Role of Polarons in Single-Atom Catalysts: Case Study of Me1 [Au1, Pt1, and Rh1] on TiO2(110).

The local environment of metal-oxide supported single-atom catalysts plays a decisive role in the surface reactivity and related catalytic properties. The study of such systems is complicated by the presence of point defects on the surface, which are often associated with the localization of excess charge in the form of polarons. This can affect the stability, the electronic configuration, and the local geometry of the adsorbed adatoms. In this work, through the use of density functional theory and surface-sensitive experiments, we study the adsorption of Rh1, Pt1, and Au1 metals on the reduced TiO2(110) surface, a prototypical polaronic material. A systematic analysis of the adsorption configurations and oxidation states of the adsorbed metals reveals different types of couplings between adsorbates and polarons. As confirmed by scanning tunneling microscopy measurements, the favored Pt1 and Au1 adsorption at oxygen vacancy sites is associated with a strong electronic charge transfer from polaronic states to adatom orbitals, which results in a reduction of the adsorbed metal. In contrast, the Rh1 adatoms interact weakly with the excess charge, which leaves the polarons largely unaffected. Our results show that an accurate understanding of the properties of single-atom catalysts on oxide surfaces requires a careful account of the interplay between adatoms, vacancy sites, and polarons. Supplementary Information: The online version contains supplementary material available at 10.1007/s11244-022-01651-0.

Collection of propagating electromagnetic fields by uncoated probe.

Understanding light-matter interaction at the nanoscale by observation of fine details of electromagnetic fields is achieved by bringing nanoscale probes into the nearfield of light sources, capturing information that is lost in the far field. Although metal coated probes are often used for nearfield microscopy, they strongly perturb the electromagnetic fields under study. Here, through experiment and simulation, we detail light collection by uncoated fiber probes, which minimize such perturbation. Second-harmonic light from intensely-irradiated sub-wavelength sub-surface features was imaged to avoid otherwise dominating fundamental light background, yielding clear nearfield details through a 50 nm aperture uncoated probe with ∼23 nm optical resolution. Simulations show how a metallic coating distorts optical nearfields and limits optical coupling into the probe in comparison to an uncoated probe.

Characterization of Phase Separated Planar Lipid Bilayer Membrane by Fluorescence Ratio Imaging and Scanning Probe Microscope.

The lipid membrane forms nanodomains (rafts) and shows heterogeneous properties. These nanodomains relate to significant roles in various cell functions, and thus the analysis of the nanodomains in phase-separated lipid membranes is important to clarify the function and role of the nanodomains. However, the lipid membrane possesses small-sized nanodomains and shows a small height difference between the nanodomains and their surroundings at certain lipid compositions. In addition, nanodomain analysis sometimes requires highly sensitive and expensive apparatus, such as a two-photon microscope. These have prevented the analysis by the conventional fluorescence microscope and by the topography of the scanning probe microscope (SPM), even though these are promising methods in macroscale and microscale analysis, respectively. Therefore, this study aimed to overcome these problems in nanodomain analysis. We successfully demonstrated that solvatochromic dye, LipiORDER, could analyze the phase state of the lipid membrane at the macroscale with low magnification lenses. Furthermore, we could prove that the phase mode of SPM was effective in the visualization of specific nanodomains by properties difference as well as topographic images of SPM. Hence, this combination method successfully gave much information on the phase state at the micro/macro scale, and thus this would be applied to the analysis of heterogeneous lipid membranes.

Ferroelectricity and Piezoelectricity in 2D Van der Waals CuInP2S6 Ferroelectric Tunnel Junctions.

