In situ transmission electron microscopy as a toolbox for the emerging science of nanometallurgy.

Potential applications of nanomaterials range from electronics to environmental technology, thus a better understanding of their manufacturing and manipulation is of paramount importance. The present study demonstrates a methodology for the use of metallic nanomaterials as reactants to examine nanoalloying in situ within a transmission electron microscope. The method is further utilised as a starting point of a metallurgical toolbox, e.g. to study subsequent alloying of materials by using a nanoscale-sized chemical reactor for nanometallurgy. Cu nanowires and Au nanoparticles are used for alloying with pure Al, which served as the matrix material in the form of electron transparent lamellae. The results showed that both the Au and Cu nanomaterials alloyed when Al was melted in the transmission electron microscope. However, the eutectic reaction was more pronounced in the Al-Cu system, as predicted from the phase diagram. Interestingly, the mixing of the alloying agents occurred independently of the presence of an oxide layer surrounding the nanowires, nanoparticles, or the Al lamellae while performing the experiments. Overall, these results suggest that transmission electron microscope-based in situ melting and alloying is a valuable lab-on-a-chip technique to study the metallurgical processing of nanomaterials for the future development of advanced nanostructured materials.

Irradiation stability and induced ferromagnetism in a nanocrystalline CoCrCuFeNi highly-concentrated alloy.

In the field of radiation damage of crystalline solids, new highly-concentrated alloys (HCAs) are now considered to be suitable candidate materials for next generation fission/fusion reactors due to recently recorded outstanding radiation tolerance. Despite the preliminarily reported extraordinary properties, the mechanisms of degradation, phase instabilities and decomposition of HCAs are still largely unexplored fields of research. Herein, we investigate the response of a nanocrystalline CoCrCuFeNi HCA to thermal annealing and heavy ion irradiation in the temperature range from 293 to 773 K with the objective to analyze the stability of the nanocrystalline HCA in extreme conditions. The results led to the identification of two regimes of response to irradiation: (i) in which the alloy was observed to be tolerant under extreme irradiation conditions and (ii) in which the alloy is subject to matrix phase instabilities. The formation of FeCo monodomain nanoparticles under these conditions is also reported and a differential phase contrast study in the analytical electron-microscope is carried out to qualitatively probe its magnetic properties.

A Fast and Implantation-Free Sample Production Method for Large Scale Electron-Transparent Metallic Samples Destined for MEMS-Based In Situ S/TEM Experiments.

Microelectromechanical systems (MEMS) are currently supporting ground-breaking basic research in materials science and metallurgy as they allow in situ experiments on materials at the nanoscale within electron microscopes in a wide variety of different conditions such as extreme materials dynamics under ultrafast heating and quenching rates as well as in complex electro-chemical environments. Electron-transparent sample preparation for MEMS e-chips remains a challenge for this technology as the existing methodologies can introduce contaminants, thus disrupting the experiments and the analysis of results. Herein we introduce a methodology for simple and fast electron-transparent sample preparation for MEMS e-chips without significant contamination. The quality of the samples as well as their performance during a MEMS e-chip experiment in situ within an electron microscope are evaluated during a heat treatment of a crossover AlMgZn(Cu) alloy.

Prototypic Lightweight Alloy Design for Stellar-Radiation Environments.

The existing literature data shows that conventional aluminium alloys may not be suitable for use in stellar-radiation environments as their hardening phases are prone to dissolve upon exposure to energetic irradiation, resulting in alloy softening which may reduce the lifetime of such materials impairing future human-based space missions. The innovative methodology of crossover alloying is herein used to synthesize an aluminium alloy with a radiation resistant hardening phase. This alloy-a crossover of 5xxx and 7xxx series Al-alloys-is subjected to extreme heavy ion irradiations in situ within a TEM up to a dose of 1 dpa and major experimental observations are made: the Mg32(Zn,Al)49 hardening precipitates (denoted as T-phase) for this alloy system surprisingly survive the extreme irradiation conditions, no cavities are found to nucleate and displacement damage is observed to develop in the form of black-spots. This discovery indicates that a high phase fraction of hardening precipitates is a crucial parameter for achieving superior radiation tolerance. Based on such observations, this current work sets new guidelines for the design of metallic alloys for space exploration.

