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During the past decades, several stand-alone and combinatorial methods have been developed to investigate the chemistry (i.e., mapping of elemental, isotopic, and molecular composition) and the role of microbes in soil and rhizosphere. However, none of these approaches are currently applicable to characterize soil-root-microbe interactions simultaneously in their spatial arrangement. Here we present a novel approach that allows for simultaneous microbial identification and chemical analysis of the rhizosphere at micro− to nano-meter spatial resolution. Our approach includes (i) a resin embedding and sectioning method suitable for simultaneous correlative characterization of Zea mays rhizosphere, (ii) an analytical work flow that allows up to six instruments/techniques to be used correlatively, and (iii) data and image correlation. Hydrophilic, immunohistochemistry compatible, low viscosity LR white resin was used to embed the rhizosphere sample. We employed waterjet cutting and avoided polishing the surface to prevent smearing of the sample surface at nanoscale. The quality of embedding was analyzed by Helium Ion Microscopy (HIM). Bacteria in the embedded soil were identified by Catalyzed Reporter Deposition-Fluorescence in situ Hybridization (CARD-FISH) to avoid interferences from high levels of autofluorescence emitted by soil particles and organic matter. Chemical mapping of the rhizosphere was done by Scanning Electron Microscopy (SEM) with Energy-dispersive X-ray analysis (SEM-EDX), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), nano-focused Secondary Ion mass Spectrometry (nanoSIMS), and confocal Raman spectroscopy (μ-Raman). High-resolution correlative characterization by six different techniques followed by image registration shows that this method can meet the demanding requirements of multiple characterization techniques to identify spatial organization of bacteria and chemically map the rhizosphere. Finally, we presented individual and correlative workflows for imaging and image registration to analyze data. We hope this method will be a platform to combine various 2D analytics for an improved understanding of the rhizosphere processes and their ecological significance.

We fabricate plasmonic heptamer-arranged nanohole (HNH) arrays by helium (He) focused ion beam (HeFIB) milling, which is a resist-free, maskless, direct-write method. The small He+ beam spot size and high milling resolution achieved by the gas field-ionization source used in our HeFIB allows the milling of high aspect ratio (4:1) nanoscale features in metal, such as HNHs incorporating 15 nm walls of high verticality between holes in a 55-nm-thick gold film. Drifts encountered during the HeFIB milling of large arrays, due to sample stage vibrations or He beam instability, were compensated by a drift correction technique based on in situ He ion imaging of alignment features. Our drift correction technique yielded 20 nm maximum dislocation of HNHs, with 6.9 and 4.6 nm average dislocations along the horizontal and vertical directions, respectively. The measured optical resonance spectra of the fabricated plasmonic HNH arrays are presented to support the fabrication technique. Defects associated with HeFIB milling are also discussed.

A dedicated transmission helium ion microscope (THIM) for sub-50 keV helium has been constructed to investigate ion scatteringprocesses and contrast mechanisms, aiding the development of new imaging and analysis modalities. Unlike a commercial heliumion microscope (HIM), the in-house built instrument allows full flexibility in experimental configuration. Here, we report projectionimaging and intensity patterns obtained from powder and bulk crystalline samples using stationary broad-beam as well asconvergent-beam illumination conditions in THIM. The He+ ions formed unexpected spot patterns in the far field for MgO, BN andNaCl powder samples, but not for Au-coated MgO. The origin of the spot patterns in these samples was investigated. Surfacediffraction of ions was excluded as a possible cause because the recorded scattering angles do not correspond to the predicted Braggangles. Complementary secondary electron (SE) imaging in the HIM revealed that these samples charge significantly under He+ ionirradiation. The spot patterns obtained in the THIM experiments are explained as artefacts related to sample charging. The resultspresented here indicate that factors other than channeling, blocking and surface diffraction of ions have an impact on the final intensitydistribution in the far field. Hence, the different processes contributing to the final intensities will need to be understood in order to decouple and study the relevant ion-beam scattering and deflection phenomena.

The main goal of this study was to apply magnetic bead surface functionalization in the form of immunomagnetic separation (IMS) combined with real-time polymerase chain reaction (qPCR) (IMS-qPCR) to detect Human mastadenovirus species C (HAdV-C) and F (HAdV-F) in water samples. The technique efficiency was compared to a nonfunctionalized method (ultracentrifugation) followed by laboratory detection. Tests were carried out to standardize IMS parameters followed by tests on 15 water samples concentrated by IMS and ultracentrifugation. Microscopic analyses detected a successful beads&ndash, antibody attachment. HAdV was detected up to dilutions of 10&minus, 6 by IMS-qPCR, and samples concentrated by IMS were able to infect cell cultures. In water samples, HAdV-C was detected in 60% (monoclonal) and 47% (polyclonal) by IMS-qPCR, while 13% of samples concentrated by ultracentrifugation gave a positive result. HAdV-F was positive in 27% of samples by IMS-qPCR (polyclonal) and ultracentrifugation and 20% by IMS-qPCR (monoclonal). The rate of detection varied from 4.55 &times, 102 to 5.83 &times, 106 genomic copies/L for IMS-qPCR and from 2.00 &times, 102 to 2.11 &times, 103 GC/L for ultracentrifugation. IMS showed to be a more effective concentration technique for HAdV than ultracentrifugation, improving the assessment of infectious HAdV in water resources.

