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Nanowire Facilitated Transfer of Sensitive TEM Samples in a FIB
Abstract
We introduce a fast and facile approach to transfer thin films and other mechanically sensitive TEM samples inside a FIB with minimal introduction of stress and bending. The method is making use of a pre-synthetized flexible freestanding Ag nanowire attached to the tip of a typical tungsten micromanipulator inside the FIB. The main advantages of this approach are the significantly reduced stress-induced bending during transfer and attachment of the TEM sample, the very short time required to attach and cut the nanowire and the operation at very low dose and ion current. This results in a reduced sample preparation time and reduced exposure to the ion beam or e-beam for Pt deposition during the sample preparation and thus also reduced contamination and beam damage. The method was applied to a number of thin films and different TEM samples in order to illustrate the advantageous benefits of the concept. In particular, the technique has been successfully tested for the transfer of a thin film onto a MEMS heating chip for in situ TEM experiments.
... Metal bands of any length, from nanometers to hundreds of micrometers, can be deposited using tungsten. A local deposition is also a possibility for other elements like platinum, cobalt, carbon, gold, etc. (Gorji et al., 2020). SiO 2 O 2 and tetra methoxy silane or O 2 and tetraetoxysilane 5 Aluminium Trimethylamine alane Source: Aravindan et al., 2010 In the semiconductor business, FIB is frequently used to patch or alter an existing semiconductor device. ...
Focused ion beam is a versatile top-down nanofabrication method that can be used for atomic-scale material removal and applications. (FIB). Furthermore, a broad range of materials (including metals, ceramics, alloys, plastics, and so on) can be characterized. The dual-beam platform combines a high-resolution scanning electron microscope with an FIB column and includes extra tools, such as gas assisted deposition, micromanipulators, and energy dispersive spectroscopy. Because of these various purposes, the FIB is a versatile tool for the nano processing and nano fabrication industries. Micromanipulators can be used to conduct ultra-precision advanced sample preparation for transmission electron microscopy. When working with hard materials, FIB is the technique for site-specific micro- and nano structuring. Additionally, FIB sectioning and sampling techniques frequently show structural and morphological scattering of material systems with three-dimensional (3D) networks at the micro- and nano scale. This chapter primarily discusses the fundamental principles of FIB machining, with a variety of machining parameters. This chapter also discussed different ion sources that are available in the market and their associated benefits and drawbacks. There are many uses for FIB systems and same will be described with an example later in the chapter.
... Non-epitaxially grown thin films might be deposited directly on an electron transparent membrane. The detachment of the thin layer can be done by chemical etching of the substrate, and the film is then transferred onto the TEM grid [90]. The TEM grid geometry is in Figure 2.5. ...
Complex magnetic materials at the nanoscale are essential in many areas of modern devices, such as digital memories or sensors. Novel technological approaches require the control and understanding of modern magnetic materials down to the atomic scale. One possibility is to exploit high-resolution transmission electron microscopy (TEM), characteristic for its outstanding subatomic resolution. This thesis investigates the options of TEM imaging of metamagnetic materials. These materials are characteristic by displaying coexistence of magnetic phases upon external control. Thin films of metamagnetic FeRh are used as an experimental platform to investigate the various aspects of TEM imaging. FeRh undergoes the metamagnetic phase transition from antiferromagnetic to ferromagnetic phase upon heating. We start with evaluating the sample fabrication processes suitable for our system, which is essential for successful TEM analysis. The differential phase contrast (DPC) technique in TEM is used for the magnetic analysis due to its direct access to the sample magnetic field configuration. An in-depth discussion of DPC signal formation is presented, which is crucial for understanding and analysis of resulting images. Furthermore, we perform structural, chemical, and particularly magnetic imaging of both magnetic phases present in FeRh. Finally, the process of in-situ heating of metamagnetic FeRh lamellae is presented.
... Inspired by our recent work on the successful transfer of a thin film onto a MEMS in situ heating chip by using a pre-synthetized freestanding Ag nanowire (Gorji et al., 2020), we propose a new sample preparation method that enables the transfer of selected individual nanoparticle or a few separated nanoparticles sitting on a piece of carbon film onto a full-range tomography tip with the help of an easily prepared tungsten tip. Since the selected specimen particles are left intact on the original carbon film and they are not attached to the tip directly, it allows picking ultrafine nanoparticles without size limitation, avoiding the risk of mechanical sample damage and performing the full-range electron tomographic analysis. ...
Electron tomography (ET) has gained increasing attention for the 3D characterization of nanoparticles. However, the missing wedge problem due to a limited tilt angle range is still the main challenge for accurate reconstruction in most experimental TEM setups. Advanced algorithms could in-paint or compensate to some extent the missing wedge artifacts, but cannot recover the missing structural information completely. 360° ET provides an option to solve this problem by tilting a needle-shaped specimen over the full tilt range and thus filling the missing information. However, sample preparation especially for fine powders to perform full-range ET is still challenging, thus limiting its application. In this work, we propose a new universal sample preparation method that enables the transfer of selected individual nanoparticle or a few separated nanoparticles by cutting a piece of carbon film supporting the specimen particles and mounting them onto the full-range tomography holder tip with the help of an easily prepared sharp tungsten tip. This method is demonstrated by 360° ET of Pt@TiO2 hollow cage catalyst showing high quality reconstruction without missing wedge.
