Trapping and moving metal atoms with a six-leg molecule

Putting to work a molecule able to collect and carry adatoms in a controlled way on a surface is a solution for fabricating atomic structures atom by atom. Investigations have shown that the interaction of an organic molecule with the surface of a metal can induce surface reconstruction down to the atomic scale. In this way, well-defined nanostructures such as chains of adatoms, atomic trenches and metal-ligand compounds have been formed. Moreover, the progress in manipulation techniques induced by a scanning tunnelling microscope (STM) has opened up the possibility of studying artificially built molecular-metal atomic scale structures, and allowed the atom-by-atom doping of a single C(60) molecule by picking up K atoms. The present work goes a step further and combines STM manipulation techniques with the ability of a molecule to assemble an atomic nanostructure. We present a well-designed six-leg single hexa-t-butyl-hexaphenylbenzene (HB-HPB) molecule, which collects and carries up to six copper adatoms on a Cu(111) surface when manipulated with a STM tip. The 'HB-HPB-Cu atoms' complex can be further manipulated, bringing its Cu freight to a predetermined position on the surface where the metal atoms can finally be released.     

A reversible molecular switch based on pattern-change in chlorobenzene and toluene on a Si(111)-(7x7) surface

A reversible molecular switch is proposed, based on an observed change in a physisorbed pattern of chlorobenzene or toluene at Si(111)-(7x7), from "triangles" to "circles". Electronic excitation, at an applied surface voltage of Vs = -2.0 V, caused molecular migration, by one atomic site, from under the tip (switch "off"). Thereafter, the adsorbate pattern reverted thermally from circles to triangles (switch "on") across a measured activation barrier of Ea = 0.3 eV for chlorobenzene and 0.2 eV for toluene.     

Selective Supramolecular Fullerene-Porphyrin Interactions and Switching in Surface-Confined C(60)-Ce(TPP)(2) Dyads

The control of organic molecules, supramolecular complexes and donor-acceptor systems at interfaces is a key issue in the development of novel hybrid architectures for regulation of charge-carrier transport pathways in nanoelectronics or organic photovoltaics. However, at present little is known regarding the intricate features of stacked molecular nanostructures stabilized by noncovalent interactions. Here we explore at the single molecule level the geometry and electronic properties of model donor-acceptor dyads stabilized by van der Waals interactions on a single crystal Ag(111) support. Our combined scanning tunneling microscopy/spectroscopy (STM/STS) and first-principles computational modeling study reveals site-selective positioning of C(60) molecules on Ce(TPP)(2) porphyrin double-decker arrays with the fullerene centered on the π-system of the top bowl-shaped tetrapyrrole macrocycle. Three specific orientations of the C(60) cage in the van der Waals complex are identified that can be reversibly switched by STM manipulation protocols. Each configuration presents a distinct conductivity, which accounts for a tristable molecular switch and the tunability of the intradyad coupling. In addition, STS data evidence electronic decoupling of the hovering C(60) units from the metal substrate, a prerequisite for photophysical applications.     

Comparative study of adatom manipulation on several fcc metal surfaces

For a set of fcc metals, our total energy calculations based on many body potentials show that activation barriers for lateral manipulation of an adatom at a step edge depend on the tip/substrate composition. Of the six homogeneous systems studied, manipulation on stepped Ag(111) showed the lowest energy barrier for adatom hopping toward the tip, although the relative probability for this process was largest on Cu(111). For a representative Cu/Pt heterogeneous system, we find lateral manipulation of a Pt adatom along a step on Pt(111) by a Cu(100) tip to be energetically much less favorable than the reverse case of a Cu adatom manipulated by a Pt(100) tip. In the case of vertical manipulation, atomic relaxations of the tip and its neighboring atoms are found to be prominent and tip-induced changes in the bonding of the adatom to its low coordinated surroundings help explain the relative ease with which an adatom next to a step edge or a kink site may be pulled as compared to that on a flat surface.     