Metallic nanostructures can transport electromagnetic fields in the form of surface plasmon polariton (SPP) excitations, focus them into nanometric spots, and transfer them to nearby nanostructures by near-field coupling. This provides a basic functionality for designing new plasmonic devices that can greatly enhance light-matter coupling and facilitate ultrafast and efficient all-optical switching on the nanoscale. Here, we study a prototypical device geometry, a bow-tie antenna equipped with curved line gratings, for the efficient coupling of light into and across the antenna nanogap. We experimentally demonstrate the spectrally broadband launching and propagation of SPP waves over more than 10 mu m on one arm of the antenna, their focusing into and transmission across the gap being studied by the plasmon outcoupling on the other arm. A substantial increase in the coupling efficiency for antennas with gap widths below 20 nm proves that the optical near-field coupling between the two antenna arms dominates the gap transmission. We find overall transmission efficiencies for nanofocusing, gap transmission, and plasmon outcoupling of up to 4%. A finite-difference time-domain simulation supports our experimental findings. This makes such bow-tie couplers an interesting platform for sensitively probing near-field coupling to single quantum emitters and for the ultrafast switching of light by light on the nanoscale.

Nanoparticles occur in various environments as a consequence of man-madeprocesses, which raises concerns about their impact on the environment andhuman health. To allow for proper risk assessment, a precise and statisticallyrelevant analysis of particle characteristics (such as size, shape, and composition)is required that would greatly benefit from automated imageanalysisprocedures. While deep learning shows impressive results in object detectiontasks, its applicability is limited by the amount of representative, experimentallycollected and manually annotated training data. Here, an elegant,flexible, and versatile method to bypass this costly and tedious data acquisitionprocess is presented. It shows that using a rendering software allows togenerate realistic, synthetic training data to train a state-of-the art deep neuralnetwork. Using this approach, a segmentation accuracy can be derived that iscomparable to man-made annotations for toxicologically relevant metal-oxidenanoparticle ensembles which were chosen as examples. The presentedstudy paves the way toward the use of deep learning for automated, highthroughputparticle detection in a variety of imaging techniques such as inmicroscopies and spectroscopies, for a wide range of applications, includingthe detection of micro- and nanoplastic particles in water and tissue samples.

Complete hydration is essential for the production of structured dairy products from powders. It is essential that the ingredients used hydrate completely. Determination of an end point of rehydration is non-trivial, but ultrasound-based methodologies have demonstrated potential in this area and are well suited to measuring bulk samples in situ. Here, acoustic attenuation spectroscopy (AAS) is used to monitor rehydration of skim milk powder, and recombined systems of micellar casein isolate with lactose and whey protein isolate. Dynamic light scattering, zeta-potential measurements and AAS as a function of pH characterise each component around its isoelectric point to assess its functionality. Scanning helium ion microscopy was used to image the dry powders, without any conductive coating, producing resolution equivalent to scanning electron microscopy, but with much larger focal lengths and fewer imaging artefacts. Imaging the powders provides information on particle size and morphology which can affect dissolution behaviour. Reconstituted skim milk powder and recombined samples were monitored showing there are changes occurring over several hours. Attenuation coefficients are shown to predict the end point of hydration. Model fitting is used to extract volume fractions and average particle sizes of large and small particle populations in recombined samples over time. AAS is demonstrated to be capable of tracking the dynamics in rehydrating dispersions over time. Physical parameters such as the volume fraction and particle size of the dispersed phase can be determined.

