True atomic resolution by atomic force microscopy through repulsive and attractive forces

The (1014) cleavage plane of calcite has been investigated by atomic force microscopy in water at room temperature. True lateral atomic-scale resolution was achieved; the atomic-scale periodicities as well as the expected relative positions of the atoms within each unit cell were obtained. Along monoatomic step lines, atomic-scale kinks, representing point-like defects, were resolved. Attractive forces on the order of 10(-11) newton acting between single atomic sites on the sample and the front atoms of the tip were directly measured and provided the highest, most reliable resolution on a flat, well-ordered surface.     

Field-Induced Nanometer- to Atomic-Scale Manipulation of Silicon Surfaces with the STM

The controlled manipulation of silicon at the nanometer scale will facilitate the fabrication of new types of electronic devices. The scanning tunneling microscope (STM) can be used to manipulate strongly bound silicon atoms or clusters at room temperature. Specifically, by using a combination of electrostatic and chemical forces, surface atoms can be removed and deposited on the STM tip. The tip can then move to a predetermined surface site, and the atom or cluster can be redeposited. The magnitude of such forces and the amount of material removed can be controlled by applying voltage pulses at different tip-surface separations.     

Dissociation of individual molecules with electrons from the tip of a scanning tunneling microscope

The scanning tunneling microscope (STM) can be used to select a particular adsorbed molecule, probe its electronic structure, dissociate the molecule by using electrons from the STM tip, and then examine the dissociation products. These capabilities are demonstrated for decaborane(14) (B(10)H(14)) molecules adsorbed on a silicon(111)-(7 x 7) surface. In addition to basic studies, such selective dissociation processes can be used in a variety of applications to control surface chemistry on the molecular scale.     

An atomic seesaw switch formed by tilted asymmetric Sn-Ge dimers on a Ge (001) surface

When tin (Sn) atoms are deposited on a clean germanium (Ge) (001) surface at room temperature, buckled dimers originating from the Sn atoms are formed at the Ge-dimer position. We identified the dimer as a heterogeneous Sn-Ge dimer by reversing its buckling orientation with a scanning tunneling microscope (STM) at 80 kelvin. An atomic seesaw switch was formed for one-dimensional electronic conduction in the Ge dimer-row direction by using the STM to reversibly flip the buckling orientation of the Sn-Ge dimer and to set up standing-wave states.     

Manipulation of the Reconstruction of the Au(111) Surface with the STM

Modification of the reconstruction of an Au(111) surface with a scanning tunneling microscope (STM) is demonstrated. This modification is accomplished by transferring a number of surface atoms to the STM tip to generate a surface multivacancy (hole), which modifies the stress distribution at the surface. The structural changes that follow the tip-induced surface perturbation are imaged in a time-resolved manner. The structural modification is the result of both short-range interactions, which lead to local atomic relaxation, and long-range elastic interactions, which produce large-scale rearrangements.     

Dimer preparation that mimics the transition state for the adsorption of H2 on the Si(100)-2 x 1 surface

A chemically induced dimer configuration was prepared on the silicon (Si) (100) surface and was characterized by scanning tunneling microscopy (STM) and spectroscopy (STS). These prepared dimers, which are essentially untilted and differ both electronically and structurally from the dynamically tilting dimers normally found on this surface, are more reactive than normal dimers. For molecular hydrogen (H2) adsorption, the enhancement is about 10(9) at room temperature. There is no appreciable barrier for the H2 reaction at prepared sites, indicating the prepared configuration closely approximates the actual dimer structure in the transition state. This previously unknown ability to prepare specific surface configurations has important implications for understanding and controlling reaction dynamics on semiconductor surfaces.     

Manipulating Chlorine Atom Bonding on the Si(100)-(2 x 1) Surface with the STM

Chlorine atoms strongly chemisorbed at dangling bond sites on the Si(100)-(2 x 1) surface are observed by scanning tunneling microscopy (STM) to hop between adjacent sites. The origin of this behavior is suggested to be an interaction between the field of the probe tip and the dipole moment of the silicon-chlorine bond. Chlorine atom migration is shown to be facilitated by the presence of a metastable chlorine bridge-bonded minimum. The STM probe was used to excite single chlorine atoms into this bridging configuration, resulting in a local population inversion. Selective application of voltage pulses between the probe tip and the surface rearranged the local bonding and induced transformations between different types of chlorine sites. In this manner, adsorbed species can be dissected and their composition and structure directly probed.     

