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.     

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.     

Visualization of the molecular Jahn-Teller effect in an insulating K4C60 monolayer

We present a low-temperature scanning tunneling microscopy (STM) study of K(x)C60 monolayers on Au(111) for 3 < or = x < or = 4. The STM spectrum evolves from one that is characteristic of a metal at x = 3 to one that is characteristic of an insulator at x = 4. This electronic transition is accompanied by a dramatic structural rearrangement of the C60 molecules. The Jahn-Teller effect, a charge-induced mechanical deformation of molecular structure, is directly visualized in the K4C60 monolayer at the single-molecule level. These results, along with theoretical analyses, provide strong evidence that the transition from metal to insulator in K(x)C60 monolayers is caused by the Jahn-Teller effect.     

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.     

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.     

Graphite: a mimic for DNA and other biomolecules in scanning tunneling microscope studies

Highly ordered pyrolytic graphite (HOPG) is the substrate often used in scanning tunneling microscope (STM) studies of biomolecules such as DNA. All of the images presented in this article are of freshly cleaved HOPG surfaces upon which no deposition has occurred. These images illustrate features previously thought to be due to biological molecules, such as periodicity and meandering of "molecules" over steps. These features can no longer be used to distinguish real molecules from features of the native substrate. The feasibility of the continued use of HOPG as a substrate for biological STM studies is discussed.     

Scanning tunneling microscopy of recA-DNA complexes coated with a conducting film

A link between scanning tunneling microscopy (STM) and conventional transmission electron microscopy has been established for biological material by applying STM on freeze-dried recA-DNA complexes coated with a conducting film. The topography of the complexes observed by means of STM revealed a right-handed single helix composed of about six recA monomers per helical turn.     

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.     

In situ scanning tunneling microscopy of corrosion of silver-gold alloys

An in situ scanning tunneling microscope (STM) was used to observe the morphological changes accompanying the selective dissolution of Ag from low-Ag content Ag-Au alloys in dilute perchloric acid. This study was undertaken to explore the role of surface diffusion in alloy corrosion processes. These results are interpreted within the framework of the kink-ledge-terrace model of a crystal surface and a recent model of alloy corrosion based on a variant of percolation theory. The corrosion process leads to roughening of the surface by dissolution of Ag atoms from terrace sites. Annealing or smoothening of the surface occurs by vacancy migration through clusters and the subsequent annihilation of clusters at terrace ledges.     

Creating favorable geometries for directing organic photoreactions in alkanethiolate monolayers

The products of photoreactions of conjugated organic molecules may be allowed by selection rules but not observed in solution reactions because of unfavorable reaction geometries. We have used defect sites in self-assembled alkanethiolate monolayers on gold surfaces to direct geometrically unfavorable photochemical reactions between individual organic molecules. High conductivity and stochastic switching of anthracene-terminated phenylethynylthiolates within alkanethiolate monolayers, as well as in situ photochemical transformations, have been observed and distinguished with the scanning tunneling microscope (STM). Ultraviolet light absorbed during imaging increases the apparent heights of excited molecules in STM images, a direct manifestation of probing electronically excited states.     

Identification of the products from the reaction of chlorine with the silicon(111)-(7x7) surface

The various products from the reaction of chlorine (Cl) with the adatom layer of the Si(111)-(7x7) surface have been identified with scanning tunneling microscopy (STM). Initially, a single Cl atom reacts with the adatom dangling bond. At higher surface coverage, additional Cl atoms insert themselves into the Si-Si backbonds between the adatom and rest-atom layers, producing adatoms that have reacted with two or three Cl atoms. These products are characterized by different registries with respect to the underlying rest layer and appear in STM images as adatoms of different sizes, consistent with the breaking of Si-Si backbonds and the formation ofnew Si-Cl bonds.     

Reversible rotation of antimony dimers on the silicon (001) surface with a scanning tunneling microscope

The scanning tunneling microscope (STM) was used to control the configuration of antimony clusters on the (001) surface of silicon. In particular, the STM tip induced a reversible rotation between two orthogonal orientations of individual antimony dimers on the surface. This simple rotation can be explained by an atomic-scale torque exerted on the antimony dimers by the STM tip. The reversibility of this process could provide a basis for making atomic-scale memory cells.     

