Atomic scale volume and grain boundary diffusion elucidated by in situ STEM.

Diffusion is one of the most important phenomena studied in science ranging from physics to biology and, in abstract form, even in social sciences. In the field of materials science, diffusion in crystalline solids is of particular interest as it plays a pivotal role in materials synthesis, processing and applications. While this subject has been studied extensively for a long time there are still some fundamental knowledge gaps to be filled. In particular, atomic scale observations of thermally stimulated volume diffusion and its mechanisms are still lacking. In addition, the mechanisms and kinetics of diffusion along defects such as grain boundaries are not yet fully understood. In this work we show volume diffusion processes of tungsten atoms in a metal matrix on the atomic scale. Using in situ high resolution scanning transmission electron microscopy we are able to follow the random movement of single atoms within a lattice at elevated temperatures. The direct observation allows us to confirm random walk processes, quantify diffusion kinetics and distinctly separate diffusion in the volume from diffusion along defects. This work solidifies and refines our knowledge of the broadly essential mechanism of volume diffusion.

Thermally Stable Nanotwins: New Heights for Cu Mechanics.

Nanocrystalline and nanotwinned materials achieve exceptional strengths through small grain sizes. Due to large areas of crystal interfaces, they are highly susceptible to grain growth and creep deformation, even at ambient temperatures. Here, ultrahigh strength nanotwinned copper microstructures have been stabilized against high temperature exposure while largely retaining electrical conductivity. By incorporating less than 1 vol% insoluble tungsten nanoparticles by a novel hybrid deposition method, both the ease of formation and the high temperature stability of nanotwins are dramatically enhanced up to at least 400 °C. By avoiding grain coarsening, improved high temperature creep properties arise as the coherent twin boundaries are poor diffusion paths, while some size-based nanotwin strengthening is retained. Such microstructures hold promise for more robust microchip interconnects and stronger electric motor components.

Composition Dependent Electrical Transport in Si1-x Gex Nanosheets with Monolithic Single-Elementary Al Contacts.

Si1-x Gex is a key material in modern complementary metal-oxide-semiconductor and bipolar devices. However, despite considerable efforts in metal-silicide and -germanide compound material systems, reliability concerns have so far hindered the implementation of metal-Si1-x Gex junctions that are vital for diverse emerging "More than Moore" and quantum computing paradigms. In this respect, the systematic structural and electronic properties of Al-Si1-x Gex heterostructures, obtained from a thermally induced exchange between ultra-thin Si1-x Gex nanosheets and Al layers are reported. Remarkably, no intermetallic phases are found after the exchange process. Instead, abrupt, flat, and void-free junctions of high structural quality can be obtained. Interestingly, ultra-thin interfacial Si layers are formed between the metal and Si1-x Gex segments, explaining the morphologic stability. Integrated into omega-gated Schottky barrier transistors with the channel length being defined by the selective transformation of Si1-x Gex into single-elementary Al leads, a detailed analysis of the transport is conducted. In this respect, a report on a highly versatile platform with Si1-x Gex composition-dependent properties ranging from highly transparent contacts to distinct Schottky barriers is provided. Most notably, the presented abrupt, robust, and reliable metal-Si1-x Gex junctions can open up new device implementations for different types of emerging nanoelectronic, optoelectronic, and quantum devices.

Mapping pure plastic strains against locally applied stress: Revealing toughening plasticity.

The deformation of all materials can be separated into elastic and plastic parts. Measuring the purely plastic component is complex but crucial to fully characterize, understand, and engineer structural materials to "bend, not break." Our approach has mapped this to answer the long-standing riddle in materials mechanics: The low toughness of body-centered cubic metals, where we advance an experimentally led mitigative theory. At a micromechanically loaded crack, we measured in situ the stress state applied locally on slip systems, and the dislocation content, and then correlatively compared with the occurrence-or not-of toughness-inducing local plasticity. We highlight limitations and potential misinterpretations of commonly used postmortem transmission electron imaging. This should enable better-informed design for beneficial plasticity and strength in crystalline and amorphous solids alike.

