npSCOPE: A New Multimodal Instrument for In Situ Correlative Analysis of Nanoparticles.

Over the last few decades, nanoparticles have become a key element in a number of scientific and technological fields, spanning from materials science to life sciences. The characterization of nanoparticles or samples containing nanoparticles, in terms of morphology, chemical composition, and other parameters, typically involves investigations with various analytical tools, requiring complex workflows and extending the duration of such studies to several days or even weeks. Here, we report on the development of a new unique in situ correlative instrument, allowing us to answer questions about the shape, size, size distribution, and chemical composition of the nanoparticles using a single probe. Combining various microscopic and analytical capabilities in one single instrument allows a considerable increase in flexibility and a reduction in the duration of such complex investigations. The new instrument is based on focused ion beam microscopy technology using a gas field ion source as a key enabler and combining it with specifically developed secondary ion mass spectrometry and scanning transmission ion microscopy technology. We will present the underlying concept, the instrument and its main components, and proof-of-concept studies performed on this novel instrument. For this purpose, different pure titanium dioxide nanoparticle samples were investigated. Furthermore, the distribution and localization of the nanoparticles in biological model systems were studied. Our results demonstrate the performance and usefulness of the instrument for nanoparticle investigations, paving the way for a number of future applications, in particular, nanotoxicological research.

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.

Helium Ion Microscopy for Reduced Spin Orbit Torque Switching Currents.

Spin orbit torque driven switching is a favorable way to manipulate nanoscale magnetic objects for both memory and wireless communication devices. The critical current required to switch from one magnetic state to another depends on the geometry and the intrinsic properties of the materials used, which are difficult to control locally. Here, we demonstrate how focused helium ion beam irradiation can modulate the local magnetic anisotropy of a Co thin film at the microscopic scale. Real-time in situ characterization using the anomalous Hall effect showed up to an order of magnitude reduction of the magnetic anisotropy under irradiation, with multilevel switching demonstrated. The result is that spin-switching current densities, down to 800 kA cm-2, can be achieved on predetermined areas of the film, without the need for lithography. The ability to vary critical currents spatially has implications not only for storage elements but also neuromorphic and probabilistic computing.

Channeling effects in gold nanoclusters under He ion irradiation: insights from molecular dynamics simulations.

The interpretation of helium ion microscopy (HIM) images of crystalline metal clusters requires microscopic understanding of the effects of He ion irradiation on the system, including energy deposition and associated heating, as well as channeling patterns. While channeling in bulk metals has been studied at length, there is no quantitative data for small clusters. We carry out molecular dynamics simulations to investigate the behavior of gold nanoparticles with diameters of 5-15 nm under 30 keV He ion irradiation. We show that impacts of the ions can give rise to substantial heating of the clusters through deposition of energy into electronic degrees of freedom, but it does not affect channeling, as clusters cool down between consecutive impact of the ions under typical imaging conditions. At the same time, high temperatures and small cluster sizes should give rise to fast annealing of defects so that the system remains crystalline. Our results show that ion-channeling occurs not only in the principal low-index, but also in the intermediate directions. The strengths of different channels are specified, and their correlations with sputtering-yield and damage production is discussed, along with size-dependence of these properties. The effects of planar defects, such as stacking faults on channeling were also investigated. Finally, we discuss the implications of our results for the analysis of HIM images of metal clusters.

Strain Anisotropy and Magnetic Domains in Embedded Nanomagnets.

Nanoscale modifications of strain and magnetic anisotropy can open pathways to engineering magnetic domains for device applications. A periodic magnetic domain structure can be stabilized in sub-200 nm wide linear as well as curved magnets, embedded within a flat non-ferromagnetic thin film. The nanomagnets are produced within a non-ferromagnetic B2-ordered Fe60 Al40 thin film, where local irradiation by a focused ion beam causes the formation of disordered and strongly ferromagnetic regions of A2 Fe60 Al40 . An anisotropic lattice relaxation is observed, such that the in-plane lattice parameter is larger when measured parallel to the magnet short-axis as compared to its length. This in-plane structural anisotropy manifests a magnetic anisotropy contribution, generating an easy-axis parallel to the short axis. The competing effect of the strain and shape anisotropies stabilizes a periodic domain pattern in linear as well as spiral nanomagnets, providing a versatile and geometrically controllable path to engineering the strain and thereby the magnetic anisotropy at the nanoscale.

