Donor graphite intercalation compounds studied with a high stability STM

We have designed a small, rigid and easy operable scanning tunnelling microscope (STM) which shows low thermal drift rates due to its compact construction and the chosen materials. Using this instrument we have studied stage 1 donor graphite intercalation compounds (C₆Li and C₈K) with atomic resolution either in the current imaging, constant current or local tunnelling barrier height mode of operation. Ordered superlattices commensurate as well as incommensurate with the graphite lattice have been observed on the C₆Li surface. STM images on C₈K revealed a graphitic surface structure.     

Scanning probe microscopy of biological samples and other surfaces

Scanning probe microscopes derived from the scanning tunnelling microscope (STM) offer new ways to examine surfaces of biological samples and technologically important materials. The surfaces of conductive and semiconductive samples can readily be imaged with the STM. Unfortunately, most surfaces are not conductive. Three alternative approaches were used in our laboratory to image such surfaces. 1. Crystals of an amino acid were imaged with the atomic force microscope (AFM) to molecular resolution with a force of order 10^?8 N. However, it appears that for most biological systems to be imaged, the atomic force microscope should be able to operate at forces at least one and perhaps several orders of magnitude smaller. The substitution of optical detection of the cantilever bending for the measurement by electron tunnelling improved the reliability of the instrument considerably. 2. Conductive replicas of non-conductive surfaces enabled the imaging of biological surfaces with an STM with a lateral resolution comparable to that of the transmission electron microscope. Unlike the transmission electron microscope, the STM also measures the heights of the features. 3. The scanning ion conductance microscope scans a micropipette with an opening diameter of 0·04-0·1 μm at constant ionic conductance over a surface covered with a conducting solution (e.g., the surface of plant leaves in saline solution).     

The STM as an information storage device

The high spatial resolution of the scanning tunnelling microscope (STM) makes its use as an information storage device very attractive. However, even without specifying the means of information storage, several limits can be placed on the characteristics of these devices. One would expect that a bit of information could not be stored in a dimension smaller than an atom. This limits the storage density to 10¹⁵ bits/cm². Present-day STM have fields of view that range up to 2times10^?6cm² yielding a total potential capacity of 2times10⁹ bits. This capacity would be expected to grow as STM design becomes more refined. At 1 nA, shot noise will limit the read rate to 20 Mbits/s. This limit can only be overcome by using larger currents. The write rate may also be limited by this phenomenon if the writing mechanism demands that a certain charge threshold be reached to write a bit. For a particular device structure, operating conditions will be identified where the above limitations will become important. The above analysis leads to the conclusion that an STM storage device with reasonable read/write rates and a large storage capacity should be possible.     

Imaging an optical disc by the combined use of scanning tunnelling microscopy and scanning electron microscopy

We present the data obtained by scanning tunnelling microscopy combined with scanning electron microscopy of the digitally encoded structure on a stamper used to fabricate optical discs. The combination allows us to focus the STM tip on a preselected spot with a precision of ?0·3 μm. The data show the superiority of STM for a more detailed characterization of shape, width, length, height and fine structure appearing on the sample. We also show the influence of tip shape on STM resolution. Simultaneous use of both microscopes is possible but high electron doses produce an insulating layer of contaminants thick enough to make STM operation impossible.     

Real-time scanning tunnelling microscopy of surfaces under active electrochemical control

A scanning tunnelling microscope has been designed which allows tunnelling microscopy to be performed in the presence of an externally applied electrochemical current. Separate, isolated electrodes were used for electrochemical control, and up to 1 mA was passed during real-time, video-rate, in situ STM observation of the surfaces, without interfering with the operation of the STM. The noise level of these STM images is only slightly higher than images taken with the electrochemical circuitry disconnected. Surfaces were observed during the formation of surface films in aqueous electrolytes.     

