Sc, Zr, Hf, and Mn Metal Nanoparticles: Reactive Starting Materials for Synthesis Near Room Temperature.

Zerovalent scandium, zirconium, hafnium, and manganese nanoparticles are prepared by reduction of ScCl3, ZrCl4, HfCl4, and MnCl2 with lithium or sodium naphthalenide in a one-pot, liquid-phase synthesis. Small-sized monocrystalline nanoparticles are obtained with diameters of 2.4 ± 0.2 nm (Sc), 4.0 ± 0.9 nm (Zr), 8.0 ± 3.9 nm (Hf) and 2.4 ± 0.3 nm (Mn). Thereof, Zr(0) and Hf(0) nanoparticles with such size are shown for the first time. To probe the reactivity and reactions of the as-prepared Sc(0), Zr(0), Hf(0), and Mn(0) nanoparticles, they are exemplarily reacted in the liquid phase (e.g., THF, toluene, ionic liquids) with different sterically demanding, monodentate to multidentate ligands, mainly comprising O-H and N-H acidic alcohols and amines. These include isopropanol (HOiPr), 1,1'-bi-2-naphthol (H2binol), N,N'-bis(salicylidene)ethylenediamine (H2salen), 2-mercaptopyridine (2-Hmpy), 2,6-diisopropylaniline (H2dipa), carbazole (Hcz), triphenylphosphane (PPh3), N,N,N',N'-tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bipy), N,N'-diphenylformamidine (Hdpfa), N,N'-(2,6-diisopropylphenyl)-2,4-pentanediimine ((dipp)2nacnacH), 2,2'-dipydridylamine (Hdpa), and 2,6-bis(2-benzimidazolyl)pyridine (H2bbp). As a result, 22 new compounds are obtained, which frequently exhibit a metal center coordinated only by the sterically demanding ligand. Options and restrictions for the liquid-phase syntheses of novel coordination compounds using the oxidation of base-metal nanoparticles near room temperature are evaluated.

SMART RHESINs-Superparamagnetic Magnetite Architecture Made of Phenolic Resin Hollow Spheres Coated with Eu(III) Containing Silica Nanoparticles for Future Quantitative Magnetic Particle Imaging Applications.

Magnetic particle imaging (MPI) is a powerful and rapidly growing tomographic imaging technique that allows for the non-invasive visualization of superparamagnetic nanoparticles (NPs) in living matter. Despite its potential for a wide range of applications, the intrinsic quantitative nature of MPI has not been fully exploited in biological environments. In this study, a novel NP architecture that overcomes this limitation by maintaining a virtually unchanged effective relaxation (Brownian plus Néel) even when immobilized is presented. This superparamagnetic magnetite architecture made of phenolic resin hollow spheres coated with Eu(III) containing silica nanoparticles (SMART RHESINs) was synthesized and studied. Magnetic particle spectroscopy (MPS) measurements confirm their suitability for potential MPI applications. Photobleaching studies show an unexpected photodynamic due to the fluorescence emission peak of the europium ion in combination with the phenol formaldehyde resin (PFR). Cell metabolic activity and proliferation behavior are not affected. Colocalization experiments reveal the distinct accumulation of SMART RHESINs near the Golgi apparatus. Overall, SMART RHESINs show superparamagnetic behavior and special luminescent properties without acute cytotoxicity, making them suitable for bimodal imaging probes for medical use like cancer diagnosis and treatment. SMART RHESINs have the potential to enable quantitative MPS and MPI measurements both in mobile and immobilized environments.

Quantitative analysis of backscattered-electron contrast in scanning electron microscopy.

Backscattered-electron scanning electron microscopy (BSE-SEM) imaging is a valuable technique for materials characterisation because it provides information about the homogeneity of the material in the analysed specimen and is therefore an important technique in modern electron microscopy. However, the information contained in BSE-SEM images is up to now rarely quantitatively evaluated. The main challenge of quantitative BSE-SEM imaging is to relate the measured BSE intensity to the backscattering coefficient η and the (average) atomic number Z to derive chemical information from the BSE-SEM image. We propose a quantitative BSE-SEM method, which is based on the comparison of Monte-Carlo (MC) simulated and measured BSE intensities acquired from wedge-shaped electron-transparent specimens with known thickness profile. The new method also includes measures to improve and validate the agreement of the MC simulations with experimental data. Two different challenging samples (ZnS/Zn(Ox S1- x )/ZnO/Si-multilayer and PTB7/PC71 BM-multilayer systems) are quantitatively analysed, which demonstrates the validity of the proposed method and emphasises the importance of realistic MC simulations for quantitative BSE-SEM analysis. Moreover, MC simulations can be used to optimise the imaging parameters (electron energy, detection-angle range) in advance to avoid tedious experimental trial and error optimisation. Under optimised imaging conditions pre-determined by MC simulations, the BSE-SEM technique is capable of distinguishing materials with small composition differences.