Long Jumps of an Organic Molecule Induced by Atomic Force Microscopy Manipulation

Non‐contact atomic force microscopy at cryogenic temperatures is used for the controlled lateral manipulation of individual 3,4,9,10‐perylene‐tetracarboxylicacid‐dianhydride (PTCDA) molecules on the Ag(111) surface. The molecules are moved along the [‐110] direction of the Ag lattice in the regime of repulsive tip‐molecule forces performing discrete jumps that span distances from single to multiple lattice spacings. The analysis of the two‐dimensional force field measured before and during the manipulation reveals that the displacement beyond nearest neighbor sites cannot be explained by long range tip‐molecule forces but instead has to involve an energy transfer to translational modes of the molecule. Combined with the results of the simultaneous measurement of the energy dissipation, these findings allow to identify a likely manipulation mechanism and provide insight into the process of energy transfer between excited large molecules and metal surfaces. Furthermore, implications for the theoretical treatment of NC‐AFM based molecule manipulation are discussed.     

Organizational Structure and Electronic Decoupling of Surface Bound Chiral Domains and Biomolecules

For the development of reagentless biological and chemical species detection at the single molecule level using external fields, including terahertz radiation, it is paramount to study model systems that uncover how intermolecular and molecule-surface interactions dictate monolayer ordering and electronic properties. This paper addresses two types of molecule-surface interactions and two distinct molecular systems, both of which impact our fundamental understanding of confined molecular domains and single molecule detection. We will first discuss the ordering and electronic characteristics of a chiral molecule, tartaric acid , weakly bound to an achiral metal surface, Ag(111), as studied with low temperature scanning tunneling microscopy (STM). This particular molecule-surface system contains many key elements, including hydrogen bonding interactions and stereochemical features, that would be common to other functional detection schemes. This paper will also treat the characterization of isolated, thiolated DNA molecules chemically bound to Au(111) terraces. Ambient STM and atomic force microscopy (AFM) measurements of both short and long DNA structures in both single and double strand configurations will be discussed with particular attention paid to imaging mechanisms involved. These results are particularly relevant to systems involving biomolecules anchored to inert metal surfaces, such as those used in external field-based assays.     

Interplay of adsorbate-adsorbate and adsorbate-substrate interactions in self-assembled molecular surface nanostructures

The adsorption of 2,6-naphthalenedicarboxylic acid (NDCA) molecules on the Ag(110), Cu(110), and Ag(111) surfaces at room temperature has been studied by means of scanning tunnelling microscopy (STM). Further supporting results were obtained using X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectroscopy (XAS). On the Ag(110) support, which had an average terrace width of only 15 nm, the NDCA molecules form extended one-dimensional (1-D) assemblies, which are oriented perpendicular to the step edges and have lengths of several hundred nanometres. This shows that the assemblies have a large tolerance to monatomic surface steps on the Ag(110) surface. The observed behaviour is explained in terms of strong intermolecular hydrogen bonding and a strong surface-mediated directionality, assisted by a sufficient degree of molecular backbone flexibility. In contrast, the same kind of step-edge crossing is not observed when the molecules are adsorbed on the isotropic Ag(111) or more reactive Cu(110) surfaces. On Ag(111), similar 1-D assemblies are formed to those on Ag(110), but they are oriented along the step edges. On Cu(110), the carboxylic groups of NDCA are deprotonated and form covalent bonds to the surface, a situation which is also achieved on Ag(110) by annealing to 200 °C. These results show that the formation of particular self-assembled molecular nanostructures depends significantly on a subtle balance between the adsorbate-adsorbate and adsorbate-substrate interactions and that kinetic factors play an important role.      