... There are several ways to manipulate nano objects directly in the SEM camera [19]. For example, with commercial micromanipulators with an ultrafine tungsten needle it is possible to extract from the original array and perform threedimensional manipulations with various nano-objects, such as nanowires [20] or multi-walled nanotubes [21]. However, in the process of manipulation, the nanowhisker should be fixed and then detached from the tungsten tip. ...
Nanotweezers based on the shape memory effect have been developed and tested. In combination with a commercial nanomanipulator, they allow 3D nanoscale operation controlled in a scanning electron microscope. Here we apply the tweezers for the fabrication of nanostructures based on whiskers of NbS3, a quasi one-dimensional compound with room-temperature charge density wave (CDW). The nanowhiskers were separated without damage from the growth batch, an entangled array, and safely transferred to a substrate with a preliminary deposited Au film. The contacts were fabricated with Pt sputtering on top of the whisker and the film. The high degree of synchronization of the sliding CDW under a RF field with a frequency up to 600 MHz confirms the high quality of the contacts and of the sample structure after the manipulations. The proposed technique paves the way to novel type micro- and nanostructures fabrication and their various applications.
... It became possible to measure adhesion between the metal matrix and diamond by using microelectromechanical systems (MEMS) in situ in the TEM column. Mechanical tests were performed using Push-to-Pull (PTP) devices (Bruker, USA) [32][33][34][35][36][37] . These devices consist of a silicon spring with a slot for sample mounting and a platform (Fig. 1a) at which the diamond indenter presses (Fig. 1b). ...
The procedure for in situ TEM measurements of bonding strength (adhesion) between diamond and the metal matrix using a Hysitron PI 95 TEM Picoindenter holder for mechanical tests and Push-to-Pull devices was proposed. For tensile tests, dog-bone shaped lamellae 280–330 nm thick and ~ 2.5 µm long were used as objects of study. The lamellae were manufactured using the focused ion beam technology from the metal–diamond interface of diamond-containing composite material with a single-phase binder made of Fe–Co–Ni alloy. The experimentally determined bonding strength was 110 MPa.
Although in situ transmission electron microscopy (TEM) of nanomaterials has been gaining importance in recent years, difficulties in sample preparation have limited the number of studies on electrical properties. Here, a support‐based preparation method of individual 1D and 2D materials is presented, which yields a reproducible sample transfer for electrical investigation by in situ TEM. A mechanically rigid support grid facilitates the transfer and contacting to in situ chips by focused ion beam with minimum damage and contamination. The transfer quality is assessed by exemplary specimens of different nanomaterials, including a monolayer of WS 2 . Possible studies concern the interplay between structural properties and electrical characteristics on the individual nanomaterial level as well as failure analysis under electrical current or studies of electromigration, Joule heating, and related effects. The TEM measurements can be enriched by additional correlative microscopy and spectroscopy carried out on the identical object with techniques that allow a characterization with a spatial resolution in the range of a few microns. Although developed for in situ TEM, the present transfer method is also applicable to transferring nanomaterials to similar chips for performing further studies or even for using them in potential electrical/optoelectronic/sensing devices.
The fabrication of nanodevices on the delicate membrane window of the TEM (transmission electron microscopy) chip has the risk of breakage failure, limiting in-depth research in this area. This work proposed a methodology to address this issue, enabling secure in-situ transmission electron microscopic observation of many devices and materials that would otherwise be difficult to achieve. Combining semi-custom TEM chip design and front-side protected release technology, a variety of nanodevices were successfully fabricated onto the window membrane of the TEM chip and studied in situ. Moreover, the pressure tolerance of window membrane was investigated and enhanced with a reinforcing structure. As an example of typical applications, MoS2 devices on the TEM chip have been fabricated and electron beam-induced gate modulation and irradiation damage effects, have been demonstrated.
In the last few decades, nanostructuring has driven significant attention towards the development of novel metallic materials with advanced mechanical properties. Nanocrystalline (nc) metals are a class of nanostructured materials with grain sizes smaller than about 100 nm. These exhibit outstanding mechanical strength and fatigue properties compared to their coarse-grained (cg) counterparts. These are promising candidates for application as structural or functional materials. Nc metals in the form of thin films are employed as hard coatings on bulk components, structural components, and conductive layers in various micro-/nanoscale devices. These structural components and devices are often subjected to cyclic stresses or fatigue loading. Under these cyclic stresses, nc metals tend to exhibit the Bauschinger effect (BE). The strength loss during the BE is of great importance concerning the strength-ductility trade-off in nc metals. Furthermore, contact surfaces of the engineering components in service often undergo relative motion and are subject to both friction and wear. These extreme loading conditions demand nc metals with tailored interfacial characteristics for improved tribological performance. Aiming at ensuring high reliability and mechanical robustness for optimum performance of these components, there has been a strong motivation for understanding the mechanical properties and governing deformation mechanisms in nc metallic materials. This thesis aimed at in-depth investigation of microstructures at micro-/nanoscales using state-of-the-art in situ and ex situ transmission electron microscopy (TEM) to develop a closer link between the deformation structure and underlying deformation mechanisms in some nc metallic materials.