[Sm6O4(cbz)10(thf)6]·2C7H8: A Polynuclear Samarium Oxo Cluster Obtained from Carbazole-Driven Oxidation of Samarium Nanoparticles.

Zerovalent samarium nanoparticles (1.7 ± 0.2 nm in size) are used as the starting material to prepare single crystals of the novel polynuclear samarium oxo cluster [Sm6O4(cbz)10(thf)6]·2C7H8. The reaction is performed by oxidation with carbazole (CbzH) in tetrahydrofuran (THF) at 50 °C with subsequent crystallization in toluene (C7H8). The oxo cluster contains noncharged molecular units with a central Sm6O4 core. Single-crystal structure analysis and infrared spectroscopy confirm the oxidation of CbzH with the formation of (cbz)-. Polynuclear carbazole complexes are generally rare and here prepared using metal nanoparticles as a reactive starting material for the first time. The reaction with CbzH as a sterically demanding ligand exemplarily shows the feasibility of rare-earth-metal nanoparticles for obtaining new compounds with complex composition and structure.

Interface Pattern Engineering in Core-Shell Upconverting Nanocrystals: Shedding Light on Critical Parameters and Consequences for the Photoluminescence Properties.

Advances in controlling energy migration pathways in core-shell lanthanide (Ln)-based hetero-nanocrystals (HNCs) have relied heavily on assumptions about how optically active centers are distributed within individual HNCs. In this article, it is demonstrated that different types of interface patterns can be formed depending on shell growth conditions. Such interface patterns are not only identified but also characterized with spatial resolution ranging from the nanometer- to the atomic-scale. In the most favorable cases, atomic-scale resolved maps of individual particles are obtained. It is also demonstrated that, for the same type of core-shell architecture, the interface pattern can be engineered with thicknesses of just 1 nm up to several tens of nanometers. Total alloying between the core and shell domains is also possible when using ultra-small particles as seeds. Finally, with different types of interface patterns (same architecture and chemical composition of the core and shell domains) it is possible to modify the output color (yellow, red, and green-yellow) or change (improvement or degradation) the absolute upconversion quantum yield. The results presented in this article introduce an important paradigm shift and pave the way toward the emergence of a new generation of core-shell Ln-based HNCs with better control over their atomic-scale organization.

Liquid-Phase Synthesis of Highly Reactive Rare-Earth Metal Nanoparticles.

The first liquid-phase synthesis of high-quality, small-sized rare-earth metal nanoparticles (1-3 nm)-ranging from lanthanum as one of the largest (187 pm) to scandium as the smallest (161 pm) rare-earth metal-is shown. Size, oxidation state, and reactivity of the nanoparticles are examined (e.g., electron microscopy, electron spectroscopy, X-ray absorption spectroscopy, selected reactions). Whereas the nanoparticles are highly reactive (e.g. in contact to air and water), they are chemically stable as THF suspensions and powders under inert conditions. The reactivity can be controlled to obtain inorganic and metal-organic compounds at room temperature.

Structural Properties and ELNES of Polycrystalline and Nanoporous Mg3N2.

Nanoporous, high-purity magnesium nitride (Mg3N2) was synthesized with a liquid ammonia-based process, for potential applications in optoelectronics, gas separation and catalysis, since these applications require high material purity and crystallinity, which has seldom been demonstrated in the past. One way to evaluate the degree of crystalline near-range order and atomic environment is electron energy-loss spectroscopy (EELS) in a transmission electron microscope. However, there are hardly any data on Mg3N2, which makes identification of electron energy-loss near-edge structure (ELNES) features difficult. Therefore, we have studied nanoporous Mg3N2 with EELS in detail in comparison to EELS spectra of bulk Mg3N2, which was analyzed as a reference material. The N-K and Mg-K edges of both materials are similar. Despite having the same crystal structure, however, there are differences in fine-structural features, such as shifts and absences of peaks in the N-K and Mg-K edges of nanoporous Mg3N2. These differences in ELNES are attributed to coordination changes in nanoporous Mg3N2 caused by the significantly smaller crystallite size of 2-6 nm compared to the larger (25-125 nm) crystal size in a bulk material.

