Reversible superdense ordering of lithium between two graphene sheets.

Many carbon allotropes can act as host materials for reversible lithium uptake1,2, thereby laying the foundations for existing and future electrochemical energy storage. However, insight into how lithium is arranged within these hosts is difficult to obtain from a working system. For example, the use of in situ transmission electron microscopy3-5 to probe light elements (especially lithium)6,7 is severely hampered by their low scattering cross-section for impinging electrons and their susceptibility to knock-on damage8. Here we study the reversible intercalation of lithium into bilayer graphene by in situ low-voltage transmission electron microscopy, using both spherical and chromatic aberration correction9 to enhance contrast and resolution to the required levels. The microscopy is supported by electron energy-loss spectroscopy and density functional theory calculations. On their remote insertion from an electrochemical cell covering one end of the long but narrow bilayer, we observe lithium atoms to assume multi-layered close-packed order between the two carbon sheets. The lithium storage capacity associated with this superdense phase far exceeds that expected from formation of LiC6, which is the densest configuration known under normal conditions for lithium intercalation within bulk graphitic carbon10. Our findings thus point to the possible existence of distinct storage arrangements of ions in two-dimensional layered materials as compared to their bulk parent compounds.

Identification of Semiconductive Patches in Thermally Processed Monolayer Oxo-Functionalized Graphene.

The thermal decomposition of graphene oxide (GO) is a complex process at the atomic level and not fully understood. Here, a subclass of GO, oxo-functionalized graphene (oxo-G), was used to study its thermal disproportionation. We present the impact of annealing on the electronic properties of a monolayer oxo-G flake and correlated the chemical composition and topography corrugation by two-probe transport measurements, XPS, TEM, FTIR and STM. Surprisingly, we found that oxo-G, processed at 300 °C, displays C-C sp3 -patches and possibly C-O-C bonds, next to graphene domains and holes. It is striking that those C-O-C/C-C sp3 -separated sp2 -patches a few nanometers in diameter possess semiconducting properties with a band gap of about 0.4 eV. We propose that sp3 -patches confine conjugated sp2 -C atoms, which leads to the local semiconductor properties. Accordingly, graphene with sp3 -C in double layer areas is a potential class of semiconductors and a potential target for future chemical modifications.

γ-Iron Phase Stabilized at Room Temperature by Thermally Processed Graphene Oxide.

Stabilizing nanoparticles on surfaces, such as graphene, is a growing field of research. Thereby, iron particle stabilization on carbon materials is attractive and finds applications in charge-storage devices, catalysis, and others. In this work, we describe the discovery of iron nanoparticles with the face-centered cubic structure that was postulated not to exist at ambient conditions. In bulk, the γ-iron phase is formed only above 917 °C, and transforms back to the thermodynamically favored α-phase upon cooling. Here, with X-ray diffraction and Mössbauer spectroscopy we unambiguously demonstrate the unexpected room-temperature stability of the γ-phase of iron in the form of the austenitic nanoparticles with low carbon content from 0.60% through 0.93%. The nanoparticles have controllable diameter range from 30 nm through 200 nm. They are stabilized by a layer of Fe/C solid solution on the surface, serving as the buffer controlling carbon content in the core, and by a few-layer graphene as an outermost shell.

Electron Source Brightness and Illumination Semi-Angle Distribution Measurement in a Transmission Electron Microscope.

The electron source brightness is an important parameter of an electron microscope. Reliable and easy brightness measurement routes are not easily found. A determination method for the illumination semi-angle distribution in transmission electron microscopy is even less well documented. Herein, we report a facile measurement route for both entities and demonstrate it on a state-of-the-art instrument. The reduced axial brightness of the FEI X-FEG with a monochromator was determined to be larger than 108 A/(m2 sr V).

Thermal Disproportionation of Oxo-Functionalized Graphene.

Graphene production by wet chemistry is an ongoing scientific challenge. Controlled oxidation of graphite introduces oxo functional groups; this material can be processed and converted back to graphene by reductive defunctionalization. Although thermal processing yields conductive carbon, a ruptured and undefined carbon lattice is produced as a consequence of CO2 formation. This thermal process is not understood, but it is believed that graphene is not accessible. Here, we thermally process oxo-functionalized graphene (oxo-G) with a low (4-6 %) and high degree of functionalization (50-60 %) and find on the basis of Raman spectroscopy and transmission electron microscopy performed at atomic resolution (HRTEM) that thermal processing leads predominantly to an intact carbon framework with a density of lattice defects as low as 0.8 %. We attribute this finding to reorganization effects of oxo groups. This finding holds out the prospect of thermal graphene formation from oxo-G derivatives.

Chromatic Aberration Correction for Atomic Resolution TEM Imaging from 20 to 80 kV.

