STM study of the effects of pulsed laser irradiation on semiconductor surfaces

A clean Si(111) flat surface was irradiated by pulsed Nd-YAG laser beams. STM observation of the irradiated surfaces indicates that the laser irradiation generates two kinds of corrugations: rounded hills 100 Å high and 600 Å wide and small spikes 20 Å high and 35 Å wide. The corrugations grew and spread with repeated irradiation and increased laser power. The heating of the irradiated surface at 1200°C for 5 s smoothed the surface atomically, but no ordered structure was observed, possibly due to the covering contaminants released from the surfaces surrounding the specimen by laser irradiation and heating.     

STM imaging of molecular collagen and phospholipid membranes

The application of STM to biological materiais has been limited by poor conductivity, sample geometry and stability of biological materials. In this paper we describe an STM study of the monomeric helical forms of collagen, a stable, conductive and widely prevalent structural protein. We have also used STM to image artificial Langmuir DPE (dipalmitoyl phosphatidyl ethanolamine) phospholipid membranes. Both molecular collagen and the phospholipid membranes were dried in air on highly oriented pyrolytic graphite (HOPG). Our STM images of collagen dried on HOPG reveal strands 15Å in diameter with a periodicity of about 30Å which correlates with that known to occur in collagen. Spikes which periodically protrude from strands in our STM images of collagen appear to represent pyrrolidine ring structures in the amino acids proline and hydroxyproline. Thus, we report the first STM imaging of native biomolecules revealing intramolecular details and what appear to be specific amino acids. STM imaging of phospholipid membranes show a lattice pattern with densities spaced ～4–5Å apart. These are thought to represent individual phospholipid molecules in an artificial membrane formed on the HOPG. We believe STM and its related technologies will have great future utility in biomolecular studies.     

STM study of silver intercalation into 2H-NbSe2 crystals

We have made scanning tunnelling microscope (STM) studies of the lattice expansion and topography of cleaved crystals of 2H-NbSe₂ which were intercalated in situ with silver ions entering along one edge of the samples. The measurements confirm the high surface mobility of silver seen in earlier electrochemical studies. The expansion measurements made with optimum 2 Å resolution showed no convincing evidence of silver staging domains. Topographic images revealed noisy patches and shallow depressions on cleaved surfaces of intercalated samples. It is suggested that these depressions might represent silver-poor regions in the first intercalation layer.     

Analytical scanning electron microscopy for solid surface

A scanning electron microscope of ultra-high-vacuum (UHV-SEM) with a field emission gun (FEG) is operated at the primary electron energies of from 100 eV to 3 keV. The instrument can form the images that contain information on surface chemical composition, chemical bonding state (electronic structure), and surface crystal structure in a microscopic resolution of several hundred angstroms (Å) using the techniques of scanning Auger electron microscope, scanning electron energy loss microscope, and scanning low-energy electron diffraction (LEED) microscope. A scanning tunneling microscope (STM) also has been combined with the SEM in order to obtain the atomic resolution for the solid surface. The instrumentation and examples of their applications are presented both for scanning LEED microscopy and STM.     

Comparison of LEED and STM measurements of vicinal Si(111)

LEED beam-profile and STM measurements have been used in combination to study the ordering of stepped Si(111) surfaces misoriented by 4° toward the [***211] direction. LEED measurements show that ordering of the surface steps is dependent on the thermal history of the sample, but give little clue about the reasons. An initial cleaning at 1250°C followed by slow cooling is required to obtain a well-ordered step structure. STM measurements show that cleaning at a lower temperature (850°C) results in a surface containing highly disordered patches which are possibly correlated with residual carbon. These disordered regions evidently inhibit step order. STM images of rapidly quenched surfaces show a very different sort of disorder consisting of long wavelength (5–10 nm) corrugations of rms vertical amplitude 2 nm.     

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.     

Scanning tunneling microscope combined with scanning electron microscope

A scanning tunneling microscope (STM) has been installed in a usual scanning electron microscope (SEM) with a vacuum of 10⁻⁶ Torr. The STM image is displayed on the cathode ray tube of the SEM, 512 × 512 pixels, with a scanning rate of 80 s/picture. The spatial resolution of the STM is about 1 Å, while that of the SEM is several tens of ångströms. The combined scanning microscope covers a wide magnification range from 10 to 10⁷, where STM covers the high magnification region from 10⁵ to 10⁷.     

