Stable contrast mode on TiO2(110) surface with metal-coated tips using AFM.

We investigated a method to obtain a stable contrast mode on the TiO2(110) surface. The stable contrast rate is approximately 95% with a W-coated Si cantilever, which demonstrates that a stable tip apex plays an important role to obtain the real geometry of the surface during atomic force microscopy measurement. Information related to surface structure and tunnelling current on the TiO2(110) surface can be obtained by the W-coated Si cantilever. It is possible to investigate the electronic structure and surface potential on the TiO2(110) surface with atomic resolution. In particular, the proposed method could be widely applied to investigate the catalytic activity and the mechanism of a catalytic reaction by a metal-coated tip in the future.

KPFM/AFM imaging on TiO2(110) surface in O2 gas.

We have carried out high-speed imaging of the topography and local contact potential difference (LCPD) on rutile TiO2(110) in O2 gas by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We succeeded in KPFM/AFM imaging with atomic resolution at 1 frame min-1 and observed the adsorbate on a hydroxylated TiO2(110) surface. The observed adsorbate is considered to be oxygen adatoms (Oa), hydroperoxyls (HO2), or terminal hydroxyls (OHt). After adsorption, changes in the topography and the LCPD of the adsorbate were observed. This phenomenon is thought to be caused by the charge transfer of the adsorbate. This technique has the potential to observe catalytic behavior with atomic resolution.

Separation of atomic-scale spin contrast on NiO(0 0 1) by magnetic resonance force microscopy.

In magnetic exchange force microscopy, images contain the topographic contrast mixed with the spin contrast on the sample surface. In this study, we propose a new method of magnetic resonance force microscopy using ferromagnetic resonance to extract only the spin contrast. In this method, the magnetization of a magnetic cantilever is modulated by ferromagnetic resonance to separate the spin contrast and topographic contrast. We succeeded in obtaining a spin image of Ni atoms on a NiO (0 0 1) surface. Furthermore, we successfully detected the superexchange interaction between the tip apex atom and the second layer of Ni atoms.

Investigation of tunneling current and local contact potential difference on the TiO2(110) surface by AFM/KPFM at 78 K.

We propose a new multi-image method for obtaining the frequency shift, tunneling current and local contact potential difference (LCPD) on a TiO2(110) surface with atomic resolution. The tunneling current image reveals rarely observed surface oxygen atoms contrary to the conventional results. We analyze how the surface and subsurface defects affect the distribution of the LCPD. In addition, the subsurface defects are observed clearly in the tunneling current image, in contrast to a topographic image. To clarify the origin of the atomic contrast, we perform site-dependent spectroscopy as a function of the tip-sample distance. The multi-image method is expected to be widely used to investigate the charge transfer phenomena between the nanoparticles and surface sites, and it is useful for elucidating the mechanisms of catalytic reactions.

Development of low temperature atomic force microscopy with an optical beam deflection system capable of simultaneously detecting the lateral and vertical forces.

The atomic force microscopy (AFM) is a very important tool for imaging and investigating the complex force interactions on sample surfaces with high spatial resolution. In the AFM, two types of detection systems of the tip-sample interaction forces have been used: an optical detection system and an electrical detection system. In optical detection systems, such as optical beam deflection system or optical fiber interferometer system, both the lateral and the vertical tip-sample forces can be measured simultaneously. In electrical detection systems, such as qPlus or Kolibri sensors, either the lateral or vertical forces can be measured. Simultaneous measurement of the lateral and vertical interaction forces effectively allows investigation of force interactions because the force is a vector with magnitude and direction. In this study, we developed a low-temperature, frequency-modulation AFM using an optical beam deflection system to simultaneously measure the vertical and lateral forces. In this system, the heat sources, such as a laser diode and a current-to-voltage converter, for measuring the photocurrent of the four-segmented photodiode are located outside the observation chamber to avoid a temperature increase of the AFM unit. The focused optical beam is three-dimensionally adjustable on the back side of the cantilever. We demonstrate low-noise displacement measurement of the cantilever and successful atomic resolution imaging using the vertical and lateral forces at low temperatures.