The next generation optical, electronic, biological, and sensing devices as well as platforms will inevitably extend their architecture into the 3rd dimension to enhance functionality. In focused ion beam induced deposition (FIBID), a helium gas field ion source can be used with an organometallic precursor gas to fabricate nanoscale structures in 3D with high-precision and smaller critical dimensions than focused electron beam induced deposition (FEBID), traditional liquid metal source FIBID, or other additive manufacturing technology. In this work, we report the effect of beam current, dwell time, and pixel pitch on the resultant segment and angle growth for nanoscale 3D mesh objects. We note subtle beam heating effects, which impact the segment angle and the feature size. Additionally, we investigate the competition of material deposition and sputtering during the 3D FIBID process, with helium ion microscopy experiments and Monte Carlo simulations. Our results show complex 3D mesh structures measuring ~300 nm in the largest dimension, with individual features as small as 16 nm at full width half maximum (FWHM). These assemblies can be completed in minutes, with the underlying fabrication technology compatible with existing lithographic techniques, suggesting a higher-throughput pathway to integrating FIBID with established nanofabrication techniques.

Helium-ion-induced swelling and blistering of single-crystal tungsten is investigated using a Helium Ion Microscope for site-specific dose-controlled irradiation (at 25 keV) with analysis by Helium Ion Microscopy, Atomic Force Microscopy and Transmission Electron Microscopy (cross-sectioning by Focused Ion Beam milling). Our measurements show that the blister cavity forms at the depth of the helium peak and that nanobubbles coalesce to form nanocracks within the envelope of the ion stopping range, causing swelling of the blister shell. These results provide the first direct experimental evidence for the interbubble fracture mechanism proposed in the framework of the gas pressure model for blister formation.

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., P Orús acknowledges Aragón Government for funding. This work was supported by a STSM grant from COST Action CA16218. The HIM works were performed in the Ion Beam Center at the Helmholz-Zentrum Dresden-Rossendorf, the access to which and whose support is acknowledged. The project that gave rise to these results received the support of a fellowship from 'la Caixa' Foundation (ID 100010434). The fellowship code is LCF/BQ/PR19/11700008. Authors acknowledge financial support from the Spanish Ministry of Economy and Competitiveness through Projects MAT2018-102627-T and MAT2017-82970-C2, from CSIC through project PIE202060E187, and from the Aragon Regional Government (Construyendo Europa desde Aragón) through Project E13_20R, with European Social Fund funding.

In various research areas ranging from materials science to life sciences it becomes more and more important to be able to analyze the structure as well as the chemical composition at the nano-scale. For example, the size of electronic components becomes smaller and smaller increasing the need of having techniques to precisely follow dopant distributions with high spatial resolution. In the field of renewable energy devices, e.g. solar cells and batteries, the performance typically depends on the chosen material composition and distribution. Linking the underlying structure and composition at the nano-scale to the device’s performance is therefore of utmost importance [1,2]. Similar needs for having high spatial resolution and high-sensitivity chemical information can be found in life sciences [3]. In nano-toxicology for instance, it is important to be able to reveal sub-cellular structures and simultaneously determine their chemical, elemental or isotopic composition in order to better understand relevant processes [4]. In most of the afore mentioned studies a number of different instruments is nowadays used to perform these investigations using correlative approaches. Being able to do such correlative studies in one single instrument is definitely beneficial for reducing the analysis time, speeding up the throughput as well as for facilitating the precise localization of the region of interests on the investigated samples. Therefore, we developed a multimodal nano-analytical platform allowing in-situ analysis of a same sample using different information channels. The instrument is equipped with the ultra-high resolution Gas Field Ion Source (GFIS) technology [5] allowing the sample to be irradiated with very finely focused He+ and Ne+ primary ion beams. This allows sub-nanometer spatial resolution when working with the secondary electron (SE) detection mode as imaging mode. Furthermore, the instrument incorporates a compact secondary ion mass spectrometer (SIMS) for chemical analysis of samples with excellent sensitivity and high dynamic range. The mass spectrometer is based on a double focusing magnetic sector design and allows sub-20 nm chemical imaging resolution [6-8]. Moreover, the SIMS system incorporates a new kind of detector for parallel mass detection providing a full mass spectrum for each analyzed pixel. The third newly developed detection mode available within the instrument is a position sensitive transmission detector located at the backside of the sample in order to detect the transmitted He beam. This scanning transmission helium ion microscopy (STHIM) mode provides further in-situ structural/compositional data with tomographic capabilities. In order to optimize the analysis of biological samples, one further key feature of the instrument is a 5-axis cryo-stage along with cryo-capabilities for sample transfers. This cryo-capability allows biological samples to be analyzed in a frozen-hydrated state, thus avoiding artefacts caused by classical sample preparation (e.g. chemical fixation) used for HV or UHV imaging of biological specimens at room temperature. Moreover, the cryo-mode can be beneficial for analyzing beam sensitive samples in materials science such as OLEDs and polymers. In this work we will present the npSCOPE concept and the instrument’s overall setup, report on the performance of the different detection modes and discuss the correlative microscopy capabilities. We will present results from case studies in different fields, with a particular focus on nanoparticles (see Figure 1) [9].