Lithiumpyridinyl-Driven Synthesis of High-Purity Zero-Valent Iron Nanoparticles and Their Use in Follow-Up Reactions.

The synthesis of zero-valent iron (Fe(0)) nanoparticles in pyridine using lithium bipyridinyl ([LiBipy]) or lithium pyridinyl ([LiPy]) is presented. FeCl3 is used as the most simple starting material and reduced either in a [LiBipy]-driven two-step approach or in a [LiPy]-driven one-pot synthesis. High-quality nanoparticles are obtained with uniform, spherical shape, and mean diameters of 2.9 ± 0.5 nm ([LiBipy]) or 4.1 ± 0.7 nm ([LiPy]). The as-prepared, high purity Fe(0) nanoparticles are monocrystalline. In addition to particle characterization (high-resolution transmission electron microscopy, scanning transmission electron microscopy, dynamic light scattering), composition and purity are examined in detail based on electron diffraction, X-ray powder diffraction, elemental analysis, infrared spectroscopy, 57 Fe Mössbauer spectroscopy, and magnetic measurements. Due to their small size and high purity, the Fe(0) nanoparticles are highly reactive. They can be used in follow-up reactions to obtain a variety of iron compounds, which is exemplarily shown for the transformation to iron carbide (Fe3 C) nanoparticles, the reaction with sulfur to obtain FeS nanoparticles, or the direct reaction with pentamethylcyclopentadiene to FeCp*2 (Cp*: pentamethylcyclopentadienyl).

Biocompatibility of Amine-Functionalized Silica Nanoparticles: The Role of Surface Coverage.

Here, amorphous silica nanoparticles (NPs), one of the most abundant nanomaterials, are used as an example to illustrate the utmost importance of surface coverage by functional groups which critically determines biocompatibility. Silica NPs are functionalized with increasing amounts of amino groups, and the number of surface exposed groups is quantified and characterized by detailed NMR and fluorescamine binding studies. Subsequent biocompatibility studies in the absence of serum demonstrate that, irrespective of surface modification, both plain and amine-modified silica NPs trigger cell death in RAW 264.7 macrophages. The in vitro results can be confirmed in vivo and are predictive for the inflammatory potential in murine lungs. In the presence of serum proteins, on the other hand, a replacement of only 10% of surface-active silanol groups by amines is sufficient to suppress cytotoxicity, emphasizing the relevance of exposure conditions. Mechanistic investigations identify a key role of lysosomal injury for cytotoxicity only in the presence, but not in the absence, of serum proteins. In conclusion, this work shows the critical need to rigorously characterize the surface coverage of NPs by their constituent functional groups, as well as the impact of serum, to reliably establish quantitative nanostructure activity relationships and develop safe nanomaterials.

Assessment of in vitro particle dosimetry models at the single cell and particle level by scanning electron microscopy.

BACKGROUND: Particokinetic models are important to predict the effective cellular dose, which is key to understanding the interactions of particles with biological systems. For the reliable establishment of dose-response curves in, e.g., the field of pharmacology and toxicology, mostly the In vitro Sedimentation, Diffusion and Dosimetry (ISDD) and Distorted Grid (DG) models have been employed. Here, we used high resolution scanning electron microscopy to quantify deposited numbers of particles on cellular and intercellular surfaces and compare experimental findings with results predicted by the ISDD and DG models. RESULTS: Exposure of human lung epithelial A549 cells to various concentrations of differently sized silica particles (100, 200 and 500 nm) revealed a remarkably higher dose deposited on intercellular regions compared to cellular surfaces. The ISDD and DG models correctly predicted the areal densities of particles in the intercellular space when a high adsorption ("stickiness") to the surface was emulated. In contrast, the lower dose on cells was accurately inferred by the DG model in the case of "non-sticky" boundary conditions. Finally, the presence of cells seemed to enhance particle deposition, as aerial densities on cell-free substrates were clearly reduced. CONCLUSIONS: Our results further validate the use of particokinetic models but also demonstrate their limitations, specifically, with respect to the spatial distribution of particles on heterogeneous surfaces. Consideration of surface properties with respect to adhesion and desorption should advance modelling approaches to ultimately predict the cellular dose with higher precision.

On the Progress of Scanning Transmission Electron Microscopy (STEM) Imaging in a Scanning Electron Microscope.

