Reliable lateral and vertical manipulations of a single Cu adatom on a Cu(111) surface with multi-atom apex tip: semiempirical and first-principles simulations

We study the reliability of the lateral manipulation of a single Cu adatom on a Cu(111) surface with single-atom, dimer and trimer apex tips using both semiempirical and first-principles simulations. The dependence of the manipulation reliability on tip height is investigated. For the single-atom apex tip the manipulation reliability increases monotonically with decreasing tip height. For the dimer and trimer apex tips the manipulation reliability is greatly improved compared to that for the single-atom apex tip over a certain tip-height range. Two kinds of mechanism are found responsible for this improvement. One is the so-called enhanced interaction mechanism in which the lateral tip-adatom interaction in the manipulation direction is improved. The other is the suspended atom mechanism in which the relative lateral trapping ability of the tip is improved due to the strong vertical attraction of the tip on the adatom. Both mechanisms occur in the manipulations with the trimer apex tip, while in those with the dimer apex tip only the former is effective. Moreover, we present a method to realize reversible vertical manipulation of a single atom on a Cu(111) surface with the trimer apex tip, based on its strong vertical and lateral attraction on the adatom.     

Surface self-diffusion of adatom on Pt cluster with truncated octahedron structure

Surface diffusion of single Pt adatom on Pt cluster with truncated octahedron structure is investigated through a combination of molecular dynamics and nudged elastic band method. Using an embedded atom method to describe the atomic interactions, the minimum energy paths are determined and the energy barriers for adatom diffusion across and along step are evaluated. The diffusion of adatom crossing step edge between {111} and {100} facets has a surprisingly low barrier of 0.03 eV, which is 0.12 eV lower than the barrier for adatom diffusion from {111} to neighboring {111} facet. Owing to the small barrier of adatom diffusion across the step edge between {111} and {100} facets, the diffusion of adatom along the step edge cannot occur. The molecular dynamics simulations at low temperatures also support these results. Our results show that mass transport will prefer step with {100} microfacet and the Pt clusters can have only {111} facets in epitaxial growth.     

Equilibrium structures and shapes of clusters on metal fcc(111) surfaces

Using embedded-atom-method potentials, the lower-energy structures (LESs) of adatom clusters are obtained directly on a series of metal fcc(111) surfaces by the method based on the genetic algorithm. The structural features, energy distributions, number of LESs and their differences on different surfaces are discussed and explained in terms of the nearest-neighbor and next-nearest-neighbor (NN, NNN) adatom-adatom interactions, and the edge-type difference. When the energetic preference for one edge type over another is slight, e.g., on Ag(111), only one type of structure is included, and it does not change with the increment of cluster size. However, when there is a strong energetic preference for one of the edge types, e.g., on Pt(111), an interesting phenomenon of structure replacement is revealed, by which the structures in the LES group deviate more and more from the configuration with the maximum number of NN bonds as the cluster size increases. The structure replacement also finally leads to the shape of the two-dimensional island on Pt(111) being quite distinct from that on Ag(111). Based on these results, the general trend of the variation of lower-energy structures with cluster size is discussed further for other metal fcc(111) surfaces.     

Co nanoislands on Au(111) and Cu(111) surfaces studied by scanning tunneling microscopy and spectroscopy

Co nanoislands on the Au(111) and Cu(111) surfaces have been studied by scanning tunneling microscopy and spectroscopy. The experimental results showed that Co nanoislands prefer to aggregate at the step edge and dislocation sites on the reconstructed Au(111) surface and at the step edge on the Cu(111) surface, respectively. In addition, based on dZ/dV-V spectra, in both the Co/Au(111) and the Co/Cu(111) systems, Gundlach oscillation was observed. From the peak shift of dZ/dV-V spectra between Co nanoisland and substrate surface, we can quantitatively obtain that the constant energy separation is -0.13 +/- 0.01 eV for the Co/Au(111) system, and 0.41 +/- 0.02 eV for the Co/Cu(111) system, respectively. These values indicate the work function difference between Co nanoisland and these surfaces.     