Quantitative analysis of image contrast in electron micrographs of beam-sensitive crystals

The contrast in high resolution electron micrographs of three different thin crystals has been compared quantitatively with that predicted theoretically from separate measurements of thier electron diffraction patterns. The crystals were vermiculite, a mineral which is not greatly affected by the electron beam, and two organic specimens, n-paraffin and purple membrane, which are both destroyed by doses of about 1 electron/Ų. The results, all at 4.0 to 4.5 Å resolution, show that the absolute contrast in images of vermiculite is roughly 1/5th of that expected for a theoretically perfect microscope, whereas images of paraffin and purple membrane seldom reach more than 1/25th of theoretical contrast. Much of this loss of contrast can be explained on the basis of known microscope parameters in the case of the non-beam-sensitive specimens. However, for the images of paraffin and purple membrane, it is necessary to postulate that beam-induced specimen movement results in further substantial blurring of the image. The tendency for such movement to occur may be unavoidable since the molecular structure is being destroyed during the exposure. The magnitude of this movement must be reduced before the image contrast will be able to approach the theoretical limit.     

Characterization and local modification of atomically flat gold surfaces by STM

In order to characterize the surface of epitaxial gold on mica in air we have used a scanning tunnelling microscope (STM) to image and to modify this surface. It was possible to create controlled features by applying voltage pulses on the tip while scanning. The voltage threshold for writing (about 3 V, 100 ns pulses) was dependent of the tip condition. The lowest pulses were associated with sub-50 Å feature size. We observed that at ambient temperature the written features disappeared in a time scale of half an hour for the smallest (<30 Å) to a few hours for the bigger features (～500 Å). We have used the same surface as a substrate for organic imaging. We also present images of a polymer deposited on gold.     

The STM learning curve and where it may take us*

The scanning tunnelling microscope (STM) has proved to be an extraordinary method to investigate surfaces in vacuum, air and liquid environments. Several issues regarding the use of the STM for atomic resolution studies are discussed. These include electronic contributions to STM images, the role of the tip in resolution and spectroscopy, as well as the need for complementary information about chemical composition or sub-surface structure.     

The fatty acid monolayer technique for preparing frozen-hydrated specimens

A major difficulty in preparing frozen-hydrated specimens from solutions is to control an optimal thickness of water remaining on the EM grid just before it is immersed in liquid nitrogen. In this report, we describe a modification of the fatty acid monolayer technique for preparing frozen-hydrated specimens. With the use of this technique, all excess solvent is removed when a behenic acid (a fatty acid) monolayer film is picked up over the surface of the electron microscope grid. Low-dose electron diffraction patterns and optical diffraction patterns of low-dose micrographs of bacteriorhodopsin (bR) of Halobacterium halobium thus prepared show strong reflection orders at a resolution of ∽4 Å and ∽10 Å, respectively. Because the preparation of thin, hydrated specimens by the behenic acid monolayer technique does not depend upon evaporation of water, a dramatic change of ion concentration and pH is not expected to occur. The method should be applicable to specimens which need to be kept in a specific buffer and/or at a specific ionic strength.     

Effect of fabrication process parameters on the apex‐radius of STM tungsten nanotip

Scanning tunneling microscope (STM) has found a wide application in nanoscience and nanotechnology. This microscope uses an ultra‐sharp metallic tip for image acquisition. Resolution of STM images depends largely on the radius of the tip apex; the smaller the radius the higher the resolution. In the present research, an experimental set‐up was designed and implemented for fabrication of STM tungsten nanotip using electrochemical‐etching method with the aim of optimization of nanotip fabrication process parameters by using Taguchi method. These parameters are electrolyte concentration, immersion length of the tungsten wire, inner diameter of the cathode tube, and the process voltage. It was found that the optimum level of the process parameters for gaining minimum radius of the nanotip apex is electrolyte concentration of 2 M/lit, wire immersion length of 4 mm, cathode tube inner diameter of 55 mm, and voltage of 3.5 V within the range of experiments. By setting the process parameters on the optimum level, the radius of the nanotip apex was decreased by five times in comparison to the mean value of the experimental results. The radius of the nanotip apex was improved down to about 10 nm under the optimum conditions. SCANNING 31: 65–74, 2009. © 2009 Wiley Periodicals, Inc.     