Tailoring crosstalk between localized 1D spin-wave nanochannels using focused ion beams.

1D spin-wave conduits are envisioned as nanoscale components of magnonics-based logic and computing schemes for future generation electronics. À-la-carte methods of versatile control of the local magnetization dynamics in such nanochannels are highly desired for efficient steering of the spin waves in magnonic devices. Here, we present a study of localized dynamical modes in 1-[Formula: see text]m-wide permalloy conduits probed by microresonator ferromagnetic resonance technique. We clearly observe the lowest-energy edge mode in the microstrip after its edges were finely trimmed by means of focused Ne[Formula: see text] ion irradiation. Furthermore, after milling the microstrip along its long axis by focused ion beams, creating consecutively [Formula: see text]50 and [Formula: see text]100 nm gaps, additional resonances emerge and are attributed to modes localized at the inner edges of the separated strips. To visualize the mode distribution, spatially resolved Brillouin light scattering microscopy was used showing an excellent agreement with the ferromagnetic resonance data and confirming the mode localization at the outer/inner edges of the strips depending on the magnitude of the applied magnetic field. Micromagnetic simulations confirm that the lowest-energy modes are localized within [Formula: see text]15-nm-wide regions at the edges of the strips and their frequencies can be tuned in a wide range (up to 5 GHz) by changing the magnetostatic coupling (i.e., spatial separation) between the microstrips.

Universal radiation tolerant semiconductor.

Radiation tolerance is determined as the ability of crystalline materials to withstand the accumulation of the radiation induced disorder. Nevertheless, for sufficiently high fluences, in all by far known semiconductors it ends up with either very high disorder levels or amorphization. Here we show that gamma/beta (γ/ß) double polymorph Ga2O3 structures exhibit remarkably high radiation tolerance. Specifically, for room temperature experiments, they tolerate a disorder equivalent to hundreds of displacements per atom, without severe degradations of crystallinity; in comparison with, e.g., Si amorphizable already with the lattice atoms displaced just once. We explain this behavior by an interesting combination of the Ga- and O- sublattice properties in γ-Ga2O3. In particular, O-sublattice exhibits a strong recrystallization trend to recover the face-centered-cubic stacking despite the stronger displacement of O atoms compared to Ga during the active periods of cascades. Notably, we also explained the origin of the ß-to-γ Ga2O3 transformation, as a function of the increased disorder in ß-Ga2O3 and studied the phenomena as a function of the chemical nature of the implanted atoms. As a result, we conclude that γ/ß double polymorph Ga2O3 structures, in terms of their radiation tolerance properties, benchmark a class of universal radiation tolerant semiconductors.

Nanoscale patterning of organosilane molecular thin films from the gas phase and its applications: fabrication of multifunctional surfaces and large area molecular templates for site-selective material deposition.

A simple methodology to fabricate micrometer- and nanometer-scale patterned surfaces with multiple chemical functionalities is presented. Patterns with lateral dimensions down to 110 nm were made. The fabrication process involves multistep gas-phase patterning of amine, thiol, alkyl, and fluorinated alkyl-functional organosilane molecules using PDMS molds as shadow masks. Also, a combination process of channel diffused plasma etching of organosilane molecular thin films in combination with masked gas-phase deposition to fabricate multilength scale, multifunctional surfaces is demonstrated.

Substrate selected polymorphism of epitaxially aligned tetraphenyl-porphyrin thin films.

Porphyrin molecules, of interest as versatile materials for organic electronics, are highly prone to formation of significantly different polymorphic phases. To elucidate the determinants for the specific polymorphic phase formed in thin films as well as for the arrangement of the molecules on a given substrate two different anisotropic substrate surfaces have been selected: KCl(100) and the oxygen reconstructed Cu(110) surface. We observe that the crystal structure of the thin films depends on the substrate, whereas the relative molecular orientations in both cases are similar. X-Ray and transmission electron diffraction of 30 nm thick tetraphenyl-porphyrin (H(2)TPP) and platinum tetraphenyl-porphyrin (PtTPP) thin films deposited on KCl(100) surfaces reveals that both kinds of molecules crystallize in a tetragonal polymorph with the (001) lattice planes, i.e. with their macrocycles, parallel to the substrate. Films deposited on the oxygen reconstructed Cu(110)-(2 × 1)O surface exhibit in contrast the triclinic polymorph even though molecules again align nearly parallel to the substrate surface as observed by LEED and X-ray diffraction. On both substrates we identify two driving forces for the epitaxial alignment of porphyrins: (i) molecules aligning with their macrocycles (nearly) parallel to the substrate surface and (ii) the porphyrin molecules forming a commensurate unit cell with the respective substrate. The polymorphic phase meeting both requirements is the most favorable to be formed on a given substrate and due to this structural flexibility in both cases well-ordered, epitaxially aligned porphyrin thin films are achieved.