Nanogranular Fe-Cu-Ag thin films: structure, microstructure and giant magnetoresistance

Fe(x)Cu(y)Ag(z) granular thin films with several compositions were prepared by dc magnetron sputtering. These films consist of small Fe magnetic particles embedded in a nonmagnetic CuAg matrix. Structure, microstructure, morphology and magnetotransport properties were studied. The compositions of these samples were determined by energy-dispersive X-ray analysis. X-ray diffraction results showed strong Ag(111) peaks and broad Cu(111) peaks in all the samples. The variation of the (111) lattice spacings indicates a partial intermixing of Fe, Cu and Ag atoms. Microstructural studies using transmission electron microscopy (TEM) on a selected sample showed only Ag reflections and no reflection from Cu and Fe. Both XRD and TEM studies did not reveal any diffraction peak due to Fe and Cu for this sample. The fitting of the experimental grain size data obtained from TEM micrograph to the lognormal distribution function has allowed an estimation of the average grain diameter of 3.7 nm. The surface image of the Fe22Ag78 film observed using a scanning electron microscope showed the presence of droplet like Ag particles on the film surface. The Cu substitution results in smooth films without any Ag particles on the surface. Surface morphology by atomic force microscopy shows that the Fe39Cu13Ag48 film has a surface roughness of 0.75 nm. Finally, we have obtained a maximum giant magnetoresistance ratio of 3.2% in these films measured at 300 K for an in-plane magnetic field of 20 kOe.     

Growth of oriented Ag nanocrystals on air-oxidized Si surfaces: An in-situ reflection high energy electron diffraction study

Growth of Ag nanoislands on air-oxidized Si(001), (111) and (110) surfaces has been investigated by reflection high energy electron diffraction (RHEED), scanning tunneling microscopy (STM) and cross-sectional transmission electron microscopy. We have shown that the oriented nanocrystalline Ag, similar to the epitaxial growth of Ag on clean Si surfaces, can be grown on oxide-covered Si surfaces. A thin oxide layer (~ 2-3 nm thick) is formed on ultra-high vacuum (UHV)-cleaned Si surfaces via exposure of the clean reconstructed surface to air. Deposition of Ag was carried out under UHV at different substrate temperatures and monitored by RHEED. RHEED results reveal that Ag deposition at room temperature leads to the growth of randomly oriented Ag islands while, in spite of the presence of the oxide layer between Ag islands and Si, preferred orientations with an epitaxial relationship with the substrate evolve when Ag is deposited at higher substrate temperatures. STM images of the oxidized surfaces, prior to Ag deposition, apparently do not show any order. However, Fourier transforms of STM images show the presence of a short range order on the oxidized surface following the unit cells of the underlying reconstructed Si surface. It is intriguing that Ag nanoislands follow an epitaxial orientational relationship with the substrate in spite of the presence of a 2-3 nm thick oxide layer between Ag and Si. Apparently, the short range order existing on the oxide surface influences the orientation of the Ag nanoislands.     

Implementation of atomically defined field ion microscopy tips in scanning probe microscopy

The field ion microscope (FIM) can be used to characterize the atomic configuration of the apices of sharp tips. These tips are well suited for scanning probe microscope (SPM) use since they predetermine the SPM resolution and the electronic structure for spectroscopy. A protocol is proposed for preserving the atomic structure of the tip apex from etching due to gas impurities during the period of transfer from the FIM to the SPM, and estimations are made regarding the time limitations of such an experiment due to contamination with ultra-high vacuum rest gases. While avoiding any current setpoint overshoot to preserve the tip integrity, we present results from approaches of atomically defined tungsten tips to the tunneling regime with Au(111), HOPG (highly oriented pyrolytic graphite) and Si(111) surfaces at room temperature. We conclude from these experiments that adatom mobility and physisorbed gas on the sample surface limit the choice of surfaces for which the tip integrity is preserved in tunneling experiments at room temperature. The atomic structure of FIM tip apices is unchanged only after tunneling to the highly reactive Si(111) surface.     

Creating pseudo-Kondo resonances by field-induced diffusion of atomic hydrogen

In low-temperature scanning tunneling microscopy (STM) experiments a cerium adatom on Ag(100) possesses two discrete states with significantly different apparent heights. These atomic switches also exhibit a Kondo-like feature in spectroscopy experiments. By extensive theoretical simulations we find that this behavior is due to diffusion of hydrogen from the surface onto the Ce adatom in the presence of the STM tip field. The cerium adatom possesses vibrational modes of very low energy (3-4?meV) and very high efficiency (≥20%), which are due to the large changes of Ce states in the presence of hydrogen. The atomic vibrations lead to a Kondo-like feature at very low bias voltages.     