The thesis has primarily focused on the in situ TEM nanomechanics of the BE and rotational deformation of grains in nc palladium thin films. A sputtered thin film of nc Pd was deformed inside TEM by cyclic loading-unloading experiments and the evolving microstructure was studied in real-time under different TEM imaging modes. The stress-strain response of the film exhibited a characteristic non-linear unloading behavior confirming the BE in the film. The corresponding bright-field TEM imaging revealed evidence of partially reversible dislocation activity. Towards a quantitative understanding of the deformation structure in real-time, in situ nanomechanical testing was coupled with precession-assisted automated crystal orientation mapping in scanning TEM (ACOM-STEM). Global ACOM-STEM analysis offered crystal orientation of a large number of grains at different states of deformation and confirmed partially reversible rotations of nanosized grains fitting to the observed BE during loading and unloading. Analysis of intragranular rotations showed substantial changes in the sub-structure within most of these grains indicating a dominant role of dislocation-based processes in driving these rotations. Globally, an unusually random evolution of texture was seen that demonstrated the influence of deformation heterogeneity and grain interactions on the resulting texture characteristics in nc metals. In the quest of understanding the grain interactions, local investigations based on annular dark-field STEM imaging during loading-unloading showed reversible changes in the contrast of grains with sets of adjoining grains exhibiting a unique cooperative rotation. Local analysis of the density of geometrically necessary dislocations (GNDs) showed the formation of dislocation pile-up at grain boundaries due to the generation of back-stresses during unloading. Critical observations of the evolution of GND density offered greater insights into the mechanism of cooperative grain rotations and these rotations were related to grain structure and grain boundary characteristics.
In addition to understanding the influence of grain structure and grain boundaries, the thesis has further investigated the role of heterointerfaces in sputtered Au-Cu and Cu-Cr nanocrystalline multilayered composites (NMCs) deformed under cyclic sliding contact. The microstructural evolution in the NMCs was investigated at different deformation states by classical TEM imaging, ACOM-STEM as well as energy-filtered TEM (EFTEM). Au-Cu NMC with an initial high density of twin boundaries deformed by stress-driven detwinning with a concurrent change in grain structure in both Au and Cu. The formation of a vortex structure was observed due to plastic flow instabilities at Au-Cu interfaces that led to codeformation and mechanical intermixing. Cu-Cr NMC showed a preferential grain growth in Cu layers whereas no noticeable change in the grain sizes was seen in Cr layers. The phase maps revealed sharp interfaces between Cu and Cr layers indicating no intermixing between the immiscible phases. EFTEM results exposed the cracking processes in Cr layers with a concurrent migration of Cu in the cracks. Overall, the thesis has attempted to analyze the competing deformation processes and relate these with the microstructural heterogeneity in terms of grain structure and GB and interfacial characteristics in nc metallic materials.
We present here the development of a system that allows for in-situ studies inside the Transmission Electron Microscope (TEM). Functionalized Microelectromechanical Systems (MEMS) used as sample carriers, referred to as Nano-Chips, contain up to eight electrodes used for simultaneous biasing and heating purposes, enabling electro-thermal characterization of various sample types inside the TEM under real life dynamic conditions. This operando approach is an ideal method to study failure analysis of semiconductor materials, performance of resistive switching devices, batteries, fuel cells, piezoceramics and many more.
Equi-atomic FeRh is a very interesting material as it undergoes a magnetostructural transition from an antiferromagnetic (AF) to a ferromagnetic (FM) phase between 75-105 °C. Its ability to present phase co-existence separated by domain walls (DWs) above room temperature provides immense potential for exploitation of their DW motion in spintronic devices. To be able to effectively control the DWs associated with AF/FM coexistence in FeRh thin films we must fully understand the magnetostructural transition and thermomagnetic behaviour of DWs at a localised scale. Here we present a transmission electron microscopy investigation of the transition in planar FeRh thin-film samples by combining differential phase contrast (DPC) magnetic imaging with in situ heating. We perform quantitative measurements from individual DWs as a function of temperature, showing that FeRh on NiAl exhibits thermomagnetic behaviour consistent with the transition from AF to FM. DPC imaging of an FeRh sample with HF-etched substrate reveals a state of AF/FM co-existence and shows the transition from AF to FM regions proceeds via nucleation of small vortex structures, which then grow by combining with newly nucleated vortex states into larger complex magnetic domains, until it is in a fully-FM state.
Optimizing Van der Waals Forces For FIB ex situ Lift Out - Volume 23 Issue S1 - Lucille A. Giannuzzi, Trevor Clark
We present phonon dispersions, element-resolved vibrational density of states (VDOS) and corresponding thermodynamic properties obtained by a combination of density functional theory (DFT) and nuclear resonant inelastic X-ray scattering (NRIXS) across the metamagnetic transition of B2 FeRh in the bulk material and thin epitaxial films. We see distinct differences in the VDOS of the antiferromagnetic (AF) and ferromagnetic (FM) phase which provide a microscopic proof of strong spin-phonon coupling in FeRh. The FM VDOS exhibits a particular sensitivity to the slight tetragonal distortions present in epitaxial films, which is not encountered in the AF phase. This results in a notable change in lattice entropy, which is important for the comparison between thin film and bulk results. Our calculations confirm the recently reported lattice instability in the AF phase. The imaginary frequencies at the $X$-point depend critically on the Fe magnetic moment and atomic volume. Analyzing these non vibrational modes leads to the discovery of a stable monoclinic ground state structure which is robustly predicted from DFT but not verified in our thin film experiments. Specific heat, entropy and free energy calculated within the quasiharmonic approximation suggest that the new phase is possibly suppressed because of its relatively smaller lattice entropy. In the bulk phase, lattice degrees of freedom contribute with the same sign and in similar magnitude to the isostructural AF-FM phase transition as the electronic and magnetic subsystems and therefore needs to be included in thermodynamic modeling.