Atomic resolution in transmission electron microscopy of thin and light-atom materials requires a rigorous reduction of the beam energy to reduce knockon damage. However, at the same time, the chromatic aberration deteriorates the resolution of the TEM image dramatically. Within the framework of the SALVE project, we introduce a newly developed C_{c}/C_{s} corrector that is capable of correcting both the chromatic and the spherical aberration in the range of accelerating voltages from 20 to 80 kV. The corrector allows correcting axial aberrations up to fifth order as well as the dominating off-axial aberrations. Over the entire voltage range, optimum phase-contrast imaging conditions for weak signals from light atoms can be adjusted for an optical aperture of at least 55 mrad. The information transfer within this aperture is no longer limited by chromatic aberrations. We demonstrate the performance of the microscope using the examples of 30 kV phase-contrast TEM images of graphene and molybdenum disulfide, showing unprecedented contrast and resolution that matches image calculations.

Confined crystals of the smallest phase-change material.

The demand for high-density memory in tandem with limitations imposed by the minimum feature size of current storage devices has created a need for new materials that can store information in smaller volumes than currently possible. Successfully employed in commercial optical data storage products, phase-change materials, that can reversibly and rapidly change from an amorphous phase to a crystalline phase when subject to heating or cooling have been identified for the development of the next generation electronic memories. There are limitations to the miniaturization of these devices due to current synthesis and theoretical considerations that place a lower limit of 2 nm on the minimum bit size, below which the material does not transform in the structural phase. We show here that by using carbon nanotubes of less than 2 nm diameter as templates phase-change nanowires confined to their smallest conceivable scale are obtained. Contrary to previous experimental evidence and theoretical expectations, the nanowires are found to crystallize at this scale and display amorphous-to-crystalline phase changes, fulfilling an important prerequisite of a memory element. We show evidence for the smallest phase-change material, extending thus the size limit to explore phase-change memory devices at extreme scales.

Transport of intensity phase retrieval of arbitrary wave fields including vortices.

The phase problem can be considered as one of the cornerstones of quantum mechanics intimately connected to the detection process and the uncertainty relation. The latter impose fundamental limits on the manifold phase reconstruction schemes invented to date, in particular, at small magnitudes of the quantum wave. Here, we show that a rigorous solution of the transport of intensity reconstruction (TIE) scheme in terms of a linear elliptic partial differential equation for the phase provides reconstructions even in the presence of wave zeros if particular boundary conditions are given. We furthermore discuss how partial coherence hampers phase reconstruction and show that a modified version of the TIE reconstructs the curl-free current density at arbitrary (in)coherence. Our results open the way for TIE-based phase retrieval of arbitrary wave fields, eventually containing zeros such as phase vortices.

Lattice expansion in seamless bilayer graphene constrictions at high bias.

Our understanding of sp(2) carbon nanostructures is still emerging and is important for the development of high performance all carbon devices. For example, in terms of the structural behavior of graphene or bilayer graphene at high bias, little to nothing is known. To this end, we investigated bilayer graphene constrictions with closed edges (seamless) at high bias using in situ atomic resolution transmission electron microscopy. We directly observe a highly localized anomalously large lattice expansion inside the constriction. Both the current density and lattice expansion increase as the bilayer graphene constriction narrows. As the constriction width decreases below 10 nm, shortly before failure, the current density rises to 4 × 10(9) A cm(-2) and the constriction exhibits a lattice expansion with a uniaxial component showing an expansion approaching 5% and an isotropic component showing an expansion exceeding 1%. The origin of the lattice expansion is hard to fully ascribe to thermal expansion. Impact ionization is a process in which charge carriers transfer from bonding states to antibonding states, thus weakening bonds. The altered character of C-C bonds by impact ionization could explain the anomalously large lattice expansion we observe in seamless bilayer graphene constrictions. Moreover, impact ionization might also contribute to the observed anisotropy in the lattice expansion, although strain is probably the predominant factor.

A novel ground-potential monochromator design.

An electron monochromator design is presented as an instrumental development for electron energy loss spectroscopy (EELS) and imaging in (scanning) transmission electron microscopy ((S)TEM). The main purpose of this development is enhancing the energy resolving power in spectroscopy and filtering. In addition, it helps reducing the effect of the objective lens' chromatic aberration Cc in imaging and therefore, enhancing the spatial resolving power of electron microscopes. General estimates for the performance of a monochromator in energy distribution and the resulting usable beam currents are given. The special monochromator design presented is a ground-potential monochromator based on magnetic sector fields. The monochromator generates a spatially and angular un-dispersed spot and has no mechanically actuated parts in the filter sections. The optics can be operated at electron acceleration voltages from 30kV to 300kV and shows an energy resolving power of better than 2⋅10-7 relative to the primary electron energy. The actual device is designed to be retro-fittable to microscopes from various manufacturers.

Metallization and investigation of electrical properties of in vitro recrystallized mSbsC-eGFP assemblies.

