Charge State of Au Atoms on an Oxidized Rutile TiO2(110) Surface by AFM/KPFM at 78 K.

The charge state of noble metal atoms on a semiconductor surface is an important factor in surface catalysis. In this study, Au atoms were deposited on the rutile TiO2(110) surface to characterize its charge properties using atomic force microscopy with Kelvin probe force microscopy at 78 K. Au single atoms, dimers, and trimers at different sites on the surface were investigated. Positively charged Au atoms were verified at oxygen sites, while negatively charged Au atoms were found near oxygen vacancy sites. Furthermore, the charge states of small Au nanoclusters were clarified. Understanding the charge states of Au atoms is significant for identifying their efficient catalytic effects in surface catalysis.

Optical Imaging of a Single Molecule with Subnanometer Resolution by Photoinduced Force Microscopy.

Visualizing the optical response of individual molecules is a long-standing goal in catalysis, molecular nanotechnology, and biotechnology. The molecular response is dominated not only by the electronic states in their isolated environment but also by neighboring molecules and the substrate. Information about the transfer of energy and charge in real environments is essential for the design of the desired molecular functions. However, visualizing these factors with spatial resolution beyond the molecular scale has been challenging. Here, by combining photoinduced force microscopy and Kelvin probe force microscopy, we have mapped the photoinduced force in a pentacene bilayer with a spatial resolution of 0.6 nm and observed its "multipole excitation". We identified the excitation as the result of energy and charge transfer between the molecules and to the Ag substrate. These findings can be achieved only by combining microscopy techniques to simultaneously visualize the optical response of the molecules and the charge transfer between the neighboring environments. Our approach and findings provide insights into designing molecular functions by considering the optical response at each step of layering molecules.

Tip-activated single-atom catalysis: CO oxidation on Au adatom on oxidized rutile TiO2 surface.

Single-atom catalysis of carbon monoxide oxidation on metal-oxide surfaces is crucial for greenhouse recycling, automotive catalysis, and beyond, but reports of the atomic-scale mechanism are still scarce. Here, using scanning probe microscopy, we show that charging single gold atoms on oxidized rutile titanium dioxide surface, both positively and negatively, considerably promotes adsorption of carbon monoxide. No carbon monoxide adsorption is observed on neutral gold atoms. Two different carbon monoxide adsorption geometries on gold atoms are identified. We demonstrate full control over the redox state of adsorbed gold single atoms, carbon monoxide adsorption geometry, and carbon monoxide adsorption/desorption by the atomic force microscopy tip. On charged gold atoms, we activate Eley-Rideal oxidation reaction between carbon monoxide and a neighboring oxygen adatom by the tip. Our results provide unprecedented insights into carbon monoxide adsorption and suggest that the gold dual activity for carbon monoxide oxidation after electron or hole attachment is also the key ingredient in photocatalysis under realistic conditions.

Effect of Preparation Processes on Structural Thermal Stability and Collision Energy Dissipation of Common Antirelaxation Coatings on Quartz Substrates.

Paraffin and octadecyltrichlorosilane (OTS) coatings can alleviate collisions between alkali-metal atoms and cell walls and then prolong the atomic spin-polarization lifetime. The surface structure and collision effects of these antirelaxation coatings, as well as the methods to avoid antirelaxation invalidity, have been the focus of researchers. This study investigated the thermolability of coating surface structure and the collision interactions between alkali metal atoms and coatings, considering the influence of various coating preparation factors, where this collision interaction is indirectly analyzed by measuring the collision energy dissipation between an atomic force microscopy (AFM) probe and the atoms on the coating surface. We found that appropriate evaporation time, carbochain length, and postannealing process can enhance the thermostability of the paraffin coating and eliminate its morphological defects. Furthermore, the OTS/water concentration, the soaking time, and the type of solvent have different levels of influence on the cluster formation and the thermostability of the OTS coatings. Moreover, the antirelaxation performance of coatings has been shown to be characterized by counting the energy dissipated when the AFM probe collides with the antirelaxation coating, replacing the conventional light-atom interaction- based method for measuring the relaxation characteristics, but requiring specific coating preparation factors to be maintained.

