Theory for the effect of the tip–surface interaction potential on atomic resolution in forced vibration system of noncontact AFM

We present a perturbation theory which enables us to understand the physics of the cantilever-forced vibration in noncontact atomic-force microscopy (nc-AFM). Analytical expressions of the resonance curve and frequency shift are given. This theory is applied to the model system with a van der Waals tip–surface interaction potential. Based on this case study, it is elucidated how the resonance frequency shift is analytically described by an integral of the tip–surface interaction force. Then nc-AFM image of Si(111) 7×7 surface is calculated by the present theory. It is examined that this theory works as an algorithm for nc-AFM image simulator.     

Site discrimination of adatoms in Si(111)-7 × 7 by noncontact atomic force microscopy

Site discrimination of adatoms in Si(111)-7 × 7 by dynamic mode noncontact atomic force microscopy (NC-AFM) in ultrahigh vacuum has been demonstrated. At a fixed frequency shift, NC-AFM images were acquired at various amplitudes. At amplitudes less than 30 nm_p-p, no atomic image was observed. At 33 nm_p-p, clearly resolved atomic images showed 6 bright atoms in one half of each 7 × 7 unit cell and 6 less bright atoms in the other half of each unit cell. Furthermore, the corner adatoms were observed to be higher. At 36 nm_p-p, such differences were not observed. The observed site differences are not derived by the differences in the actual positions of adatoms, but by the differences in the interactions between the atom at the AFM tip apex and the adatoms on the Si surface.     

The role of repulsive interactions in molecular bromine adsorption and patterning of Si(100)-2×1

Scanning tunneling microscopy (STM) was used to investigate the role of repulsive interactions in the adsorption and patterning of molecular bromine on the Si(100) surface. At room temperature and low coverage, chemisorption of bromine occurs dissociatively on the same side of adjacent dimers of the same row. Using the STM tip as a probe, we demonstrate the existence of repulsive interactions at adjacent sites on the Si(100)-2×1 surface. These repulsive interactions also contribute to the arrangement of adatoms on the surface. In particular, we report the presence of a stable c(4×2) surface phase that results after exposing the Si(100) surface to bromine under certain conditions. This phase involves adsorption on non-neighboring dimers and is stabilized by repulsive interactions that force bromine adatoms to occupy alternating dimers within rows with an out-of-phase occupancy between adjacent rows.     

Origin of p(2 x 1) phase on Si(001) by noncontact atomic force microscopy at 5 k

The controversial issue of the origin of the p(2 x 1) reconstruction of the Si(001) surface observed in recent low temperature scanning tunneling microscopy experiments is clarified here using 5 K noncontact atomic force microscopy. The c(4 x 2) phase is observed at separations corresponding to weak tip-surface interactions, confirming that it is the ground state of the surface. At larger frequency shifts the p(2 x 1) phase of symmetric dimers is observed. By studying the interaction of a reactive Si tip with the c(4 x 2) Si(001) surface using an ab initio method, we find that the observed change in the surface reconstruction is an apparent effect caused by tip induced dimer flipping resulting in a modification of the surface structure and appearance of the p(2 x 1) phase in the image. Using an appropriate scanning protocol, one can manipulate the surface reconstruction at will, which has significance in nanotechnology.     

Dimer elongation on the monohydride-covered Ge/Si(100) surface

Using transmission ion channeling, we have made the first measurement of the Ge dimer geometry for the monohydride-covered Ge/Si(100)-2×1 surface. Comparison of calculated angular scans with experimental angular scans near the 100 and 110 directions has resulted in a measured Ge dimer bond length of 2.8 Å, which is 8% longer than the corresponding dimer bond length reported for Ge on Si(100) in the absence of H. This elongation is similar to that reported for Si dimers on the Si(100) surface. Also, relative to the (100) surface plane, the dimers change from tilted without H to untilted with H.     