Transmission electron microscopy (TEM) with low-energy electrons has been recognized as an important addition to the family of electron microscopies as it may avoid knock-on damage and increase the contrast of weakly scattering objects. Scanning electron microscopes (SEMs) are well suited for low-energy electron microscopy with maximum electron energies of 30 keV, but they are mainly used for topography imaging of bulk samples. Implementation of a scanning transmission electron microscopy (STEM) detector and a charge-coupled-device camera for the acquisition of on-axis transmission electron diffraction (TED) patterns, in combination with recent resolution improvements, make SEMs highly interesting for structure analysis of some electron-transparent specimens which are traditionally investigated by TEM. A new aspect is correlative SEM, STEM, and TED imaging from the same specimen region in a SEM which leads to a wealth of information. Simultaneous image acquisition gives information on surface topography, inner structure including crystal defects and qualitative material contrast. Lattice-fringe resolution is obtained in bright-field STEM imaging. The benefits of correlative SEM/STEM/TED imaging in a SEM are exemplified by structure analyses from representative sample classes such as nanoparticulates and bulk materials.

Luminescence mechanisms of defective ZnO nanoparticles.

ZnO nanoparticles (NPs) synthesized by pulsed laser ablation (PLAL) of a zinc plate in deionized water were investigated by time-resolved photoluminescence (PL) and complementary techniques (TEM, AFM, µRaman). HRTEM images show that PLAL produces crystalline ZnO NPs in wurtzite structure with a slightly distorted lattice parameter a. Consistently, optical spectra show the typical absorption edge of wurtzite ZnO (Eg = 3.38 eV) and the related excitonic PL peaked at 3.32 eV with a subnanosecond lifetime. ZnO NPs display a further PL peaking at 2.2 eV related to defects, which shows a power law decay kinetics. Thermal annealing in O2 and in a He atmosphere produces a reduction of the A1(LO) Raman mode at 565 cm(-1) associated with oxygen vacancies, accompanied by a decrease of defect-related emission at 2.2 eV. Based on our experimental results the emission at 2.2 eV is proposed to originate from a photo-generated hole in the valence band recombining with an electron deeply trapped in a singly ionized oxygen vacancy. This investigation clarifies important aspects of the photophysics of ZnO NPs and indicates that ZnO emission can be controlled by thermal annealing, which is important in view of optoelectronic applications.

Dopant-Site Determination in Y- and Sc-Doped (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ by Atom Location by Channeling Enhanced Microanalysis and the Role of Dopant Site on Secondary Phase Formation.

(Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) is a promising material with mixed ionic and electronic conductivity which is considered for oxygen separation membranes. Selective improvement of material properties, e.g. oxygen diffusivity or suppression of secondary phase formation, can be achieved by B-site doping. This study is concerned with the formation of Co-oxide precipitates in undoped BSCF at typical homogenization temperatures of 1,000°C, which act as undesirable nucleation sites for other secondary phases in the application-relevant temperature range. Y-doping successfully suppresses Co-oxide formation, whereas only minor improvements are achieved by Sc-doping. To understand the reason for the different behavior of Y and Sc, the lattice sites of dopant cations in BSCF were experimentally determined in this work. Energy-dispersive X-ray spectroscopy in a transmission electron microscope was applied to locate dopant sites exploiting the atom location by channeling enhanced microanalysis technique. It is shown that Sc exclusively occupies B-cation sites, whereas Y is detected on A- and B-cation sites in Y-doped BSCF, although solely B-site doping was intended. A model is presented for the suppression of Co-oxide formation in Y-doped BSCF based on Y double-site occupancy.

Thin-Film Phase Plates for Transmission Electron Microscopy Fabricated from Metallic Glasses.

Thin-film phase plates (PPs) have become an interesting tool to enhance the contrast of weak-phase objects in transmission electron microscopy (TEM). The thin film usually consists of amorphous carbon, which suffers from quick degeneration under the intense electron-beam illumination. Recent investigations have focused on the search for alternative materials with an improved material stability. This work presents thin-film PPs fabricated from metallic glass alloys, which are characterized by a high electrical conductivity and an amorphous structure. Thin films of the zirconium-based alloy Zr65.0Al7.5Cu27.5 (ZAC) were fabricated and their phase-shifting properties were evaluated. The ZAC film was investigated by different TEM techniques, which reveal beneficial properties compared with amorphous carbon PPs. Particularly favorable is the small probability for inelastic plasmon scattering, which results from the combined effect of a moderate inelastic mean free path and a reduced film thickness due to a high mean inner potential. Small probability plasmon scattering improves contrast transfer at high spatial frequencies, which makes the ZAC alloy a promising material for PP fabrication.