Molecular structure of DNA by scanning tunneling microscopy

Uncoated DNA molecules marked with an activated tris(l-aziridinyl) phosphine oxide (TAPO) solution were deposited on gold substrates and imaged in air with the use of a high-resolution scanning tunneling microscope (STM). Constant-current and gap-modulated STM images show clear evidence of the helicity of the DNA structure: pitch periodicity ranges from 25 to 35 angstroms, whereas the average diameter is 20 angstroms. Molecular structure within a single helix turn was also observed.     

Structural and Electronic Role of Lead in (PbBi)2Sr2CaCu2O8 Superconductors by STM

The structural and electronic effects of lead substitution in the high-temperature superconducting materials Pb(x)Bi(2-x)Sr(2)CaCu(2)O(8) have been characterized by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Large-area STM images of the Bi(Pb)-O layers show that lead substitution distorts and disorders the one-dimensional superlattice found in these materials. Atomic-resolution images indicate that extra oxygen atoms are present in the Bi(Pb)-O layers. STS data show that the electronic structure of the Bi(Pb)-O layers is insensitive to lead substitution within +/-0.5 electron volt of the Fermi level; however, a systematic decrease in the density of states is observed at approximately 1 electron volt above the Fermi level. Because the superconducting transition temperatures are independent of x(Pb) (x 相似文献   

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.     

Scanning tunneling microscopy of freeze-fracture replicas of biomembranes

The high resolution of the scanning tunneling microscope (STM) makes it a potentially important tool for the study of biomaterials. Biological materials can be imaged with the STM by a procedure in which fluid, nonconductive biomaterials are replaced by rigid and highly conductive freeze-fracture replicas. The three-dimensional contours of the ripple phase of dimyristoylphosphatidylcholine bilayers were imaged with unprecedented resolution with commercial STMs and standard freeze-fracture techniques. Details of the ripple amplitude, asymmetry, and configuration unobtainable by electron microscopy or x-ray diffraction can be observed relatively easily with the STM.     

Scanning tunneling microscopy of electrodeposited ceramic superlattices

Cleaved cross sections of nanometer-scale ceramic superlattices fabricated from materials of the lead-thallium-oxygen system were imaged in the scanning tunneling microscope (STM). The apparent height differences between the layers were attributed to composition-dependent variations in local electrical properties. For a typical superlattice, the measured modulation wavelength was 10.6 nanometers by STM and 10.8 nanometers by x-ray diffraction. The apparent height profile for potentiostatically deposited superlattices was more square than that for galvanostatically deposited samples. These results suggest that the composition follows the applied potential more closely than it follows the applied current. The x-ray diffraction pattern of a superlattice produced under potential control had satellites out to the fourth order around the (420) Bragg reflection.     

Rectification of STM Current to Graphite Covered with Phthalocyanine Molecules

The scanning tunneling microscope (STM) can be used to measure current-voltage characteristics on an atomic scale. The attachment of copper phthalocyanine molecules, in contrast to a variety of other molecules, to graphite changes the electrical characteristics of the STM from relatively symmetric to highly asymmetric or rectifying. Evidence is presented to show that the asymmetry arises because of the electronic energy levels of the copper phthalocyanine. The organic molecules were bonded to the graphite by an acid-base reaction that may have wide applicability.     

Infrared Reflection-Absorption Spectroscopy and STM Studies of Model Silica-Supported Copper Catalysts

The structure of model silica-supported copper catalysts has been investigated with scanning tunneling microscopy (STM) and infrared reflection-absorption spectroscopy (IRAS). The IRAS studies of CO on the model silica-supported copper catalysts indicate that there are several types of copper clusters with surface structures similar to (111), (110), and other high-index planes of single-crystal copper. The STM studies show several types of copper clusters on silica and reveal images of metal clusters on an amorphous oxide support with atomic resolution.     

Water-mediated proton hopping on an iron oxide surface

The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H(3)O(+)-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO(2)(110), where water dissociation is a key step in proton diffusion.