The atomistic mechanisms active during plastic deformation of nanocrystalline metals are still a subject of controversy. The recently developed approach of combining automated crystal orientation mapping (ACOM) and in situ straining inside a transmission electron microscope was applied to study the deformation of nanocrystalline Pd x Au1- x thin films. This combination enables direct imaging of simultaneously occurring plastic deformation processes in one experiment, such as grain boundary motion, twin activity and grain rotation. Large-angle grain rotations with ≈39° and ≈60° occur and can be related to twin formation, twin migration and twin-twin interaction as a result of partial dislocation activity. Furthermore, plastic deformation in nanocrystalline thin films was found to be partially reversible upon rupture of the film. In conclusion, conventional deformation mechanisms are still active in nanocrystalline metals but with different weighting as compared with conventional materials with coarser grains.
We report on a strain-induced martensitic transformation, accompanied by a suppression of magnetic order in epitaxial films of chemically disordered FeRh. X-ray diffraction, transmission electron microscopy and electronic structure calculations reveal that the lowering of symmetry (from cubic to tetragonal) imposed by the epitaxial relation leads to a further, unexpected, tetragonal-to-orthorhombic transition, triggered by a band-Jahn-Teller-type lattice instability. The collapse of magnetic order is a direct consequence of this structural change, which upsets the subtle balance between ferromagnetic nearest-neighbor interactions arising from Fe-Rh hybridization and frustrated antiferromagnetic coupling among localized Fe moments at larger distances.
Raman mapping is performed to study the lateral damage in supported monolayer
graphene carved by 30 keV focused Ga+
beams. The evolution of the lateral damage is tracked based on the profiles of the intensity ratio between the D (1341 cm−1) and G (1582 cm−1) peaks (ID/IG) of the Raman spectra. The ID/IG profile clearly reveals the transition from stage 2 disorder into stage 1 disorder in graphene along the direction away from the carved area. The critical lateral damage distance spans from <1 μm up to more than 30 μm in the experiment, depending on the parameters used for carving the graphene. The wide damage in the lateral direction is attributed to the deleterious tail of unfocused ions in the ion beam probe. The study raises the attention on potential sample damage during direct patterning of graphene nanostructures using the focused ion beam technique. Minimizing the total carving time is recommended to mitigate the lateral damage.
The bistability of ordered spin states in ferromagnets provides the basis for magnetic memory functionality. The latest generation of magnetic random access memories rely on an efficient approach in which magnetic fields are replaced by electrical means for writing and reading the information in ferromagnets. This concept may eventually reduce the sensitivity of ferromagnets to magnetic field perturbations to being a weakness for data retention and the ferromagnetic stray fields to an obstacle for high-density memory integration. Here we report a room-temperature bistable antiferromagnetic (AFM) memory that produces negligible stray fields and is insensitive to strong magnetic fields. We use a resistor made of a FeRh AFM, which orders ferromagnetically roughly 100 K above room temperature, and therefore allows us to set different collective directions for the Fe moments by applied magnetic field. On cooling to room temperature, AFM order sets in with the direction of the AFM moments predetermined by the field and moment direction in the high-temperature ferromagnetic state. For electrical reading, we use an AFM analogue of the anisotropic magnetoresistance. Our microscopic theory modelling confirms that this archetypical spintronic effect, discovered more than 150 years ago in ferromagnets, is also present in AFMs. Our work demonstrates the feasibility of fabricating room-temperature spintronic memories with AFMs, which in turn expands the base of available magnetic materials for devices with properties that cannot be achieved with ferromagnets.
We report on the magnetic properties of B2-type ordered FeRh epitaxial thin films deposited on MgO(001) substarates as a function of film thickness. All the films show a clear magnetic phase transition from the antiferromagnetic state to the ferromagnetic state with increasing temperature while the transition temperature of a 10-nm-thick film decreases down to 300 K. The 10-nm-thick film also shows a large magnetization even in the antiferromagnetic state compared with other thicker films. These magnetization data indicate that the ferromagnetic state is becoming more stable than the antiferromagnetic state with decreasing film thickness. Such thickness dependent magnetic properties are qualitatively compatible with a theoretical prediction for FeRh(001) thin layers.