A detection system based on a microchannel plate with a delay line readout structure has been developed to perform scanning transmissionionmicroscopy (STIM) in the helium ion microscope (HIM). This system is an improvement over other existing approachessince it combines the information of the scanning beam position on the sample with the position (scattering angle) andtime of the transmission events. Various imaging modes, such as bright field and dark field or the direct image of the transmittedsignal, can be created by post-processing the collected STIM data. Furthermore, the detector has high spatial and temporal resolution,is sensitive to both ions and neutral particles over a wide energy range, and shows robustness against ion beam-induceddamage. A special in-vacuum movable support gives the possibility of moving the detector vertically, placing the detector closer tothe sample for the detection of high-angle scattering events, or moving it down to increase the angular resolution and distance fortime-of-flight measurements. With this new system, we show composition-dependent contrast for amorphous materials and thecontrast difference between small-angle and high-angle scattering signals. We also detect channeling-related contrast on polycrystallinesilicon, thallium chloride nanocrystals, and single-crystalline silicon by comparing the signal transmitted at different directionsfor the same data set.

For future nanoelectronic devices - such as room-temperature single electron transistors - the site-controlled formation of single Si nanocrystals (NCs) is a crucial prerequisite. Here, we report an approach to fabricate single Si NCs via medium-energy Si+ or Ne+ ion beam mixing of Si into a buried SiO2 layer followed by thermally activated phase separation. Binary collision approximation and kinetic Monte Carlo methods are conducted to gain atomistic insight into the influence of relevant experimental parameters on the Si NC formation process. Energy-filtered transmission electron microscopy is performed to obtain quantitative values on the Si NC size and distribution in dependence of the layer stack geometry, ion fluence and thermal budget. Employing a focused Ne+ beam from a helium ion microscope, we demonstrate site-controlled self-assembly of single Si NCs. Line irradiation with a fluence of 3000 Ne+/nm2 and a line width of 4 nm leads to the formation of a chain of Si NCs, and a single NC with 2.2 nm diameter is subsequently isolated and visualized in a few nanometer thin lamella prepared by a focused ion beam (FIB). The Si NC is centered between the SiO2 layers and perpendicular to the incident Ne+ beam., Comment: 10 pages, 6 figures

High-aspect ratio porous structures with controllable pore diameters and without a stiff substrate can be fabricated using the ion track technique. Atomic layer deposition is an ideal technique for depositing thin films and functional surfaces on complicated 3D structures due to the high conformality of the films. In this work, we studied Al2O3 and TiO2 films grown by ALD on pristine polyimide (Kapton HN) membranes as well as polyimide membranes etched in sodium hypochlorite (NaOCl) and boric acid (BO3) solution by means of RBS, PIXE, SEM-EDX and helium ion microcopy (HIM). The focus was on the first ALD growth cycles. The areal density of Al2O3 film in the 400 cycle sample was determined to be 51 ± 3 × 1016 at./cm2, corresponding to the thickness of 55 ± 3 nm. Furthermore, the growth per cycle was 1.4 A/cycle. The growth is highly linear from the first cycles. In the case of TiO2, the growth per cycle is clearly slower during the first 200 cycles but then it increases significantly. The growth rate based on RBS measurements is 0.24 A/cycle from 3 to 200 cycles and then 0.6 A/cycle between 200 and 400 cycles. The final areal density of TiO2 film after 400 cycles is 148 ± 3 × 1015 at./cm2 which corresponds to the thickness of 17.4 ± 0.4 nm. The modification of the polyimide surface by etching prior to the deposition did not have an effect on the Al2O3 and TiO2 growth.

