge regions of lanthanum cuprate induced by two-dimensional doping.

The exploitation of interface effects turned out to be a powerful tool for generating exciting material properties. Such properties include magnetism, electronic and ionic transport and even superconductivity. Here, instead of using conventional homogeneous doping to enhance the hole concentration in lanthanum cuprate and achieve superconductivity, we replace single LaO planes with SrO dopant planes using atomic-layer-by-layer molecular beam epitaxy (two-dimensional doping). Electron spectroscopy and microscopy, conductivity measurements and zinc tomography reveal such negatively charged interfaces to induce layer-dependent superconductivity (Tc up to 35 K) in the space-charge zone at the side of the planes facing the substrate, where the strontium (Sr) profile is abrupt. Owing to the growth conditions, the other side exhibits instead a Sr redistribution resulting in superconductivity due to conventional doping. The present study represents a successful example of two-dimensional doping of superconducting oxide systems and demonstrates its power in this field.

Valence electron energy loss study of Fe-doped SrTiO3 and a sigma13 boundary: electronic structure and dispersion forces.

Valence electron energy loss spectroscopy in a dedicated scanning transmission electron microscope has been used to obtain the interband transition strength of a sigma13 tilt grain boundary in SrTiO3. In a first step the electronic structure of bulk SrTiO3 has been analysed quantitatively by comparing VEELS spectra with vacuum ultraviolet spectra and with ab initio density of states calculations. The electronic structure of a near sigma13 grain boundary and the corresponding dispersion forces were then determined by spatially resolved VEELS. Also the effects of delocalization of the inelastic scattering processes were estimated and compared with results from the literature.

Plasmon energy mapping in energy-filtering transmission electron microscopy.

In this paper, we demonstrate the two-dimensional mapping of plasmon energies by energy-filtering transmission electron microscopy. The maps are obtained from a series of energy-filtered images in the plasmon energy region. Examples are shown for a nano-crystalline Si-B-C-N ceramic. This material contains SiC and Si(3)N(4) grains as well as intergranular regions composed of hexagonal BN (h-BN) and turbostratic carbon (t-C). The different phases can be clearly identified by their specific plasmon energies. An energy resolution of < or =0.1eV is achieved. In addition, the plasmon map of an amorphous carbon film is used to visualize the non-isochromaticity of the Corrected Omega filter (90 degrees filter) of the SESAM2. A procedure is proposed for the correction of the non-isochromaticity.

Direct imaging of surface plasmon resonances on single triangular silver nanoprisms at optical wavelength using low-loss EFTEM imaging.

Using low-loss energy-filtering transmission electron microscopy (EFTEM) imaging, we map surface plasmon resonances (SPRs) at optical wavelengths on single triangular silver nanoprisms. We show that EFTEM imaging combining high spatial sampling and high energy resolution enables the detection and for the first time, to the best of our knowledge, mapping at the nanoscale of an extra multipolar SPR on these nanoparticles. As illustrated on a 276.5 nm long nanoprism, this eigenmode is found to be enhanced on the three edges where it exhibits a two-lobe distribution.

Childhood mortality and quality of care among abandoned children in nineteenth-century Italy.

A great deal of scholarly attention has been devoted in recent years to the large-scale abandonment of new born babies in the European past, with special emphasis given to the staggering rates of infant mortality among the foundlings. For the most part, scholars have agreed with the foundling home officials of the past in assigning much of the blame for this excess mortality to the women who took in the foundlings as wetnurses and subsequently as foster mothers. This article takes issue with this view, based on an examination of the children abandoned at the foundling home of Bologna, Italy in the nineteenth century. Four cohorts of foundlings are examined - those abandoned in 1809-30, 1829-30, 1849-50, and 1869-70 (N=3615) - as we trace the changing pattern of infant and early childhood mortality. Longitudinal methods are used in examining the life course of these foundlings and the determinants of their mortality.

Plasticity and an inverse brittle-to-ductile transition in strontium titanate.

The use of ceramic materials is often restricted by a transition from ductile behavior to brittle fracture with decreasing temperature. For example, strontium titanate ( SrTiO3) is known to be extremely fragile and brittle below 1300 K. It is therefore surprising to find that SrTiO3 single crystals can be deformed in compression below 1050 K again. Extensive plastic deformation up to 7% strain at low yield stresses of the order of only 120 MPa is possible at room temperature. Low temperature plasticity is carried by the same [110] [110] dislocations as the high temperature deformation along the [001] axis. From this we conclude that these dislocations must exist in two different core configurations.

Advances in energy-filtering transmission electron microscopy.

First experiments using a new energy-filtering microscope (Sub-eV-Sub-A microscope, or SESAM) are shown. They make use of the high transmissivity of the 90 degree filter. This allows the mapping of chemical bonding of large specimen areas, even if narrow energy selecting slits are used. Because large scattering angles are accepted by this filter, energy-filtered diffraction patterns extending to 150 mrad can be recorded by a single exposure. This can be used to determine the reduced density function of amorphous materials and reduces the exposure time of the investigated area by three orders of magnitude as compared with previous approaches.

Advances in EELS spectroscopy by using new detector and new specimen preparation technologies.

First results obtained with a Gatan UHV Enfina system, which was attached to a VG HB 501 UX dedicated STEM, are reported. The Enfina system is based on a CCD detector and offers, compared to the previously used photodiode array, a narrower point-spread function, higher sensitivity, and faster read-out capabilities. These improvements are demonstrated with electron energy-loss measurements on various oxides, such as Al2O3, TiO2 and SrTiO3. It is shown that a better energy resolution is achieved and that acquisition of high-energy absorption edges with a reasonable signal-to-noise ratio becomes possible. Furthermore, we report on the influence of the TEM specimen quality on the energy-loss spectra. Thin amorphous layers at the specimen surfaces, which are induced by ion-milling processes, can modify specific electron energy-loss near-edge structure features. We found that for the investigated ceramics the use of low-energy ion-milling systems is highly recommended, since the loss of energy-loss near-edge structure details by the presence of the amorphous layers is considerably reduced. This is especially true for very thin specimens.