Long-Term Performance of Magnetic Force Microscopy Tips Grown by Focused Electron Beam Induced Deposition.

High-resolution micro- and nanostructures can be grown using Focused Electron Beam Induced Deposition (FEBID), a direct-write, resist-free nanolithography technology which allows additive patterning, typically with sub-100 nm lateral resolution, and down to 10 nm in optimal conditions. This technique has been used to grow magnetic tips for use in Magnetic Force Microscopy (MFM). Due to their high aspect ratio and good magnetic behavior, these FEBID magnetic tips provide several advantages over commercial magnetic tips when used for simultaneous topographical and magnetic measurements. Here, we report a study of the durability of these excellent candidates for high-resolution MFM measurements. A batch of FEBID-grown magnetic tips was subjected to a systematic analysis of MFM magnetic contrast for 30 weeks, using magnetic storage tape as a test specimen. Our results indicate that these FEBID magnetic tips operate effectively over a long period of time. The magnetic signal was well preserved, with a maximum reduction of 60% after 21 weeks of recurrent use. No significant contrast degradation was observed after 30 weeks in storage.

Low-resistivity Pd nanopatterns created by a direct electron beam irradiation process free of post-treatment steps.

The ability to create metallic patterned nanostructures with excellent control of size, shape and spatial orientation is of utmost importance in the construction of next-generation electronic and optical devices as well as in other applications such as (bio)sensors, reactive surfaces for catalysis, etc. Moreover, development of simple, rapid and low-cost fabrication processes of metallic patterned nanostructures is a challenging issue for the incorporation of such devices in real market applications. In this contribution, a direct-write method that results in highly conducting palladium-based nanopatterned structures without the need of applying subsequent curing processes is presented. Spin-coated films of palladium acetate were irradiated with an electron beam to produce palladium nanodeposits (PdNDs) with controlled size, shape and height. The use of different electron doses was investigated and its influence on the PdNDs features determined, namely: (1) thickness of the deposits, (2) atomic percentage of palladium content, (3) oxidation state of palladium in the deposit, (4) morphology of the sample and grain size of the Pd nanocrystals and (5) resistivity. It has been probed that the use of high electron doses, 30000µC cm-2results in the lowest resistivity reported to date for PdNDs, namely 145µΩ cm, which is only one order of magnitude higher than bulk palladium. This result paves the way for development of simplified lithography processes of nanostructured deposits avoiding subsequent post-treatment steps.

Superconducting properties of in-plane W-C nanowires grown by He+ focused ion beam induced deposition.

Focused ion beam induced deposition (FIBID) is a nanopatterning technique that uses a focused beam of charged ions to decompose a gaseous precursor. So far, the flexible patterning capabilities of FIBID have been widely exploited in the fabrication of superconducting nanostructures, using the W(CO)6 precursor mostly in combination with a focused beam of Ga+ ions. Here, the fabrication and characterization of superconducting in-plane tungsten-carbon (W-C) nanostructures by He+ FIBID of the W(CO)6 precursor is reported. A patterning resolution of 10 nm has been achieved, which is virtually unattainable for Ga+ FIBID. When the nanowires are patterned with widths of 20 nm and above, the deposited material is superconducting below 3.5-4 K. In addition, nanowires with widths of 60 and 90 nm have been found to sustain long-range controlled nonlocal superconducting vortex transfer along 3 µm. Overall, these findings strengthen the capabilities of He+ FIBID of W-C in the growth and patterning of in-plane superconducting nanodevices.

Three-Dimensional Superconducting Nanohelices Grown by He+-Focused-Ion-Beam Direct Writing.

Novel schemes based on the design of complex three-dimensional (3D) nanoscale architectures are required for the development of the next generation of advanced electronic components. He+ focused-ion-beam (FIB) microscopy in combination with a precursor gas allows one to fabricate 3D nanostructures with an extreme resolution and a considerably higher aspect ratio than FIB-based methods, such as Ga+ FIB-induced deposition, or other additive manufacturing technologies. In this work, we report the fabrication of 3D tungsten carbide nanohelices with on-demand geometries via controlling key deposition parameters. Our results show the smallest and highest-densely packed nanohelix ever fabricated so far, with dimensions of 100 nm in diameter and aspect ratio up to 65. These nanohelices become superconducting at 7 K and show a large critical magnetic field and critical current density. In addition, given its helical 3D geometry, fingerprints of vortex and phase-slip patterns are experimentally identified and supported by numerical simulations based on the time-dependent Ginzburg-Landau equation. These results can be understood by the helical geometry that induces specific superconducting properties and paves the way for future electronic components, such as sensors, energy storage elements, and nanoantennas, based on 3D compact nanosuperconductors.

