Structural characterization of bulk and nanoparticle lead halide perovskite thin films by (S)TEM techniques.

Lead halide (APbX3) perovskites, in polycrystalline thin films but also perovskite nanoparticles (NPs) has demonstrated excellent performance to implement a new generation of photovoltaic and photonic devices. The structural characterization of APbX3 thin films using (scanning) transmission electron microscopy ((S)TEM) techniques can provide valuable information that can be used to understand and model their optoelectronic performance and device properties. However, since APbX3 perovskites are soft materials, their characterization using (S)TEM is challenging. Here, we study and compare the structural properties of two different metal halide APbX3 perovskite thin films: bulk CH3NH3PbI3 prepared by spin-coating of the precursors in solution and CsPbBr3 colloidal NPs synthetized and deposited by doctor blading. Both specimen preparation methods and working conditions for analysis by (S)TEM are properly optimized. We show that CH3NH3PbI3 thin films grown by a one-step method are composed of independent grains with random orientations. The growth method results in the formation of tetragonal perovskite thin films with good adherence to an underlying TiO2 layer, which is characterized by a photoluminescence (PL) emission band centered at 775 nm. The perovskite thin films based on CsPbBr3 colloidal NPs, which are used as the building blocks of the film, are preserved by the deposition process, even if small gaps are observed between adjacent NPs. The crystal structure of CsPbBr3 NPs is cubic, which is beneficial for optical properties due to its optimal band gap. The absorption and PL spectra measured in both the thin film and the colloidal solution of CsPbBr3 NPs are very similar, indicating a good homogeneity of the thin films and the absence of aggregation of NPs. However, a particular care was required to avoid long electron irradiation times during our structural studies, even at a low voltage of 80 kV, as the material was observed to decompose through Pb segregation.

Homogeneity and variation of donor doping in Verneuil-grown SrTiO3:Nb single crystals.

The homogeneity of Verneuil-grown SrTiO3:Nb crystals was investigated. Due to the fast crystal growth process, inhomogeneities in the donor dopant distribution and variation in the dislocation density are expected to occur. In fact, for some crystals optical studies show variations in the density of Ti(3+) states on the microscale and a cluster-like surface conductivity was reported in tip-induced resistive switching studies. However, our investigations by TEM, EDX mapping, and 3D atom probe reveal that the Nb donors are distributed in a statistically random manner, indicating that there is clearly no inhomogeneity on the macro-, micro-, and nanoscale in high quality Verneuil-grown crystals. In consequence, the electronic transport in the bulk of donor-doped crystals is homogeneous and it is not significantly channelled by extended defects such as dislocations which justifies using this material, for example, as electronically conducting substrate for epitaxial oxide film growth.

Interface Engineering to Create a Strong Spin Filter Contact to Silicon.

Integrating epitaxial and ferromagnetic Europium Oxide (EuO) directly on silicon is a perfect route to enrich silicon nanotechnology with spin filter functionality. To date, the inherent chemical reactivity between EuO and Si has prevented a heteroepitaxial integration without significant contaminations of the interface with Eu silicides and Si oxides. We present a solution to this long-standing problem by applying two complementary passivation techniques for the reactive EuO/Si interface: (i) an in situ hydrogen-Si (001) passivation and (ii) the application of oxygen-protective Eu monolayers-without using any additional buffer layers. By careful chemical depth profiling of the oxide-semiconductor interface via hard x-ray photoemission spectroscopy, we show how to systematically minimize both Eu silicide and Si oxide formation to the sub-monolayer regime-and how to ultimately interface-engineer chemically clean, heteroepitaxial and ferromagnetic EuO/Si (001) in order to create a strong spin filter contact to silicon.

Magnetic heating properties and neutron activation of tungsten-oxide coated biocompatible FePt core-shell nanoparticles.