SNOM/STM using a tetrahedral tip and a sensitive current-to-voltage converter

Scanning near-field optical microscopes (SNOM) using the tetrahedral-tip (T-tip) with scanning tunnelling microscopy (STM) distance control have been realized in transmission and reflection mode. Both set-ups used ordinary STM current-to-voltage converters allowing measurement of metallic samples. In the transmission mode, a resolution of 10 nm to 1 nm with regard to material contrast can be achieved on binary metal samples. Because of the great near-field optical potential of the T-tip with respect to the optical resolution, it is a challenging task to find out whether these results can be transferred to non-metallic sample systems as well. This paper reports on a newly designed SNOM/STM transmission mode set-up using the tetrahedral-tip. It implements a sensitive current-to-voltage converter to widen the field of measurable sample systems. Beyond this, mechanical and optical measuring conditions are substantially improved compared to previous set-ups. The new set-up provides a basis for the routine investigation of metal nanostructures and adsorbed organic monolayers at resolutions in the 10 nm range.     

Scanning tunnelling engineering

The great potential for building molecular scale machines and other structures was first noted by Richard Feynman (1960). He also proposed the development of tools to construct nanoscale mechanisms and devices. The range of technology that he proposed is now called nanotechnology, a term coined by Taniguchi (1974). Emergence of STM and related technology should greatly facilitate the development of nanotechnology in the decades to come. Franks' (1987b) review of nanotechnology notes the tremendous potential of STM-derived tools for what he terms ‘scanning tunneling engineering’. However, STM technology can also augment the ‘bottom up’ approaches to nanotechnology, exemplified for example by Forrest Carter's (1979, 1980, 1982, 1983) proposals for building molecular electronic devices (nanocomputers) using synthetic ‘modular chemistry’ and related techniques of supramolecular chemistry (Kuhn & Mobius, 1971; Kuhn, 1983; Lehn, 1980, 1988). A multi-tip STM system integrated with an optical microscope was proposed in 1986 as a ‘nanotechnology workstation’ suitable for scanning tunnelling engineering (Schneiker & Hameroff, 1988). In this paper, we describe an overview of scanning tunnelling engineering, present concepts for nanosensors and nanoswitches, and discuss design considerations for dual tip STM. Finally, we repeat an announcement of a series of ‘Feynman’ prizes for miniature STM.     

In-situ STM studies of electrochemical underpotential deposition of Pb on Au(111)

A modified scanning tunnelling microscope (STM) has been used to observe in-situ deposition and stripping of an electrochemical film. With STM tip and sample immersed in an acid electrolyte, single atomic steps on Au(111) have been imaged during the deposition and stripping of a monolayer-thick, underpotential deposit (UPD) of Pb. Integration of the electrochemical current passed during the film deposition and evidence from the STM images themselves confirm monolayer coverage. Our images show enhanced film growth at step edges and defect sites. Observations of single plating and stripping cycles indicate that the Au substrate returns unaltered. Except for atomic resolution images of Au(111), which we have not yet achieved in an electrolyte, all types of Au surface features seen in air are reproduced under the electrolytic solution. The modifications made to our STM in order to perform in-situ electrochemical experiments are described.     

Scanning probe microscopy studies of cereal seed storage protein structures

Scanning probe microscopes (SPMs) share a number of common features which give the techniques advantages over conventional light and electron microscopy. First, high resolution, up to the atomic level, is possible in certain cases, and second, they are nondestructive, requiring no staining or coating and the images can be obtained in the hydrated state or under water. Scanning probe microscopes, particularly scanning tunnelling microscopes (STM) and atomic force microscopes (AFM), have been used to study food-related systems, ranging from relatively large structures such as starch granules to the organisation of secondary structures in proteins and the interaction of proteins. The seed storage proteins (gluten) of wheat are responsible for the viscous and elastic properties of wheat doughs that allow them to be used for a wide range of different food products. Using AFM and STM, images of individual and groups of proteins have been obtained in both the dry and hydrated states. The ability to work in liquid environments allows the conformation of proteins to be determined under conditions approaching “native.” The AFM and STM have been used to image both gliadins and glutenins and to study their aggregative behaviour in relation to gluten and dough systems.     

