Probe Microscopy Research Articles

Unearthing Atomic Dynamics in Nanocatalysts.

Being able to access the rich atomic-scale phenomenology, which occurs during the reactions pathways, is a pressing need toward the pursued knowledge-based design of more efficient nanocatalysts, precisely tailored atom by atom for each reaction. However, to reach this goal of achieving maximum optimization, it is mandatory, first, to address how exposure to the experimental conditions, which will be needed to activate the processes, affects the internal configuration of the nanoparticles at the atomic level. In particular, the most critical experimental parameter is probably the temperature, which among other unwanted effects can induce nanocatalyst aggregation. This work highlights the high potential of experimental techniques such as the scanning probe microscopies, which are able to investigate matter in real space with atomic resolution, to reach the key challenge in heterogeneous catalysis of achieving access to the atomic-scale processes taking place in the nanocatalysts. Specifically, the phenomenology occurring in a nanoparticle system during annealing is studied with atomic precision by scanning tunneling microscopy. As a result, the existence of an internal atomic restructuring, occurring already at relatively low temperatures, within Ir nanoparticles grown over h-BN/Ru(0001) surfaces is demonstrated. Such restructuration, which reduces the undercoordination of the outer Ir atoms, is expected to have a significant effect on the reactivity of the nanoparticles. Going a step further, an internal restructuring of the nanoparticles during their involvement as catalysts has also been also identified.

Atomic Force Microscopy and Scanning Ion-Conductance Microscopy for Investigation of Biomechanical Characteristics of Neutrophils

Scanning probe microscopy (SPM) is a versatile tool for studying a wide range of materials. It is well suited for investigating living matter, for example, in single-cell neutrophil studies. SPM has been extensively utilized to analyze cell physical properties, providing detailed insights into their structural and functional characteristics at the nanoscale. Its long-standing application in this field highlights its essential role in cell biology and immunology research, significantly contributing to understanding cellular mechanics and interactions. In this review, we discuss the application of SPM techniques, specifically atomic force microscopy (AFM) and scanning ion-conductance microscopy (SICM), to study the fundamental functions of neutrophils. In addition, recent advances in the application of SPM in single-cell immunology are discussed. The application of these techniques allows for obtaining data on the morphology, topography, and mechanical and electrochemical properties of neutrophils with high accuracy.

Phonon-polariton Bragg generation at the surface of silicon carbide

Phonon-polaritons are known to emerge at the surface of solids under infrared (IR) irradiation at frequencies close to the optical phonon resonance. Metal, patterned on the top of the polariton-active surface, locally blocks the excitation of surface waves due to plasmonic screening and can be used for the design of wave patterns. We excite polaritonic waves at the surface of SiC under the irradiation of a CO2 laser (λ∼10μm) and visualize them using apertureless near-field interference scanning probe microscopy. From the near-field scans in the vicinity of gold film periodical strip structures, we identify the Bragg scattering (diffraction) outside the grating with the contribution from separate strips coherently summed up, provided that the wavelength matching condition is fulfilled. The observed phenomena agree with wavefield calculations. Our observations demonstrate the potential of metal-patterned silicon carbide for the fabrication of on-chip polaritonic IR circuits.

Degradation of alkali‐activated Fe‐rich slag in magnesium sulfate solution

AbstractThe potential of Fe‐rich non‐ferrous metallurgical slag (NFMS) in alkali‐activated materials has been demonstrated, exhibiting promising mechanical strength and fire resistance. However, the durability of alkali‐activated NFMS (AA‐NFMS) in terms of sulfate salt resistance remains unexplored. Additionally, the variability in the chemical composition of NFMS presents challenges in directly assessing the durability of AA‐NFMS. This study investigates the interplay between the Ca/Si and Mg/Ca ratios in Fe‐rich NFMS and the resulting MgSO4 resistance of the AA‐NFMS made thereof. To do so, mass change and compressive strength retention were monitored for six months on AA‐NFMS immersed in 5 wt% MgSO4, whereas microstructure was investigated using scanning electron microscope (SEM) and electron probe microanalyzer (EPMA). The results show that the MgSO4 solution attacked selectively the reacted binder matrix of AA‐NFMS rather than the unreacted slag. The corrosion primarily occurs at the sulfate exposure surface of AA‐NFMS, forming a dense, thin layer of Mg(OH)2, which acts as a barrier and impedes further attack. Dissolution of Ca is the most pronounced among the major elements (Ca, Fe, Al, and Si) in the NFMS. The mass of the specimens increased linearly with the initial Ca content. The medium Ca concentration (∼10%) retained the highest strength.