CuInP2S6 (CIPS) is a novel two-dimensional (2D) van der Waals (vdW) ferroelectric layered material with a Curie temperature of TC~315 K, making it promising for great potential applications in electronic and photoelectric devices. Herein, the ferroelectric and electric properties of CIPS at different thicknesses are carefully evaluated by scanning probe microscopy techniques. Some defects in some local regions due to Cu deficiency lead to a CuInP2S6-In4/3P2S6 (CIPS-IPS) paraelectric phase coexisting with the CIPS ferroelectric phase. An electrochemical strain microscopy (ESM) study reveals that the relaxation times corresponding to the Cu ions and the IPS ionospheres are not the same, with a significant difference in their response to DC voltage, related to the rectification effect of the ferroelectric tunnel junction (FTJ). The electric properties of the FTJ indicate Cu+ ion migration and propose that the current flow and device performance are dynamically controlled by an interfacial Schottky barrier. The addition of the ferroelectricity of CIPS opens up applications in memories and sensors, actuators, and even spin-orbit devices based on 2D vdW heterostructures.

Response and Implication of NASICON Solid-State Electrolytes to Local Electrical Stimulation: From Surface Engineering to Interfacial Manipulation.

The surface feature of solid electrolytes fundamentally governs their own physical properties and significantly affects the interaction with the electrode materials. The evaluation of interfacial contact between the electrolyte and the metallic anode is largely relied on the macroscopic contact angle measurement, which is influenced by the intrinsic wettability and the microstructure of the electrolyte. In this work, the surface chemistry of the solid electrolyte is first regulated via facile thermal treatments. Then, scanning probe microscopy (SPM)-based techniques are comprehensively adopted to study the interaction between the electrolyte and metallic anode at the nanoscale. By manipulating the overpotential applied on the SPM tip, the mobile sodium ions at the subsurface of the solid electrolyte can be extracted toward the surface, and the eventual topography of the products is deliberately correlated with the sodium wettability. In this context, the impact of surface treatment on the sodium wettability of the surface layer is systematically evaluated based on the topographic evolution at the nanoscale. Furthermore, the local electrochemical reaction dynamics is revealed by correlating the surface ionic activity and current-voltage (I-V) curves. This work presents a new methodology to effectively evaluate the sodium wettability of the solid electrolyte, and these findings can provide meaningful implications to the surface engineering of ceramic electrolytes for high-performance solid-state batteries.

Impact of three-dimensional tortuous pore structure on polyethersulfone membrane morphology and mass transfer properties from a manufacturing perspective.

We examined typical commercial poly(ethersulfone) (PESf) hemodialysis and hemoconcentration membranes successfully used in manufacturing, and employed scanning probe microscope (SPM) to achieve a structural observation of the pores in the inner membrane surfaces, as well as measure the pore diameters and their distribution, verifying the relationship between the typical mass transfer properties. We focused on the differences between the PESf membranes which were expected to further improve the advanced pore structure control and functional design for various medical uses. The three-dimensional tortuous capillary pores on the inner surface of hollow fiber hemodialysis and hemoconcentrator membranes were investigated using dynamic force microscopy (DFM), and the pore diameter and distribution were measured through a line analysis. Compared with PUREMA-A, PES-Sα hemodialysis membranes have smaller three-dimensional tortuous capillary pore diameters and pore areas, as well as a smaller pore diameter distribution and pore area distribution, which make the accurate measurements of the pore diameter using FE-SEM impossible. These PESf membranes are almost the same in pure water permeability, but greatly differ in pore diameter and pore diameter distribution. By comparing and verifying as above, we may gain insight into the flexibility, versatility, and superior structural and functional controllability of PESf membrane pore structures, which could advance the development of pore structure control. Pending issues include the fact that, using a line analysis software of SPM devices, it is very difficult to measure hundred pores which clearly reflects the poor quality of pore size distributions obtained in this study, measurement accuracy must be improved further.

Development of a Novel Scanning Thermal Microscopy (SThM) Method to Measure the Thermal Conductivity of Biological Cells.

　Differences in the physical properties of individual cells cannot be evaluated with conventional experimental methods that are used to study groups of cells obtained from pure cultures. To examine the differences in the thermal tolerance of individual cells that are genetically identical, a method is needed to measure the thermal energy required to kill single cells. We developed a scanning thermal microscopy (SThM) system and measured the thermal conductivity of various bacterial cells, for example, spore formeing Bacillus genus and non spore-forming bacteria such as Escherichia coli. The thermal conductivity of vegetative cells (0.61 to 0.75 W/m・K) was found to be higher than that of spores (0.29 to 0.45 W/m・K). Furthermore the newly developed method enables us to estimate the thermal energy needed to kill individual cells or spores. We believe that this method can estimate the thermal energy required to achieve the cell for sterilization by heating.