Magnetic nanoparticles are highly desirable for biomedical research and treatment of cancer especially when combined with hyperthermia. The efficacy of nanoparticle-based therapies could be improved by generating radioactive nanoparticles with a convenient decay time and which simultaneously have the capability to be used for locally confined heating. The core-shell morphology of such novel nanoparticles presented in this work involves a polysilico-tungstate molecule of the polyoxometalate family as a precursor coating material, which transforms into an amorphous tungsten oxide coating upon annealing of the FePt core-shell nanoparticles. The content of tungsten atoms in the nanoparticle shell is neutron activated using cold neutrons at the Heinz Maier-Leibnitz (FRMII) neutron facility and thereby transformed into the radioisotope W-187. The sizeable natural abundance of 28% for the W-186 precursor isotope, a radiopharmaceutically advantageous gamma-beta ratio of γß≈30% and a range of approximately 1mm in biological tissue for the 1.3MeV ß-radiation are promising features of the nanoparticles' potential for cancer therapy. Moreover, a high temperature annealing treatment enhances the magnetic moment of nanoparticles in such a way that a magnetic heating effect of several degrees Celsius in liquid suspension - a prerequisite for hyperthermia treatment of cancer - was observed. A rise in temperature of approximately 3°C in aqueous suspension is shown for a moderate nanoparticle concentration of 0.5mg/ml after 15min in an 831kHz high-frequency alternating magnetic field of 250Gauss field strength (25mT). The biocompatibility based on a low cytotoxicity in the non-neutron-activated state in combination with the hydrophilic nature of the tungsten oxide shell makes the coated magnetic FePt nanoparticles ideal candidates for advanced radiopharmaceutical applications.

Polyoxometalate-stabilized, water dispersible Fe2Pt magnetic nanoparticles.

Magnetic Fe2Pt core-shell nanoparticles with 2 nm cores were synthesized with a monolayer coating of silicotungstate Keggin clusters. The core-shell composition is substantiated by structural analysis performed using high-resolution scanning transmission electron microscopy (HR-STEM) and small angle X-ray scattering (SAXS) in a liquid suspension. The molecular metal oxide cluster shell introduces an enhanced dispersibility of the magnetic Fe-Pt core-shell nanoparticles in aqueous media and thereby opens up new routes to nanoparticle bio-functionalization, for example, using pre-functionalized polyoxometalates.

Electronic phase coherence in InAs nanowires.

Magnetotransport measurements at low temperatures have been performed on InAs nanowires grown by In-assisted molecular beam epitaxy. Information on the electron phase coherence is obtained from universal conductance fluctuations measured in a perpendicular magnetic field. By analysis of the universal conductance fluctuations pattern of a series of nanowires of different length, the phase-coherence length could be determined quantitatively. Furthermore, indications of a pronounced flux cancelation effect were found, which is attributed to the topology of the nanowire. Additionally, we present measurements in a parallel configuration between wire and magnetic field. In contrast to previous results on InN and InAs nanowires, we do not find periodic oscillations of the magnetoconductance in this configuration. An explanation of this behavior is suggested in terms of the high density of stacking faults present in our InAs wires.

Strain-induce shift of the crystal-field splitting of SrTiO3 embedded in scandate multilayers.

Strained SrTiO3 layers have become of interest, since the paraelectric-to-ferroelectric transition temperature can be increased to room temperature. A linear relationship between strain and energy splitting of the fundamental transitions in the fine structure of Ti L(2,3) and O K edges is observed, that can be exploited to measure strain from electronic transitions, complementary to measuring local strain directly via high-resolution transmission electron microscopy (HRTEM) images. In particular, for both methods, the geometrical phase analysis performed on high-resolution images and the measurement of the energy splitting by energy loss spectroscopy, tensile strain of SrTiO3 layers was measured when grown on DyScO3 and GdScO3 substrates. The effect of strain on the electron loss near edge structure (ELNES) of the Ti L(2,3) edge in comparison to unstrained samples is analyzed. Ab initio calculations of the Ti L(2,3) and O K edge show a linear variation of the crystal field splitting with strain. Calculated and experimental values of the crystal field splitting show a very good agreement.

Quantitative atomic resolution mapping using high-angle annular dark field scanning transmission electron microscopy.

