This chapter introduces the research of in situ high-resolution transmission electron microscope (HRTEM) methods combined with the functions of atomic force microscope and scanning tunneling microscope. Using this method, we demonstrate fabrication, dynamic observation on an atomistic scale, and mechanical and electrical measurements of nanometer-sized contact simultaneously. We evaluate the silver atomic-sized wire (ASW) which appeared at the final stage of the rupture process of the silver nano-contact.
- atomic-sized wires
- atomic force microscopy
- high-resolution transmission electron microscopy
Currently, miniaturization of electronics is underway. Now device development is heading toward atomistic and molecular scales . Devices included in these circuits are nanometer-sized contacts (NCs), atomic-sized wires (ASWs), single molecular junctions (SMJs), etc. (Figure 1) . SMJ is a system of single molecule sandwiched by a pair of nanometer-sized metallic electrodes. SMJs enable single electronic operation, high-density integration, and electric power saving [3-7]. To engineer SMJs, we need to reveal that the structure of device configuration includes interfaces between molecules and electrodes and mechanical and electrical properties. Metallic NCs and ASWs are fundamental materials that have the potential for device applications as well as being the key factors required for the application of SMJs .
Actually, to observe the formation and deformation of NCs, two
In 2001, Kizuka et al. observed the deformation process of Au NCs with atomistic resolution using HRTEM based on the
Further, as Kizuka et al. improved the
At elastic deformation regions undergoing stress–strain, the Young’s modulus of Au ASWs was estimated to be between 47 and 116 GPa. This value is remarkably comparable with that of a single crystal Au.
As described above, common problems in research in metallic ASWs and NCs existed, revealing corresponding relationships between structure and electrical properties. As research in ASWs has concentrated on Au, the structural dynamics of ASW formation is uncertain. For some of the metallic ASWs already researched, only the structures that appeared in the tensile deformation process of NCs were observed. Therefore, the stable structure and electrical conductivity of the NCs have not yet been revealed. In order to produce a general rule for the basic phenomenon that appears in metallic NCs and ASWs, it is necessary to examine structural dynamics, electrical conductivity, and mechanical properties, in order to clarify the corresponding relationship between the structure and properties directly. The method is limited to
2. Combined HRTEM
3. Sample preparation
For samples, we use a cut-out metal foil and the metal sputtered tip of the AFM cantilever. In the case of metallic foil, first we cut out the foil with a thickness of below 0.05 mm to a size of 1 mm by 10 mm and sharpen one side of the plate (Figure 6(a)). After that, we polish this side mechanically using emery papers and aluminum or diamond wrapping film. In rare cases, although a burr part of cut is sometimes thin enough for HRTEM observation, the yield is poor and the workability of nano-tip creation processes in a HRTEM is not good because the sample is affected by a stress concentration where there is a sudden change in thickness. This sample is then thinned further by an Ar ion polish of 3–10 kV (Figure 6(b)). It may be that an ionic cleaner is used just before introducing it into a vacuum.
When performing the mechanical tests simultaneously, it is suggested that you use a metallic sputtered Si tip on the cantilever for AFM for one of the samples (Figure 7). For high-resolution (HR) observations, in order to detect the small force needed to deform the fine structure, the spring constant of the cantilever is required to be small (5 N/m or less is preferred). Metal is sputtered on the cantilever and the tip under a reduced pressure Ar atmosphere. The thickness of metallic film is approximately 20 nm. The requirements in this process are (i) depositing metal atoms on the tip for use in contact with the counter sample and (ii) ensuring the cantilever surface is covered with a uniform continuous metallic film to offer sufficient conductivity. In order to achieve the latter requirement, it would be preferable to sputter in the same way on both sides of cantilever. Moreover, even if the required amount of sputtering is achieved, the spring constant of the cantilever is not changed.
Both samples are attached to a specimen holder respectively, then inserted into the HRTEM specimen chambers. Because the sample is exposed to air for several minutes during this preparation process, a natural oxide or sulfide film is deposited on the sample surface. After the first contact with the sample each other, once we should make the contact larger than a width of several tens nanometers. This is because we pull a clean metal part to the surface from inside the samples.