Nano-textured surfaces (NTS) are critical to organisms as self-adaptation and survival tools. These NTS have been actively mimicked in the process of developing bactericidal surfaces for diverse biomedical and hygiene applications. To design and fabricate bactericidal topographies effectively for various applications, understanding the bactericidal mechanism of NTS in nature is essential. The current mechanistic explanations on natural bactericidal activity of nanopillars have not utilized recent advances in microscopy to study the natural interaction. This research reveals the natural bactericidal interaction between E.coli and a dragonfly wing's NTS using advanced microscopy techniques and propose a model. Contrary to the existing mechanistic models, this experimental approach demonstrated that the NTS of dragonfly wings has two prominent nanopillar populations and the resolved interface shows membrane damage occurred without direct contact of the bacterial cell membrane with the nanopillars. We propose that the bacterial membrane damage is initiated by a combination of strong adhesion between nanopillars and bacterium EPS layer as well as shear force when immobilised bacterium attempt to move on the NTS. These findings could help guide the design of novel bio-mimetic nanomaterials by maximising the synergies between both biochemical and mechanical bactericidal effects.Nano-textured surfaces (NTS) are critical to organisms as self-adaptation and survival tools. These NTS have been actively mimicked in the process of developing bactericidal surfaces for diverse biomedical and hygiene applications. To design and fabricate bactericidal topographies effectively for various applications, understanding the bactericidal mechanism of NTS in nature is essential. The current mechanistic explanations on natural bactericidal activity of nanopillars have not utilized recent advances in microscopy to study the natural interaction. This research reveals the natural bactericidal interaction between E.coli and a dragonfly wing's NTS using advanced microscopy techniques and propose a model. Contrary to the existing mechanistic models, this experimental approach demonstrated that the NTS of dragonfly wings has two prominent nanopillar populations and the resolved interface shows membrane damage occurred without direct contact of the bacterial cell membrane with the nanopillars. We propose that the bacterial membrane damage is initiated by a combination of strong adhesion between nanopillars and bacterium EPS layer as well as shear force when immobilised bacterium attempt to move on the NTS. These findings could help guide the design of novel bio-mimetic nanomaterials by maximising the synergies between both biochemical and mechanical bactericidal effects.

Titanium hexafluoride pretreatments are known to improve paint adhesion and function as a barrier between the coating and the hot dip galvanized (HDG) steel surface. Interactions at the zinc/pretreatment interface are of utmost importance for the formation of pretreatment layers and the corrosion resistance of color coated hot dip galvanized steels. Removal rate of inert aluminum oxide from HDG steel samples by chemical dissolution was studied. XPS measurements showed that the surface Al2O3 layer thickness decreased rapidly already at mild alkaline cleaning, while complete removal of Al required severe etching. Low reactivity of an Al2O3-rich surface was confirmed by impaired formation of a titanium hexafluoride pretreatment layer. Grain boundaries and deformation twinnings were shown to be of importance for the reactivity of the HDG surface and for the precipitation of the pretreatment chemical. Helium ion microscopy images and electron probe microanalysis (EPMA) of a pretreated sample showed accumulation of the pretreatment chemical at the grain boundaries. Al removal rate was fast at the deformation twinnings at the grain plateaus. Slow Al removal was observed at dendritic valleys and grain boundaries. The results increase understanding of the reactivity of hot dip galvanized steel surface. peerReviewed

Made available in DSpace on 2019-10-06T15:40:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-07-05 Tekes Academy of Finland Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) The molecular fingerprints of yeasts Saccharomyces cerevisiae, Dekkera bruxellensis, and Wickerhamomyces anomalus (former name Pichia anomala) have been examined using surface-enhanced Raman spectroscopy (SERS) and helium ion microscopy (HIM). The SERS spectra obtained from cell cultures (lysate and non-treated cells) distinguish between these very closely related fungal species. Highly SERS active silver nano-particles suitable for detecting complex biomolecules were fabricated using a simple synthesis route. The yeast samples mixed with aggregated Ag nanoparticles yielded highly enhanced and reproducible Raman signal owing to the high density of the hot spots at the junctions of two or more Ag nanoparticles and enabled to differentiate the three species based on their unique features (spectral fingerprint). We also collected SERS spectra of the three yeast species in beer medium to demonstrate the potential of the method for industrial application. These findings demonstrate the great potential of SERS for detection and identification of fungi species based on the biochemical compositions, even in a chemically complex sample. Faculdade de Clências e Tecnologia (FCT)-Universidade Estadual Paulista (UNESP)-Presidente Prudente Institute of Intelligent Machines Chinese Academy of Sciences NanoScience Center Department of Physics University of Jyväskylä, P.O. Box 35 (YN) Faculty of Medicine and Health Technology BioMediTech Tampere University, Arvo Ylpön katu 34 Fimlab Laboratories, Biokatu 4 Faculdade de Clências e Tecnologia (FCT)-Universidade Estadual Paulista (UNESP)-Presidente Prudente Tekes: 1185/31/2013 Academy of Finland: 136288 FAPESP: 2013/14262-7 FAPESP: 2016/06424-5 Academy of Finland: 263526

The helium ion microscope (HIM) has emerged as an instrument of choice for patterning, imaging and, more recently, analytics at the nanoscale. Here, we review secondary electron imaging on the HIM and the various methodologies and hardware components that have been developed to confer analytical capabilities to the HIM. Secondary electron–based imaging can be performed at resolutions down to 0.5 nm with high contrast, with high depth of field, and directly on insulating samples. Analytical methods include secondary electron hyperspectral imaging (SEHI), scanning transmission ion microscopy (STIM), backscattering spectrometry and, in particular, secondary ion mass spectrometry (SIMS). The SIMS system that was specifically designed for the HIM allows the detection of all elements, the differentiation between isotopes, and the detection of trace elements. It provides mass spectra, depth profiles, and 2D or 3D images with lateral resolutions down to 10 nm.