Diameter modulation of 3D nanostructures in focused electron beam induced deposition using local electric fields and beam defocus.

Focused electron beam induced deposition (FEBID) is a leading nanolithography technique in terms of resolution and the capability for three-dimensional (3D) growth of functional nanostructures. However, FEBID still presents some limitations with respect to the precise control of the dimensions of the grown nano-objects as well as its use on insulating substrates. In the present work, we overcome both limitations by employing electrically-biased metal structures patterned on the surface of insulating substrates. Such patterned metal structures serve for charge dissipation and also allow the application of spatially-dependent electric fields. We demonstrate that such electric fields can dramatically change the dimensions of the growing 3D nanostructures by acting on the primary electron beam and the generated secondary electrons. In the performed experiments, the diameter of Pt-C and W-C vertical nanowires grown on quartz, MgO and amorphous SiO2 is tuned by application of moderate voltages (up to 200 V) on the patterned metal microstructures during growth, achieving diameters as small as 50 nm. We identify two competing effects arising from the generated electric fields: a slight change in the primary beam focus point and a strong action on the secondary electrons. Beam defocus is exploited to achieve the in situ modulation of the diameter of 3D FEBID structures during growth.

Suspended tungsten-based nanowires with enhanced mechanical properties grown by focused ion beam induced deposition.

The implementation of three-dimensional (3D) nano-objects as building blocks for the next generation of electro-mechanical, memory and sensing nano-devices is at the forefront of technology. The direct writing of functional 3D nanostructures is made feasible by using a method based on focused ion beam induced deposition (FIBID). We use this technique to grow horizontally suspended tungsten nanowires and then study their nano-mechanical properties by three-point bending method with atomic force microscopy. These measurements reveal that these nanowires exhibit a yield strength up to 12 times higher than that of the bulk tungsten, and near the theoretical value of 0.1 times the Young's modulus (E). We find a size dependence of E that is adequately described by a core-shell model, which has been confirmed by transmission electron microscopy and compositional analysis at the nanoscale. Additionally, we show that experimental resonance frequencies of suspended nanowires (in the MHz range) are in good agreement with theoretical values. These extraordinary mechanical properties are key to designing electro-mechanically robust nanodevices based on FIBID tungsten nanowires.

Three-dimensional core-shell ferromagnetic nanowires grown by focused electron beam induced deposition.

Functional nanostructured materials often rely on the combination of more than one material to confer the desired functionality or an enhanced performance of the device. Here we report the procedure to create nanoscale heterostructured materials in the form of core-shell nanowires by focused electron beam induced deposition (FEBID) technologies. In our case, three-dimensional (3D) nanowires (<100 nm in diameter) with metallic ferromagnetic cores of Co- and Fe-FEBID have been grown and coated with a protective Pt-FEBID shell (ranging 10-20 nm in thickness) aimed to minimize the degradation of magnetic properties caused by the surface oxidation of the core to a non-ferromagnetic material. The structure, chemistry and magnetism of nanowire cores of Co and Fe have been characterized in Pt-coated and uncoated nanostructures to demonstrate that the morphology of the shell is conserved during Pt coating, the surface oxidation is suppressed or confined to the Pt layer, and the average magnetization of the core is strengthened up to 30%. The proposed approach paves the way to the fabrication of 3D FEBID nanostructures based on the smart alternate deposition of two or more materials combining different physical properties or added functionalities.

Focused Helium Ion and Electron Beam-Induced Deposition of Organometallic Tips for Dynamic Atomic Force Microscopy of Biomolecules in Liquid.

We demonstrate the fabrication of sharp nanopillars of high aspect ratio onto specialized atomic force microscopy (AFM) microcantilevers and their use for high-speed AFM of DNA and nucleoproteins in liquid. The fabrication technique uses localized charged-particle-induced deposition with either a focused beam of helium ions or electrons in a helium ion microscope (HIM) or scanning electron microscope (SEM). This approach enables customized growth onto delicate substrates with nanometer-scale placement precision and in situ imaging of the final tip structures using the HIM or SEM. Tip radii of <10 nm are obtained and the underlying microcantilever remains intact. Instead of the more commonly used organic precursors employed for bio-AFM applications, we use an organometallic precursor (tungsten hexacarbonyl) resulting in tungsten-containing tips. Transmission electron microscopy reveals a thin layer of carbon on the tips. The interaction of the new tips with biological specimens is therefore likely very similar to that of standard carbonaceous tips, with the added benefit of robustness. A further advantage of the organometallic tips is that compared to carbonaceous tips they better withstand UV-ozone cleaning treatments to remove residual organic contaminants between experiments, which are inevitable during the scanning of soft biomolecules in liquid. Our tips can also be grown onto the blunted tips of previously used cantilevers, thus providing a means to recycle specialized cantilevers and restore their performance to the original manufacturer specifications. Finally, a focused helium ion beam milling technique to reduce the tip radii and thus further improve lateral spatial resolution in the AFM scans is demonstrated.