In-situ examination of the selective etching of an alkanethiol monolayer covered Au{111} surface

An examination of the selective etching mechanism of a 1-alkanethiol self-assembled monolayer (SAM) covered Au{111} surface using in-situ atomic force microscopy (AFM) and molecular resolution scanning tunnelling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au{111} surface and typically contains nanoscale non-uniformities such as pinholes, domain boundaries and monatomic depressions. During etching in a ferri/ferrocyanide water-based etchant, selective and preferential etching occurs at SAM covered Au(111) terrace and step edges where a lower SAM packing density is observed, resulting in triangular islands being relieved. The triangular islands are commensurate with the Au(111) lattice with their long edges parallel to its [11¯0] direction. Thus, SAM etching is selective and preferential attack is localized to defects and step edges at sites of high molecular density contrast.     

Zinc porphyrin-driven assembly of gold nanofingers

Nanofingers of gold covered by porphyrins are prepared by a combination of atomic manipulation and surface self-organization. A submonolayer of zinc(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin (ZnTBPP) axially ligated to a self-assembled monolayer of 4-aminothiophenol (4-ATP) on Au(111) is prepared and studied using a combination of ultrahigh vacuum techniques. Under the electric field produced by the STM tip, the relatively weakly bound Au surface atoms along the discommensuration lines become mobile due to the strong bond to 4-ATP, while the tendency of the porphyrins towards self-assembly result in a collective motion of gold clusters. The clusters diffuse onto the surface following well-defined pathways along the [112] direction and then reach the step edges where they assembled, thus forming nanofingers. First-principles density functional theory calculations demonstrate the reduction of the binding energies between the surface gold clusters and the substrate induced by adsorption of thiols. Scanning tunneling microscopy images show assemblies across three adjacent discommensuration lines of the Au(111)-(22 x square root 3) reconstruction, which collectively diffuse along these lines to form islands nucleated at step edges.     

Highly resolved non-contact atomic force microscopy images of the Sn/Si(111)-([Formula: see text]) surface

The Sn/Si(111)-([Formula: see text]) surface is observed by using non-contact atomic force microscopy (NC-AFM) at room temperature. The images at relatively far tip-surface distances show four protrusions in each ([Formula: see text]) unit cell, which are similar to previously reported scanning tunnelling microscopy (STM) images. On the other hand, it is found that, at closer tip-surface distances, eight protrusions are clearly resolved, which indicates that the spatial resolution of NC-AFM is higher than that of STM as far as imaging this surface is concerned. Our high-resolution NC-AFM images are in good agreement with a recently proposed model based on 13 Sn atoms per unit cell.     

Structure, microstructure, and giant magnetoresistance in nanogranular FeAgNi thin films

Structural, microstructural, and magnetoresistive properties of metallic Fe(x)Ag(y)Ni(z) granular thin films were studied. These films with several compositions were prepared by dc magnetron sputtering. X-ray diffraction (XRD) measurements carried out on the samples show only Ag(111) peaks. The d-spacings determined from the Ag(111) peaks are smaller than the standard value for bulk Ag indicating a partial intermixing of Fe and Ni atoms in Ag. The diffraction pattern obtained using Transmission electron microscope (TEM) shows a number of Ag rings. Both XRD and TEM studies did not reveal any diffraction peaks due to Fe or Ni. The average particle size determined from the TEM micrograph is 5.5 nm whereas that determined from the XRD patterns is always higher. The magnetoresistance ratio for all the samples lies in the range 3 to 4.3%, except for a sample.     