A small scanning tunnelling microscope with large scan range for biological studies

We have developed a scanning tunnelling microscope specially designed for biological applications presenting some new features: the scanner tube is mounted parallel to the surface of the sample which enables a high resolution optical microscope to be brought close to the sample when working in air or liquids. The maximum scan range is 5×20 μm with a vertical range of 20 μm and the total size of the system does not exceed 10×40 mm. The piezo-sensitivity of the scanner tube versus applied voltage was analysed by interferometry measurements and by using scanning tunnelling microscopes. We found a value for the piezoelectric constant d₁₃ of ?1·71 Å/V at low voltages (under a few volts) going up to ?2 Å/V for higher voltages. Large-scale images of a carbon grid showed a surprisingly good linearity of the scanner tube.     

Imaging biological macromolecules by STM: quantitative interpretation of topographs

Methods are discussed which permit the calibration of x-, y-, z-sensitivities, non-linearities and frequency responses of the scanning device of a scanning tunneling microscope (STM) either by interferometry or directly from STM topographs. A technique is presented to measure the frequency response of the complete STM feedback unit and to derive a maximum speed in z direction which allows one to estimate the maximum scanning speed still permitting one to track surface corrugations. The signal transfer characteristics of a STM are evaluated in a direct comparison with high resolution transmission electron microscopy on an identical specimen area. The various effects of contaminants between tip and specimen and the finite tip radius receive special attention.     

Oxygen ordering and twinning in YBa2Cu3O7−x

Direct structure images of the YBa₂Cu₃O_7−x high T_c superconducting ceramic (also called the 1–2–3 compound) at 1.7 Å resolution have been obtained for the [100] and [001] orientations. It was found that for the purposes of studying oxygen ordering in this compound it is better to use lattice images of lower resolution. The oxygen ordering was studied via the measurement of the bending of (100) and (11 0) lattice planes on crossing the (110) twin boundaries in crystals oriented in the [001] zone. Significant variations were found in the b/a ratios, owning to a variation in oxygen ordering, between different crystal grains, and between different regions in the same grain. For the three different 1–2–2 samples studied, the average b/a ration was 1.016, the same value as was found in neutron diffraction studies. The twin boundaries in the orthorhombic 1–2–3 phase are sharp and planar. It seems likely that the transformation from the high-temperature tetragonal phase to the lower-temperature orthorhombic phase is martensitic in nature. A new phase has been discovered on some of the twin boundaries. The new phase can be indexed as tetragonal with a = 7.5 ± 0.2 Å, and c = 6.8 ± 0.2 Å. It is possible that the new phase is stabilized by the stress which occurs at the twin boundaries.     

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.     

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.     

Soft X-ray microscopy with a cryo scanning transmission X-ray microscope: I. Instrumentation, imaging and spectroscopy

We have developed a cryo scanning transmission X-ray microscope which uses soft X-rays from the National Synchrotron Light Source. The system is capable of imaging frozen hydrated specimens with a thickness of up to 10 μm at temperatures of around 100 K. We show images and spectra from frozen hydrated eukaryotic cells, and a demonstration that biological specimens do not suffer mass loss or morphological changes at radiation doses up to about 10¹⁰ Gray. This makes possible studies where multiple images of the same specimen area are needed, such as tomography ( Wang et al. (2000 ) Soft X-ray microscopy with a cryo scanning transmission X-ray microscope: II. Tomography. J. Microsc . 197, 80–93) or spectroscopic analysis.     

The importance of current density ‘focusing’ in STM image resolution

In a previous paper we incorporated Tersoff and Hamann's model of an STM tip into Lang's transfer Hamiltonian result for the tunnelling current density and applied the resulting simple expression to Tersoff's six-plane-wave model of a monolayer of graphite. In this paper the results for a more realistic model of a graphite surface and a more complete selection of tip positions are presented. They support the previous conclusions that the normal component of the current density takes on both positive and negative values in a complex flow pattern and that its lateral falloff away from the (projected) tip position is much slower than expected from the extraordinary lateral resolution (～1 Å) evident in the best STM images of graphite. This shows that sharp ‘focusing’ of the current density directly under the tip is not a necessary condition for high lateral resolution.     

Extending the limit of atomic level grain boundary structure imaging using high-resolution electron microscopy

It has been possible to image ∑ = 21/[111]21.8° tilt boundaries in thin Au films and to deduce their atomic arrangements. These results represent an electron microscopic resolution level of 1.43 Å, attainable with a small amount of image processing, which produces interpretable structure images. This substantial improvement over other recent grain boundary studies, which required about 1.9–2.0 Å resolution, clearly demonstrates that many more tilt grain boundary orientations are now accessible instead of a limited subset.