Graphene removal by water-assisted focused electron-beam-induced etching - unveiling the dose and dwell time impact on the etch profile and topographical changes in SiO2 substrates.

Graphene is one of the most extensively studied 2D materials, exhibiting extraordinary mechanical and electronic properties. Although many years have passed since its discovery, manipulating single graphene layers is still challenging using standard resist-based lithography techniques. Recently, it has been shown that it is possible to etch graphene directly in water-assisted processes using the so-called focused electron-beam-induced etching (FEBIE), with a spatial resolution of ten nanometers. Nanopatterning graphene with such a method in one single step and without using a physical mask or resist is a very appealing approach. During the process, on top of graphene nanopatterning, we have found significant morphological changes induced in the SiO2 substrate even at low electron dose values (<8 nC/µm2). We demonstrate that graphene etching and topographical changes in SiO2 substrates can be controlled via electron beam parameters such as dwell time and dose.

Gas-Phase Synthesis of Iron Silicide Nanostructures Using a Single-Source Precursor: Comparing Direct-Write Processing and Thermal Conversion.

The investigation of precursor classes for the fabrication of nanostructures is of specific interest for maskless fabrication and direct nanoprinting. In this study, the differences in material composition depending on the employed process are illustrated for focused-ion-beam- and focused-electron-beam-induced deposition (FIBID/FEBID) and compared to the thermal decomposition in chemical vapor deposition (CVD). This article reports on specific differences in the deposit composition and microstructure when the (H3Si)2Fe(CO)4 precursor is converted into an inorganic material. Maximum metal/metalloid contents of up to 90 at. % are obtained in FIBID deposits and higher than 90 at. % in CVD films, while FEBID with the same precursor provides material containing less than 45 at. % total metal/metalloid content. Moreover, the Fe:Si ratio is retained well in FEBID and CVD processes, but FIBID using Ga+ ions liberates more than 50% of the initial Si provided by the precursor. This suggests that precursors for FIBID processes targeting binary materials should include multiple bonding such as bridging positions for nonmetals. In addition, an in situ method for investigations of supporting thermal effects of precursor fragmentation during the direct-writing processes is presented, and the applicability of the precursor for nanoscale 3D FEBID writing is demonstrated.

Superconducting Materials and Devices Grown by Focused Ion and Electron Beam Induced Deposition.

Since its discovery in 1911, superconductivity has represented an equally inciting and fascinating field of study in several areas of physics and materials science, ranging from its most fundamental theoretical understanding, to its practical application in different areas of engineering. The fabrication of superconducting materials can be downsized to the nanoscale by means of Focused Ion/Electron Beam Induced Deposition: nanopatterning techniques that make use of a focused beam of ions or electrons to decompose a gaseous precursor in a single step. Overcoming the need to use a resist, these approaches allow for targeted, highly-flexible nanopatterning of nanostructures with lateral resolution in the range of 10 nm to 30 nm. In this review, the fundamentals of these nanofabrication techniques are presented, followed by a literature revision on the published work that makes use of them to grow superconducting materials, the most remarkable of which are based on tungsten, niobium, molybdenum, carbon, and lead. Several examples of the application of these materials to functional devices are presented, related to the superconducting proximity effect, vortex dynamics, electric-field effect, and to the nanofabrication of Josephson junctions and nanoSQUIDs. Owing to the patterning flexibility they offer, both of these techniques represent a powerful and convenient approach towards both fundamental and applied research in superconductivity.

Low-resistivity, high-resolution W-C electrical contacts fabricated by direct-write focused electron beam induced deposition.