Investigating Gold Deposition with High-Power Impulse Magnetron Sputtering and Direct-Current Magnetron Sputtering on Polystyrene, Poly-4-vinylpyridine, and Polystyrene Sulfonic Acid.

Fabricating thin metal layers and particularly observing their formation process in situ is of fundamental interest to tailor the quality of such a layer on polymers for organic electronics. In particular, the process of high power impulse magnetron sputtering (HiPIMS) for establishing thin metal layers has sparsely been explored in situ. Hence, in this study, we investigate the growth of thin gold (Au) layers with HiPIMS and compare their growth with thin Au layers prepared by conventional direct current magnetron sputtering (dcMS). Au was chosen because it is an inert noble metal and has a high scattering length density. This allows us to track the growing nanostructures via grazing incidence scattering. In particular, Au deposition on the polymer polystyrene (PS) with the respective structural analogues poly-4-vinlypyridine (P4VP) and polystyrene sulfonic acid (PSS) is studied. Additionally, the nanostructured layers on these different polymer films are further probed by field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray reflectometry (XRR), and four-point probe measurements. We report that HiPIMS leads to smaller island-to-island distances throughout the whole sputter process. Moreover, an increased cluster density and an earlier percolation threshold are achieved compared to dcMS. Additionally, in the early stage, we observe a significant increase in coverage by HiPIMS, which is favorable for the improvement of the polymer-metal interface.

Oxidation behavior of 9Cr-RAFM steel at high temperature

The effect of yttrium on the mechanism of oxidation film formation of the 9Cr reduced activation ferritic/martensitic (9Cr-RAFM) steel was investigated. Four alloys yttrium contents ranging from 0 to 0.065% were melted in a vacuum induction furnace and subjected to continuous isothermal oxidation experiments. The alloys were oxidized in air at 600, 700, 800 and 900 °C for 100 h. Oxidation kinetic curves were obtained and analyzed to study the effect of yttrium on the oxidation resistance of the alloys at high temperatures. The oxide films formed on the alloys were observed and analyzed by X-ray diffractometry, scanning electron microscopy and electron probe X-ray microanalysis. The results indicated that the oxidation weight gain of the samples varied with the yttrium content, with the highest gain observed in the yttrium-free alloy sample, and the least in those containing 0.065% yttrium. Adding yttrium significantly enhanced the high temperature oxidation resistance of 9Cr-RAFM alloy by promoting the formation of a selective Cr2O3 oxide film. The film improved the adhesion of the oxide layer to the base metal, reduced the oxidation rate, and thereby enhanced the high-temperature oxidation resistance of the alloy.

Mitochondrial disruption resulting from Cepharanthine-mediated TOM inhibition triggers ferroptosis in colorectal cancer cells

BackgroundChemotherapy for colorectal cancer (CRC) urgently needs low-toxicity and highly effective phytomedicine. Cepharanthine (Cep) shown to have multiple anti-tumor effects, including colorectal cancer, whose pivotal mechanisms are not fully understood. Herein, the present work aims to reveal the impact of Cep on the mitochondrial and anti-injury functions of CRC cells.MethodsThe TOM70/20 expression was screened by bioinformatic databases. SW480 cells were utilized as the colorectal cancer cell model. The expression of TOM70/20 and the downstream molecules were measured by western blots (WB). The ferroptosis was analyzed using Transmission electron microscopy (TEM), C11-BODIPY, PGSK, and DCFH-DA probes, wherein the detection was performed by flow cytometry and laser confocal microscopy. The anti-cancer efficacy was conducted by CCK-8 and Annexin-V/PI assay. The rescue experiments were carried out using Fer-1 and TOM70 plasmid transfection.ResultsBioinformatic data identified TOM20 and TOM70 were highly expressed in colorectal cancer, which could be down-regulated by Cep. Further findings disclosed that Cep treatment destroyed the mitochondria and inactivated the NRF2 signaling pathway, an essential pathway for resistance to ferroptosis, thereby promoting reactive oxygen species (ROS) generation in CRC cells. As a result, prominent ferroptosis could be observed in CRC cells in response to Cep, which thereby led to the reduced cell viability of cancer cells. On the contrary, recovery of TOM70 dampened the Cep-elicited mitochondria damage, ferroptosis, and anti-cancer efficacy.ConclusionIn summary, Cep-mediated TOM inhibition inactivates the NRF2 signaling pathway, thereby triggering ferroptosis and achieving an anti-colorectal cancer effect. The current study provides an innovative chemotherapeutic approach for colorectal cancer with phytomedicine.