Development of low-temperature and ultrahigh-vacuum photoinduced force microscopy.

In this paper, we develop optical and electronic systems for photoinduced force microscopy (PiFM) that can measure photoinduced forces under low temperature and ultrahigh vacuum (LT-UHV) without artifacts. For our LT-UHV PiFM, light is irradiated from the side on the tip-sample junction, which can be adjusted through the combination of an objective lens inside the vacuum chamber and a 90° mirror outside the vacuum chamber. We measured photoinduced forces due to the electric field enhancement between the tip and the Ag surface, and confirmed that photoinduced force mapping and measurement of photoinduced force curves were possible using the PiFM that we developed. The Ag surface was used to measure the photoinduced force with high sensitivity, and it is effective in enhancing the electric field using the plasmon gap mode between the metal tip and the metal surface. Additionally, we confirmed the necessity of Kelvin feedback during the measurement of photoinduced forces, to avoid artifacts due to electrostatic forces, by measuring photoinduced forces on organic thin films. The PiFM, operating under low temperature and ultrahigh vacuum developed here, is a promising tool to investigate the optical properties of various materials with very high spatial resolution.

High-low Kelvin probe force spectroscopy for measuring the interface state density.

The recently proposed high-low Kelvin probe force microscopy (KPFM) enables evaluation of the effects of semiconductor interface states with high spatial resolution using high and low AC bias frequencies compared with the cutoff frequency of the carrier transfer between the interface and bulk states. Information on the energy spectrum of the interface state density is important for actual semiconductor device evaluation, and there is a need to develop a method for obtaining such physical quantities. Here, we propose high-low Kelvin probe force spectroscopy (high-low KPFS), an electrostatic force spectroscopy method using high- and low-frequency AC bias voltages to measure the interface state density inside semiconductors. We derive an analytical expression for the electrostatic forces between a tip and a semiconductor sample in the accumulation, depletion, and inversion regions, taking into account the charge transfer between the bulk and interface states in semiconductors. We show that the analysis of electrostatic forces in the depletion region at high- and low-frequency AC bias voltages provides information about the interface state density in the semiconductor bandgap. As a preliminary experiment, high-low KPFS measurements were performed on ion-implanted silicon surfaces to confirm the dependence of the electrostatic force on the frequency of the AC bias voltage and obtain the interface state density.

Investigation of semiconductor properties of Co/Si(111)-7 × 7 by AFM/KPFS.

Studies of the physics underlying carrier transport characteristics and band bending of semiconductors are critical for developing new types of devices. In this work, we investigated the physical properties of Co ring-like cluster (RC) reconstruction with a low Co coverage on a Si(111)-7 × 7 surface at atomic resolution by atomic force microscopy/Kelvin probe force microscopy at 78 K. We compared the applied bias dependence of frequency shift between two types of structure: Si(111)-7 × 7 and Co-RC reconstructions. As a result, the accumulation, depletion, and reversion layers were identified in the Co-RC reconstruction by bias spectroscopy. For the first time, we found that Co-RC reconstruction on the Si(111)-7 × 7 surface shows semiconductor properties by Kelvin probe force spectroscopy. The findings of this study are useful for developing new materials for semiconductor devices.

Near-field circular dichroism of single molecules.

