First evidence of octacalcium phosphate@osteocalcin nanocomplex as skeletal bone component directing collagen triple-helix nanofibril mineralization.

Tibia trabeculae and vertebrae of rats as well as human femur were investigated by high-resolution TEM at the atomic scale in order to reveal snapshots of the morphogenetic processes of local bone ultrastructure formation. By taking into account reflections of hydroxyapatite for Fourier filtering the appearance of individual alpha-chains within the triple-helix clearly shows that bone bears the feature of an intergrowth composite structure extending from the atomic to the nanoscale, thus representing a molecular composite of collagen and apatite. Careful Fourier analysis reveals that the non-collagenous protein osteocalcin is present directly combined with octacalcium phosphate. Besides single spherical specimen of about 2 nm in diameter, osteocalcin is spread between and over collagen fibrils and is often observed as pearl necklace strings. In high-resolution TEM, the three binding sites of the γ-carboxylated glutamic acid groups of the mineralized osteocalcin were successfully imaged, which provide the chemical binding to octacalcium phosphate. Osteocalcin is attached to the collagen structure and interacts with the Ca-sites on the (100) dominated hydroxyapatite platelets with Ca-Ca distances of about 9.5 Å. Thus, osteocalcin takes on the functions of Ca-ion transport and suppression of hydroxyapatite expansion.

Synthesis and Three-Dimensional Magnetic Field Mapping of Co2FeGa Heusler Nanowires at 5 nm Resolution.

We present the synthesis of Co2FeGa Heusler nanowires and the results of our investigations on their three-dimensional (3D) electric and magnetic internal and external fields mapped by electron holographic tomography (EHT). These fields will be of great importance in next-generation nanomagnets integrated in spintronics and memory devices. The Co2FeGa nanowires with a L21 ordered structure are prepared by a SBA-15 silica-assisted method. The magnetic dipole-like stray fields of several Co2FeGa nanowires are revealed by holographically reconstructed phase images. Based on the measured magnetic phase shifts of an individual nanowire and its 3D reconstruction using EHT, we obtain an internal magnetic induction with a magnitude of 1.15 T and a nonmagnetic surface layer of 10 nm thickness. Furthermore, we also reconstruct the 3D distribution of the electrostatic potential of the same nanowire.

Direct Depth- and Lateral- Imaging of Nanoscale Magnets Generated by Ion Impact.

Nanomagnets form the building blocks for a variety of spin-transport, spin-wave and data storage devices. In this work we generated nanoscale magnets by exploiting the phenomenon of disorder-induced ferromagnetism; disorder was induced locally on a chemically ordered, initially non-ferromagnetic, Fe60Al40 precursor film using nm diameter beam of Ne(+) ions at 25 keV energy. The beam of energetic ions randomized the atomic arrangement locally, leading to the formation of ferromagnetism in the ion-affected regime. The interaction of a penetrating ion with host atoms is known to be spatially inhomogeneous, raising questions on the magnetic homogeneity of nanostructures caused by ion-induced collision cascades. Direct holographic observations of the flux-lines emergent from the disorder-induced magnetic nanostructures were made in order to measure the depth- and lateral- magnetization variation at ferromagnetic/non-ferromagnetic interfaces. Our results suggest that high-resolution nanomagnets of practically any desired 2-dimensional geometry can be directly written onto selected alloy thin films using a nano-focussed ion-beam stylus, thus enabling the rapid prototyping and testing of novel magnetization configurations for their magneto-coupling and spin-wave properties.

A flexible multi-stimuli in situ (S)TEM: concept, optical performance, and outlook.

The progress in (scanning) transmission electron microscopy development had led to an unprecedented knowledge of the microscopic structure of functional materials at the atomic level. Additionally, although not widely used yet, electron holography is capable to map the electric and magnetic potential distributions at the sub-nanometer scale. Nevertheless, in situ studies inside a (scanning) transmission electron microscope ((S)TEM) are extremely challenging because of the much restricted size and accessibility of the sample space. Here, we introduce a concept for a dedicated in situ (S)TEM with a large sample chamber for flexible multi-stimuli experimental setups and report about the electron optical performance of the instrument. We demonstrate a maximum resolving power of about 1 nm in conventional imaging mode and substantially better than 5 nm in scanning mode while providing an effectively usable "pole piece gap" of 70 mm.

3D Magnetic Induction Maps of Nanoscale Materials Revealed by Electron Holographic Tomography.

The investigation of three-dimensional (3D) ferromagnetic nanoscale materials constitutes one of the key research areas of the current magnetism roadmap and carries great potential to impact areas such as data storage, sensing, and biomagnetism. The properties of such nanostructures are closely connected with their 3D magnetic nanostructure, making their determination highly valuable. Up to now, quantitative 3D maps providing both the internal magnetic and electric configuration of the same specimen with high spatial resolution are missing. Here, we demonstrate the quantitative 3D reconstruction of the dominant axial component of the magnetic induction and electrostatic potential within a cobalt nanowire (NW) of 100 nm in diameter with spatial resolution below 10 nm by applying electron holographic tomography. The tomogram was obtained using a dedicated TEM sample holder for acquisition, in combination with advanced alignment and tomographic reconstruction routines. The powerful approach presented here is widely applicable to a broad range of 3D magnetic nanostructures and may trigger the progress of novel spintronic nonplanar nanodevices.