Atomic-scale coupling of photons to single-molecule junctions

Spatial resolution at the atomic scale has been achieved in the coupling of light to single molecules adsorbed on a surface. Electron transfer to a single molecule induced by green to near-infrared light in the junction of a scanning tunneling microscope (STM) exhibited spatially varying probability that is confined within the molecule. The mechanism involves photo-induced resonant tunneling in which a photoexcited electron in the STM tip is transferred to the molecule. The coupling of photons to the tunneling process provides a pathway to explore molecular dynamics with the combined capabilities of lasers and the STM.     

利用下端腐蚀法制备纳米级STM探针

在深入分析电化学腐蚀原理的基础上,发现了一种提高针尖的尖锐程度的新方法,即:利用下端腐蚀方法得到了比传统的上端腐蚀方法更尖锐的针尖.通过对腐蚀电压、腐蚀溶液浓度、切断时间的研究和分析,总结出下端腐蚀法制备纳米级STM探针的最佳综合条件;并通过对前人方案的修改和完善,研制了一套自动控制切断电路装置,该电路装置可以任意设置切断条件,以此得到不同粗细的针尖;最后将据此制作的纳米级针尖成功地应用于Unisoku-STM仪器的扫描,得到了清晰、稳定的原子级分辨Bi(0001)图像.     

Atomistic mechanisms and dynamics of adhesion, nanoindentation, and fracture

Molecular dynamics simulations and atomic force microscopy are used to investigate the atomistic mechanisms of adhesion, contact formation, nanoindentation, separation, and fracture that occur when a nickel tip interacts with a gold surface. The theoretically predicted and experimentally measured hysteresis in the force versus tip-to-sample distance relationship, found upon approach and subsequent separation of the tip from the sample, is related to inelastic deformation of the sample surface characterized by adhesion of gold atoms to the nickel tip and formation of a connective neck of atoms. At small tipsample distances, mechanical instability causes the tip and surface to jump-to-contact, which in turn leads to adhesion-induced wetting of the nickel tip by gold atoms. Subsequent indentation of the substrate results in the onset of plastic deformation of the gold surface. The atomic-scale mechanisms underlying the formation and elongation of a connective neck, which forms upon separation, consist of structural transformations involving elastic and yielding stages.     

Quantitative measurement of short-range chemical bonding forces

We report direct force measurements of the formation of a chemical bond. The experiments were performed using a low-temperature atomic force microscope, a silicon tip, and a silicon (111) 7x7 surface. The measured site-dependent attractive short-range force, which attains a maximum value of 2.1 nanonewtons, is in good agreement with first-principles calculations of an incipient covalent bond in an analogous model system. The resolution was sufficient to distinguish differences in the interaction potential between inequivalent adatoms, demonstrating the ability of atomic force microscopy to provide quantitative, atomic-scale information on surface chemical reactivity.     

Single-bond formation and characterization with a scanning tunneling microscope

A scanning tunneling microscope (STM) was used to manipulate the bonding of a carbon monoxide (CO) molecule and to analyze the structure and vibrational properties of individual products. Individual iron (Fe) atoms were evaporated and coadsorbed with CO molecules on a silver (110) surface at 13 kelvin. A CO molecule was transferred from the surface to the STM tip and bonded with an Fe atom to form Fe(CO). A second CO molecule was similarly transferred and bonded with Fe(CO) to form Fe(CO)(2). Controlled bond formation and characterization at the single-bond level probe chemistry at the spatial limit.     

Confinement of electrons to quantum corrals on a metal surface

A method for confining electrons to artificial structures at the nanometer lengthscale is presented. Surface state electrons on a copper(111) surface were confined to closed structures (corrals) defined by barriers built from iron adatoms. The barriers were assembled by individually positioning iron adatoms with the tip of a 4-kelvin scanning tunneling microscope (STM). A circular corral of radius 71.3 A was constructed in this way out of 48 iron adatoms. Tunneling spectroscopy performed inside of the corral revealed a series of discrete resonances, providing evidence for size quantization. STM images show that the corral's interior local density of states is dominated by the eigenstate density expected for an electron trapped in a round two-dimensional box.     