Near-field images of molecules provide information about their excited orbitals, giving rise to photonic and chemical functions. Such information is crucial to the elucidation of the full potential of molecules as components in functional materials and devices at the nanoscale. However, direct imaging inside single molecules with a complex structure in the near-field is still challenging because it requires in situ observation at a higher resolution than the molecular scale. Here, using a proven theoretical method that has demonstrated sub-nanoscale resolution based on photoinduced force microscopy (PiFM) experiment [Nat. Commun.12, 3865 (2021)10.1038/s41467-021-24136-2], we propose an approach to obtaining the near-field imaging with spatial patterns of electronic transitions of single molecules. We use an extended discrete dipole approximation method that incorporates microscopic nonlocal optical response of molecules and demonstrate that PiFM can visualize circular-dichroism signal patterns at sub-nanometer scale for both optically allowed and forbidden transitions. The result will open the possibility for the direct observation of complex spatial patterns of electronic transitions in a single molecule, providing insight into the optical function of single molecules and helping realize new functional materials and devices.

Hybrid mode atomic force microscopy of phase modulation and frequency modulation.

We propose hybrid phase modulation (PM)/frequency modulation (FM) atomic force microscopy (AFM) to increase the imaging speed of AFM in high-Q environments. We derive the relationship between the phase shift, the frequency shift and the tip-sample interaction force from the equation of motion for the cantilever in high-Q environments. The tip-sample conservative force is approximately given by the sum of the conservative force with respect to the phase shift in the PM mode and that with respect to the frequency shift in the FM mode. We preliminarily demonstrate that the hybrid PM/FM-AFM is a new and very promising AFM operation mode that can increase imaging speed.

Role of personality traits in determining the association between social participation and mental health: A cross-sectional study in Japan.

The role of personality in determining the association between social participation and mental health was examined by a cross-sectional study. We analyzed data from 4981 older adults aged 65-84 years who were recruited via a mail survey in one region of Japan. We defined poor mental health using a score ≤12 points on the World Health Organization-Five Well-Being Index-Japanese. Personality traits were measured by 10 Item Personality Inventory-Japanese. In women, higher openness positively moderated the association between private group participation (volunteering, sports, hobby, and learning) and mental health, while higher neuroticism negatively moderated it. This study contributes to knowledge about mental health, personality, and participation. The findings provide provisional evidence about recommending private group participation for women with high openness but not those with high neuroticism.

Direct measurement of surface photovoltage by AC bias Kelvin probe force microscopy.

Surface photovoltage (SPV) measurements are a crucial way of investigating optoelectronic and photocatalytic semiconductors. The local SPV is generally measured consecutively by Kelvin probe force microscopy (KPFM) in darkness and under illumination, in which thermal drift degrades spatial and energy resolutions. In this study, we propose the method of AC bias Kelvin probe force microscopy (AC-KPFM), which controls the AC bias to nullify the modulated signal. We succeeded in directly measuring the local SPV by AC-KPFM with higher resolution, thanks to the exclusion of the thermal drift. We found that AC-KPFM can achieve a SPV response faster by about one to eight orders of magnitude than classical KPFM. Moreover, AC-KPFM is applicable in both amplitude modulation and frequency modulation mode. Thus, it contributes to advancing SPV measurements in various environments, such as vacuum, air, and liquids. This method can be utilized for direct measurements of changes in surface potential induced by modulated external disturbances.

Study of high-low KPFM on a pn-patterned Si surface.

Comparative measurements between frequency modulation Kelvin probe force microscopy (FM-KPFM) using low frequency bias voltage and heterodyne FM-KPFM using high frequency bias voltage were performed on the surface potential measurement. A silicon substrate patterned with p- and n-type impurities was used as a quantitative sample. The multi-pass scanning method in the measurements of FM-KPFM and heterodyne FM-KPFM was used to eliminate the effect of the tip-sample distance dependence. The measured surface potentials become lower in the order of the p-type region, n-type region and n+-type region by both FM-KPFM and heterodyne FM-KPFM, which are in good agreement with the order of the work functions of the pn-patterned Si sample. We observed the difference in the surface potentials due to the surface band bending measured by FM-KPFM and heterodyne FM-KPFM. The difference is due to the fact that the charge transfer between the surface and bulk levels may or may not respond to AC bias voltage.

The Kesennuma Study in Miyagi, Japan: Study Design and Baseline Profiles of Participants.