Surface layer (SL) proteins are self-assembling nanosized arrays which can be recrystallized in solution or on surfaces. In this paper, we investigate the metallization, contact potential difference and conductivity of in vitro recrystallized mSbsC-eGFP tube-like assemblies for possible applications in nanobiotechnology. Treatment of mSbsC-eGFP tube-like structures with 150 mM Pt salt solution resulted in the formation of metallized SL assemblies decorated with Pt nanoparticles (∅ > 3 nm) which were closely packed and aggregated into metal clusters. Kelvin probe force microscopy (KPFM) measurements revealed that metallized and unmetallized SL templates showed different surface potential behaviours, demonstrating that the metal coating changes the electrostatic surface characteristics of SL assemblies. In situ conductivity measurements showed that unmetallized SL assemblies were not conductive. Metallized samples showed linear I-V dependence between - 1 and + 1 V with a conductivity of ∼ 10(3) S m( - 1).

The Dresden in-situ (S)TEM special with a continuous-flow liquid-helium cryostat.

Fundamental solid state physics phenomena often occur at very low temperatures, requiring liquid helium cooling in experimental studies. Transmission electron microscopy is a well-established characterization method, which allows probing crucial materials properties down to nanometre and even atomic resolution. Due to the limited space in the object plane, however, suitable liquid-helium cooling is very challenging. To overcome this limitation, resolving power was sacrificed in our Dresden in-situ (S)TEM special, resulting in more than 60 mm usable experimental space in all directions with the specimen in the centre. With the installation of a continuous-flow liquid-helium cryostat, any temperature between 6.5 K and 400 K can be set precisely and kept for days. The information limit of the Dresden in-situ (S)TEM special is about 5 nm. It is shown that the resolution of the Dresden in-situ (S)TEM special is currently not limited by aberrations, but by external instabilities.

Effect of friction on oxidative graphite intercalation and high-quality graphene formation.

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

In Situ Crystallization of the Insoluble Anhydrite AII Phase in Graphene Pockets.

Single-distilled water encapsulated in graphene pockets has been studied by aberration-corrected high-resolution transmission electron microscopy and electron energy loss spectroscopy at an acceleration voltage of 80 kV. Inside the graphene pockets, crystallization and in situ crystal growth are reported and identified as the insoluble AII phase of CaSO4 (anhydrite) in a quasi-two-dimensional system. Its formation condition is discussed with respect to the possible temperature and van der Waals pressure between the graphene sheets.

Thoughts about next-generation (S)TEM instruments in science.

Different aspects of desirable developments in (scanning) transmission electron microscopes are discussed. Topics are the issues with closed data and control channels, the fixed optical design, and the layout of the sample environment. A solution concept to some of these issues on the basis of current technology and already demonstrated concepts is presented and future possibilities in in situ and multi-dimensional microscopy with the new concept are laid out.

A new bifunctional hybrid nanostructure as an active platform for photothermal therapy and MR imaging.

As a bi-functional cancer treatment agent, a new hybrid nanostructure is presented which can be used for photothermal therapy by exposure to one order of magnitude lower laser powers compared to similar nanostructures in addition to substantial enhancment in magnetic resonance imaging (MRI) contrast. This gold-iron oxide hybrid nanostructure (GIHN) is synthesized by a cost-effective and high yield water-based approach. The GIHN is sheilded by PEG. Therefore, it shows high hemo and biocompatibility and more than six month stability. Alongside earlier nanostructures, the heat generation rate of GIHN is compareable with surfactnat-capped gold nanorods (GNRs). Two reasons are behind this enhancement: Firstly the distance between GNRs and SPIONs is adjusted in a way that the surface plasmon resonance of the new nanostructure is similar to bare GNRs and secondly the fraction of GNRs is raised in the hybrid nanostructure. GIHN is then applied as a photothermal agent using laser irradiation with power as low as 0.5 W.cm(-2) and only 32% of human breast adenocarcinoma cells could survive. The GIHN also acts as a dose-dependent transvers relaxation time (T2) MRI contrast agent. The results show that the GINH can be considered as a good candidate for multimodal photothermal therapy and MRI.

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.

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.

Programmable sub-nanometer sculpting of graphene with electron beams.

Electron beams in transmission electron microscopes are very attractive to engineer and pattern graphene toward all-carbon device fabrication. The use of condensed beams typically used for sequential raster imaging is particularly exciting since they potentially provide high degrees of precision. However, technical difficulties, such as the formation of electron beam induced deposits on sample surfaces, have hindered the development of this technique. We demonstrate how one can successfully use a condensed electron beam, either with or without C(s) correction, to structure graphene with sub-nanometer precision in a programmable manner. We further demonstrate the potential of the developed technique by combining it with an established route to engineer graphene nanoribbons to single-atom carbon chains.