Ab initio studies of single-height Si(001) steps

We have studied the Si(001) surface with single-height steps by ab initio molecular dynamics simulations. Surface dimers were found to be unstable with respect to buckling for all geometries considered. However, the ground state reconstruction depends on the type of step. For the SA step, the c(2 × 4) geometry is induced by the step edge, while, for the SB step, the p(2 × 2) reconstruction is more stable. The binding sites and diffusion barriers for a single Si adatom were investigated via the adiabatic trajectory method. In agreement with other studies of the flat surface, fast diffusion takes place along the dimer rows. The local changes to buckling induced by the adatom are sizable and lead to changes in the activation barriers for diffusion, in particular for the path perpendicular to the dimer rows. We also investigated the diffusion of the adatom over the rebonded SB step. The calculations show that there is no additional barrier for the arrival of the adatom at the edge from the upper terrace, while a barrier of at least 1 eV exists for the arrival of the adatom from the lower edge. In step flow growth involving the rebonded SB step, most of the adatoms will thus arrive from the upper terrace.     

Atom manipulation with the STM: nanostructuring,tip functionalization,and femtochemistry

We briefly survey our recent studies on the soft lateral manipulation of atoms and small molecules with the scanning tunneling microscope (STM), whereby mainly the tip–surface forces are employed. Repulsive (pushing) as well as discontinuous (pulling) and continuous (sliding) attractive manipulation modes could be distinguished on Cu(2 1 1) for CO molecules and metal atoms, respectively. In the case of pulling of Cu atoms on Cu(1 1 1) even finer details could be discerned: the adparticle may show various movement patterns visiting different surface sites upon applying different tip forces. Lateral manipulation also allows modifications of the Cu(2 1 1) substrate itself in an atom-by-atom manner by releasing atoms from six-fold coordinated kink sites and even seven-fold coordinated regular step sites. Furthermore, investigations concerning controlled vertical manipulation with emphasis on picking up single CO molecules are reported. The mechanism behind vertical transfer of CO molecules relates to ultrafast chemical processes. Vertical manipulation implies besides extending the possibilities for the build-up of nanostructures the important possibility of creating structurally and compositionally well defined tips, which may eventually lead to chemical sensitivity with the STM.     

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.     

Vibrational coupling as a probe of adsorption at different structural sites on a stepped single-crystal electrode

Adsorption of carbon monoxide at step and terrace sites on a Pt(557) ≡ Pt(s)-[6(111) × (100)] electrode was detected with infrared spectroscopy. Vibrational coupling between adsorbates provided insights into the assembly of molecules at the different structural sites. The intermolecular coupling was weak at low coverages as CO ordered along the steps. For coverages between 40 and 70% of saturation, separate bands assignable to CO on steps and CO on terraces appeared. Coupling across this coverage range was markedly weaker on Pt(557) than on the structurally related Pt(335) ≡ Pt(s)-[4(111) × (100)] electrode surface. The results indicate that, after the steps fill, CO populates the terraces on Pt(557) at random rather than by ordering in alignment with the steps. At coverages below saturation, vibrational bands assignable to CO molecules at step and terrace sites are affected differently by changes in electrode potential. The potential-induced spectral changes for the terrace CO bands are similar to those of Pt(111)/CO, but the step CO bands show deviations from this trend at hydrogen adsorption potentials.     

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.     

Ab initio explanation of tunneling line shapes for the kondo impurity state

We report an ab initio study of the Kondo states formed from a Co adatom on Cu(111) and Cu(100). The model consists of a CoCun cluster ( n = 5-19) embedded in (111) and (100) Cu slabs. An embedding potential derived from density functional theory treats the interaction between the periodic crystal surroundings and the CoCun cluster, while strong electron correlations within CoCun are explicitly accounted for via configuration interaction (CI) methods. Analysis of the embedded CI wave function provides insight into the nature of the Kondo state, specifically into the influence of the crystal host on the Co d-electronic structure. We predict that different d-orbitals are preferentially singly occupied in Co on Cu(111) versus Cu(100) as a result of the different crystalline environment. We propose that these variations in the local d-electronic structure on Co, not accounted for in previous theories, are responsible for the drastically different Kondo resonance line shapes observed in scanning tunneling microscopy experiments on these two surfaces.     