The development of micromechanical devices (MEMS and NEMS) on the basis of nanostructured shape memory alloys is reported. A Ti50Ni25Cu25 (at. %) alloy fabricated by the melt spinning technique in the form of a ribbon with a thickness around 40 μm and a width about 1.5 mm was chosen as a starting material. Technological parameters were optimized to produce the alloy in an amorphous state. The thickness of the ribbon was reduced to 5–14 μm by means of electrochemical polishing. A nanostructural state of the thin ribbons was obtained via the dynamic crystallization of the amorphous alloy by application of a single electric pulse with duration in the range of 300–900 μs. A microtweezers prototype with a composite cantilever of 0.8 μm thick and 8 μm long was developed and produced on the basis of the obtained nanostructured thin ribbons by means of the focused ion beam technique. Controlled deformation of the micromanipulator was achieved by heating using semiconductor laser radiation in a vacuum chamber of scanning ion-probe microscope.
The evolution of ferromagnetic domains across the temperature-driven antiferromagnetic (AF) to ferromagnetic (FM) phase transition in uncapped and capped epitaxial FeRh thin films was studied by x-ray magnetic circular dichroism and photoemission electron microscopy. The coexistence of the AF and FM phases was evidenced across the broad transition and the different stages of nucleation, growth and coalescence were observed. The FM phase nucleates into single domain islands and the width of the transition of the individual nuclei is sharper than that of the macroscopic transition.
In situ Lorentz Transmission Electron Microscopy of FeRh Thin Films - Volume 24 Supplement - M. Saleh Gorji, Di Wang, Ralf Witte, Xiake Mu, Robert Kruk, Christian Kübel, Horst Hahn
In this work we present our advanced in situ heating sample carrier for transmission electron microscopy (TEM). The TEM is a powerful tool for materials characterization, especially when combined with micro electro-mechanical systems (MEMS). These deliver in situ stimuli such as heating, in which case temperatures up to 1300 °C can be reached with high temporal stability without affecting the original TEM spatial resolution: indeed, atomic resolution imaging can be routinely performed. Previously, the thermal expansion of suspended microheaters caused vertical displacement of the sample (bulging). As a result, changing temperatures required either continuous focus or stage adjustments, inducing resolution loss or mechanical drift, respectively. Moreover, those actions hinder the possibility to capture fast dynamic events. This new MEMS-based sample carrier, however, keeps the sample at constant z-position (no bulging) up to 700 °C. Furthermore, it enables energy dispersive x-ray spectroscopy (EDS) acquisition in the TEM up to an unmatched temperature of 1000 °C, with a drift rate down to 0.1 nm/min. Its viewable area of 850 µm2 features a temperature homogeneity up to 99.5%.
In-situ transmission electron microscopy is rapidly emerging as the premier technique for characterising materials in a dynamic state on the atomic scale. The most important aspect of in-situ studies is specimen preparation. Specimens must be electron transparent and representative of the material in its operational state, amongst others. Here, a novel fabrication technique for the facile preparation of lamellae for in-situ transmission electron microscopy experimentation using focused ion beam milling is developed. This method involves the use of rotating microgrippers during the lift-out procedure, as opposed to the traditional micromanipulator needle and platinum weld. Using rotating grippers, and a unique adhesive substance, lamellae are mounted onto a MEMS device for in-situ TEM annealing experiments. We demonstrate how this technique can be used to avoid platinum deposition as well as minimising damage to the MEMS device during the thinning process. Our technique is both a cost effective and readily implementable alternative to the current generation of preparation methods for in-situ liquid, electrical, mechanical and thermal experimentation within the TEM as well as traditional cross-sectional lamella preparation.
The lateral damage induced by focused ion beam on silicon carbide was characterized using electrical scanning probe microscopy (SPM), namely, scanning spreading resistance microscopy and conductive atomic force microscopy (c-AFM). It is shown that the damage exceeds the purposely irradiated circles with a radius of 0.5 μm by several micrometres, up to 8 μm for the maximum applied ion dose of 10¹⁸ cm⁻². Obtained SPM results are critically compared with earlier findings on silicon. For doses above the amorphization threshold, in both cases, three different areas can be distinguished. The purposely irradiated area exhibits resistances smaller than the non-affected substrate. A second region with strongly increasing resistance and a maximum saturation value surrounds it. The third region shows the transition from maximum resistance to the base resistance of the unaffected substrate. It correlates to the transition from amorphized to defect-rich to pristine crystalline substrate. Additionally, conventional transmission electron microscopy (TEM) and annular dark-field STEM were used to complement and explain the SPM results and get a further understanding of the defect spreading underneath the surface. Those measurements also show three different regions that correlate well with the regions observed from electrical SPM. TEM results further allow to explain observed differences in the electrical results for silicon and silicon carbide which are most prominent for ion doses above 3 × 10¹⁶ cm⁻². Furthermore, the conventional approach to perform current-voltage measurements by c-AFM was critically reviewed and several improvements for measurement and analysis process were suggested that result in more reliable and impactful c-AFM data.
The gallium ion beam heating on electron transparent transmission electron microscopy (TEM) samples of Au/Ni bilayer films supported by SiO2 substrates was studied by in-situ TEM combined with energy dispersive X-ray spectroscopy. Brief Ga+ ion beam irradiation during sample transfer inside the focused ion beam instrument was found to induce dewetting of bilayer films. The observed morphological changes of the metal films are complemented by considerable Au diffusion through the underlying polycrystalline Ni film and adsorption at the Ni/substrate interface. In-situ heating experiments confirm that alterations of the metal bilayer films caused by ion beam irradiation are consistent with thermal annealing at 400 °C for several minutes in the absence of any ion bombardment. Ion beam damage effects equivalent to prolonged heating may pose considerable limitations to ion beam microscopy of samples with reduced dimensions. Ex-situ lift-out procedures of electron transparent samples in the absence of any ion beam irradiation lead to successful conservation of sample morphologies.