Scanning Transmission Soft X-Ray Microscopy Probes Topical Drug Delivery of Rapamycin Facilitated by Microneedles.

Scanning Transmission X-ray microscopy (STXM) is a sensitive and selective probe for the penetration of rapamycin which is topically applied to human skin ex vivo and is facilitated by skin treatment with microneedles puncturing the skin. Inner-shell excitation serves as a selective probe for detecting rapamycin by changes in optical density as well as linear combination modeling using reference spectra of the most abundant species. The results indicate that mechanical damage induced by microneedles allows this drug to accumulate in the stratum corneum without reaching the viable skin layers. This is unlike intact skin which shows no drug penetration at all and underscores the mechanical impact of microneedle skin treatment. These results are compared to drug penetration profiles of other drugs highlighting the importance of skin barriers. High spatial resolution studies also indicate that the lipophilic drug rapamycin is observed in corneocytes. Attempts in data evaluation are reported to probe rapamycin also in the lipid layers between the corneocytes, which was not accomplished before. These results are compared to recent results on rapamycin uptake in skin where barrier impairment was induced by pre-treatment with the enzyme trypsin and drug formulations leading to occlusion.

On-Surface Atomic Scale Qubit Platform.

Recent advances in scanning probe microscopy combined with electron spin resonance have revealed that localized electron spins on or near surfaces can be utilized as building blocks for the bottom-up assembly of functional quantum-coherent nanostructures. In this perspective, we review the recent advances, lay out advantages of this platform and outline the challenges that lie ahead on the way to the application of on-surface atomic spins to quantum information science and quantum computing.

LOCAL DIELECTRIC SPECTROSCOPY AND ITS APPLICATION TO POLYMERS

ABSTRACT The advent of nanodielectrics, nanocomposite materials based on a polymeric matrix, and materials with physical properties ruled by interfacial effects in general demands techniques to characterize functional properties on a local scale with high spatial resolution. Scanning probe microscopies (SPMs), in their electrical modes, have emerged as indispensable tools to access physical quantities such as dielectric constant, surface potential, and static charge, with nanometer-scale lateral resolution and with surface selectivity, being influenced mainly by the outermost layer of the specimen. In this tribute, the development of various SPM electrical modes is illustrated, focusing on the measurement of dielectric permittivity and its spectroscopic extension to access the local, frequency-dependent dielectric function (local dielectric spectroscopy [LDS]). The application to nanostructured polymers in the form of ultrathin films, nanometer-scale–separated blends, and self-assembled block copolymer structures is described. LDS appears to be a promising technique for characterizing the electric properties of polymers and their composites as well as other glass formers and nanostructured systems.

Stitching accuracy in large area scanning probe microscopy

Stitching accuracy in large area scanning probe microscopy

A Review of Analytical Techniques to Characterise Nanomaterial Associations with Minerals, Organic Matter and Organisms

Nanomaterials (NMs) have unique properties and control processes relevant to the fate of contaminants in soils, air, and aquatic systems and within the carbon cycle. Many NMs often occur in association with larger mineral grains, organic matter, or living organisms such as microbes, plants and fungi. The preservation of the spatial, textural, chemical, and mineralogical relations between NMs and minerals, organic matter, and organism (NM‐associations) is of fundamental importance as it provides information about the origin and formation mechanisms of NMs. Here we review analytical approaches and techniques to study NM‐associations at the bulk‐, micro‐, nano‐ and atomic‐scale. We will focus on (a) X‐ray diffraction and mass‐spectroscopy techniques; (2) automatisms within software packages that permit the search of features without operators; (3) preparation and analytical techniques such as the focused‐ion beam technology, transmission electron microscopy and atom probe tomography; (4) nano‐spectroscopic techniques such as tip‐enhanced Raman spectroscopy, synchrotron infrared nanospectroscopy, and nano‐X‐ray fluorescence spectroscopy; (5) ptychographic X‐ray computer tomography. This review paper concludes with selected new perspectives such as (a) the characterisation of NM‐precursors, (b) the role of NM‐associations in the stabilisation of soil organic matter and (c) the interaction of NM‐associations in wildfire smoke with contaminants from other sources.