Negative differential resistance on the atomic scale: implications for atomic scale devices

Negative differential resistance (NDR) is the essential property that allows fast switching in certain types of electronic devices. With scanning tunneling microscopy (STM) and scanning tunneling spectroscopy, it is shown that the current-voltage characteristics of a diode configuration consisting of an STM tip over specific sites of a boron-exposed silicon(111) surface exhibit NDR. These NDR-active sites are of atomic dimensions ( approximately 1 nanometer). NDR in this case is the result of tunneling through localized, atomic-like states. Thus, desirable device characteristics can be obtained even on the atomic scale.     

Controlling the charge state of individual gold adatoms

The nature and control of individual metal atoms on insulators are of great importance in emerging atomic-scale technologies. Individual gold atoms on an ultrathin insulating sodium chloride film supported by a copper surface exhibit two different charge states, which are stabilized by the large ionic polarizability of the film. The charge state and associated physical and chemical properties such as diffusion can be controlled by adding or removing a single electron to or from the adatom with a scanning tunneling microscope tip. The simple physical mechanism behind the charge bistability in this case suggests that this is a common phenomenon for adsorbates on polar insulating films.     

Photon emission at molecular resolution induced by a scanning tunneling microscope

The tip-surface region of a scanning tunneling microscope (STM) emits light when the energy of the tunneling electrons is sufficient to excite luminescent processes. These processes provide access to dynamic aspects of the local electronic structure that are not directly amenable to conventional STM experiments. From monolayer films of carbon-60 fullerenes on gold(110) surfaces, intense emission is observed when the STM tip is placed above an individual molecule. The diameter of this emission spot associated with carbon-60 is approximately 4 angstroms. These results demonstrate the highest spatial resolution of light emission to date with a scanning probe technique.     

Inducing and viewing the rotational motion of a single molecule

Tunneling electrons from the tip of a scanning tunneling microscope were used to induce and monitor the reversible rotation of single molecules of molecular oxygen among three equivalent orientations on the platinum(111) surface. Detailed studies of the rotation rates indicate a crossover from a single-electron process to a multielectron process below a threshold tunneling voltage. Values for the energy barrier to rotation and the vibrational relaxation rate of the molecule were obtained by comparing the experimental data with a theoretical model. The ability to induce the controlled motion of single molecules enhances our understanding of basic chemical processes on surfaces and may lead to useful single-molecule devices.     

Electromechanical properties of graphene drumheads

We determined the electromechanical properties of a suspended graphene layer by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) measurements, as well as computational simulations of the graphene-membrane mechanics and morphology. A graphene membrane was continuously deformed by controlling the competing interactions with a STM probe tip and the electric field from a back-gate electrode. The probe tip-induced deformation created a localized strain field in the graphene lattice. STS measurements on the deformed suspended graphene display an electronic spectrum completely different from that of graphene supported by a substrate. The spectrum indicates the formation of a spatially confined quantum dot, in agreement with recent predictions of confinement by strain-induced pseudomagnetic fields.     

Chemistry. How to assemble a molecular junction

Junctions between metals and molecules play an important role in molecular electronics. Advances in this field are hampered by the lack of understanding of the electronic structure of organic-metal interfaces. In his Perspective, Kummel highlights the report by Nazin et al. (3), who have used scanning tunneling microscopy (STM) to assemble a metal-molecule-metal junction. Subsequently, they employed the STM tip to probe the atomic structure and local electronic properties of the metal-molecule interface in unprecedented detail. They find evidence for strong coupling between the molecular and metal states. Such coupling affects the conductivity of metal-molecule-metal junctions.     

Vibrationally resolved fluorescence excited with submolecular precision

Tunneling electrons from a scanning tunneling microscope (STM) were used to excite photon emission from individual porphyrin molecules adsorbed on an ultrathin alumina film grown on a NiAl(110) surface. Vibrational features were observed in the light-emission spectra that depended sensitively on the different molecular conformations and corresponding electronic states obtained by scanning tunneling spectroscopy. The high spatial resolution of the STM enabled the demonstration of variations in light-emission spectra from different parts of the molecule. These experiments realize the feasibility of fluorescence spectroscopy with the STM and enable the integration of optical spectroscopy with a nanoprobe for the investigation of single molecules.