In situ transmission electron microscopy (TEM) with the ability to reveal materials dynamic processes with high spatial and temporal resolution has attracted significant interest. The recent advances in in situ methods, including liquid and gas sample environment, pump-probe ultrafast microscopy, nanomechanics and ferroelectric domain switching the aberration corrected electron optics as well as fast electron detector has opened new opportunities to extend the impact of in situ TEM in broad areas of research ranging from materials science to chemistry, physics and biology. In this article, we highlight the development of liquid environment electron microscopy and its applications in the study of colloidal nanoparticle growth, electrochemical processes and others; in situ study of topological vortices in ferroelectric and ferromagnetic materials. At the end, perspectives of future in situ TEM are provided.
Trustworthy preparation and contacting of micron-sized batteries is an essential task to enable reliable in situ TEM studies during electrochemical biasing. Some of the challenges and solutions for the preparation of all-solid-state batteries for in situ TEM electrochemical studies are discussed using an optimized focused ion beam (FIB) approach. In particular redeposition, resistivity, porosity of the electrodes/electrolyte and leakage current are addressed. Overcoming these challenges, an all-solid-state fluoride ion battery has been prepared as a model system for in situ TEM electrochemical biasing studies and first results on a Bi/La0.9Ba0.1F2.9 half-cell are presented.
Long and smooth tungsten probe is useful for nano-manipulation. In this paper, an ameliorated straightforward dynamic electrochemical etching method and process for long and smooth tungsten probe fabrication have been developed. The relationships between the apex diameter and the aspect ratio of the probe and the fabrication process parameters have been systematically investigated. It's noticed that by process parameter control, the apex size and the shape of the ultra-sharp probe are controllable and reproducible, and the diameter of the probe can be consistently less than 200 nm while its aspect ratio larger than 8 with the same gradient. To get high efficient yield, the consuming time is also researched. Through practical testing and applications as end-effectors in nano-manipulation, the usability and good quality of the fabricated probes have been verified because of their easy availability, high hardness and wear resistance.
The
ex situ
lift out (EXLO) adhesion forces are reviewed and new applications of EXLO for focused ion beam (FIB)-prepared specimens are described. EXLO is used to manipulate electron transparent specimens on microelectromechanical systems carrier devices designed for
in situ
electron microscope analysis. A new patented grid design without a support film is described for EXLO. This new slotted grid design provides a surface for holding the specimen in place and also allows for post lift out processing. Specimens may be easily manipulated into a backside orientation to reduce FIB curtaining artifacts with this slotted grid. Large EXLO specimens can be manipulated from Xe
+
plasma FIB prepared specimens. Finally, applications of EXLO and manipulation of FIB specimens using a vacuum probe lift out method are shown. The vacuum probe provides more control for placing specimens on the new slotted grids and also allows for easy manipulation into a backside configuration.
A site specific technique for cross-section transmission electron microscopy specimen preparation of difficult materials is presented. Focused ion beams are used to slice an electron transparent sliver of the specimen from a specific area of interest. Micromanipulation lift-out procedures are then used to transport the electron transparent specimen to a carbon coated copper grid for subsequent TEM analysis. The experimental procedures are described in detail and an example of the lift-out technique is presented.
A procedure based on focused ion beam milling and in situ lift-out is introduced for the preparation of high-quality specimens for in situ annealing experiments in the transmission electron microscope. The procedure allows an electron-transparent lamella to be cleaned directly on a heating chip using a low ion energy and back-side milling in order to minimize redeposition and damage. The approach is illustrated through the preparation of an Al-Mn-Fe complex metallic alloy specimen.
Reliable and accurate tools for nanoscale manipulation are constantly sought to complement new breakthroughs in nanomaterials and nanotechnology. In this study, a new design of electrically actuated nanotweezers was developed for manipulation of individual nanowires. The design featured two chemically etched tungsten tips attached to a carbon fiber-reinforced polymer and two shape memory alloy actuators. The shape recovery effect of the spring actuators was exploited as a control mechanism for the bending and relaxation modes of the nanotweezers. This was activated by driving a potential difference of less than 1 V across the coils, which was considerably lower than for electromechanical micro/nanotweezers previously developed. To demonstrate the pick-and-place capability of the system, experiments were implemented inside the vacuum chamber of a JEOL-JSM 6300 SEM. Individual Au nanowires averaging 5–10 µm in length and 200 nm in diameter were assembled on silicon substrates using the tungsten tips to draw initials out of various nanowire shapes such as curls, loops, crosses, and zigzags. With such capability, the nanotweezers may find applications in the manufacturing of complex nanostructures or modification of surface properties of materials.