Understanding amorphization mechanisms using ion irradiation in situ a TEM and 3D damage reconstruction.

In this work, ion irradiations in-situ of a transmission electron microscope are performed on single-crystal germanium specimens with either xenon, krypton, argon, neon or helium. Using analysis of selected area diffraction patterns and a custom implementation of the Stopping and Range of Ions in Matter (SRIM) within MATLAB (which allows both the 3D reconstruction of the collision cascades and the calculation of the density of vacancies) the mechanisms behind amorphization are revealed. An intriguing finding regarding the threshold displacements per atom (dpa) required for amorphization results from this study: even though the heavier ions generate more displacements than lighter ions, it is observed that the threshold dpa for amorphization is lower for the krypton-irradiated specimens than for the xenon-irradiated ones. The 3D reconstructions of the collision cascades show that this counter-intuitive observation is the consequence of a heterogeneous amorphization mechanism. Furthermore, it is also shown that such a heterogeneous process occurs even for helium ions, which, on average induce only three recoils per ion in the specimen. It is revealed that at relatively high dpa, the stochastic nature of the collision cascade ensures complete amorphization via the accumulation of large clusters of defects and even amorphous zones generated by single-helium-ion strikes.

Thermal stability and irradiation response of nanocrystalline CoCrCuFeNi high-entropy alloy.

Grain growth and phase stability of a nanocrystalline face-centered cubic (fcc) Ni0.2Fe0.2Co0.2Cr0.2Cu0.2 high-entropy alloy (HEA), either thermally- or irradiation-induced, are investigated through in situ and post-irradiation transmission electron microscopy (TEM) characterization. Synchrotron and lab x-ray diffraction measurements are carried out to determine the microstructural evolution and phase stability with improved statistics. Under in situ TEM observation, the fcc structure is stable at 300 °C with a small amount of grain growth from 15.8 to ∼20 nm being observed after 1800 s. At 500 °C, however, some abnormal growth activities are observed after 1400 s, and secondary phases are formed. Under 3 MeV Ni room temperature ion irradiation up to an extreme dose of nearly 600 displacements per atom, the fcc phase is stable and the average grain size increases from 15.6 to 25.2 nm. Grain growth mechanisms driven by grain rotation, grain boundary curvature, and disorder are discussed.

Ion-beam-induced bending of semiconductor nanowires.

The miniaturisation of technology increasingly requires the development of both new structures as well as novel techniques for their manufacture and modification. Semiconductor nanowires (NWs) are a prime example of this and as such have been the subject of intense scientific research for applications ranging from microelectronics to nano-electromechanical devices. Ion irradiation has long been a key processing step for semiconductors and the natural extension of this technique to the modification of semiconductor NWs has led to the discovery of ion beam-induced deformation effects. In this work, transmission electron microscopy with in situ ion bombardment has been used to directly observe the evolution of individual silicon and germanium NWs under irradiation. Silicon NWs were irradiated with either 6 keV neon ions or xenon ions at 5, 7 or 9.5 keV with a flux of 3 × 1013 ions cm-2 s-1. Germanium NWs were irradiated with 30 or 70 keV xenon ions with a flux of 1013 ions cm-2 s-1. These new results are combined with those reported in the literature in a systematic analysis using a custom implementation of the transport of ions in matter Monte Carlo computer code to facilitate a direct comparison with experimental results taking into account the wide range of experimental conditions. Across the various studies this has revealed underlying trends and forms the basis of a critical review of the various mechanisms which have been proposed to explain the deformation of semiconductor NWs under ion irradiation.