The chemisorption of coronene on Si(001)-2 x 1

Coronene (C24H12) adsorption on the clean Si(001)-2 x 1 surface was investigated by scanning tunneling microscopy and by density-functional calculations. The coronene adsorbed randomly at 25 degrees C on the surface and did not form two-dimensional islands. The scanning tunneling microscopy measurements revealed three adsorption sites for the coronene molecule on the Si(001) surface at low coverage. The major adsorption configuration involves coronene bonding to four underlying Si atoms spaced two lattice spacings apart in a dimer row. The two minor adsorption configurations involve asymmetrical bonding of a coronene molecule between Si dimer rows and form surface species with a mirror plane symmetry to their chiral neighbor species. The two minor bonding arrangements are stabilized by a type-C defect on the Si(001) surface.     

Identification of color centers on MgO(001) thin films with scanning tunneling microscopy

Localized electronic defects on the surface of a 4 monolayer (ML) thin MgO(001) film deposited on Ag(001) have been investigated by low-temperature scanning tunneling microscopy and spectroscopy. Depending on the location of the defect, we observe for the first time different defect energy levels in the band gap of MgO. The charge state of defects can be manipulated by interactions with the scanning tunneling microscope tip. Comparison with ground state energy levels of color centers on the MgO surface obtained from embedded cluster calculations corroborates the assignment of the defects to singly and doubly charged color centers.     

Bulk and surface oxygen vacancy formation and diffusion in single crystals, ultrathin films, and metal grown oxide structures

The neutral oxygen vacancy (OV) energy formation for bulk, subsurface sites at different depths from the surface and various surface sites has been estimated for single crystals, unsupported ultrathin films of MgO, CaO, and BaO, and MgO ultrathin films supported on Ag(001). From the calculated energy barriers for diffusion through the surface and from the surface to the bulk it is found that diffusion is a hindered event, especially for MgO. Nevertheless, diffusion from the terrace to step edges is largely favored while diffusion through terrace sites is less likely and surface to bulk has a very low probability. It is argued that this explains recent scanning tunneling microscopy images for MgO thin films supported on Ag(001) showing OV populating preferentially the step edge sites.     

Roughing titanium quantum wire on patterned monohydride diamond (001) surface

The authors have performed the roughing of titanium (Ti) quantum wires forming on a hydrogen-terminated diamond (001)-2x1 surface patterned with an ordered bare strip array and demonstrated that well-ordered Ti quantum wires are achieved only if the growth conditions (temperature and flux) have optimal values via kinetic Monte Carlo simulations. Considering that a scanning tunneling microscope is capable of selectively desorbing H from diamond (001)-2x1-H surface, they proposed a viable and easy approach to fabricate "ideal quantum wires" on the patterned hydrogen-terminated diamond (001) surface. The physical origin of the Ti quantum wire formation was pursued.     

Single P and As dopants in the Si(001) surface

Using first-principles density functional theory, we discuss doping of the Si(001) surface by a single substitutional phosphorus or arsenic atom. We show that there are two competing atomic structures for isolated Si-P and Si-As heterodimers, and that the donor electron is delocalized over the surface. We also show that the Si atom dangling bond of one of these heterodimer structures can be progressively charged by additional electrons. It is predicted that surface charge accumulation as a result of tip-induced band bending leads to structural and electronic changes of the Si-P and Si-As heterodimers which could be observed experimentally. Scanning tunneling microscopy (STM) measurements of the Si-P heterodimer on a n-type Si(001) surface reveal structural characteristics and a bias-voltage dependent appearance, consistent with these predictions. STM measurements for the As:Si(001) system are predicted to exhibit similar behavior to P:Si(001).     