The influence of substrate temperature on growth of para-sexiphenyl thin films on Ir{111} supported graphene studied by LEEM.

The growth of para-sexiphenyl (6P) thin films as a function of substrate temperature on Ir{111} supported graphene flakes has been studied in real-time with Low Energy Electron Microscopy (LEEM). Micro Low Energy Electron Diffraction (µLEED) has been used to determine the structure of the different 6P features formed on the surface. We observe the nucleation and growth of a wetting layer consisting of lying molecules in the initial stages of growth. Graphene defects - wrinkles - are found to be preferential sites for the nucleation of the wetting layer and of the 6P needles that grow on top of the wetting layer in the later stages of deposition. The molecular structure of the wetting layer and needles is found to be similar. As a result, only a limited number of growth directions are observed for the needles. In contrast, on the bare Ir{111} surface 6P molecules assume an upright orientation. The formation of ramified islands is observed on the bare Ir{111} surface at 320 K and 352 K, whereas at 405 K the formation of a continuous layer of upright standing molecules growing in a step flow like manner is observed.

Smooth growth of organic semiconductor films on graphene for high-efficiency electronics.

High-quality thin films of conjugated molecules with smooth interfaces are important to assist the advent of organic electronics. Here, we report on the layer-by-layer growth of the organic semiconductor molecule p-sexiphenyl (6P) on the transparent electrode material graphene. Low energy electron microscopy and micro low energy electron diffraction reveal the morphological and structural evolution of the thin film. The layer-by-layer growth of 6P on graphene proceeds by subsequent adding of {111} layers.

Resonance behavior of embedded and freestanding microscale ferromagnets.

The ferromagnetic resonance of a disordered A2 Fe60Al40 ferromagnetic stripe, of dimensions 5 µm × 1 µm × 32 nm, has been observed in two vastly differing surroundings: in the first case, the ferromagnetic region was surrounded by ordered B2 Fe60Al40, and in the second case it was free standing, adhering only to the oxide substrate. The embedded ferromagnet possesses a periodic magnetic domain structure, which transforms to a single domain structure in the freestanding case. The two cases differ in their dynamic response, for instance, the resonance field for the uniform (k = 0) mode at ~ 14 GHz excitation displays a shift from 209 to 194 mT, respectively for the embedded and freestanding cases, with the external magnetic field applied along the long axis. The resonant behavior of a microscopic ferromagnet can thus be finely tailored via control of its near-interfacial surrounding.

Wafer-scale nanofabrication of telecom single-photon emitters in silicon.

A highly promising route to scale millions of qubits is to use quantum photonic integrated circuits (PICs), where deterministic photon sources, reconfigurable optical elements, and single-photon detectors are monolithically integrated on the same silicon chip. The isolation of single-photon emitters, such as the G centers and W centers, in the optical telecommunication O-band, has recently been realized in silicon. In all previous cases, however, single-photon emitters were created uncontrollably in random locations, preventing their scalability. Here, we report the controllable fabrication of single G and W centers in silicon wafers using focused ion beams (FIB) with high probability. We also implement a scalable, broad-beam implantation protocol compatible with the complementary-metal-oxide-semiconductor (CMOS) technology to fabricate single telecom emitters at desired positions on the nanoscale. Our findings unlock a clear and easily exploitable pathway for industrial-scale photonic quantum processors with technology nodes below 100 nm.

Atomistic Simulations of Defect Production in Monolayer and Bulk Hexagonal Boron Nitride under Low- and High-Fluence Ion Irradiation.