Tip cleaning and sharpening processes for noncontact atomic force microscope in ultrahigh vacuum

Tip cleaning and sharpening processes for noncontact atomic force microscope (AFM) operated in ultrahigh vacuum (UHV) were carried out and evaluated by a scanning Auger microscope (SAM) with a field emission electron gun and a noncontact AFM in UHV combined with a scanning tunneling microscope and a field emission microscope. The cantilever used in this study was piezoresistive, which can be heated by passing a current through the resistive legs of the cantilever. As a pretreatment, the tip was irradiated with ultraviolet light in oxygen to remove carbon contaminants. It was heated at about 750°C to form a clean oxide layer in oxygen of 5×10⁻⁵ Torr in an SAM chamber. The desorption of the layer can make a remained tip apex sharper by heating under electron beam irradiation. A thermally oxidized layer was also eliminated by HF etching to sharpen the tip apex. The procedures are useful to obtain a well-defined Si tip suitable for a noncontact AFM.     

Three-dimensional scanning force/tunneling spectroscopy at room temperature

We simultaneously measured the force and tunneling current in three-dimensional (3D) space on the Si(111)-(7 × 7) surface using scanning force/tunneling microscopy at room temperature. The observables, the frequency shift and the time-averaged tunneling current were converted to the physical quantities of interest, i.e. the interaction force and the instantaneous tunneling current. Using the same tip, the local density of states (LDOS) was mapped on the same surface area at constant height by measuring the time-averaged tunneling current as a function of the bias voltage at every lateral position. LDOS images at negative sample voltages indicate that the tip apex is covered with Si atoms, which is consistent with the Si-Si covalent bonding mechanism for AFM imaging. A measurement technique for 3D force/current mapping and LDOS imaging on the equivalent surface area using the same tip was thus demonstrated.     

An AFM study of the processing of hydrogen passivated silicon(1 1 1) of a low miscut angle

We present atomic force microscopy (AFM) measurements from a passivated silicon crystal miscut by 0.1° and show the etching regime to be significantly different from surfaces with a larger miscut angle. A simple kinetic model is developed to explain the results and is used to derive the optimal etching conditions for nominally flat Si(1 1 1)–(1×1)H. We show that small changes in miscut angle can alter the kinetic steady state and promote the formation of deep etch pits, even on the least stable, miscut surface. Collisions of steps with these pits result in arrays of stable, self-aligned ‘etch hillocks' over micron dimensions. Following preparation, we use AFM to observe the initial growth of native oxide on the Si(1 1 1)–(1×1)H surface, and demonstrate that AFM is a sensitive probe to surface oxidation in the sub-monolayer regime.     

Noncontact AFM imaging on a Si(111)2×1-Sb surface with occupied lone-pair orbitals

Force interaction between an orbital of a dangling bond out of a Si tip apex and an occupied lone-pair orbital on a Si(111)2ǵ-Sb surface is experimentally investigated to clarify the imaging mechanism of noncontact AFM. Sb adatoms with occupied lone-pair orbitals are clearly observed on the 2ǵ zigzag chain structure surface. The discontinuity in the frequency-shift curve is not observed at the Sb sites. Possible contrast mechanisms are discussed and the most understandable in terms of the chemical bonding interaction weaken by the existence of the anti-bonding orbital with one electron.     

Investigations of C60 molecules deposited on Si(111) by noncontact atomic force microscopy

We demonstrated the high resolution imaging of the organic molecules using noncontact atomic force microscopy in ultrahigh vacuum. The sample was C₆₀ molecules deposited on the Si(111)-7×7 reconstructed surface. When the thickness of the C₆₀ film was submonolayer, we could image some isolated C₆₀ molecules and the reconstructed Si surface simultaneously. However, the imaging was highly unstable not only because of the large structure but also due to the large difference between the interaction forces on the molecules and on the Si surface. On the other hand, when the thickness of the C₆₀ molecules was almost monolayer, individual molecules could be stably imaged.     