Chemisorption and dissociation of single oxygen molecules on Ag110

The chemisorption of single oxygen molecules on Ag110 and the dissociation of the adsorbed molecules induced by tunneling electrons were studied at 13 K using a variable-low-temperature scanning tunneling microscope. Two predominant types of chemisorbed O2 molecules were identified, one with the O2 molecular axis aligned along the [001] direction of the substrate [O2(001)], and the other with the molecular axis aligned along the [110] direction [O2(110)]. Tunneling of electrons between the scanning tunneling microscope tip and O2(001) caused the molecule either to rotate or dissociate, depending on the direction of electron tunneling. In contrast, electron tunneling caused O2(110) to dissociate regardless of tunneling direction. In addition to O2(001) and O2(110), several other oxygen species and their dynamical behaviors were observed.     

Scanning tunneling microscopy/spectroscopy study of atomic and electronic structures of In2O on InAs and In0.53Ga0.47As(001)-(4×2) surfaces

Interfacial bonding geometry and electronic structures of In(2)O on InAs and In(0.53)Ga(0.47)As(001)-(4×2) have been investigated by scanning tunneling microscopy/scanning tunneling spectroscopy (STM/STS). STM images show that the In(2)O forms an ordered monolayer on both InAs and InGaAs surfaces. In(2)O deposition on the InAs(001)-(4×2) surface does not displace any surface atoms during both room temperature deposition and postdeposition annealing. Oxygen atoms from In(2)O molecules bond with trough In/Ga atoms on the surface to form a new layer of O-In/Ga bonds, which restore many of the strained trough In/Ga atoms into more bulklike tetrahedral sp(3) bonding environments. STS reveals that for both p-type and n-type clean In(0.53)Ga(0.47)As(001)-(4×2) surfaces, the Fermi level resides near the valence band maximum (VBM); however, after In(2)O deposition and postdeposition annealings, the Fermi level position is close to the VBM for p-type samples and close to the conduction band minimum for n-type samples. This result indicates that In(2)O bonding eliminates surface states within the bandgap and forms an unpinned interface when bonding with In(0.53)Ga(0.47)As/InP(001)-(4×2). Density function theory is used to confirm the experimental finding.     

The initiation and characterization of single bimolecular reactions with a scanning tunneling microscope

A scanning tunneling microscope (STM) operating at 9 K in ultrahigh vacuum was used to initiate a bimolecular reaction between isolated hydrogen sulfide and dicarbon molecules on the Cu(001) surface. The reaction products ethynyl (CCH) and sulfhydryl (SH) were identified by inelastic electron tunneling spectroscopy (STM-IETS) and by sequentially removing hydrogen atoms from an H2S molecule using energetic tunneling electrons. For comparison, the thermal diffusion and reaction of H2S and CC at 45 K and H2O and CC at 9 K were also observed.     

Complex Surface Chemistry of an Otherwise Inert Solvent Molecule: Tetrahydrofuran on Si(001)

The reaction of tetrahydrofuran (THF), an otherwise inert solvent molecule, on Si(001) was experimentally studied in ultra‐high vacuum. Using scanning tunneling microscopy (STM) and photoelectron spectroscopy at variable temperature, we could both isolate a datively bound intermediate state of THF on Si(001), as well as the final configuration that bridges two dimer rows of the Si(001) surface after ether cleavage. The latter configuration implies splitting of the O?C bond, which is typically kinetically suppressed. THF thus exhibits a hitherto unknown reactivity on Si(001).     

Electronic effects induced by single hydrogen atoms on the Ge(001) surface

The properties of an isolated dangling bond formed by the chemisorption of a single hydrogen atom on a dimer of the Ge(001) surface are investigated by first-principles density functional theory (DFT) calculations, and scanning tunneling microscopy (STM) measurements. Two stable atomic configurations of the Ge-Ge-H hemihydride with respect to the neighboring bare Ge-Ge dimers are predicted by DFT. For both configurations, the unpaired electron of the HGe(001) system is found to be delocalized over the surface, rendering the isolated dangling bond of the hemihydride unoccupied. However, local surface charge accumulation, such as may occur during STM imaging, leads to the localization of two electrons onto the hemihydride dangling bond. The calculated surface densities of states for one of the charged Ge-Ge-H hemihydride configurations are found to be in good agreement with atomic-resolution STM measurements on n-type Ge(001). Comparison with a Si-Si-H hemihydride of the Si(001) surface shows similarities in structural properties, but substantial differences in electronic properties.     