BACKGROUND: To clarify the association between psychosocial problems and frailty in the areas affected by the Great East Japan Earthquake, and to develop strategies for preventive long-term care in the community, we launched the Kesennuma Study in 2019. This report describes the study design and the participants' profiles at baseline. METHODS: The prospective study comprised 9,754 people (4,548 men and 5,206 women) randomly selected from community-dwelling independent adults aged 65 to 84 who were living in Kesennuma City, Miyagi. The baseline survey was conducted in October 2019. It included information on general health, socio-economic status, frailty, lifestyle, psychological factors (eg, personality, depressive moods), and social factors (eg, social isolation, social capital). A follow-up questionnaire survey is planned. Mortality, incident disability, and long-term care insurance certifications will also be collected. RESULTS: A total of 8,150 questionnaires were returned (83.6% response rate), and 7,845 were included in the analysis (80.4%; mean age 73.6 [standard deviation, 5.5] years; 44.7% male). About 23.5% were considered frail. Regarding psychological and social functions, 42.7% had depressive moods, 29.1% were socially isolated, and only 37.0% participated in social activities at least once a month. However, 82.5% trusted their neighbors. CONCLUSION: While local ties were strong, low social activity and poor mental health were revealed as issues in the affected area. Focusing on the association between psychological and social factors and frailty, we aim to delay the need for long-term care for as long as possible, through exercise, nutrition, social participation, and improvement of mental health.

Charge Behavior of Terminal Hydroxyl on Rutile TiO2(110).

Titanium dioxide (TiO2) is of considerable interest as a photocatalyst and a catalyst support. Surface hydroxyl groups (OH) are the most common adsorbates on the TiO2 surface and are believed to play crucial roles in their applications. Although the characteristics of bridging hydroxyl (OHbr) have been well understood, the adsorption structure and charged states of terminal hydroxyl (OHt) have not yet been experimentally elucidated at an atomic scale. In this study, we have investigated an isolated OHt on the rutile TiO2(110) surface by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We found that OHt is in a negatively charged state. The unique characteristic of OHt is different from that of OHbr and involves the amphoterism and diversity of catalytic reactions of TiO2.

Size-dependent strain-engineered nanostructures in MoS2monolayer investigated by atomic force microscopy.

The strain has been employed for controlled modification of electronical and mechanical properties of two-dimensional (2D) materials. However, the thermal strain-engineered behaviors of the CVD-grown MoS2have not been systematically explored. Here, we investigated the strain-induced structure and properties of CVD-grown triangular MoS2flakes by several advanced atomic force microscopy. Two different kinds of flakes with sharp-corner or vein-like nanostructures are experimentally discovered due to the size-dependent strain behaviors. The critical size of these two kinds of flakes can be roughly estimated at âˆ¼17µm. Within the small flakes, the sharp-corner regions show specific strain-modified properties due to the suffering of large tensile strain. While in the large MoS2flakes, the complicated vein-like nanoripple structures were formed due to the interface slipping process under the larger tensile strain. Our work not only demonstrates the size-specific strain behaviors of MoS2flakes but also sheds light on the artificial design and preparation of strain-engineered nanostructures for the devices based on the 2D materials.

Optical force mapping at the single-nanometre scale.

Three-dimensional (3D) information of the optical response in the nanometre scale is important in the field of nanophotonics science. Using photoinduced force microscopy (PiFM), we can visualize the nano-scale optical field using the optical gradient force between the tip and sample. Here, we demonstrate 3D photoinduced force field visualization around a quantum dot in the single-nanometre spatial resolution with heterodyne frequency modulation technique, using which, the effect of the photothermal expansion of the tip and sample in the ultra-high vacuum condition can be avoided. The obtained 3D mapping shows the spatially localized photoinduced interaction potential and force field vectors in the single nano-scale for composite quantum dots with photocatalytic activity. Furthermore, the spatial resolution of PiFM imaging achieved is ~0.7 nm. The single-nanometer scale photoinduced field visualization is crucial for applications such as photo catalysts, optical functional devices, and optical manipulation.