Chemical interactions in noncontact AFM on semiconductor surfaces: Si(111), Si(100) and GaAs(110)

Total-energy pseudopotential calculations are used to study the imaging process in noncontact atomic force microscopy (AFM) on Si(111), Si(100) and GaAs(110) surfaces. The chemical bonding interaction between a localised dangling bond on the atom at the apex of the tip and the dangling bonds on the adatoms in the surface is shown to dominate the forces and the force gradients and, hence, to provide atomic resolution. The lateral resolution capabilities are tested in both the Si(100) and the GaAs(110) surfaces. In the first case, the two atoms in a dimer can be resolved due to the dimer flip induced by the interaction with the tip during the scan, while in the GaAs(110), we identify the anion sublattice as the one observed in the experimental images.     

Atomic structure of β-SiC(100) surfaces: an ab initio study

We examine several different reconstructions of the β-SiC(100) surface by the ab initio Car-Parrinello method. Our results confirm that the lowest energy c(2 × 2) reconstructed surface consists of triply bonded carbon dimers in a bridging position between neighboring underlying silicon dimers. Added hydrogen atoms bond to the carbon dimers, resulting in a lengthened double-bonded dimer, and a larger separation for the underlying silicon dimers, although those Si bonds do not disappear. The most stable structure found for the (3 × 2) reconstructed surface with a 1/3 monolayer excess of silicon is an alternate dimer row structure rather than the added dimer row model proposed by others. The energetics of various surface reactions that may be involved in growth of SiC are discussed.     

Imaging of atomic-scale structure of oxide surfaces and adsorbed molecules by noncontact atomic force microscopy

Atom-resolved images of a TiO₂(110)-(1×1) surface and individual formate and acetate ions adsorbed on the surface were obtained by noncontact atomic force microscopy (NC-AFM) in ultrahigh vacuum. In contrast to previous scanning tunneling microscopic studies imaging five-fold coordinated Ti atoms, outermost atoms of bridge-bound oxygen ridges of the surface were resolved as protruding rows by NC-AFM. High-resolution image of the surface revealed that the bridging oxygen atoms on terraces ordered in a (1×1) periodicity. Randomly distributed point and multiple defects of oxygen atoms were also imaged as dark spots. The (2×1) overlayer of formate and acetate ions were resolved as ordered bright spots. Dispersed formate ions at a low coverage were also observed as bright spots between the bridging oxygen ridges along the [001] direction.     

Single-atom contact mechanics: from atomic scale energy barrier to mechanical relaxation hysteresis

The potential energy landscape of surfaces governs the dynamics of adsorbed molecules, as well as atomic scale friction processes. We measure the potential energy landscape of a single-atom tip interacting with a vicinal nonconducting NaCl(100) surface in real space using noncontact atomic force microscopy. We find that the shape of the potential energy profile is of sinusoidal form with a barrier height of 48 meV. Furthermore, we observe a discontinuity in the force curves at specific lattice sites, indicating the onset of reversible yet hysteretic mechanical relaxations.     

Observation of triangular terraces and triangular craters of CaF2 film on Si(1 1 1) substrate

We have investigated the growth mode and surface morphology of CaF₂ film on Si(1 1 1)7×7 substrate by reflection high-energy electron diffraction (RHEED) using very weak electron beam and atomic force microscopy (AFM). It was found by RHEED intensity oscillation measurements and AFM observations that three-dimensional (3D) islands grow at RT; however, rather flat surface appears with two-dimensional (2D) islands around 300 °C. Especially, at high temperature of 700 °C, characteristic equilateral triangular terraces (or islands) with flat and wide shape grow with the tops directed toward [1 1 −2] of substrate Si(1 1 1). On the other hand, the desorption process of the CaF₂ film due to electron stimulated desorption (ESD) was also examined. It was found that the ESD process at 300 °C forms characteristic equilateral triangular craters on the film surface with the tops (or corners) directed toward [−1 −1 2] of substrate Si(1 1 1), provided that the film was grown at 700 °C.     