A surface x-ray study of the structure and morphology of the oxidized Pd001 surface

The oxidation of Pd(100) and the formation of PdO was studied in situ using surface x-ray diffraction. A bulklike, epitaxial PdO film is formed at oxygen partial pressures beyond 1 mbar and sample temperatures exceeding 650 K. The main orientation is PdO(001)/Pd(001), based upon bulk reflections from the PdO film. By comparing with measurements from the Pd crystal truncation rods, we estimate an rms surface roughness of 6 A, in good agreement with previous high pressure scanning tunneling microscopy measurements. Finally, we observed the transformation from the (radical5 x radical5) surface oxide to PdO bulk oxide at 675 K and 50 mbar O(2) pressure.     

Dimer pinning and the assignment of semiconductor-adsorbate surface structures

It has been observed in scanning tunneling microscopy (STM) that the adsorption of molecules on the (001) surface of a Group IV semiconductor can lead to an asymmetric ordering of the dimers immediately adjacent to the adsorbate. This so-called pinning may occur along the dimer row on only one, or both sides of the adsorbate. Here we present a straightforward methodology for predicting such pinning and illustrate this approach for several different adsorbate structures on the Si(001) surface. This approach extends earlier work by including the effects of coupling across the adsorbate as well as the nearest-neighbor interactions between the chemisorbed dimer and its adjacent dimers. The results are shown to be in excellent agreement with the room temperature experimental STM data. The examples also show how this approach can serve as a powerful tool for discriminating between alternative possible adsorbate structures on a dimerized semiconductor (001) surface, especially in cases of molecular adsorption where the STM measurements provide insufficient details of the underlying atomic structure.     

Encapsulated Pd nanocrystals supported by nanoline-structured SrTiO3(001)

Palladium nanocrystals were grown on a nanostructured SrTiO(3)(001) surface and annealed in ultrahigh vacuum at 620 degrees C. This leads to the so-called strong metal-support interaction (SMSI) state, characterized by encapsulation of the metal clusters with an oxide layer. Scanning tunneling microscopy (STM) of the oxide adlayer on the Pd(111) cluster surface reveals two superstructures with different lattice parameters and crystallographic rotations. Interpretation of the STM images is most readily achieved via noncommensurate TiO(x)() surface layers which result in two distinct Moiré patterns.     

Two dissociation pathways of water and ammonia on the Si(001) surface

Using first-principles density-functional calculations, we investigated two competing pathways for the dissociation of water and ammonia on a Si(001) surface. For both systems, we found that, in addition to the conventionally accepted intradimer transfer of the H atom, the interdimer transfer of the H atom can be equally probable with the same reaction mechanism. Our analysis shows that the two dissociation pathways occur through the Lewis acid-base reaction between the partially positive H ion and the electron-abundant up atom of the buckled Si dimer. The result of the interdimer H transfer not only supports a recently proposed model for C-defect on Si(001) but also corresponds to the recent scanning tunneling microscopy data of ammonia dissociation on Si(001).     

Molecular beam investigation of hydrogen dissociation on Si(001) and Si(111) surfaces

The influence of molecular vibrations on the reaction dynamics of H2 on Si(001) as well as isotopic effects have been investigated by means of optical second-harmonic generation and molecular beam techniques. Enhanced dissociation of vibrationally excited H2 on Si(001)2 x 1 has been found corresponding to a reduction of the mean adsorption barrier to 390 meV and 180 meV for nu=1 and nu=2, respectively. The adsorption dynamics of the isotopes H2 and D2 show only small differences in the accessible range of beam energies between 50 meV and 350 meV. They are traced back to different degrees of vibrational excitation and do not point to an important influence of quantum tunneling in crossing the adsorption barrier. The sticking probability of H2 on the 7 x 7-reconstructed Si(111) surface was found to be activated both by H2 kinetic energy and surface temperature in a qualitatively similar fashion as H2/Si(001)2 x 1. Quantitatively, the overall sticking probabilities of H2 on the Si(111) surface are about one order of magnitude lower than on Si(001), the influence of surface temperature is generally stronger.     