Monitoring the thin film formation during sputter deposition of vanadium carbide.

The thin film formation of magnetron sputtered polycrystalline coatings was monitored by in situ X-ray reflectivity measurements. The measured intensity was analyzed using the Parratt algorithm for time-dependent thin film systems. Guidelines for the on-line interpretation of the data were developed. For thick coatings, the experimental resolution needs to be included in the data evaluation in order to avoid misinterpretations. Based on a simple layer model, the time-dependent mean electron density, roughness and growth velocity were extracted from the data. As an example, the method was applied to the hard coating material vanadium carbide. Both instantaneous and slowly varying changes of the coating could be detected. It was shown that the growth velocity is proportional to the DC power. Significant changes of the microstructure induced by the working gas pressure are mainly driven by the chemical composition.

Atomic structure and composition distribution in wetting layers and islands of germanium grown on silicon (001) substrates.

We present a comprehensive structural investigation of the Ge wetting layer (WL) and island growth on Si(001) substrates by a combination of AFM, high resolution transmission electron microscopy and the energy-differential coherent Bragg rod analysis (COBRA) x-ray method. By considering the influence of the initial Si surface morphology on the deposited Ge, these techniques provide quantitative information on the Ge content and its distribution, in particular within the WL which plays a crucial role in the formation of epitaxial nanostructures. In the WL, the Ge content was found to be above 80% for our growth conditions. Furthermore, from the digital analysis of high-resolution transmission electron microscope images, quantitative information on the strain relaxation is obtained, which complements the COBRA analysis of the Ge distribution and content in these nanostructures.

Sodium-Naphthalenide-Driven Synthesis of Base-Metal Nanoparticles and Follow-up Reactions.

Mo(0), W(0), Fe(0), Ru(0), Re(0), and Zn(0) nanoparticles­essentially base metals­are prepared as a general strategy by a sodium naphthalenide ([NaNaph])-driven reduction of simple metal chlorides in ethers (1,2-dimethoxyethane (DME), tetrahydrofuran (THF)). All the nanoparticles have diameters ≤10 nm, and they can be obtained either as powder samples or long-term stable suspensions. Direct follow-up reactions (e.g., Mo(0)+S8, FeCl3+AsCl3, ReCl5+MoCl5), moreover, allow the preparation of MoS2, FeAs2, or Re4Mo nanoparticles of similar size as the pristine metals (≤10 nm).

Sample thickness determination by scanning transmission electron microscopy at low electron energies.

Sample thickness is a decisive parameter for any quantification of image information and composition in transmission electron microscopy. In this context, we present a method to determine the local sample thickness by scanning transmission electron microscopy at primary energies below 30 keV. The image intensity is measured with respect to the intensity of the incident electron beam and can be directly compared with Monte Carlo simulations. Screened Rutherford and Mott scattering cross-sections are evaluated with respect to fitting experimental data with simulated image intensities as a function of the atomic number of the sample material and primary electron energy. The presented method is tested for sample materials covering a wide range of atomic numbers Z, that is, fluorenyl hexa-peri-hexabenzocoronene (Z = 3.5), carbon (Z = 6), silicon (Z = 14), gallium nitride (Z = 19), and tungsten (Z = 74). Investigations were conducted for two primary energies (15 and 30 keV) and a sample thickness range between 50 and 400 nm.

In-focus electrostatic Zach phase plate imaging for transmission electron microscopy with tunable phase contrast of frozen hydrated biological samples.

Transmission electron microscopy (TEM) images of beam sensitive weak-phase objects such as biological cryo samples usually show a very low signal-to-noise ratio. These samples have almost no amplitude contrast and instead structural information is mainly encoded in the phase contrast. To increase the sample contrast in the image, especially for low spatial frequencies, the use of phase plates for close to focus phase contrast enhancement in TEM has long been discussed. Electrostatic phase plates are favorable in particular, as their tunable potential will allow an optimal phase shift adjustment and higher resolution than film phase plates as they avoid additional scattering events in matter. Here we show the first realization of close to focus phase contrast images of actin filament cryo samples acquired using an electrostatic Zach phase plate. Both positive and negative phase contrast is shown, which is obtained by applying appropriate potentials to the phase plate. The dependence of phase contrast improvement on sample orientation with respect to the phase plate is demonstrated and single-sideband artifacts are discussed. Additionally, possibilities to reduce contamination and charging effects of the phase plate are shown.