Naritaka Kobayashi

Atomic-resolution imaging in liquid by frequency modulation atomic force microscopy using small cantilevers with megahertz-order resonance frequencies

In this study, we have investigated the performance of liquid-environment FM-AFM with various cantilevers having different dimensions from theoretical and experimental aspects. The results show that reduction of the cantilever dimensions provides improvement in the minimum detectable force as long as the tip height is sufficiently long compared with the width of the cantilever. However, we also found two important issues to be overcome to achieve this theoretically expected performance. The stable photothermal excitation of a small cantilever requires much higher pointing stability of the exciting laser beam than that for a long cantilever. We present a way to satisfy this stringent requirement using a temperature controlled laser diode module and a polarization-maintaining optical fiber. Another issue is associated with the tip. While a small carbon tip formed by electron beam deposition (EBD) is desirable for small cantilevers, we found that an EBD tip is not suitable for atomic-scale applications due to the weak tip-sample interaction. Here we show that the tip-sample interaction can be greatly enhanced by coating the tip with Si. With these improvements, we demonstrate atomic-resolution imaging of mica in liquid using a small cantilever with a megahertz-order resonance frequency. In addition, we experimentally demonstrate the improvement in the minimum detectable force obtained by the small cantilever in measurements of oscillatory hydration forces.

Nanoscale potential measurements in liquid by frequency modulation atomic force microscopy

We have developed a method for local potential measurements in liquid using frequency modulation atomic force microscopy. In this method, local potential is calculated from the first and second harmonic vibrations of a cantilever induced by applying an ac bias voltage between a tip and a sample. The use of an ac bias voltage with a relatively high frequency prevents uncontrolled electrochemical reactions and redistribution of ions and water. The nanoscale resolution of the method is demonstrated by imaging potential distribution of a dodecylamine thin film deposited on a graphite surface in 1 mM NaCl solution.

Quantitative potential measurements of nanoparticles with different surface charges in liquid by open-loop electric potential microscopy

Local potential distribution plays important roles in physical, chemical and biological processes at a solid/liquid interface. However, the measurement of a local potential distribution in liquid has been a long-standing challenge, which has hindered understanding of the mechanisms for the various interfacial phenomena. Recently, we have developed a method to overcome this problem [Kobayashi et al., Rev. Sci. Instrum. 81, 123705 (2010)], which is referred to as open-loop electric potential microscopy (OL-EPM). Here, we present its first application to quantitative measurements of local potential distribution in liquid. In OL-EPM, an ac bias voltage is applied between a tip and sample and the first and second harmonic cantilever oscillations induced by the electrostatic force are detected and used for the calculation of a potential value. In the equation for the potential calculation, here we introduce a correction factor to cancel out the error caused by the difference in the deflection sensitivity to the...

Elimination of instabilities in phase shift curves in phase-modulation atomic force microscopy in constant-amplitude mode

The authors propose phase-modulation atomic force microscopy (PM-AFM) in constant-amplitude mode using automatic gain control to prevent the instabilities of cantilever dynamics. Under the condition that the driving frequency is set to the resonant frequency of the cantilever, phase shift curve in constant-amplitude mode shows no discontinuity, which resembles a typical behavior of the frequency shift curve in frequency-modulation AFM. They demonstrate that PM-AFM in constant-amplitude mode can clearly resolve phase-separated structures on polymer blend film without instability. These results indicate that PM-AFM in constant-amplitude mode is more stable than that in constant-excitation mode.

High-sensitivity force detection by phase-modulation atomic force microscopy

Performance of phase-modulation atomic force microscopy (PM-AFM) is investigated to achieve high force sensitivity and high-resolution imaging. PM-AFM detects the phase change of the oscillating cantilever relative to the excitation signal and uses it as the feedback signal. We compare the force sensitivity of PM-AFM with that of amplitude-modulation AFM (AM-AFM) theoretically as well as experimentally. We show that PM-AFM has a better signal-to-noise ratio than AM-AFM. We demonstrate that the electrostatic force images obtained by PM-AFM have clearer contrast than those obtained by AM-AFM.

Multifrequency high-speed phase-modulation atomic force microscopy in liquids.