Electromechanical coupling is a topic of current interest in nanostructures, such as metallic and semiconducting nanowires, for a variety of electronic and energy applications. As a result, the determination of structure-property relations that dictate the electromechanical coupling requires the development of experimental tools to perform accurate metrology. Here, a novel micro-electro-mechanical system (MEMS) that allows integrated four-point, uniaxial, electromechanical measurements of freestanding nanostructures in-situ electron microscopy, is reported. Coupled mechanical and electrical measurements are carried out for penta-twinned silver nanowires, their resistance is identified as a function of strain, and it is shown that resistance variations are the result of nanowire dimensional changes. Furthermore, in situ SEM piezoresistive measurements on n-type, [111]-oriented silicon nanowires up to unprecedented levels of ∼7% strain are demonstrated. The piezoresistance coefficients are found to be similar to bulk values. For both metallic and semiconducting nanowires, variations of the contact resistance as strain is applied are observed. These variations must be considered in the interpretation of future two-point electromechanical measurements.
We investigated a low-energy ion-beam irradiation process for the magnetic modification of FeRh thin films using a focused ion beam system. Low-energy ion-beam irradiation induced ferromagnetic states in the FeRh thin films at low temperatures, that originally exhibited antiferromagnetism, as effectively as high-energy ion-beam irradiation. Because the energy deposited by the elastic collisions caused by the irradiation determined the magnetic properties of the samples, the magnetic state of the FeRh thin films could be quantitatively controlled. The low-energy ion-beam irradiation using a focused ion beam system is a potential technique to modify the magnetic properties of materials on the nano- and micro-scales, which may lead to a variety of novel spin devices and applications.
Nanoelectromechanical devices, which can be used as nanotools in nanofactories, were fabricated by focused ion beam chemical vapor deposition (FIB-CVD). The devices are made of diamond-like carbon (DLC), deposited on a Si substrate using gasified phenanthrene (C14H10) as a carbon source. The Young modulus and density of the deposited DLC were measured as 190 GPa and 3.8 g cm-3, respectively. The work function was smaller for DLC (2.9 eV) than for W (4.7 eV) and Fe (5.2 eV) deposited by FIB-CVD. A nanomanipulator was manufactured by FIB-CVD and used for actual manipulations. A glass capillary based local field emitter was developed and produced as a tool for spot deposition, and its electron field emission was confirmed. FIB-CVD is proven as an efficient fabrication technology of novel nanoelectromechanical devices.
Highly oriented Ag(TCNQ) nanowires have been prepared on Si(111) wafer at 100 degrees C by the vapour-transport reaction between silver and TCNQ without any other catalyst. X-ray diffraction analysis shows that the composition and crystal structure of the obtained nanostructure were Ag(TCNQ) crystalline. Most Ag(TCNQ) nanowires were grown uniformly and vertically on the substrate with diameters ranging from 50 to 300 nm and the lengths measuring from 2 to 50 mum by scanning electron microscopy. Ag particles were observed on the substrate from pure thin Ag film heated under the same conditions as used in synthesizing the nanowires. Nucleation and short Ag(TCNQ) nanowires were prepared by controlling the reaction time, providing direct evidence of the growth mechanism in a nanometre scale. The growth process was explained according to the vapour-liquid-solid model. The gradient of temperature and the densely distributed Ag particles may contribute to the vertically aligned growth. These results will be helpful for the controllable synthesis of Ag(TCNQ) nanowires.
In this paper, we propose a new method to make a nanotweezer composed of two carbon nanotube (CNT) arms. We fabricated the CNT arm by attaching a multi-wall carbon nanotube on a tungsten-tip via manual assembly. The closing actuation of the nanotweezer is simulated and the simulation is compared with experimental results. Since each CNT arm has a macro actuator, namely a separated tweezer arm, it is possible to close and open the nanotweezer repeatedly. Electrochemical etching is used to cut the carbon nanotube in the CNT arm and the cutting resolution is approximately a few hundred nanometers.
Nanocrystalline metals are expected to exhibit different deformation mechanisms when compared to their coarse grained counterparts because the dislocation storage capacity decreases and the grain boundary mediated processes become more pronounced with decreasing grain size. As a new approach to directly image and quantify the plastic deformation processes in nanocrystalline thin films, a combination of automated crystal orientation mapping in microprobe STEM mode with in situ straining inside a TEM was developed. ACOM-TEM closes the gap between EBSD and BF/DFTEM by providing full orientation maps with nanometer resolution. The novel combination with in situ straining provided for the first time the possibility to directly image and quantify the structural changes of all crystallites in the ensemble of a thin film at the nanometer scale during mechanical deformation. It was used to characterize the metallographic changes during tensile deformation of a nanocrystalline Au thin film prepared by magnetron sputtering. The investigation of the grain size, grain orientation and twinning on a global (grain average over a micron sized area) and local (assembly of selected grains) scale allowed for the development of an in depth picture of the deformation processes. Grain boundary motion and local grain rotation were two of the processes acting to dissipate the applied stress. Additionally, twinning/detwinning occurred simultaneously during straining. These processes, which occurred locally already in the micro-plastic regime, led to global grain growth starting at the transition to the macro-plastic deformation regime.