Monolithic and Single-Crystalline Aluminum-Silicon Heterostructures.

Overcoming the difficulty in the precise definition of the metal phase of metal-Si heterostructures is among the key prerequisites to enable reproducible next-generation nanoelectronic, optoelectronic, and quantum devices. Here, we report on the formation of monolithic Al-Si heterostructures obtained from both bottom-up and top-down fabricated Si nanostructures and Al contacts. This is enabled by a thermally induced Al-Si exchange reaction, which forms abrupt and void-free metal-semiconductor interfaces in contrast to their bulk counterparts. The selective and controllable transformation of Si NWs into Al provides a nanodevice fabrication platform with high-quality monolithic and single-crystalline Al contacts, revealing resistivities as low as ρ = (6.31 ± 1.17) × 10-8 Ω m and breakdown current densities of Jmax = (1 ± 0.13) × 1012 Ω m-2. Combining transmission electron microscopy and energy-dispersive X-ray spectroscopy confirmed the composition as well as the crystalline nature of the presented Al-Si-Al heterostructures, with no intermetallic phases formed during the exchange process in contrast to state-of-the-art metal silicides. The thereof formed single-element Al contacts explain the robustness and reproducibility of the junctions. Detailed and systematic electrical characterizations carried out on back- and top-gated heterostructure devices revealed symmetric effective Schottky barriers for electrons and holes. Most importantly, fulfilling compatibility with modern complementary metal-oxide semiconductor fabrication, the proposed thermally induced Al-Si exchange reaction may give rise to the development of next-generation reconfigurable electronics relying on reproducible nanojunctions.

Monolithic Metal-Semiconductor-Metal Heterostructures Enabling Next-Generation Germanium Nanodevices.

Low-dimensional Ge is perceived as a promising building block for emerging optoelectronic devices. Here, we present a wafer-scale platform technology enabling monolithic Al-Ge-Al nanostructures fabricated by a thermally induced Al-Ge exchange reaction. Transmission electron microscopy confirmed the purity and crystallinity of the formed Al segments with an abrupt interface to the remaining Ge segment. In good agreement with the theoretical value of bulk Al-Ge Schottky junctions, a barrier height of 200 ± 20 meV was determined. Photoluminescence and µ-Raman measurements proved the optical quality of the Ge channel embedded in the monolithic Al-Ge-Al heterostructure. Together with the wafer-scale accessibility, the proposed fabrication scheme may give rise to the development of key components of a broad spectrum of emerging Ge-based devices requiring monolithic metal-semiconductor-metal heterostructures with high-quality interfaces.

3D Bi2Te3 Interconnected Nanowire Networks to Increase Thermoelectric Efficiency.

3D interconnected nanowire scaffoldings are shown to increase the thermoelectric efficiency in comparison to similar diameter 1D nanowires and films grown under similar electrodeposition conditions. Bi2Te3 3D nanonetworks offer a reduction in thermal conductivity (κT) while preserving the high electrical conductivity of the films. The reduction in κT is modeled using the hydrodynamic heat transport equation, and it can be understood as a heat viscosity effect due to the 3D nanostructuration. In addition, the Seebeck coefficient is twice that of nanowires and films, and up to 50% higher than in a single crystal. This increase is interpreted as a nonequilibrium effect that the geometry of the structure induces on the distribution function of the phonons, producing an enhanced phonon drag. These thermoelectric metamaterials have higher performance and are fabricated with large areas by a cost-effective method, which makes them suitable for up-scale production.

In Situ Atomic Force Microscopy Depth-Corrected Three-Dimensional Focused Ion Beam Based Time-of-Flight Secondary Ion Mass Spectroscopy: Spatial Resolution, Surface Roughness, Oxidation.