Quantitative imaging of the magnetic configuration of modulated nanostructures by electron holography.

By means of off-axis electron holography the local distribution of the magnetic induction within and around a poly-crystalline Permalloy (Ni81Fe19) thin film is studied. In addition the stray field above the sample is measured by magnetic force microscopy on a larger area. The film is deposited on a periodically nanostructured (rippled) Si substrate, which was formed by Xe(+) ion beam erosion. This introduces the periodical ripple shape to the Permalloy film. The created ripple morphology is expected to modify the magnetization distribution within the Permalloy and to induce dipolar stray fields. These stray fields play an important role in spinwave dynamics of periodic nanostructures like magnonic crystals. Micromagnetic simulations estimate those stray fields in the order of only 10 mT. Consequently, their experimental determination at nanometer spatial resolution is highly demanding and requires advanced acquisition and reconstruction techniques such as electron holography. The reconstructed magnetic phase images show the magnetized thin film, in which the magnetization direction follows mainly the given morphology. Furthermore, a closer look to the Permalloy/carbon interface reveals stray fields at the detection limit of the method in the order of 10 mT, which is in qualitative agreement with the micromagnetic simulations.

Interconnection of nanoparticles within 2D superlattices of PbS/oleic acid thin films.

Make it connected! 2D close-packed layers of inorganic nanoparticles are interconnected by organic fibrils of oleic acid as clearly visualized by electron holography. These fibrils can be mineralised by PbS to transform an organic-inorganic framework to a completely interconnected inorganic semiconducting 2D array.

A cheap and quickly adaptable in situ electrical contacting TEM sample holder design.

In situ electrical characterization of nanostructures inside a transmission electron microscope provides crucial insight into the mechanisms of functioning micro- and nano-electronic devices. For such in situ investigations specialized sample holders are necessary. A simple and affordable but flexible design is important, especially, when sample geometries change, a holder should be adaptable with minimum effort. Atomic resolution imaging is standard nowadays, so a sample holder must ensure this capability. A sample holder design for on-chip samples is presented that fulfils these requisites. On-chip sample devices have the advantage that they can be manufactured via standard fabrication routes.

Electron holography for fields in solids: problems and progress.

Electron holography initially was invented by Dennis Gabor for solving the problems raised by the aberrations of electron lenses in Transmission Electron Microscopy. Nowadays, after hardware correction of aberrations allows true atomic resolution of the structure, for comprehensive understanding of solids, determination of electric and magnetic nanofields is the most challenging task. Since fields are phase objects in the TEM, electron holography is the unrivaled method of choice. After more than 40 years of experimental realization and steady improvement, holography is increasingly contributing to these highly sophisticated and essential questions in materials science, as well to the understanding of electron waves and their interaction with matter.

Electron Holography: phases matter.

Essentially, all optics is wave optics, be it with light, X-rays, neutrons or electrons. The information transfer from the object to the image can only be understood in terms of waves given by amplitude and phase. However, phases are difficult to measure: for slowly oscillating waves such as sound or low-frequency electromagnetic waves, phases can be measured directly; for high frequencies this has to be done by heterodyne detection, i.e. superposition with a reference and averaging over time. In optics, this is called interferometry. Because interference is mostly very difficult to achieve, phases have often been considered 'hidden variables' seemingly pulling the strings from backstage, only visible by their action on the image intensity. This was almost the case in conventional Electron Microscopy with the phase differences introduced by an object. However, in the face of the urgent questions from solid state physics and materials science, these phases have to be determined precisely, because they encode the most dominant object properties, such as charge distributions and electromagnetic fields. After more than six decades of very patient advancement, electron interferometry and holography offer unprecedented analytical facilities down to an atomic scale. Akira Tonomura has prominently contributed to the present state.

A holographic biprism as a perfect energy filter?

It has often been stated that a holographic biprism represents a near perfect energy filter and only elastically scattered electrons can participate in the interference fringes. This is based on the assumption that the reference wave does not contain inelastically scattered electrons. In this letter we show that this is not exactly true because of the delocalised inelastic interaction of the reference wave with the sample. We experimentally and theoretically show that inelastic scattering plays a role in the fringe formation, but it is shown that this contribution is small and can usually be neglected in practice.

Synthesis of the clathrate-I phase Ba(8-x)Si46 via redox reactions.