Si nanopillars of less than 50 nm diameter have been irradiated in a helium ion microscope with a focused Ne+ beam. The morphological changes due to ion beam irradiation at room temperature and elevated temperatures have been studied with the transmission electron microscope. We found that the shape changes of the nanopillars depend on irradiation-induced amorphization and thermally driven dynamic annealing. While at room temperature, the nanopillars evolve to a conical shape due to ion-induced plastic deformation and viscous flow of amorphized Si, simultaneous dynamic annealing during the irradiation at elevated temperatures prevents amorphization which is necessary for the viscous flow. Above the critical temperature of ion-induced amorphization, a steady decrease of the diameter was observed as a result of the dominating forward sputtering process through the nanopillar sidewalls. Under these conditions the nanopillars can be thinned down to a diameter of ∼10 nm in a well-controlled manner. A deeper understanding of the pillar thinning process has been achieved by a comparison of experimental results with 3D computer simulations based on the binary collision approximation.

The analysis of polymers by secondary ion mass spectrometry (SIMS) has been a topic of interest for many years. In recent years, the primary ion species evolved from heavy monatomic ions to cluster and massive cluster primary ions in order to preserve a maximum of organic information. The progress in less-damaging sputtering goes along with a loss in lateral resolution for 2D and 3D imaging. By contrast the development of a mass spectrometer as an add-on tool for the helium ion microscope (HIM), which uses finely focussed He+ or Ne+ beams, allows for the analysis of secondary ions and small secondary cluster ions with unprecedented lateral resolution. Irradiation induced damage and depth profiling capabilities obtained with these light rare gas species have been far less investigated than ion species used classically in SIMS. In this paper we simulated the sputtering of multi-layered polymer samples using the BCA (binary collision approximation) code SD_TRIM_SP to study preferential sputtering and atomic mixing in such samples up to a fluence of 1018 ions/cm2. Results show that helium primary ions are completely inappropriate for depth profiling applications with this kind of sample materials while results for neon are similar to argon. The latter is commonly used as primary ion species in SIMS. For the two heavier species, layers separated by 10 nm can be distinguished for impact energies of a few keV. These results are encouraging for 3D imaging applications where lateral and depth information are of importance.

Secondary ion mass spectrometry (SIMS) on the helium ion microscope (HIM) promises higher lateral resolution than on classical SIMS instruments. However, full advantage of this new technique can only be obtained when the interaction of He+ or Ne+ primary ions with the sample is fully controlled. In this work we investigate how He+ and Ne+ bombardment influences roughness formation and preferential sputtering for polymer samples and how they compare to Ar+ primary ions used in classical SIMS by combining experimental techniques with Molecular Dynamics (MD) simulations and SD_TRIM_SP modelling. The results show that diffusion coefficients for He, Ne and Ar in polymers are sufficiently high to prevent any accumulation of rare gas atoms in the polymers which could lead to some swelling and bubble formation. Roughness formation was also not observed. Preferential sputtering is more of a problem, with enrichment of carbon up to surface concentrations above 80%. In general, the preferential sputtering is largely depending on the primary ion species and the impact energies. For He+ bombardment, it is more of an issue for low keV impact energies and for the heavier primary ion species the preferential sputtering is sample dependent. For He+ steady state conditions are reached for fluences much higher than 1018 ions/cm2. For Ne+ and Ar+, the transient regime extends up to fluences of 1017–1018 ions/cm2. Hence, preferential sputtering needs to be taken into account when interpreting images recorded under He+ or Ne+ bombardment on the HIM.

Helium Ion Microscopy is known for its surface sensitivity and high lateral resolution. Here, we present results of a Helium Ion Microscopy based investigation of a surface confined alloy of Ag on Pt(111). Based on a change of the work function of 25\,meV across the atomically flat terraces we can distinguish Pt rich from Pt poor areas and visualize the single atomic layer high steps between the terraces. Furthermore, dechanneling contrast has been utilized to measure the periodicity of the hcp/fcc pattern formed in the 2--3 layers thick Ag/Pt alloy film. A periodicity of 6.65\,nm along the $\langle\overline{11}2\rangle$ surface direction has been measured. In terms of crystallography a hcp domain is obtained through a lateral displacement of a part of the outermost layer by $1/\sqrt{3}$ of a nearest neighbour spacing along $\langle\overline{11}2\rangle$. This periodicity is measured with atomic precision: coincidence between the Ag and the Pt lattices is observed for 23 Ag atoms on 24 Pt atoms. The findings are perfectly in line with results obtained with Low Energy Electron Microscopy and Phase Contrast Atomic Force Microscopy., 15 pages, 7 figures