Fast and reliable pre-approach for scanning probe microscopes based on tip-sample capacitance.

Within the last three decades Scanning Probe Microscopy has been developed to a powerful tool for measuring surfaces and their properties on an atomic scale such that users can be found nowadays not only in academia but also in industry. This development is still pushed further by researchers, who continuously exploit new possibilities of this technique, as well as companies that focus mainly on the usability. However, although imaging has become significantly easier, the time required for a safe approach (without unwanted tip-sample contact) can be very time consuming, especially if the microscope is not equipped or suited for the observation of the tip-sample distance with an additional optical microscope. Here we show that the measurement of the absolute tip-sample capacitance provides an ideal solution for a fast and reliable pre-approach. The absolute tip-sample capacitance shows a generic behavior as a function of the distance, even though we measured it on several completely different setups. Insight into this behavior is gained via an analytical and computational analysis, from which two additional advantages arise: the capacitance measurement can be applied for observing, analyzing, and fine-tuning of the approach motor, as well as for the determination of the (effective) tip radius. The latter provides important information about the sharpness of the measured tip and can be used not only to characterize new (freshly etched) tips but also for the determination of the degradation after a tip-sample contact/crash.

Method for Measuring the Distribution of Adhesion Forces on Continuous Nanoscale Protrusions Using Carbon Nanofiber Tip on a Scanning Probe Microscope Cantilever.

The adhesion force on surfaces has received attention in numerous scientific and technological fields, including catalysis, thin-film growth, and tribology. Many applications require knowledge of the strength of these forces as a function of position in three dimensions, but until now such information has only been theoretically proposed. Here, we demonstrate an approach based on scanning probe microscopy that can obtain such data and be used to image the three-dimensional surface force field of continuous nanoscale protrusions. We present adhesion force maps with nanometer and nanonewton resolution that allow detailed characterization of the interaction between a surface and a thin carbon nanofiber (CNF) rod synthesized by plasma-enhanced chemical vapor deposition (PECVD) at the end of a tip on a scanning probe microscope cantilever in three dimensions. In these maps, the positions of all continuous nanoscale protrusions are identified and the differences in the adhesive forces among limited areas at inequivalent sites are quantified.

A compact high field magnetic force microscope.

We present the design and performance of a simple and compact magnetic force microscope (MFM), whose tip-sample coarse approach is implemented by the piezoelectric tube scanner (PTS) itself. In brief, a square rod shaft is axially spring-clamped on the inner wall of a metal tube which is glued inside the free end of the PTS. The shaft can thus be driven by the PTS to realize image scan and inertial stepping coarse approach. To enhance the inertial force, each of the four outer electrodes of the PTS is driven by an independent port of the controller. The MFM scan head is so compact that it can easily fit into the 52mm low temperature bore of a 20T superconducting magnet. The performance of the MFM is demonstrated by imaging a manganite thin film at low temperature and in magnetic fields up to 15T.

Pinch-off mechanism in double-lateral-gate junctionless transistors fabricated by scanning probe microscope based lithography.

A double-lateral-gate p-type junctionless transistor is fabricated on a low-doped (10(15)) silicon-on-insulator wafer by a lithography technique based on scanning probe microscopy and two steps of wet chemical etching. The experimental transfer characteristics are obtained and compared with the numerical characteristics of the device. The simulation results are used to investigate the pinch-off mechanism, from the flat band to the off state. The study is based on the variation of the carrier density and the electric-field components. The device is a pinch-off transistor, which is normally in the on state and is driven into the off state by the application of a positive gate voltage. We demonstrate that the depletion starts from the bottom corner of the channel facing the gates and expands toward the center and top of the channel. Redistribution of the carriers due to the electric field emanating from the gates creates an electric field perpendicular to the current, toward the bottom of the channel, which provides the electrostatic squeezing of the current.