PTCDA on Cu(111) partially covered with NaCl

The organic molecule 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) was studied by means of scanning tunneling microscopy (STM) on thin insulating NaCl films grown on a Cu(111) single crystal. The deposition of approximately two monolayers (ML) of sodium chloride onto a Cu(111) substrate at a sample temperature of about 350 K causes a rather rough growth of (100)-oriented NaCl islands up to a local height of 4 ML. For submonolayer coverages (0.1 and 0.4 ML) of PTCDA on a Cu(111) surface partly covered with NaCl, two different rod structures of PTCDA were found on the copper surface, which are in contrast to previously published data for PTCDA on Cu(111) showing a herringbone-like arrangement. These findings can be explained by the formation of a Na(x)-PTCDA complex. On NaCl covered areas, single PTCDA molecules adsorb at vacancies of [010] and [001] oriented steps of the NaCl(100) islands. In this case, the electrostatic forces between the polar step edges and the PTCDA molecules are dominant. The terraces of the alkali halide surface are free of PTCDA molecules.     

Cu films formed simultaneously on (111) and (100) NaCl

Copper films were deposited simultaneously in high vacuum on three different monocrystalline NaCl substrates: evaporated (111) NaCl on mica, evaporated (100) NaCl and air-cleaved (100) NaCl. The occurence and microstructure of monocrystalline or polycrystalline copper films were determined by transmission electron microscopy and diffraction as a function of deposition rate R and substrate temperature T. When log R was plotted against 1/T, straight lines could be drawn separating the monocrystalline and the polycrystalline regions. Activation energies for the polycrystalline to monocrystalline transition of Cu films were calculated to be 1.48, 1.22 and 1.27 eV for the (111), evaporated (100) and air-cleaved (100) NaCl substrates respectively. It is shown that these results can be related to the atomistic theory of nucleation by Walton. Moreover, the results indicate that both the binding energy U between a single adatom and a growing oriented cluster and the atomic adsorption energy Q_ad on the substrate surface are proportional to the planar atom densities in the growing cluster and in the substrate surface respectively. It is further shown that while the activation energies for Cu films formed on the two (100) substrate surfaces are about the same, the actual epitaxial temperatures for the same R are significantly different.     

Atomistic simulations of reactive wetting in metallic systems

Atomistic simulations were performed to investigate high temperature wetting phenomena for metals. A sessile drop configuration was modeled for two systems: Ag(l) on Cu and Pb(l) on Cu. The former case is an eutectic binary and the wetting kinetics were greatly enhanced by the presence of aggressive interdiffusion between Ag and Cu. Wetting kinetics were directly dependent upon dissolution kinetics. The dissolution rate was nearly identical for Ag(l) on Cu(100) compared to Cu(111); as such, the spreading rate was very similar on both surfaces. Pb and Cu are bulk immiscible so spreading of Pb(l) on Cu occurred in the absence of significant substrate dissolution. For Pb(l) on Cu(111) a precursor wetting film of atomic thickness emerged from the partially wetting liquid drop and rapidly covered the surface. For Pb(l) on Cu(100), a foot was also observed to emerge from a partially wetting drop; however, spreading kinetics were dramatically slower for Pb(l) on Cu(100) than on Cu(111). For the former, a surface alloying reaction was observed to occur as the liquid wet the surface. The alloying reaction was associated with dramatically decreased wetting kinetics on Cu(100) versus Cu(111), where no alloying was observed. These two cases demonstrate markedly different atomistic mechanisms of wetting where, for Ag(l) on Cu, the dissolution reaction is associated with increased wetting kinetics while, for Pb(l) on Cu, the surface alloying reaction is associated with decreased wetting kinetics.     

Force‐Driven Single‐Atom Manipulation on a Low‐Reactive Si Surface for Tip Sharpening

A single atomic manipulation on the delta‐doped B:Si(111)‐()R30° surface using a low temperature dynamic atomic force microscopy based on the Kolibri sensor is investigated. Through a controlled vertical displacement of the probe, a single Si adatom in order to open a vacancy is removed. It is shown that this process is completely reversible, by accurately placing a Si atom back into the vacancy site. In addition, density functional theory simulations are carried out to understand the underlying mechanism of the atomic manipulation in detail. This process also rearranges the atoms at the tip apex, which can be effectively sharpened in this way. Such sharper tips allow for a deeper look into the Si adatom vacancy site. Namely, high‐resolution images of the vacancy showing subsurface Si dangling bond triplets, which surround the substitutional B dopant atom in the first bilayer, are achieved.     