Sub-Angstrom oscillation amplitude non-contact atomic force microscopy for lateral force gradient measurement

We report the first results from novel sub-Angstrom oscillation amplitude non-contact atomic force microscopy developed for lateral force gradient measurements. Quantitative lateral force gradients between a tungsten tip and Si(1 1 1)-(7 × 7) surface can be measured using this microscope. Simultaneous lateral force gradient and scanning tunnelling microscope images of single and multi atomic steps are obtained. In our measurement, tunnel current is used as feedback. The lateral stiffness contrast has been observed to be 2.5 N/m at single atomic step, in contrast to 13 N/m at multi atomic step on Si(1 1 1) surface. We also carried out a series of lateral stiffness-distance spectroscopy. We observed lateral stiffness-distance curves exhibit sharp increase in the stiffness as the sample is approached towards the surface. We usually observed positive stiffness and sometimes going into slightly negative region.     

A noncontact atomic force microscope in air using a quartz resonator and the FM detection method

Noncontact imaging was successfully performed with the quartz resonator in air by using the FM detection method. A constant frequency shift mode was used. The frequency shift was about -30 mHz, which was induced by the attractive force gradient. A noncontact image of the Si(111) atomic step was obtained with vertical and lateral resolutions of 0.8 Å and 60 Å.     

Observation of electronic states on Si(111)-(7 x 7) through short-range attractive force with noncontact atomic force spectroscopy

We experimentally reveal that the short-range attractive force between a Si tip and a Si(111)-(7 x 7) surface is enhanced at specified bias voltages; we conduct force spectroscopy based on noncontact atomic force microscopy with changing bias voltage at a fixed separation. The spectra exhibit prominent peaks and a broad peak, which are attributed to quantum mechanical resonance as the energy levels of sample surface states are tuned to those of the tip states by shifting the Fermi level through changing bias voltage, and to the resonating states over a lowered tunneling barrier, respectively.     

Infrared spectroscopy of hydrogen on silicon surfaces

This paper is a review of infrared studies of hydrogen-terminated silicon surfaces. Emphasis is given to the ideally H-terminated Si(1 1 1) surface, prepared by wet chemical techniques, because detailed information can be obtained concerning the Si-H stretching vibration, such as its precise frequency and effective charge, its lifetime and the nature of its anharmonic coupling to the SiH bending mode and to the substrate surface phonons. Comparison of this nearly ideal surface with the H-exposed Si(1 1 1)7 × 7, Si(1 1 1)2 × 1 and Si(1 0 0)2 × 1 gives some insight into the effects of reconstruction and strain on the Si-H vibrational spectrum.     

Ultrasound enhanced the binding ability of chitinase onto chitin: From an AFM insight

In order to evaluate the effect of ultrasound to chitinase from a molecular level, atomic force microscopy (AFM) was employed to investigate the interaction force of chitinase binding onto chitin surface. In the measurement of force-distance curve, a series of pull-off events were discovered using the immobilized AFM tips with chitinase either treated by ultrasound or not, whereas no interaction peak was observed by the AFM tips without chitinase, indicating that the obtained adhesion forces were coming from the binding functions between chitinase and chitin. Through the analysis of these force curves, at the loading velocity of 0.3 μm/s, the maximum binding force of the chitinase treated by ultrasound for 20 min onto chitin was measured to be 105.33 ± 23.51 pN, while the untreated onto chitin was 71.05 ± 12.73 pN, suggesting the stronger binding force between ultrasonic treated chitinase and chitin substrate. Therefore, AFM has provided a useful method to directly and quantitatively characterize the interactions between chitinase and chitin, and successfully proved that ultrasound could activate chitinase by enhancing the binding ability of chitinase onto chitin.