Nonlinear Modeling of a Piezoelectric Actuator-Driven High-Speed Atomic Force Microscope Scanner Using a Variant DenseNet-Type Neural Network

Piezoelectric actuators (PEAs) are extensively used for scanning and positioning in scanning probe microscopy (SPM) due to their high precision, simple construction, and fast response. However, there are significant challenges for instrument designers due to their nonlinear properties. Nonlinear properties make precise and accurate control difficult in cases where position feedback sensors cannot be employed. However, the performance of PEA-driven scanners can be significantly improved without position feedback sensors if an accurate mathematical model with low computational costs is applied to reduce hysteresis and other nonlinear effects. Various methods have been proposed for modeling PEAs, but most of them have limitations in terms of their accuracy and computational efficiencies. In this research, we propose a variant DenseNet-type neural network (NN) model for modeling PEAs in an AFM scanner where position feedback sensors are not available. To improve the performance of this model, the mapping of the forward and backward directions is carried out separately. The experimental results successfully demonstrate the efficacy of the proposed model by reducing the relative root-mean-square (RMS) error to less than 0.1%.

Dispersoid evolution in Al–Zn–Mg alloys by combined addition of Hf and Zr: A mechanistic approach

Coherent Al3X-type L12-structured dispersoids have the potential of effectively stabilizing the grain structure and increasing strength. This concept has been successfully demonstrated for non-hardenable and rapidly solidified Al alloys. In precipitation-hardened Al alloys, effective dispersoid addition requires both controlling their high-temperature stability and minimizing their impact on precipitation hardening. The current study focuses on dispersoid-modified AlZn5.0 Mg1.2 alloys, which exhibit MgZn precipitation upon age-hardening and include less than 1 wt% of Zr and Hf for dispersoid formation. Heat treatments between 350 °C and 500 °C for varying times were applied to evaluate dispersoid formation, thermal stability and the related strengthening potential. The microstructure was assessed using transmission electron microscopy (TEM) and atom probe tomography (APT), and the mechanical response was evaluated by hardness testing. TEM after heating at 500 °C reveals Ostwald ripening for the dispersoids. APT results on the dispersoids reveal a core–shell structure development upon longer annealing times. The Zr–Hf-modified alloy exhibits a higher initial strength than the Zr-modified alloy but the latter displays greater strength retention even after prolonged exposure to 500 °C. This effect is attributed to a destabilization of the mixed Zr–Hf dispersoids that arises from lower enthalpic benefits of Al3Hf formation over Al3Zr.

Characterization of L12-Al3Ce phase and its purification mechanism in the Al-Ce-TiCN alloy

Rare earth element Ce has a positive purifying effect on Fe and Si impurities in pure aluminum. In this study, we unveiled the mechanism of Ce purification of Fe and Si impurities in commercial pure aluminum at the atomic scale via utilizing the properties of TiCN nanoparticles, which exhibit distribution along grain boundaries and impede solute atom diffusion at specific cooling rates. The transition phase L12-Al3Ce was characterized in aluminum, which is considered to be an important transition phase to purified products. Furthermore, High Angle Dark Field Scanning Transmission Electron Microscopy (HADDF-STEM) and 3D Atom Probe Tomography (3D-APT) results showed that Ce could respectively enrich the Fe and Si impurities, resulting in the formation of Al-Ce-Fe and Al-Ce-Si clusters. Density functional theory (DFT) results indicated that Fe and Si atoms can incorporate into L12-Al3Ce crystal, forming more stable structures and therefore giving rise to the formation of Al-Ce-Si and Al-Ce-Fe nanoclusters. This study provides atomic-scale insights into the mechanism of Ce purifying Fe and Si impurities in aluminum.

Epitaxy of GaSe Coupled to Graphene: From In Situ Band Engineering to Photon Sensing.

2D semiconductors can drive advances in quantum science and technologies. However, they should be free of any contamination; also, the crystallographic ordering and coupling of adjacent layers and their electronic properties should be well-controlled, tunable, and scalable. Here, these challenges are addressed by a new approach, which combines molecular beam epitaxy and in situ band engineering in ultra-high vacuum of semiconducting gallium selenide (GaSe) on graphene. In situ studies by electron diffraction, scanning probe microscopy, and angle-resolved photoelectron spectroscopy reveal that atomically-thin layers of GaSe align in the layer plane with the underlying lattice of graphene. The GaSe/graphene heterostructure, referred to as 2semgraphene, features a centrosymmetric (group symmetry D3d) polymorph of GaSe, a charge dipole at the GaSe/graphene interface, and a band structure tunable by the layer thickness. The newly-developed, scalable 2semgraphene is used in optical sensors that exploit the photoactive GaSe layer and the built-in potential at its interface with the graphene channel. This proof of concept has the potential for further advances and device architectures that exploit 2semgraphene as a functional building block.