Controlled production of defects in hexagonal boron nitride (h-BN) through ion irradiation has recently been demonstrated to be an effective tool for adding new functionalities to this material, such as single-photon generation, and for developing optical quantum applications. Using analytical potential molecular dynamics, we study the mechanisms of vacancy creation in single- and multi-layer h-BN under low- and high-fluence ion irradiation. Our results quantify the densities of defects produced by noble gas ions in a wide range of ion energies and elucidate the types and distribution of defects in the target. The simulation data can directly be used to guide the experiment aimed at the creation of defects of particular types in h-BN targets for single-photon emission, spin-selective optical transitions and other applications by using beams of energetic ions.

Revealing Inflammatory Indications Induced by Titanium Alloy Wear Debris in Periprosthetic Tissue by Label-Free Correlative High-Resolution Ion, Electron and Optical Microspectroscopy.

The metallic-associated adverse local tissue reactions (ALTR) and events accompanying worn-broken implant materials are still poorly understood on the subcellular and molecular level. Current immunohistochemical techniques lack spatial resolution and chemical sensitivity to investigate causal relations between material and biological response on submicron and even nanoscale. In our study, new insights of titanium alloy debris-tissue interaction were revealed by the implementation of label-free high-resolution correlative microscopy approaches. We have successfully characterized its chemical and biological impact on the periprosthetic tissue obtained at revision surgery of a fractured titanium-alloy modular neck of a patient with hip osteoarthritis. We applied a combination of photon, electron and ion beam micro-spectroscopy techniques, including hybrid optical fluorescence and reflectance micro-spectroscopy, scanning electron microscopy (SEM), Energy-dispersive X-ray Spectroscopy (EDS), helium ion microscopy (HIM) and micro-particle-induced X-ray emission (micro-PIXE). Micron-sized wear debris were found as the main cause of the tissue oxidative stress exhibited through lipopigments accumulation in the nearby lysosome. This may explain the indications of chronic inflammation from prior histologic examination. Furthermore, insights on extensive fretting and corrosion of the debris on nm scale and a quantitative measure of significant Al and V release into the tissue together with hydroxyapatite-like layer formation particularly bound to the regions with the highest Al content were revealed. The functional and structural information obtained at molecular and subcellular level contributes to a better understanding of the macroscopic inflammatory processes observed in the tissue level. The established label-free correlative microscopy approach can efficiently be adopted to study any other clinical cases related to ALTR.

Quantitative nanoscale imaging using transmission He ion channelling contrast: Proof-of-concept and application to study isolated crystalline defects.

A newly developed microscope prototype, namely npSCOPE, consisting of a Gas Field Ion Source (GFIS) column and a position sensitive Delay-line Detector (DLD) was used to perform Scanning Transmission Ion Microscopy (STIM) using keV He+ ions. One experiment used 25 keV ions and a second experiment used 30 keV ions. STIM imaging of a 50 nm thick free-standing gold membrane exhibited excellent contrast due to ion channelling and revealed rich microstructural features including isolated nanoscale twin bands which matched well with the contrast in the conventional ion-induced Secondary Electron (SE) imaging mode. Transmission Kikuchi Diffraction (TKD) and Backscattered Electron (BSE) imaging were performed on the same areas to correlate and confirm the microstructural features observed in STIM. Monte Carlo simulations of the ion and electron trajectories were performed with parameters similar to the experimental conditions to derive insights related to beam broadening and its effect in the degradation of transmission image resolution. For the experimental conditions used, STIM imaging showed a lateral resolution close to30 nm. Dark twin bands in bright grains as well as bright twin bands in dark grains were observed in STIM. Some of the twin bands were invisible in STIM. For the specific experimental conditions used, the ion transmission efficiency across a particular twin band was found to decrease by a factor of 2.8. Surprisingly, some grains showed contrast reversal when the Field of View (FOV) was changed indicating the sensitivity of the channelling contrast to even small changes in illumination conditions. These observations are discussed using ion channelling conditions and crystallographic orientations of the grains and twin bands. This study demonstrates for the first time the potential of STIM imaging using keV He+ ions to quantitatively investigate channelling in nanoscale structures including isolated crystalline defects.

An atomic force microscope integrated with a helium ion microscope for correlative nanoscale characterization.