'Sub-atomic' resolution of non-contact atomic force microscope images induced by a heterogeneous tip structure: a density functional theory study

A Si adatom on a Si(111)-(7 × 7) reconstructed surface is a typical atomic feature that can rather easily be imaged by a non-contact atomic force microscope (nc-AFM) and can be thus used to test the atomic resolution of the microscope. Based on our first principles density functional theory (DFT) calculations, we demonstrate that the structure of the termination of the AFM tip plays a decisive role in determining the appearance of the adatom image. We show how the AFM image changes depending on the tip-surface distance and the composition of the atomic apex at the end of the tip. We also demonstrate that contaminated tips may give rise to image patterns displaying so-called 'sub-atomic' features even in the attractive force regime.     

Characterization of microfabricated probes for combined atomic force and high-resolution scanning electrochemical microscopy

A combined atomic force and scanning electrochemical microscope probe is presented. The probe is electrically insulated except at the very apex of the tip, which has a radius of curvature in the range of 10-15 nm. Steady-state cyclic voltammetry measurements for the reduction of Ru(NH3)6Cl3 and feedback experiments showed a distinct and reproducible response of the electrode. These experimental results agreed with finite element simulations for the corresponding diffusion process. Sequentially topographical and electrochemical studies of Pt lines deposited onto Si3N4 and spaced 100 nm apart (edge to edge) showed a lateral electrochemical resolution of 10 nm.     

低能Ar+离子束辅助沉积择优取向Pt(111)膜

采用低能Ar+离子束辅助沉积方法,在Mo/Si(100)基底上沉积Pt膜,离子/原子到达比分别为0.1、0.2、0.3.若Ar+离子的入射角为0°,XRD谱分析表明,沉积的Pt膜均呈(111)和(200)混合晶向;当Ar+离子的入射角为45°,沉积的Pt膜均呈很强的(111)择优取向.因此若合理控制Ar+离子束的入射角,可在Mo/Si(100)衬底上制备出具有显著择优取向的Pt(111)薄膜.本文采用Monte Carlo方法模拟低能Ar+离子注入 Pt单晶所引起的原子级联碰撞过程,得出Ar+离子入射单晶铂(200)晶面时,Ar+离子的溅射率与入射角的关系,对Pt膜择优取向的机理作了初步的探讨和分析.     

Low-bias conductance of single benzene molecules contacted by direct Au-C and Pt-C bonds

The electronic transport properties of a single benzene molecule connected to gold and platinum electrodes through the direct Au-C or Pt-C bond are investigated by using a self-consistent ab initio approach that combines the non-equilibrium Green's function (NEGF) formalism with density functional theory (DFT). Our calculations show that the benzene molecule can bind to the Au(111) surface via direct Au-C bond at the adatom, atop and bridge sites. The largest zero-bias conductance is calculated for the bridge site but it is only G = 0.37G(0) (G(0) = 2e(2)/h). In contrast benzene binds to the Pt(111) surface via direct Pt-C bond only at the adatom and atop sites. When the binding site is the adatom a stable molecular junction forms with a zero-bias conductance as large as 1.15G(0). This originates from the efficient coupling between the extended π-type highest occupied molecular orbital of benzene and the conducting states of the Pt electrodes via the 5d(xz) atomic orbital of the adatoms. The calculated transmission is robust to the choice of DFT functionals, illustrating the potential of the Pt-C bond for constructing future molecular electronic devices.     

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.     

Temperature‐Dependent Tip‐Induced Motion of Ga Adatom on GaAs (110) Surface

The temperature‐dependent tip‐induced‐motion of a Ga adatom on a GaAs (110) surface is experimentally demonstrated using scanning tunneling microscopy (STM). The surface adsorption energy profile obtained by first‐principle electronic structure calculations reveals that the origin of the Ga motion observed at 78 K is attributable to the tip‐induced Ga adatom hopping between the most stable potential minima among the three local minima, whereas that observed at 4.2 K is attributable to the tip‐induced hopping and sliding motions through the next stable minima as well as the most stable minima. Furthermore, it is shown that a slight progressive modification of the adatom motion observed only at 4.2 K resulting from repeated STM line scans is consistent with the overall picture taking account of the heating of the adatom owing to the tip current.