Mechanical properties of freestanding few-layer graphene/boron nitride/polymer heterostacks investigated with local and non-local techniques.

van der Waals two-dimensional materials and heterostructures combined with polymer films continue to attract research attention to elucidate their functionality and potential applications. This study presents the fabrication and mechanical testing of 2D material heterostacks, consisting of few-layer boron nitride and graphene heterostructures synthesized via chemical vapor deposition, capped with a polymethyl methacrylate layer and suspended across ∼200 μm wide trenches using a combined wet-dry transfer method. The mechanical characterization of the heterostacks was performed using two independent approaches: (a) non-local testing with a custom-built tensile testing platform and (b) local load-displacement testing employing atomic force microscopy probes, complemented by finite element simulations. Both approaches provided new results, which are in good agreement with each other. Overall, our findings offer new insights into a combined load capacity in complex multi-material two-dimensional systems, and can contribute to advancing micro and nano-scale device designs and implementations.

Machine learning approaches for improving atomic force microscopy instrumentation and data analytics

Atomic force microscopy (AFM) is a part of the scanning probe microscopy family. It provides a platform for high-resolution topographical imaging, surface analysis as well as nanomechanical property mapping for stiff and soft samples (live cells, proteins, and other biomolecules). AFM is also crucial for measuring single-molecule interaction forces and important parameters of binding dynamics for receptor-ligand interactions or protein-protein interactions on live cells. However, performing AFM measurements and the associated data analytics are tedious, laborious experimental procedures requiring specific skill sets and continuous user supervision. Significant progress has been made recently in artificial intelligence (AI) and deep learning (DL), extending into microscopy. In this review, we summarize how researchers have implemented machine learning approaches so far to improve the performance of atomic force microscopy (AFM), make AFM data analytics faster, and make data measurement procedures high-throughput. We also shed some light on the different application areas of AFM that have significantly benefited from applications of machine learning frameworks and discuss the scope and future possibilities of these crucial approaches.

Design of an FPGA-Based Controller for Fast Scanning Probe Microscopy.

Atomic-scale imaging using scanning probe microscopy is a pivotal method for investigating the morphology and physico-chemical properties of nanostructured surfaces. Time resolution represents a significant limitation of this technique, as typical image acquisition times are on the order of several seconds or even a few minutes, while dynamic processes-such as surface restructuring or particle sintering, to be observed upon external stimuli such as changes in gas atmosphere or electrochemical potential-often occur within timescales shorter than a second. In this article, we present a fully redesigned field programmable gate array (FPGA)-based instrument that can be integrated into most commercially available standard scanning probe microscopes. This instrument not only significantly accelerates the acquisition of atomic-scale images by orders of magnitude but also enables the tracking of moving features such as adatoms, vacancies, or clusters across the surface ("atom tracking") due to the parallel execution of sophisticated control and acquisition algorithms and the fast exchange of data with an external processor. Each of these measurement modes requires a complex series of operations within the FPGA that are explained in detail.

Advancing the hydrogen tolerance of ultrastrong aluminum alloys via nanoprecipitate modification

Ultrastrong metallic alloys, possessing unparalleled load-bearing abilities, are coveted in many sectors, thus attracting growing research efforts. However, these alloys encounter persistent usability challenges posed by hydrogen embrittlement, which causes unpredictable fracture through crack initiation. Due to complex hydrogen-microstructure interactions and their exacerbation under high stress, advances in hydrogen resistance in ultrastrong materials are sparse throughout their long history. Herein, we report a quantum-mechanics-informed strategy for hydrogen tolerance enhancement in ultrafine-grain-hardened Al-Zn-Mg-Cu alloys, approaching their current strength limit of approximately 1 GPa. This method involves the incorporation of hydrogen-absorbing T-phase precipitates into nanograins, to substantially reduce hydrogen coverage at potential crack initiation sites. We demonstrate, via synchrotron radiation X-ray micro-/nano-tomography, scanning transmission electron microscopy and atom probe tomography, that nanoprecipitates successfully withstand shear strains exceeding 1000 and are exploitable essentials for ultra strength-hydrogen synergy, contrasting their often-assumed secondary roles in nanocrystalline alloys due to possible strain-induced dissolution, which has intuitively excluded exploring them as central elements. Our approach potentially inspires new hydrogen-resisting alloys across a broad strength-composition space.