4. Observation of Ag ASWs
Figure 8 shows HR images during the process of miniaturization of Ag NCs. The black areas at the top and bottom of each image are Ag, the center is the NC, and the surrounding area is a vacuum. On all of the NCs, a lattice interval of Ag (0.24 nm) has appeared – as indicated by (111) in the figure. That is, the contact region is a single crystal. Therefore, the direction of incidence of the electron beam is indicated on the figure as [0-11] and the upward direction on image is identified as  in the figure. The minimum cross-sectional width of the NC is (a) 4 atoms, (b) 3 atoms, and (c–e) 1 atom. Figure 8(f) shows the contact braking.
Figure 9, it shows the calculated image and HR image for the Ag ASW. For the image calculation, we used a model in which both ends of the wire (composed of seven atoms) were connected to two pyramidal Ag crystals (Figure 9(a)). Seven of the Ag ASW atoms were along the  crystal pyramid and arranged at intervals of 0.289 nm, which is the nearest neighboring distance of the bulk Ag. Figure 9(b) is a calculated image for the model. In Figure 9(c), the image intensity along the center line of the atomic wires is shown. The centers of the models of the atoms are displaced from the centers of the black point in computational image by only 0–0.02 nm. Since the experimental spatial resolution of the current HRTEM observation is 0.1 nm, the calculated result agree with the experimentally observed image within that resolution. This correspondence is similar to that of Au atoms in a wire . Figure 9(d) is an enlarged view of the Ag ASW shown in Figure 8(e). Figure 9(c and e) shows the image intensity along the center line of the ASWs. The darkest positions are indicated by the arrows. From the results of the image calculation, the atomic positions of the ASWs can be considered to correspond to the darkest position in the image intensity.
Figure 10 shows the time variation of force and conductance in the Ag ASW formation process shown in Figure 8. Times (a–f) correspond to the times that each image in Figure 8 was observed, respectively. As the NC narrowed, the conductance stepwise reduced (a–b). Similarly, the force acting on the NC also decreased stepwise. Thereafter, when the ASW forms (c–e), both conductance and force were reduced below 0.1 and 0.5 nN.
Figure 11 shows the distribution of the interatomic distances between atoms in the wire, observed in Figure 8. When the number of atoms in the ASW was five, the interatomic distance was 0.25±0.01 nm. However, this became 0.29±0.05 nm for an ASW comprised of six or seven atoms. In other words, as the ASW becomes longer, the interatomic distance increases.
ASWs are generally considered to be formed by pulling out atoms one by one from the electrode. Bahn and Jacobsen calculated the process of pulling metal NCs (Figure 12) using the density functional method via molecular dynamics calculations and effective medium approximation . In the state where tip atoms, from two pyramid-shaped electrodes, bond to one another, the single atom located at the minimum cross-section part bonds to not only three or four atoms of the electrode side but also atoms at the opposite electrode simultaneously. They estimated the bonding strength between these atoms, then went on to discuss whether this monatomic junction can draw atoms from the electrode without leading to a fracture. As a result, for Au and Pt, the strength of the binding of atoms in the wire part is energetically three times larger than that in the electrode part; it tends to form ASWs. On the other hand, for Cu, Ag, Ni, and Pd, it is difficult to form ASWs in this way.
In the experiment shown in Figure 8, Ag ASWs were formed by tensile deformation of NCs. Since as soon as the NC is miniaturized to one atom width (Figure 8(b)), it forms four or more atomic length wires, the stretching process from a single atom contact could not be observed. In other words, the structural change from the Ag NC to the Ag ASW was faster than the frame rate available using TEM observations (~17 ms). Moreover, we have applied a voltage of 13 mV for the conductance measurement. The withdrawal of atoms from the electrode for atomic wires involved not only tensile force, but also atom transfer by electron wind force. As an example of this effect, when we apply a voltage of 100 mV to the NC, ASW with a length of ~0.88 nm formed just before breaking without applying tensile force . Therefore, even for some of the elements for which ASWs were hardly expected to form, there remains the possibility of wire formation due to the atomic diffusion effect.
In this chapter, we introduced combined microscopy techniques which are based on HRTEM, AFM, and STM. This approach was developed to meet the demand for characterization of nanostructures which needs correspondence between the structure and the physical properties directly. In fact, this research has been promoted with respect to the junction between nano-scales or atomistic scales for a single metal. In the future, this method needs to be combined with chemical reaction engineering for single molecular device fabrication, such as catalysts, corrosion, and storage devices.
This work was partly supported by Grant-in-Aid for JSPS Fellows (10J01479).
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