Direct observation of X-ray induced atomic motion using scanning tunneling microscope combined with synchrotron radiation

X-ray induced atomic motion on a Ge(111)-c(2 x 8) clean surface at room temperature was directly observed with atomic resolution using a synchrotron radiation (SR)-based scanning tunneling microscope (STM) system under ultra high vacuum condition. The atomic motion was visualized as a tracking image by developing a method to merge the STM images before and after X-ray irradiation. Using the tracking image, the atomic mobility was found to be strongly affected by defects on the surface, but was not dependent on the incident X-ray energy, although it was clearly dependent on the photon density. The atomic motion can be attributed to surface diffusion, which might not be due to core-excitation accompanied with electronic transition, but a thermal effect by X-ray irradiation. The crystal surface structure was possible to break even at a lower photon density than the conventionally known barrier. These results can alert X-ray studies in the near future about sample damage during measurements, while suggesting the possibility of new applications. Also the obtained results show a new availability of the in-situ SR-STM system.     

Mn atomic layers under inert covers of graphene and hexagonal boron nitride prepared on Rh(111)

Intercalation of metal atoms into the interface of graphene and its supporting substrate has become an intriguing topic for the sake of weakening the interface coupling and constructing metal atomic layers under inert covers. However, this novel behavior has rarely been reported on the analogous hexagonal boron nitride (h-BN) synthesized on metal substrates. Here, we describe a comparative study of Mn intercalation into the interfaces of graphene/Rh(111) and h-BN/Rh(111), by using atomically-resolved scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The intercalation was performed by annealing as-deposited Mn clusters, and the starting temperature of Mn intercalation into h-BN/Rh(111) was found to be ～80 °C higher than that for graphene/Rh(111). Moreover, the intercalated islands of h-BN/Mn/Rh(111) usually possess more irregular shapes than those of graphene/Mn/Rh(111), as illustrated by temperature-dependent STM observations. All these experimental facts suggest a stronger interaction of Mn with h-BN/Rh(111) than that with graphene/Rh(111).      

Adsorption, manipulation and self-assembling of TBrPP-Co molecules on a Ag/Si(111) surface by scanning tunnelling microscopy

Individual adsorption and two-dimensional assembling of 5,10,15,20-tetrakis-(4-bromophenyl)-porphyrin-Co (TBrPP-Co) molecules on a Si(111)-[Formula: see text] Ag reconstructed surface have been studied using low-temperature scanning tunnelling microscopy (STM). All the isolated molecules are observed in a planar shape with slight distortion. The isolated molecules can be controllably rotated with an STM tip to the orientation along the trigonal lattice ([Formula: see text] direction) of the substrate. With an increased coverage (0.07?ML) and appropriate annealing, the molecules assemble to form three types of ordered phase. The long-range ordered structures, however, disappear at higher coverage (0.75?ML).     

Manipulations of atoms and molecules by scanning probe microscopy

Scanning probe microscopy (SPM), including scanning tunneling microscopy (STM) and atomic force microscopy (AFM), has become a powerful tool in building nanoscale structures required by modern industry. In this article, the use of SPM for the manipulation of atoms and molecules for patterning nanostructures for opt-electronic and biomedical applications is reviewed. The principles and procedures of manipulation using STM and AFM-based technologies are presented with an emphasis on their ability to create a wide variety of nanostructures for different applications. The interaction among the atoms/molecules, surface, and tip are discussed. The approaches for positioning the atom/molecule from and to the desired locations and for precisely controlling its movement are elaborated for each specific manipulation technique. As an AFM-based technique, the dip-pen nanolithography is also included. Finally, concluding remarks on technological improvement and future research is provided.     

Tip-state control of rates and branching ratios in atomic manipulation

We report the atomic manipulation properties of two distinct, stable, and reproducible states of a scanning tunneling microscope tip applied to chlorobenzene/Si(111)-(7x7). We show that the tip state influences the rates of (current-driven) molecular desorption and C-Cl dissociation as well as the branching ratio between these processes, but does not change the mediating electronic channel or the required number of electrons. These manipulation properties combined with the imaging properties of the two tip-states suggest the major difference between tip-states is their coupling efficiency to the pi-states of the chlorobenzene molecule.