Background: The use of a focused ion beam to decompose a precursor gas and produce a metallic deposit is a widespread nanolithographic technique named focused ion beam induced deposition (FIBID). However, such an approach is unsuitable if the sample under study is sensitive to the somewhat aggressive exposure to the ion beam, which induces the effects of surface amorphization, local milling, and ion implantation, among others. An alternative strategy is that of focused electron beam induced deposition (FEBID), which makes use of a focused electron beam instead, and in general yields deposits with much lower metallic content than their FIBID counterparts. Methods: In this work, we optimize the deposition of tungsten-carbon (W-C) nanowires by FEBID to be used as electrical contacts by assessing the impact of the deposition parameters during growth, evaluating their chemical composition, and investigating their electrical response. Results: Under the optimized irradiation conditions, the samples exhibit a metallic content high enough for them to be utilized for this purpose, showing a room-temperature resistivity of 550 µΩ cm and maintaining their conducting properties down to 2 K. The lateral resolution of such FEBID W-C metallic nanowires is 45 nm. Conclusions: The presented optimized procedure may prove a valuable tool for the fabrication of contacts on samples where the FIBID approach is not advised.

Critical current modulation induced by an electric field in superconducting tungsten-carbon nanowires.

The critical current of a superconducting nanostructure can be suppressed by applying an electric field in its vicinity. This phenomenon is investigated throughout the fabrication and electrical characterization of superconducting tungsten-carbon (W-C) nanostructures grown by Ga[Formula: see text] focused ion beam induced deposition (FIBID). In a 45 nm-wide, 2.7 [Formula: see text]m-long W-C nanowire, an increasing side-gate voltage is found to progressively reduce the critical current of the device, down to a full suppression of the superconducting state below its critical temperature. This modulation is accounted for by the squeezing of the superconducting current by the electric field within a theoretical model based on the Ginzburg-Landau theory, in agreement with experimental data. Compared to electron beam lithography or sputtering, the single-step FIBID approach provides with enhanced patterning flexibility and yields nanodevices with figures of merit comparable to those retrieved in other superconducting materials, including Ti, Nb, and Al. Exhibiting a higher critical temperature than most of other superconductors, in which this phenomenon has been observed, as well as a reduced critical value of the gate voltage required to fully suppress superconductivity, W-C deposits are strong candidates for the fabrication of nanodevices based on the electric field-induced superconductivity modulation.

Focused-Electron-Beam Engineering of 3D Magnetic Nanowires.

Focused-electron-beam-induced deposition (FEBID) is the ultimate additive nanofabrication technique for the growth of 3D nanostructures. In the field of nanomagnetism and its technological applications, FEBID could be a viable solution to produce future high-density, low-power, fast nanoelectronic devices based on the domain wall conduit in 3D nanomagnets. While FEBID has demonstrated the flexibility to produce 3D nanostructures with almost any shape and geometry, the basic physical properties of these out-of-plane deposits are often seriously degraded from their bulk counterparts due to the presence of contaminants. This work reviews the experimental efforts to understand and control the physical processes involved in 3D FEBID growth of nanomagnets. Co and Fe FEBID straight vertical nanowires have been used as benchmark geometry to tailor their dimensions, microstructure, composition and magnetism by smartly tuning the growth parameters, post-growth purification treatments and heterostructuring.

Highly-efficient growth of cobalt nanostructures using focused ion beam induced deposition under cryogenic conditions: application to electrical contacts on graphene, magnetism and hard masking.

Emergent technologies are required in the field of nanoelectronics for improved contacts and interconnects at nano and micro-scale. In this work, we report a highly-efficient nanolithography process for the growth of cobalt nanostructures requiring an ultra-low charge dose (15 µC cm-2, unprecedented in single-step charge-based nanopatterning). This resist-free process consists in the condensation of a ∼28 nm-thick Co2(CO)8 layer on a substrate held at -100 °C, its irradiation with a Ga+ focused ion beam, and substrate heating up to room temperature. The resulting cobalt-based deposits exhibit sub-100 nm lateral resolution, display metallic behaviour (room-temperature resistivity of 200 µΩ cm), present ferromagnetic properties (magnetization at room temperature of 400 emu cm-3) and can be grown in large areas. To put these results in perspective, similar properties can be achieved by room-temperature focused ion beam induced deposition and the same precursor only if a 2 × 103 times higher charge dose is used. We demonstrate the application of such an ultra-fast growth process to directly create electrical contacts onto graphene ribbons, opening the route for a broad application of this technology to any 2D material. In addition, the application of these cryo-deposits for hard masking is demonstrated, confirming its structural functionality.

Omnipresence of Weak Antilocalization (WAL) in Bi2Se3 Thin Films: A Review on Its Origin.