The clathrate-I phase Ba(8-x)Si(46) (space group Pm3̅n) was synthesized by oxidation of Ba(4)Li(2)Si(6) with gaseous HCl. Microcrystalline powders of the clathrate phase were obtained within a few minutes. The reaction temperature and the pressure of HCl were optimized to achieve good-quality crystalline products with a composition range of 1.3 < x < 1.9. The new preparation route presented here provides an alternative to the high-pressure synthesis applied so far.

Synthesis and electron holography studies of single crystalline nanostructures of clathrate-II phases K(x)Ge136 and Na(x)Si136.

Crystalline nanosized particles of clathrate-II phases K(x)Ge(136) and Na(x)Si(136) were obtained from a dispersion of alkali metal tetrelides in ionic liquids based on DTAC/AlCl(3), which were slowly heated to 120-180 °C. The nanoparticles are bullet-shaped with typical dimensions of about 40 nm in width and 140-200 nm in length. Detailed structure investigations using high-resolution transmission electron microscopy (HRTEM) and electron holography reveal the crystallinity and dense morphology of the clathrate nanorods.

Imaging modes for potential mapping in semiconductor devices by electron holography with improved lateral resolution.

Electron holography is the highest resolving tool for dopant profiling at nanometre-scale resolution. In order to measure the object areas of interest in a hologram, both a wide field of view and a sufficient lateral resolution are required. The usual path of rays for recording holograms with an electron biprism using the standard objective lens does not meet these requirements, because the field of view amounts to some 10 nm only, however, at a resolution of 0.1 nm better than needed here. Therefore, instead of the standard objective lens, the Lorentz lens is widely used for holography of semiconductors, since it provides a field of view up to 1000 nm at a sufficient lateral resolution of about 10nm. Since the size of semiconductor structures is steadily shrinking, there is now a need for better lateral resolution at an appropriate field of view. Therefore, additional paths of rays for recording holograms are studied with special emphasis on the parameters field of view and lateral resolution. The findings allow an optimized scheme with a field of view of 200 nm and a lateral resolution of 3.3 nm filling the gap between the existing set-ups. In addition, the Lorentz lens is no longer required for investigation of non-magnetic materials, since the new paths of rays are realized with the standard objective lens and diffraction lens. An example proves the applicability of this arrangement for future semiconductor technology.

Coherent and incoherent effects on the imaging and scattering process in transmission electron microscopy and off-axis electron holography.

The standard treatment for the different plane wave components of incoming electrons in transmission electron microscope imaging is an incoherent superposition. However, projectile electrons in transmission electron microscopes are localized in space, and therefore have to be described as coherent wave-packets. Moreover, recent developments towards ultrafast electron microscopy and dynamic transmission electron microscopy require a description using highly localized wave-packets. Here we will extend the standard stationary modeling of the elastic scattering processes in high-resolution microscopy to a fully time-dependent approach, by using the direct solution of the time-dependent Schrödinger equation. We will draw the connection to the detection of coherent wave-packets, giving explicit implications for the reconstructed waves in off-axis electron holography. Additionally the description of incoherent aberrations is extended to incorporate the influence of the biprism accurately, leading to a modified form of the damping of spatial frequencies.

Aberration correction and electron holography.

Electron holography has been shown to allow a posteriori aberration correction. Therefore, an aberration corrector in the transmission electron microscope does not seem to be needed with electron holography to achieve atomic lateral resolution. However, to reach a signal resolution sufficient for detecting single light atoms and very small interatomic fields, the aberration corrector has turned out to be very helpful. The basic reason is the optimized use of the limited number of "coherent" electrons that are provided by the electron source, as described by the brightness. Finally, quantitative interpretation of atomic structures benefits from the holographic facilities of fine-tuning of the aberration coefficients a posteriori and from evaluating both amplitude and phase.

Towards automated electron holographic tomography for 3D mapping of electrostatic potentials.

Electron-holographic tomography (EHT), that is, the combination of off-axis electron holography with electron tomography, was successfully applied for the quantitative 3D mapping of electrostatic potentials at the nanoscale. Here we present the first software package (THOMAS) for semi-automated acquisition of holographic tilt series, a prerequisite for efficient data collection. Using THOMAS, the acquisition time for a holographic tilt series, consisting of object and reference holograms, is reduced by a factor of five on average, compared to the previous, completely manual approaches. Moreover, the existing software packages for retrieving amplitude and phase information from electron holograms have been extended, now including a one-step procedure for holographic tilt series reconstruction. Furthermore, a modified SIRT algorithm (WSIRT) was implemented for the quantitative 3D reconstruction of the electrostatic potential from the aligned phase tilt series. Finally, the application of EHT to a polystyrene latex sphere test-specimen and a pn-doped Ge 'needle'-shaped specimen are presented, illustrating the quantitative character of EHT. For both specimens the mean inner potential (MIP) values were accurately determined from the reconstructed 3D potential. For the Ge specimen, additionally the 'built-in' voltage across the pn junction of 0.5V was obtained.