Measurements of polyphosphoric acid on HOPG

As a sample for initial study on biological materials by using scanning tunnelling microscope (STM), we selected phosphoric acid consisting of phosphorous atoms which play biologically an important role. We measured polyphosphoric acid coated on HOPG by STM and scanning tunnelling spectroscopy (STS) in air. In order to identify molecules on STM images, local I-V curves were taken simultaneously. The averaged I-V curves and the normalized conductance spectra of graphite coated with the acid show characteristics different from those of clean graphite surface. Around a step of the substrate, we found domains where normalized conductance spectra were different from those of clean graphite surface and ascribable to that of the adsorbed molecules.     

Spatially resolved ballistic electron spectroscopy of subsurface interfaces

Buried interfaces have traditionally been inaccessible to direct investigation by surface-sensitive techniques. A unique and novel electronic probe, which is sensitive to subsurface electronic structure, has been utilized to probe Schottky barrier interfaces. The method, ballistic electron emission microscopy (BEEM), is based on scanning tunnelling microscopy (STM) techniques. A theoretical treatment has been developed to describe the ballistic electron spectra obtained by BEEM and this treatment is applied to data obtained on the Au-Si Schottky barrier interface system. Excellent agreement between experiment and theory is obtained. In addition, the treatment pradicts nanometre spatial resolution for interface imaging by BEEM.     

Adsorbate deformation as a contrast mechanism in STM images of biopolymers in an aqueous environment: images of the unstained,hydrated DNA double helix

A stable residual aggregate remains on a submerged gold surface after electrophoretic deposition of DNA. We present scanning tunnelling microscope (STM) images of these aggregates which show many objects with the geometry of DNA, clearly displaying the 3·4 nm helix pitch. These images are quite distinctive, and cannot be generated when the deposition technique is used without DNA in the buffer solution. A characteristic of these images is that the tip is observed to dip down over the DNA molecule at the same time as the apparent barrier height drops by a factor of about four. The tip displacement is accounted for by a model in which contrast is dominated by local fluctuations in the deformability of the adsorbate layer, a quantity deduced from measurements of the apparent barrier heights in air, water, over small molecule adsorbates, and over DNA.     

Anomalous voltage dependence of tunnelling microscopy in WSe2

We present scanning tunnelling microscopy (STM) investigations of the layered semiconductor WSe₂. The tunnelling experiments were performed in air and under silicone oil with markedly different results. In air, atomic resolution images of the hexagonally structured surface could be obtained for sample-to-tip voltages of both negative and positive polarities, from ?1·5 to ?0·3 V for negative sample and from +0·6 to +1·6 V for positive sample, respectively. Under silicone oil, however, good atomic images could be seen for negative sample biases down to at least ?14 V, while for positive sample biases no difference with respect to the tunnelling in air was found.     

钢中下贝氏体组织的扫描隧道显微镜研究

在大汽环境中利用扫描隧道显微镜（ＳＴＭ）观察钢铁表面的精细组织结构。对照光学显微镜（ＯＭ）、扫描电子显微镜（ＳＥＭ）、透射电子显微镜（ＴＥＭ）的观察结果,民得的钢铁的组织形貌进行分析讨论。初步建立ＳＴＭ下图像形貌和组织之间的对应关系。利用ＳＴＭ优良的表面垂直分辨能力。观察到贝氏体铁素体上人有比马氏体铁素体更高的耐蚀性。     

Digital filters to restore information from fast scanning tunnelling microscopy images

A transfer function—similar to that used in optical cases to correct blurring effects due to the circular aperture of the system—is presented here to restore scanning tunnelling microscopy (STM) images. Due to the conical geometry of the tip-sample system, we have established an analogy between the process of image formation in STM and in optical systems. The transfer function utilized, similar to that calculated by Stokseth, allows us to differentiate between the blurring effects introduced along the x and y axes. These effects are different due, mainly, to the different velocities achieved along the x and y directions. Furthermore we have measured the β parameter that characterizes the classical 1/fβ noise present in STM data, demonstrating its independence from experimental conditions. A Wiener filter is utilized to restore the images using the previous assumptions given for the transfer function and noise effects.     