In this work, we report on the integration of an atomic force microscope (AFM) into a helium ion microscope (HIM). The HIM is a powerful instrument, capable of imaging and machining of nanoscale structures with sub-nanometer resolution, while the AFM is a well-established versatile tool for multiparametric nanoscale characterization. Combining the two techniques opens the way for unprecedented in situ correlative analysis at the nanoscale. Nanomachining and analysis can be performed without contamination of the sample and environmental changes between processing steps. The practicality of the resulting tool lies in the complementarity of the two techniques. The AFM offers not only true 3D topography maps, something the HIM can only provide in an indirect way, but also allows for nanomechanical property mapping, as well as for electrical and magnetic characterization of the sample after focused ion beam materials modification with the HIM. The experimental setup is described and evaluated through a series of correlative experiments, demonstrating the feasibility of the integration.

Imaging and milling resolution of light ion beams from helium ion microscopy and FIBs driven by liquid metal alloy ion sources.

While the application of focused ion beam (FIB) techniques has become a well-established technique in research and development for patterning and prototyping on the nanometer scale, there is still a large underused potential with respect to the usage of ion species other than gallium. Light ions in the range of m = 1-28 u (hydrogen to silicon) are of increasing interest due to the available high beam resolution in the nanometer range and their special chemical and physical behavior in the substrate. In this work, helium and neon ion beams from a helium ion microscope are compared with ion beams such as lithium, beryllium, boron, and silicon, obtained from a mass-separated FIB using a liquid metal alloy ion source (LMAIS) with respect to the imaging and milling resolution, as well as the current stability. Simulations were carried out to investigate whether the experimentally smallest ion-milled trenches are limited by the size of the collision cascade. While He+ offers, experimentally and in simulations, the smallest minimum trench width, light ion species such as Li+ or Be+ from a LMAIS offer higher milling rates and ion currents while outperforming the milling resolution of Ne+ from a gas field ion source. The comparison allows one to select the best possible ion species for the specific demands in terms of resolution, beam current, and volume to be drilled.

Freestanding and Supported MoS2 Monolayers under Cluster Irradiation: Insights from Molecular Dynamics Simulations.

Two-dimensional (2D) materials with nanometer-size holes are promising systems for DNA sequencing, water purification, and molecule selection/separation. However, controllable creation of holes with uniform sizes and shapes is still a challenge, especially when the 2D material consists of several atomic layers as, e.g., MoS2, the archetypical transition metal dichalcogenide. We use analytical potential molecular dynamics simulations to study the response of 2D MoS2 to cluster irradiation. We model both freestanding and supported sheets and assess the amount of damage created in MoS2 by the impacts of noble gas clusters in a wide range of cluster energies and incident angles. We show that cluster irradiation can be used to produce uniform holes in 2D MoS2 with the diameter being dependent on cluster size and energy. Energetic clusters can also be used to displace sulfur atoms preferentially from either top or bottom layers of S atoms in MoS2 and also clean the surface of MoS2 sheets from adsorbents. Our results for MoS2, which should be relevant to other 2D transition metal dichalcogenides, suggest new routes toward cluster beam engineering of devices based on 2D inorganic materials.

Visualization and Chemical Characterization of the Cathode Electrolyte Interphase Using He-Ion Microscopy and In Situ Time-of-Flight Secondary Ion Mass Spectrometry.

Unstable cathode electrolyte interphase (CEI) formation increases degradation in high voltage Li-ion battery materials. Few techniques couple characterization of nano-scale CEI layers on the macroscale with in situ chemical characterization, and thus, information on how the underlying microstructure affects CEI formation is lost. Here, the process of CEI formation in a high voltage cathode material, LiCoPO4, has been investigated for the first time using helium ion microscopy (HIM) and in situ time-of-flight (ToF) secondary ion mass spectrometry (SIMS). The combination of HIM and Ne-ion ToF-SIMS has been used to correlate the cycle-dependent morphology of the CEI layer on LiCoPO4 with a local cathode microstructure, including position, thickness, and chemistry. HIM imaging identified partial dissolution of the CEI layer on discharge resulting in in-homogenous CEI coverage on larger LiCoPO4 agglomerates. Ne-ion ToF-SIMS characterization identified oxyfluorophosphates from HF attack by the electrolyte and a Li-rich surface region. Variable thickness of the CEI layer coupled with inactive Li on the surface of LiCoPO4 electrodes contributes to severe degradation over the course of 10 cycles. The HIM-SIMS technique has potential to further investigate the effect of microstructures on CEI formation in cathode materials or solid electrolyte interphase formation in anodes, thus aiding future electrode development.