We have developed a new technique, called multifrequency high-speed phase-modulation atomic force microscopy (PM-AFM) in constant-amplitude (CA) mode based on the simultaneous excitation of the first two flexural modes of a cantilever. By performing a theoretical investigation, we have found that this technique enables the simultaneous imaging of the surface topography, energy dissipation and elasticity (nonlinear mapping) of materials. We experimentally demonstrated high-speed imaging at a scan speed of 5 frames/s for a polystyrene (PS) and polyisobutylene (PIB) polymer-blend thin-film surface in water.

Dual frequency open-loop electric potential microscopy for local potential measurements in electrolyte solution with high ionic strength

Recent development of open-loop electric potential microscopy (OL-EPM) has enabled to measure local potential distribution at a solid/liquid interface. However, the operating environment of OL-EPM has been limited to a weak electrolyte solution (<1 mM). This has significantly limited its application range in biology and chemistry. To overcome this limitation, we have developed dual frequency (DF) mode OL-EPM. In the method, an ac bias voltage consisting of two frequency components at f(1) and f(2) is applied between a tip and sample. The local potential is calculated from the amplitudes of the f(1) and |f(1) - f(2)| components of the electrostatic force. In contrast to the conventional single frequency (SF) mode OL-EPM, the detection of the 2f(1) component is not required in DF mode. Thus, the maximum bias modulation frequency in DF mode is twice as high as that in SF mode. The high bias modulation frequency used in DF mode prevents the generation of electrochemical reactions and redistribution of ions and water, which enables to operate OL-EPM even in a strong electrolyte solution. In this study, we have performed potential measurements of nanoparticles on a graphite surface in 1 and 10 mM NaCl solution. The results demonstrate that DF mode OL-EPM allows measurements of local potential distribution in 10 mM electrolyte solution.

High-Speed Phase-Modulation Atomic Force Microscopy in Constant-Amplitude Mode Capable of Simultaneous Measurement of Topography and Energy Dissipation

We have developed high-speed phase-modulation atomic force microscopy (PM-AFM) in a constant-amplitude (CA) mode. Using this imaging mode, we have theoretically demonstrated that energy dissipation due to tip–sample interaction can be obtained from the excitation amplitude of a cantilever. Moreover, we have found that the photothermal excitation method is better than the acoustic excitation method for cantilever oscillation in liquids. For the first time, we have demonstrated that a homebuilt high-speed PM-AFM in the CA mode has the capability to simultaneously measure the topography and energy dissipation with a material-specific contrast for a PS/PIB polymer-blend film.

Visualizing Nanoscale Distribution of Corrosion Cells by Open-Loop Electric Potential Microscopy.

Corrosion is a traditional problem but still one of the most serious problems in industry. To reduce the huge economic loss caused by corrosion, tremendous effort has been made to understand, predict and prevent it. Corrosion phenomena are generally explained by the formation of corrosion cells at a metal-electrolyte interface. However, experimental verification of their nanoscale distribution has been a major challenge owing to the lack of a method able to visualize the local potential distribution in an electrolytic solution. In this study, we have investigated the nanoscale corrosion behavior of Cu fine wires and a duplex stainless steel by in situ imaging of local corrosion cells by open-loop electric potential microscopy (OL-EPM). For both materials, potential images obtained by OL-EPM show nanoscale contrasts, where areas of higher and lower potential correspond to anodic areas (i.e., corrosion sites) and cathodic areas, respectively. This imaging capability allows us to investigate the real-time transition of local corrosion sites even when surface structures show little change. This is particularly useful for investigating reactions under surface oxide layers or highly corrosion-resistant materials as demonstrated here. The proposed technique should be applicable to the study of other redox reactions on a battery electrode or a catalytic material. The results presented here open up such future applications of OL-EPM in nanoscale electrochemistry.

High force sensitivity in Q-controlled phase-modulation atomic force microscopy

We investigate the dependence of effective Q-factor on force sensitivity in Q-controlled phase-modulation atomic force microscopy. With Q-control, the phase noise density spectrum shows a characteristic dependence on modulation frequency (fm). The phase noise density spectrum is nearly constant in the low-fm region, whereas it decreases inverse-proportionally to fm in the high-fm region. Such a decrease enhances the force sensitivity. We demonstrate that force sensitivity can be markedly increased with Q-control to exceed the limit of force sensitivity without Q-control.