Single hydrogen atom manipulation for reversible deprotonation of water on a rutile TiO2 (110) surface.

The discovery of hydrogen atoms on the TiO2 surface is crucial for many practical applications, including photocatalytic water splitting. Electronically activating interfacial hydrogen atoms on the TiO2 surface is a common way to control their reactivity. Modulating the potential landscape is another way, but dedicated studies for such an activation are limited. Here we show the single hydrogen atom manipulation, and on-surface facilitated water deprotonation process on a rutile TiO2 (110) surface using low temperature atomic force microscopy and Kelvin probe force spectroscopy. The configuration of the hydrogen atom is manipulated on this surface step by step using the local field. Furthermore, we quantify the force needed to relocate the hydrogen atom on this surface using force spectroscopy and density functional theory. Reliable control of hydrogen atoms provides a new mechanistic insight of the water molecules on a metal oxide surface.

Direct observation of the Si(110)-(16×2) surface reconstruction by atomic force microscopy.

The atomic arrangement of the Si(110)-(16×2) reconstruction was directly observed using noncontact atomic force microscopy (NC-AFM) at 78 K. The pentagonal structure, which is the most important building block of the reconstruction, was concluded to consist of five atoms, while only four or five spots (depending on tip bias) have been reported with scanning tunneling microscopy (STM). Single atoms were determined to exist near step edges between upper and lower terraces, which have not been reported using STM. These findings are key evidence for establishing an atomic model of the Si(110)-(16×2) reconstruction, which indeed has a complex structure.

Comparison of Two Evacuation Shelter Operating Policies and the Role of Public Health Nurses after the Great East Japan Earthquake: A Qualitative Study.

This study describes shelter operations by public health nurses (PHNs) in Kesennuma City, located near the epicenter of the Great East Japan Earthquake, which occurred on March 11, 2011. The data were semi-structured interviews with 10 PHNs, 2 nutritionists, and 2 general administrators conducted from July 2013 to January 2014. All transcripts were analyzed using the constructivist grounded theory approach. We identified two operating methods for shelters: shelters stationed by PHNs in the Old City, and shelters patrolled by PHNs in the merged district. These methods were compared using four themes. In emergency situations, "operational periods," a predetermined short term for a leader to perform his/her duties responsibly, could be adopted for relatively small organizations on the frontline. PHNs must not only attempt to operate shelters on their own but also encourage residents to manage the shelters as well. Moreover, human resource allocation should be managed independently of personal factors, as strong relationships between shelter residents would sometimes disturb the flexibility of the response. Even when a situation requires PHNs to stay in shelters, frequent collecting of information and updating the plan according to response progress will help to maintain effective shelter operations.

Theoretical analysis of optically selective imaging in photoinduced force microscopy.

We present a theoretical study on the measurement of photoinduced force microscopy (PiFM) for composite molecular systems. Using discrete dipole approximation, we calculate the self-consistent response electric field of the entire system, including the PiFM tip, substrate, and composite molecules. We demonstrate a higher sensitivity for PiFM measurement on resonant molecules than the previously obtained tip-sample distance dependency, z-4, owing to multifold enhancement of the localized electric field induced at the tip-substrate nanogap and molecular polarization. The enhanced localized electric field in PiFM allows high-resolution observation of forbidden optical electronic transitions in dimer molecules. We investigate the wavelength dependence of PiFM for dimer molecules, obtaining images at incident light wavelengths corresponding to the allowed and forbidden transitions. We reveal that these PiFM images drastically change with the frequency-dependent spatial structures of the localized electric field vectors and resolve different types of nanoparticles beyond the resolution for the optically allowed transitions. This study demonstrates that PiFM yields multifaceted information based on microscopic interactions between nanomaterials and light.