Magnetic force microscopy using tip magnetization modulated by ferromagnetic resonance.

In magnetic force microscopy (MFM), the tip-sample distance should be reduced to analyze the microscopic magnetic domain structure with high spatial resolution. However, achieving a small tip-sample distance has been difficult because of superimposition of interaction forces such as van der Waals and electrostatic forces induced by the sample surface. In this study, we propose a new method of MFM using ferromagnetic resonance (FMR) to extract only the magnetic field near the sample surface. In this method, the magnetization of a magnetic cantilever is modulated by FMR to separate the magnetic field and topographic structure. We demonstrate the modulation of the magnetization of the cantilever and the identification of the polarities of a perpendicular magnetic medium.

Spin-selective Imaging by Magnetic Exchange Force Microscopy Using Ferromagnetic Resonance.

Techniques to analyze the surface of magnetic memory devices with high spatial resolution are very important to develop today's information technology. The magnetic exchange force is an interaction between spins and is very important for analyzing magnetic properties. Magnetic exchange force microscopy (MExFM), which can detect the magnetic exchange force between the magnetic tip and the magnetic surface, has achieved the atomic-resolution imaging of the spin state on anti-ferromagnetic surface of NiO(001) [1]. In MExFM, however, the separation between a structure and a magnetic state on the surface has not been performed.Here, we propose a new MExFM using ferromagnetic resonance to separate the magnetic and non-magnetic tip-sample interaction. In this method, magnetic tip apex is irradiated by the frequency-modulated microwave with the frequency of ferromagnetic resonance. The magnetization of magnetic tip apex is modulated from on resonance to off resonance. Tip-sample interaction is measured with frequency modulation method. Magnetic images are obtained by detecting the modulation component of the frequency shift of the oscillating cantilever using a lock-in amplifier. Topographic images are obtained by the feedback signal for the constant tip-sample interaction. As a magnetic tip, magnetic cantilever tip coated with FePt with a high coercivity was used to detect the magnetic exchange force without an external magnetic field [2]. We performed imaging on antiferromagnetic material NiO(001) surface (Fig. 1(a)) by MExFM using ferromagnetic resonance. We obtained spin selective image in atomic resolution (Fig. 1(b)). This is the first demonstration of magnetization modulation of the magnetic tip apex using ferromagnetic resonance as well as the separation of the magnetic and non-magnetic tip-sample interaction in MExFM.jmicro;63/suppl_1/i11-a/DFU053F1F1DFU053F1Fig. 1.(a) Structure of NiO(001) surface and (b) its image (phase) obtained with MExFM using ferromagnetic resonance. (4 nm x 4 nm).

Photoirradiation products of flavin derivatives, and the effects of photooxidation on guanine.

Photoirradiation in the presence of riboflavin led to guanine oxidation and the formation of imidazolone. Meanwhile, riboflavin itself was degraded by ultraviolet light A (UV-A) and visible light (VIS) radiation, and the end product was lumichrome. VIS radiation in the presence of riboflavin oxidized guanine similarly to UV-A radiation. Although UV-A radiation with lumichrome oxidized guanine, VIS radiation with lumichrome did not. Thus, UV-A radiation with riboflavin can oxidize guanine even if riboflavin is degraded to lumichrome. In contrast, following VIS radiation degradation of riboflavin to lumichrome, VIS radiation with riboflavin is hardly capable of oxidizing guanine. The consequences of riboflavin degradation and guanine photooxidation can be extended to flavin mononucleotide and flavin adenine dinucleotide. In addition, we report advanced synthesis; carboxymethylflavin was obtained by oxidation of formylmethylflavin with chlorite and hydrogen peroxide; lumichrome was obtained by heating of formylmethylflavin in 50% AcOH; lumiflavin was obtained by incubation of formylmethylflavin in 2 M NaOH, followed by isolation by step-by-step concentration.