Topological insulators are materials with time-reversal symmetric states of matter in which an insulating bulk is surrounded by protected Dirac-like edge or surface states. Among topological insulators, Bi2Se3 has attracted special attention due to its simple surface band structure and its relatively large band gap that should enhance the contribution of its surface to transport, which is usually masked by the appearance of defects. In order to avoid this difficulty, several features characteristic of topological insulators in the quantum regime, such as the weak-antilocalization effect, can be explored through magnetotransport experiments carried out on thin films of this material. Here, we review the existing literature on the magnetotransport properties of Bi2Se3 thin films, paying thorough attention to the weak-antilocalization effect, which is omnipresent no matter the film quality. We carefully follow the different situations found in reported experiments, from the most ideal situations, with a strong surface contribution, towards more realistic cases where the bulk contribution dominates. We have compared the transport data found in literature to shed light on the intrinsic properties of Bi2Se3, finding a clear relationship between the mobility and the phase coherence length of the films that could trigger further experiments on transport in topological systems.

High conductivity in hydrothermally grown AgCuO(2) single crystals verified using focused-ion-beam-deposited nanocontacts.

The silver-copper mixed oxide AgCuO(2) (also formulated as Ag(2)Cu(2)O(4)) possesses a peculiar electronic structure in which both Ag and Cu are partially oxidized, with the charge being delocalized among the three elements in the oxide. Accordingly, a quasi-metallic behavior should be expected for this oxide, and indeed bulk transport measurements show conductivity values that are orders of magnitude higher than for other members of this novel oxide family. The presence of silver makes thermal sintering an inadequate method to evaluate true conductivity, and thus such measurements were performed on low density pellets, giving an underestimated value for the conductivity. In the present work we present a new synthetic route for AgCuO(2) based on mild hydrothermal reactions that has yielded unprecedented large AgCuO(2) single-crystals well over 1 µm in size using temperatures as low as 88 °C. We have used a dual beam instrument to apply nanocontacts to those crystals, allowing the in situ measurement of transport properties of AgCuO(2) single crystals. The results show a linear relationship between applied current and measured voltage. The conductivity values obtained are 50 to 300 times higher than those obtained for bulk low density AgCuO(2) pellets, thus confirming the high conductivity of this oxide and therefore supporting the delocalized charge observed by spectroscopic techniques.

Erratum: De Teresa, J.M. et al. Comparison between Focused Electron/Ion Beam-Induced Deposition at Room Temperature and under Cryogenic Conditions. Micromachines 2019, 10, 799.

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3D superconducting hollow nanowires with tailored diameters grown by focused He+ beam direct writing.

Currently, the patterning of innovative three-dimensional (3D) nano-objects is required for the development of future advanced electronic components. Helium ion microscopy in combination with a precursor gas can be used for direct writing of three-dimensional nanostructures with a precise control of their geometry, and a significantly higher aspect ratio than other additive manufacturing technologies. We report here on the deposition of 3D hollow tungsten carbide nanowires with tailored diameters by tuning two key growth parameters, namely current and dose of the ion beam. Our results show the control of geometry in 3D hollow nanowires, with outer and inner diameters ranging from 36 to 142 nm and from 5 to 28 nm, respectively; and lengths from 0.5 to 8.9 µm. Transmission electron microscopy experiments indicate that the nanowires have a microstructure of large grains with a crystalline structure compatible with the face-centered cubic WC1- x phase. In addition, 3D electron tomographic reconstructions show that the hollow center of the nanowires is present along the whole nanowire length. Moreover, these nanowires become superconducting at 6.8 K and show high values of critical magnetic field and critical current density. Consequently, these 3D nano-objects could be implemented as components in the next generation of electronics, such as nano-antennas and sensors, based on 3D superconducting architectures.

Writing 3D Nanomagnets Using Focused Electron Beams.

Focused electron beam induced deposition (FEBID) is a direct-write nanofabrication technique able to pattern three-dimensional magnetic nanostructures at resolutions comparable to the characteristic magnetic length scales. FEBID is thus a powerful tool for 3D nanomagnetism which enables unique fundamental studies involving complex 3D geometries, as well as nano-prototyping and specialized applications compatible with low throughputs. In this focused review, we discuss recent developments of this technique for applications in 3D nanomagnetism, namely the substantial progress on FEBID computational methods, and new routes followed to tune the magnetic properties of ferromagnetic FEBID materials. We also review a selection of recent works involving FEBID 3D nanostructures in areas such as scanning probe microscopy sensing, magnetic frustration phenomena, curvilinear magnetism, magnonics and fluxonics, offering a wide perspective of the important role FEBID is likely to have in the coming years in the study of new phenomena involving 3D magnetic nanostructures.