Beilstein journal of nanotechnology 9, 2968 - 2979 (2018). doi:10.3762/bjnano.9.276, Background: The application of superparamagnetic particles as biomolecular transporters in microfluidic systems for lab-on-a-chipapplications crucially depends on the ability to control their motion. One approach for magnetic-particle motion control is thesuperposition of static magnetic stray field landscapes (MFLs) with dynamically varying external fields. These MFLs may emergefrom magnetic domains engineered both in shape and in their local anisotropies. Motion control of smaller beads does necessarilyneed smaller magnetic patterns, i.e., MFLs varying on smaller lateral scales. The achievable size limit of engineered magneticdomains depends on the magnetic patterning method and on the magnetic anisotropies of the material system. Smallest patterns areexpected to be in the range of the domain wall width of the particular material system. To explore these limits a patterning technol-ogy is needed with a spatial resolution significantly smaller than the domain wall width.Results: We demonstrate the application of a helium ion microscope with a beam diameter of 8 nm as a mask-less method for localdomain patterning of magnetic thin-film systems. For a prototypical in-plane exchange-bias system the domain wall width has beeninvestigated as a function of the angle between unidirectional anisotropy and domain wall. By shrinking the domain size of periodic domain stripes, we analyzed the influence of domain wall overlap on the domain stability. Finally, by changing the geometryof artificial two-dimensional domains, the influence of domain wall overlap and domain wall geometry on the ultimate domain sizein the chosen system was analyzed.Conclusion: The application of a helium ion microscope for magnetic patterning has been shown. It allowed for exploring thefundamental limits of domain engineering in an in-plane exchange-bias thin film as a prototypical system. For two-dimensionaldomains the limit depends on the domain geometry. The relative orientation between domain wall and anisotropy axes is a crucialparameter and therefore influences the achievable minimum domain size dramatically., Published by Beilstein-Institut zur Förderung der Chemischen Wissenschaften, Frankfurt, M.

Addition of biochar into a soil changes its water retention properties by modifying soil textural and structural properties. In addition, internal micrometer-scale porosity that is able to directly store readily plant available water affects soil water retention properties. This study shows how precise knowledge of the internal micrometer-scale pore size distribution of biochar can deepen the understanding of the biochar-water interactions in soils. The micrometer-scale porosity of willow biochar was quantitatively and qualitatively characterized using X-ray tomography, 3D image analysis and Helium ion microscopy. The effect of biochar application on clay soil water retention was studied by conventional water retention curve approach. The results indicate that the internal pores of biochar, with sizes of at 50 and 10 μm (equivalent pore diameter), increased soil porosity and the amount of readily plant available water. After biochar addition, changes in soil porosity were detected at pore size regimes 5–10 and 25 μm, i.e. biochar pore sizes multiplied by factor 0.5. The detected pore size distribution of biochar does not predict directly (1:1 compatibility) the changes observed in the soil moisture characteristics. It is likely that biochar chemistry and pore morphology affect biochar-water interactions via e.g. surface roughness and contact angle. In addition, biochar induced changes in soil structure and texture affected soil moisture characteristics. However, the approach presented is an attractive pathway to more generalized understanding on how and why biochar internal porosity affects soil moisture characteristics. publishedVersion

Helium ion microscopy (HIM), enabled by a gas field ion source (GFIS), is an emerging imaging and nanofabrication technique compatible with many applications in materials science. The scanning electron microscope (SEM) has become ubiquitous in materials science for high-resolution imaging of materials. However, due to the fundamental limitation in focusing of electron beams, ion-beam microscopy is now being developed (e.g., at 20 kV the SEM beam diameter ranges from 0.5 to 1 nm, whereas the HIM offers 0.35 nm). The key technological advantage of the HIM is in its multipurpose design that excels in a variety of disciplines. The HIM offers higher resolution than the best available SEMs as well as the traditional gallium liquid-metal ion source (LMISs) focused ion beams (FIBs), and is capable of imaging untreated biological or other insulating samples with unprecedented resolution, depth of field, materials contrast, and image quality. GFIS FIBs also offer a direct path to defect engineering via ion implantation, three-dimensional direct write using gaseous and liquid precursors, and chemical-imaging options with secondary ion mass spectrometry. HIM covers a wide range of tasks that otherwise would require multiple tools or specialized sample preparation. In this article, we describe the underlying technology, present materials, relevant applications, and offer an outlook for the potential of FIB technology in processing materials.