Fractal characterization by frequency analysis: III. Effect of noise

The effect of noise in the fractal characterization by frequency analysis of surface images obtained by scanning tunnelling microscopy (STM), atomic force microscopy (AFM) or profilometry has been studied. The origin of noise and its relationship to the signal is discussed. A procedure to simulate noisy images is presented. From the study it is concluded that the method usually used to characterize noise in STM is not valid and it is shown that fractal characterization of surfaces when noise is present by traditional frequency analysis methods is not possible. A new method to perform both the noise characterization and the fractal characterization of surfaces when noise is present is proposed.     

Scanning tunnelling microscopy of 1-D and 2-D charge-density wave systems

We have used a new variable temperature scanning tunnelling microscope (STM) to study quasi-1D and 2-D charge-density wave (CDW) systems. The 1-D systems, typified by NbSe₃ and TaS₃, are of special interest since they exhibit unusual transport phenomena associated with moving CDW above a threshold electric field. In the case of NbSe₃, room temperature STM images show both major and subtle details of the lattice structure. At present, however, images taken below the Peierls transition temperature of T_P=144 K resolve major lattice details but are not sufficiently clear to resolve the CDW. On the other hand, for the fully gapped CDW system orthorhombic-TaS₃, the CDW modulation superimposed on the lattice structure and having the correct period of four times the S-S spacing of 3·3 Å, is observed below T_P=215 K. Above T_P, the main observable feature is the S-S spacing along the chains. STM measurements have also been performed on the 2-D CDW system 1T-TaS₂ in its incommensurate, nearly commensurate, fully commensurate and trigonal phases. For the nearly commensurate phase, STM images show uniform commensurability with a relatively low concentration of small, time-varying discommensurations in contrast to models pradicting a regular domain structure. In the trigonal phase, however, evidence is seen for the striped phase composed of long, nearly parallel discommensurations.     

An entirely enclosed scanning tunnelling microscope capable of being fully immersed in liquid helium

We present an ultrahigh‐vacuum (UHV)‐sealed high‐stability scanning tunnelling microscope (STM) that can be entirely immersed in liquid helium and readily used in a commercial Dewar or superconducting magnet. The STM head features a horizontal microscanner that can become standalone and ultrastable when the coarse approach inertial motor retracts. Low voltage is enough to operate the STM even at low temperature owing to the powerful motor. It is housed in a tubular chamber of 49 mm outer diameter, which can be pumped via a detachable valve (DV), UHV‐sealed and remain sealed after the DV is removed. The entire so‐sealed chamber can then be inserted into liquid helium, where in situ sample cleavage is done via vacuum bellow. This allows sample cleavage and STM measurements to take place in better UHV with higher cooling power. Quality atomic resolution images of graphite and charge density wave on 1T‐TiSe₂ taken in ambient and 14 K conditions, respectively, are presented.     

Scanning tunnelling microscopy of tobacco mosaic virus on evaporated and sputter-coated palladium/gold substrates

We present scanning tunnelling microscope (STM) images of untreated tobacco mosaic virus (TMV) deposited on thermally evaporated and on sputter-coated palladium/gold 40:60 (Pd/Au) substrates, and imaged under ordinary atmospheric conditions. The TMV imaged on both evaporated and sputter-coated substrates was consistently several times wider than the known diameter of the virus. TMV on evaporated Pd/Au became overcoated with Pd/Au material during sample preparation and appeared elevated in STM images, whereas TMV on sputter-coated Pd/Au appeared as depressions. When naked TMV were intentionally overcoated with Pd/Au, the STM images were found to be similar to those for TMV on evaporated Pd/Au.     

An STM for biological applications: Bioscope

We present an STM with an improved coarse positioning system and a large scan area which is especially suitable for biological applications. Three stepper motors are used to move an X-Y-Z table. Movements of motor axes are geared down to drive micrometer spindles so that steps of 250 nm can be performed. The stepper motors can be uncoupled from the STM for scanning operation. A piezo tube is used to scan areas of up to 10times10μm with low voltage operation. Probes can be scanned in air or in electrochemical cells. High stability against thermal drift and vibrations is achieved by a rigid and symmetrical design.