A model-based method is proposed to relatively quantify the chemical composition of atomic columns using high angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) images. The method is based on a quantification of the total intensity of the scattered electrons for the individual atomic columns using statistical parameter estimation theory. In order to apply this theory, a model is required describing the image contrast of the HAADF STEM images. Therefore, a simple, effective incoherent model has been assumed which takes the probe intensity profile into account. The scattered intensities can then be estimated by fitting this model to an experimental HAADF STEM image. These estimates are used as a performance measure to distinguish between different atomic column types and to identify the nature of unknown columns with good accuracy and precision using statistical hypothesis testing. The reliability of the method is supported by means of simulated HAADF STEM images as well as a combination of experimental images and electron energy-loss spectra. It is experimentally shown that statistically meaningful information on the composition of individual columns can be obtained even if the difference in averaged atomic number Z is only 3. Using this method, quantitative mapping at atomic resolution using HAADF STEM images only has become possible without the need of simultaneously recorded electron energy loss spectra.

Agglomeration of As antisites in As-rich low-temperature GaAs: nucleation without a critical nucleus size.

To investigate the early stages of nucleation and growth of As precipitates in GaAs grown at low substrate temperature, we make use of a self-consistent-charge density-functional based tight-binding method. Since a pair of As antisites already shows a significant binding energy which increases when more As antisites are attached, there is no critical nucleus size. Provided that all excess As has precipitated, the clusters may grow in size since the binding energies increase with increasing agglomeration size. These findings close the gap between experimental investigation of point defects and the detection of nanometer-size precipitates in transmission electron microscopy.

Quantitative transmission electron microscopy analysis of the pressure of helium-filled cracks in implanted silicon.

The pressure of crack-shaped cavities formed in silicon upon implantation with helium and subsequent annealing is quantitatively determined from the measurement of diffraction contrast features visible in transmission electron micrographs taken under well-defined dynamical two-beam conditions. For this purpose, simulated images, based on the elastic displacements associated with a Griffith crack, are matched to experimental micrographs, thus yielding unambiguous quantitative data on the ratio p of the cavity pressure to the silicon matrix shear modulus. Experimental results demonstrate cavity radii of some 10 nm and p values up to 0.22, which may be regarded as sufficiently high for the emission of dislocation loops from the cracks.

Direct compositional analysis of AlGaAs/GaAs heterostructures by the reciprocal space segmentation of high-resolution micrographs.

A detailed description of a combined reciprocal and real space technique for the mapping of layer compositions across interior interfaces from high-resolution electron micrographs is presented. The analysis is based on the reciprocal space extraction of chemically sensitive image information encoded in lattice images of AlGaAs/GaAs heterostructures taken under optimized imaging conditions. Analysis procedures include centering a set of apertures around chemically sensitive reflections in the Fourier transform of lattice images and performing an inverse transformation, thus extracting composition related information from experimental micrographs. It is demonstrated that this approach is characterized by the same spatial resolution as real space techniques but by improved capabilities with respect to analysing images characterized by a minor signal-to-noise ratio. For illustration purposes the stability of AlAs/GaAs multiple quantum wells grown under low-temperature conditions against thermal treatment as expressed by interfacial roughness parameters is investigated.

Do arsenic interstitials really exist in As-rich GaAs?

To investigate the lattice distortion caused by point defects in As-rich GaAs, we make use of a self-consistent-charge density-functional based tight-binding method. Both relevant defects, the As antisite and the As interstitial, cause significant lattice distortion. In contrast to As interstitials, isolated As antisites lead to lattice strain as well as displacement of nearest neighbor As lattice atoms into the <110> channels, in excellent agreement with experiments. Therefore, our result gives powerful evidence for As antisites being the dominating defect in as-grown As-rich GaAs.

Reentrant mound formation in GaAs(001) homoepitaxy observed by ex situ atomic force microscopy

A study of the surface morphology of homoepitaxial GaAs(001) by means of ex situ atomic force microscopy in air reveals the reentrance of mounding behavior at low growth temperatures. A transition from statistical roughening to organized mound formation is observed as the growth temperature is reduced. We show by means of growth simulations that the observed morphology is compatible with anisotropic adatom diffusion in the presence of an Ehrlich-Schwoebel barrier. The mechanism leading to this kind of adatom kinetics at low temperatures is interpreted in terms of surfactant acting arsenic condensing on the surface.