Adsorption and assembly of copper phthalocyanine on cross-linked TiO2(110)-(1 x 2) and TiO2(210)

Copper phthalocyanine (CuPc) on reconstructed rutile TiO(2) was studied with ultrahigh vacuum variable temperature scanning tunneling microscopy. On cross-linked TiO(2)(110)-(1 x 2), the CuPc molecules at low coverages sparsely lay flat at the link sites and tilted in troughs between [001] rows. Increase of the CuPc coverage led to the trapping of the CuPc molecules by the rectangular surface cells fenced by the oxygen columns along the [001] direction and the cross-link rows. Each cell could trap one CuPc molecule at intermediate coverages and two CuPc molecules at higher coverages. On TiO(2)(210), the CuPc molecules tilted in defect-free areas and lay at defect sites with their molecular planes parallel to the substrate surface. Further increase of the CuPc coverage induced the formation of one- and two-dimensional assemblies on TiO(2)(210).     

The chemisorption of dibenzo[a,j]coronene on Si(001)-2 x 1

Adsorption structures of the dibenzo[a,j]coronene (C(32)H(16)) molecule on the clean Si(001)-2 X 1 surface were investigated by scanning tunneling microscopy (STM) in conjunction with electronic structure calculations. The dibenzo[a,j]coronene molecules were found to adsorb on three different sites: one major adsorption site and two minor adsorption sites. The formation of four to eight Si-C covalent bonds is responsible for the different surface bonding structures observed. Bond strain effects due to out-of-plane bending of the molecule play a significant role in governing the surface bond energies. The geometries of the three adsorption sites were established by comparison of the experimental and simulated STM images. By applying an electrical pulse, the molecule can be made to hop from one site to another site without breaking the dibenzo[a,j]coronene molecular structure.     

Manipulation and characterization of xenon-metalloporphyrin complexation with a scanning tunneling microscope

The formation of a series of Xe-CuEtioI [Cu(II) etioporphyrin I] complexes on Cu(001) surface was identified by scanning tunneling microscopy (STM) at cryogenic condition. The binding sites of xenon to CuEtioI molecule were directly revealed by high-resolution STM images in combination with controlled manipulation. The interaction between xenon atoms and CuEtioI in the on-top configuration is suggestive of a charge-induced dipole interaction. The structural parameters obtained with the STM complement results from spectroscopic studies of van der Waals complexes.     

c(4 × 2) and related structural units on the SrTiO3(001) surface: scanning tunneling microscopy, density functional theory, and atomic structure

Density functional theory is used to simulate high-bias, constant-current scanning tunneling micrographs for direct comparison with experimental images. Coupled to previous spectroscopic data, these simulations are used to determine the atomic structure of Ti-rich nanostructures on strontium titanate (001) surfaces. These nanostructures have three consecutive TiO(x) surface layers and exploit the distinctive structural motif of the c(4 × 2) reconstruction as their main building block. A structural model of a characteristic triline defect is also proposed.     

Binding structures of propylene glycol stereoisomers on the Si(001)-2×1 surface: a combined scanning tunneling microscopy and theoretical study

The binding configuration of propylene glycol stereoisomer molecules adsorbed on the Si(001)-2×1 surface was investigated using a combination of scanning tunneling microscopy (STM) and density functional theory calculations. Propylene glycol was found to adsorb dissociatively via two hydroxyl groups exclusively as a bridge between the ends of two adjacent dimers along the dimer row. The chirality was preserved during bonding to Si atoms and was identifiable with STM imaging. The large number of propylene glycol conformers in the gas phase was reduced to a single configuration adsorbed on the surface at low molecular coverage.