The determination of the negative ion yield of 2′-chloro-1,1′-biphenyl (2-Cl-BP), 2′-bromo-1,1′-biphenyl (2-Br-BP) and 2′-iodo-1,1′-biphenyl (2-I-BP) upon dissociative electron attachment (DEA) at an electron energy of 0 eV revealed cross section values that were more than ten times higher for iodide loss from 2-I-BP than for the other halogenides from the respective biphenyls (BPs). Comparison with dissociative ionization mass spectra shows that the ratio of the efficiency of electron impact ionization induced fragmentation of 2-I-BP, 2-Br-BP, and 2-Cl-BP amounts to approximately 1:0.7:0.6. Inspired by these results, self-assembled monolayers (SAMs) of the respective biphenyl-4-thiols, 2-Cl-BPT, 2-Br-BPT, 2-I-BPT as well as BPT, were grown on a Au(111) substrate and exposed to 50 eV electrons. The effect of electron irradiation was investigated by X-ray photoelectron spectroscopy (XPS), to determine whether the high relative DEA cross section for iodide loss from 2-I-BPT as compared to 2-Br-BP and 2-Cl-BP is reflected in the cross-linking efficiency of SAMs made from these materials. Such sensitization could reduce the electron dose needed for the cross-linking process and may thus lead to a significantly faster conversion of the respective SAMs into carbon nanomembranes (CNMs) without the need for an increased current density. XPS data support the notation that DEA sensitization may be used to achieve more efficient electron-induced cross-linking of SAMs, revealing more than ten times faster cross-linking of 2-I-BPT SAMs compared to those made from the other halogenated biphenyls or from native BPT at the same current density. Furthermore, the transfer of a freestanding membrane onto a TEM grid and the subsequent investigation by helium ion microscopy (HIM) verified the existence of a mechanically stable CNM created from 2-I-BPT after exposure to an electron dose as low as 1.8 mC/cm2. In contrast, SAMs made from BPT, 2-Cl-BPT and 2-Br-BPT did not form stable CNMs after a significantly higher electron dose of 9 mC/cm2.

Highly uniform samples of carbon nanofoam from hydrothermal sucrose carbonization were studied by helium ion microscopy (HIM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Foams with different densities were produced by changing the process temperature in the autoclave reactor. This work illustrates how the geometrical structure, electron core levels, and the vibrational signatures change when the density of the foams is varied. We find that the low-density foams have very uniform structure consisting of micropearls with ≈2–3 μm average diameter. Higher density foams contain larger-sized micropearls (≈6–9 μm diameter) which often coalesced to form nonspherical μm-sized units. Both, low- and high-density foams are comprised of predominantly sp2-type carbon. The higher density foams, however, show an advanced graphitization degree and a stronger sp3-type electronic contribution, related to the inclusion of sp3 connections in their surface network.

Physisorbed water originating from exposure to the ambient can have a strong impact on the structure and chemistry of oxide nanomaterials. The effect can be particularly pronounced when these oxides are in physical contact with a solid substrate such as the ones used for immobilization to perform electron or ion microscopy imaging. We used helium ion microscopy (HIM) and investigated morphological changes of vapor-phase-grown MgO cubes after vacuum annealing and pressing into foils of soft and high purity indium. The indium foils were either used as obtained or, for reference, subjected to vacuum drying. After four days of storage in the vacuum chamber of the microscope and at a base pressure of p < 10−7 mbar, we observed on these cubic particles the attack of residual physisorbed water molecules from the indium substrate. As a result, thin magnesium hydroxide layers spontaneously grew, giving rise to characteristic volume expansion effects, which depended on the size of the particles. Rounding of the originally sharp cube edges leads to a significant loss of the morphological definition specific to the MgO cubes. Comparison of different regions within one sample before and after exposure to liquid water reveals different transformation processes, such as the formation of Mg(OH)2 shells that act as diffusion barriers for MgO dissolution or the evolution of brucite nanosheets organized in characteristic flower-like microstructures. The findings underline the significant metastability of nanomaterials under both ambient and high-vacuum conditions and show the dramatic effect of ubiquitous water films during storage and characterization of oxide nanomaterials.

We investigate the ability of a focused helium ion beam to selectively modify and mill materials. The sub nanometer probe size of the helium ion microscope used provides lateral control not previously available for helium ion irradiation experiments. At high incidence angles the helium ions were found to remove surface material from a silicon lamella leaving the subsurface structure intact for further analysis. Surface roughness and contaminants were both reduced by the irradiation process. Fabrication is also realized with a high level of patterning acuity. Implantation of helium beneath the surface of the sample is visualized in cross section allowing direct observation of the extended effects of high dose irradiation. The effect of the irradiation on the crystal structure of the material is presented. Applications of the sample modification process are presented and further prospects discussed.