The recent emergence of the focused ion-beam (FIB) microscope as a dedicated specimen preparation tool for transmission electron microscopy (TEM) has extended the reach of TEM to a wider variety of problems in materials science. This paper highlights three examples of using FIB-SEM lift-out techniques for preparing site-specific and crystallographic orientation-specific thin-foil specimens. An in situ lift-out technique used to extract thin foils from across a local grain boundary in bulk Al alloy and from individual fine Al atomised powder particles (down to 20μm in diameter) was performed with real-time secondary electron imaging within the chamber of a FIB-SEM system. In conjunction with electron backscatter diffraction (EBSD), the FIB is used for extracting TEM foil with a specific crystallographic orientation aligned normal to the broad plane of the foil. The above technique has been demonstrated using a dual-phase Ti-Si alloy for the exploration of orientation relationship between constituent phases. Furthermore, it is suggested that FIB is more applicable for preparing thin foils from hydrogen-sensitive metals (such as titanium alloys) than conventional thinning techniques, which tend to induce ambiguous artifacts in these foils.
Magnetic cooling could be a radically different energy solution substituting conventional vapour compression refrigeration in the future. For the largest cooling effects of most potential refrigerants we need to fully exploit the different degrees of freedom such as magnetism and crystal structure. We report now for Heusler-type Ni–Mn–In–(Co) magnetic shape-memory alloys, the adiabatic temperature change ΔT(ad) = −3.6 to −6.2 K under a moderate field of 2 T. Here it is the structural transition that plays the dominant role towards the net cooling effect. A phenomenological model is established that reveals the parameters essential for such a large ΔT(ad). We also demonstrate that obstacles to the application of Heusler alloys, namely the usually large hysteresis and limited operating temperature window, can be overcome by using the multi-response to different external stimuli and/or fine-tuning the lattice parameters, and by stacking a series of alloys with tailored magnetostructural transitions.
Two complementary lift-off approaches for thin films from MgO, based on standard chemicals, are reported. Accompanied by appropriate annealing treatment they can be employed to synthesize freestanding single crystalline Fe-Pd films in the face centered tetragonal martensitic phase required for miniaturized magnetic shape memory acutation. Generalizations to other materials systems, e. g. epitaxially grown martensitic Ni-Mn-Ga magnetic shape memory alloy films, are also demonstrated.
Scanning probe microscopy techniques and, in particular, scanning spreading resistance microscopy (SSRM) were used for a detailed characterization of focused ion beam (FIB) induced damage in the surrounding of purposely irradiated areas on silicon. It is shown that the damaged area detected using these techniques extends up to several micrometers around the irradiated structures. The influence of the key FIB processing parameters on the FIB induced damage was examined. Parameters which were taken into account are the ion dose (from 10(12) to 10(18) cm(-2)), the milled structure size (circle diameters from 0.25 to 10 mu m), the beam energy (from 10 to 30 keV), and the beam current (from 1.5 to 280 pA). Moreover, the influence of the SSRM settings on the measurement results was investigated. Settings which were considered are the bias voltage and the force applied to the tip during the SSRM analysis. High resolution transmission electron microscopy and secondary ion mass spectroscopy analyses were performed to validate the SSRM results. Scattering between Ga ions and residual gas particles in the vacuum chamber of the FIB tool is identified as the main reason for the observed damaged area.
Recently designed advanced in-situ specimen holders for transmission electron microscopy (TEM) have been used in studies of gold nanoparticles. We report results of variable temperature TEM experiments in which structural transformations have been correlated with specimen temperature, allowing general trends to be identified. Transformation to a decahedral morphology for particles in the size range 5-12nm was observed for the majority of particles regardless of their initial structure. Following in-situ annealing, decahedra were found to be stable at room temperature, confirming this as the equilibrium morphology, in agreement with recently calculated phase diagrams. Other transitions at low temperature in addition to surface roughening have also been observed and correlated with the same nanoscale phase diagram. Investigations of gold particles at high temperature have revealed evidence for co-existing solid and liquid phases. Overall, these results are important in a more precise understanding of the structure and action of catalytic gold nanoparticles and in the experimental verification of theoretical calculations.
One of the basic tasks a robot has to perform is to manipulate
objects. For macroscopic applications mechanical grippers usually grasp
the workpiece. Because of the different scaling of gravity and adhesion
such tools are no more suitable in micro manipulation. A better strategy
is to use adhesion forces or vacuum. Therefore, after a brief
introduction to adhesion phenomenons this paper focuses on the
investigation of a vacuum gripping tool consisting of a glass pipette
and a computer controlled vacuum supply. Special emphasis is laid on the
optimization of the tool's parameters in order to improve its pick and
place capability. The tool has been integrated into the ETHZ NanoRobot
and tested on dedicated benchmark test. It was possible to grip 100
μm sized diamond crystals and deposit them at arbitrary positions.
Also emergency routines that allow to reliably get rid of sticking
particles are presented. Finally the new setup of the multi-tool
NanoRobot containing both the vacuum pipette and a microfabricated
gripper is presented. It enables handling of micro-parts with more
flexibility by working hand in hand
- T T Mueller
- E W Tsong
T.T. Mueller, E.W. Tsong, Field Ion Microscopy Principles and Applications, Am.
Elsevier, New York, 1969.
Nano-manipulation, nano-manufacturing, nano-measurements by new smart material-based mechanical nanotools
- V Koledov
V. Koledov, Nano-manipulation, nano-manufacturing, nano-measurements by new
smart material-based mechanical nanotools, 2018 IEEE Int. Conf. Manip. Manuf.
Meas. Nanoscale, 2018, pp. 171-176.