Atomic force microscopy (AFM) is a well-known tool for studying surface roughness and to collect depth information about features on the top atomic layers of samples. By combining secondary ion mass spectroscopy (SIMS) with focused ion beam (FIB) milling in a scanning electron microscope (SEM), chemical information of sputtered structures can be visualized and located with high lateral and depth resolution. In this paper, a high vacuum (HV) compatible AFM was installed in a TESCAN FIB-SEM instrument that was equipped with a time-of-flight SIMS (ToF-SIMS) detector. To calibrate the sputtering rate and measure the induced roughness caused by the ToF-SIMS analysis, subsequent AFM measurements were performed on an inorganic multilayer vertical cavity surface-emitting laser sample. Normalized sputtering rates were used to aid the accurate three-dimensional reconstruction of the sputtered volume's chemical composition. Achievable resolution, surface roughness during sputtering, and surface oxidation issues were analyzed. The integration of complementary detectors opens up the ability to determine the sample properties as well as to understand the influence of the Ga+ ion sputtering method on the sample surface during the analysis.

Thin-Film Engineering of Mechanical Fragmentation Properties of Atomic-Layer-Deposited Metal Oxides.

Mechanical fracture properties were studied for the common atomic-layer-deposited Al2O3, ZnO, TiO2, ZrO2, and Y2O3 thin films, and selected multilayer combinations via uniaxial tensile testing and Weibull statistics. The crack onset strains and interfacial shear strains were studied, and for crack onset strain, TiO2/Al2O3 and ZrO2/Al2O3 bilayer films exhibited the highest values. The films adhered well to the polyimide carrier substrates, as delamination of the films was not observed. For Al2O3 films, higher deposition temperatures resulted in higher crack onset strain and cohesive strain values, which was explained by the temperature dependence of the residual strain. Doping Y2O3 with Al or nanolaminating it with Al2O3 enabled control over the crystal size of Y2O3, and provided us with means for improving the mechanical properties of the Y2O3 films. Tensile fracture toughness and fracture energy are reported for Al2O3 films grown at 135 °C, 155 °C, and 220 °C. We present thin-film engineering via multilayering and residual-strain control in order to tailor the mechanical properties of thin-film systems for applications requiring mechanical stretchability and flexibility.

Crystal Structure Evolution, Microstructure Formation, and Properties of Mechanically Alloyed Ultrafine-Grained Ti-Zr-Nb Alloys at 36≤Ti≤70 (at. %).

Titanium ß-type alloys are preferred biomaterials for hard tissue replacements due to the low Young modulus and limitation of harmful aluminum and vanadium present in the commercially available Ti6Al4V alloy. The aim of this study was to develop a new ternary Ti-Zr-Nb system at 36≤Ti≤70 (at. %). The technical viability of preparing Ti-Zr-Nb alloys by high-energy ball-milling in a SPEX 8000 mill has been studied. These materials were prepared by the combination of mechanical alloying and powder metallurgy approach with cold powder compaction and sintering. Changes in the crystal structure as a function of the milling time were investigated using X-ray diffraction. Our study has shown that mechanical alloying supported by cold pressing and sintering at the temperature below αâ†’ß transus (600°C) can be applied to synthesize single-phase, ultrafine-grained, bulk Ti(ß)-type Ti30Zr17Nb, Ti23Zr25Nb, Ti30Zr26Nb, Ti22Zr34Nb, and Ti30Zr34Nb alloys. Alloys with lower content of Zr and Nb need higher sintering temperatures to have them fully recrystallized. The properties of developed materials are also engrossing in terms of their biomedical use with Young modulus significantly lower than that of pure titanium.

Pulsed current-voltage electrodeposition of stoichiometric Bi2Te3 nanowires and their crystallographic characterization by transmission electron backscatter diffraction.

Bi2Te3 nanowires with diameters ranging from 25 to 270 nm, ultra-high aspect ratio, and uniform growth front were fabricated by electrodeposition, pulsing between zero current density during the off time and constant potential during the on time (pulsed-current-voltage method, p-IV). The use of zero current density during the off time is to ensure no electrodeposition is carried out and the system is totally relaxed. By this procedure, stoichiometric nanowires oriented perpendicular to the c-axis is obtained for the different diameters of porous alumina templates. In addition, the samples show a uniform growth front with ultra-high aspect ratio single crystal nanowires. The high degree of crystallinity was verified by transmission electron backscatter diffraction. This characterization revealed that the nanowires present both large single crystalline areas and areas with alternating twin configurations.

Annealing-Based Electrical Tuning of Cobalt-Carbon Deposits Grown by Focused-Electron-Beam-Induced Deposition.

An effective postgrowth electrical tuning, via an oxygen releasing method, to enhance the content of non-noble metals in deposits directly written with gas-assisted focused-electron-beam-induced deposition (FEBID) is presented. It represents a novel and reproducible method for improving the electrical transport properties of Co-C deposits. The metal content and electrical properties of Co-C-O nanodeposits obtained by electron-induced dissociation of volatile Co2(CO)8 precursor adsorbate molecules were reproducibly tuned by applying postgrowth annealing processes at 100 °C, 200 °C, and 300 °C under high-vacuum for 10 min. Advanced thin film EDX analysis showed that during the annealing process predominantly oxygen is released from the Co-C-O deposits, yielding an atomic ratio of Co:C:O = 100:16:1 (85:14:1) with respect to the atomic composition of as-written Co:C:O = 100:21:28 (67:14:19). In-depth Raman analysis suggests that the amorphous carbon contained in the as-written deposit turns into graphite nanocrystals with size of about 22.4 nm with annealing temperature. Remarkably, these microstructural changes allow for tuning of the electrical resistivity of the deposits over 3 orders of magnitude from 26 mΩ cm down to 26 µΩ cm, achieving a residual resistivity of ρ2K/ρ300 K = 0.56, close to the value of 0.53 for pure Co films with similar dimensions, making it especially interesting and advantageous over the numerous works already published for applications such as advanced scanning-probe systems, magnetic memory, storage, and ferroelectric tunnel junction memristors, as the graphitic matrix protects the cobalt from being oxidized under an ambient atmosphere.

Silicon etch with chromium ions generated by a filtered or non-filtered cathodic arc discharge.

The pre-treatment of substrate surfaces prior to deposition is important for the adhesion of physical vapour deposition coatings. This work investigates Si surfaces after the bombardment by energetic Cr ions which are created in cathodic arc discharges. The effect of the pre-treatment is analysed by X-ray diffraction, Rutherford backscattering spectroscopy, scanning electron microscopy and in-depth X-ray photoemission spectroscopy and compared for Cr vapour produced from a filtered and non-filtered cathodic arc discharge. Cr coverage as a function of ion energy was also predicted by TRIDYN Monte Carlo calculations. Discrepancies between measured and simulated values in the transition regime between layer growth and surface removal can be explained by the chemical reactions between Cr ions and the Si substrate or between the substrate surface and the residual gases. Simulations help to find optimum and more stable parameters for specific film and substrate combinations faster than trial-and-error procedure.

Crystallographic services and technology support for industry.

The activities of CSEM's XRD Application Lab are oriented towards the analytical support of technology and product development in the fields of materials sciences, microtechnology, physics, chemistry, nanotechnology and life sciences. Non-destructive X-ray diffraction methods are used for the structural investigation of materials, components and systems. New developments are made with a focus on in situ techniques to 'watch the action' - structural transformations in dependence of applied external fields such as temperature, humidity, magnetic fields or mechanical stresses.

Crystallographic Services and Technology Support for Industry.

The activities of CSEM's XRD Application Lab are oriented towards the analytical support of technology and product development in the fields of materials sciences, microtechnology, physics, chemistry, nanotechnology and life sciences. Non-destructive X-ray diffraction methods are used for the structural investigation of materials, components and systems. New developments are made with a focus on in situ techniques to 'watch the action' - structural transformations in dependence of applied external fields such as temperature, humidity, magnetic fields or mechanical stresses.