First-principles study of oxidized Nb(1 0 0) surface structures

The atomic positions of the oxygen-induced c(2 × 2)-O, (3 × 1)-O and (4 × 1)-O surface structures on Nb(1 0 0) are determined by first-principles electronic structure calculations within the density functional theory comparing experimentally observed scanning tunneling microscopy (STM) images. STM images of these surfaces are calculated on the basis of the theory of Tersoff and Hamann. The theoretical and experimental STM images of the oxygen-chemisorbed c(2 × 2)-O structural model agree well. However, only the oxide-covered (3 × 1)-O and (4 × 1)-O structural models with two layers of NbO and contraction of the unit length along longitudinal 〈1 0 0〉 direction by 10% result in the theoretical STM images that agree with the experimental ones.     

Study of Si(0 0 1)4 × 2-Ga structure by scanning tunneling microscopy and ab initio calculation

We have studied Si(0 0 1)-Ga surface structures formed at Ga coverages of slightly above 0.50 monolayer (ML) at 250 °C by scanning tunneling microscopy (STM). 4 × 2-, 5 × 2-, and 6 × 2-Ga structures were observed in a local area on the surface. The 4 × 2-Ga structure consists of three protrusions, as observed in filled- and empty-state STM images. The characters of these structures are clearly different from those of other Si(0 0 1)-Ga structures. We also performed an ab initio calculation of the energetics for several possible models for the 4 × 2-Ga structure, and clarified that the three-orthogonal-Ga-dimer model is the most stable. Also, the results of comparing the simulated STM images and observation images at various bias voltages indicate that this structural model is the most favorable.     

Quasi-one-dimensional structures on the Si(1 1 1) surface induced by Ba adsorption

Ba-induced quasi-one-dimensional reconstructions of the Si(1 1 1) surface have been investigated by low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). While the 3 × ‘2’ surface shows double-periodicity along the stripes in STM images consistent with half-order streaks observed in LEED patterns, no sign of the double-periodicity along the chain direction was detected for the 5 × 1 surface. The 5× stripes in STM images show internal structures with multiple rows. The two rows comprising the boundaries of a 5× stripe in the filled-state STM image are found to have 3a × √3/2 spacing across the stripe. The observation of the successive 3× and 2× spacings between the boundary rows supports a structural model proposed for the Ba-induced 5 × 1 Si reconstruction composed of honeycomb chains and Seiwatz chains. The highest coverage 2 × 8 surface does not reveal a quasi-1D row structure in STM images.     

Self-assembled germanium nano-clusters on silver(1 1 0)

The adsorption of germanium on Ag(1 1 0) has been investigated by scanning tunnelling microscopy (STM), as well as surface X-ray diffraction (SXRD). At 0.5 germanium monolayer (ML) coverage, Low Energy Electron Diffraction (LEED) patterns reveals a sharp c(4 × 2) superstructure. Based on STM images and SXRD measurements, we present an atomic model of the surface structure with Ge atoms forming tetramer nano-clusters perfectly assembled in a two-dimensional array over the silver top layer. The adsorption of the germanium atoms induces a weak perturbation of the Ag surface. Upon comparison with results obtained on the (1 1 1) and (1 0 0) faces, we stress the role played by the relative interactions between silver and germanium on the observed surface structures.     

Structural and statistical analysis of Yb/Si(1 1 1) and Eu/Si(1 1 1) reconstructions

We have performed the structural and statistical analysis of Yb/Si(1 1 1) and Eu/Si(1 1 1) surfaces in the submonolayer regime utilizing low-energy electron diffraction and scanning tunneling microscopy (STM). The almost identical series of one-dimensional chain structures (e.g., 3 × 2/3 × 1, 5 × 1, 7 × 1, 9 × 1, and 2 × 1 phases) are found in order of increasing metal coverage for both adsorbed systems, however, only the Eu/Si system reveals the ‘√3’-like reconstruction before the 2 × 1 endpoint phase. The atomic models of chain structures are proposed and discussed. In particular, our results suggest the odd-order n×1 (n=5,7,9,…) intermediate reconstructions to incorporate the Seiwatz chains and honeycomb chains with the proportion of m:1, where . The statistical analysis of STM images is carried out to examine the correlation of atomic rows on Eu/Si and Yb/Si surfaces. It is found that Eu stabilizes more ordered row configuration compared to Yb, which can be explained in terms of indirect electronic interaction of atomic chains or/and different magnetic properties of adsorbed species.     

Early stages of vanadium deposition on Si(1 1 1)-7 × 7

We investigate the low-coverage regime of vanadium deposition on the Si(1 1 1)-7 × 7 surface using a combination of scanning tunnelling microscopy (STM) and density-functional theory (DFT) adsorption energy calculations. We theoretically identify the most stable structures in this system: (i) substitutional vanadium atoms at silicon adatom positions; (ii) interstitial vanadium atoms between silicon adatoms and rest atoms; and (iii) interstitial vanadium - silicon adatom vacancy complexes. STM images reveal two simple vanadium-related features near the Si adatom positions: bright spots at both polarities (BB) and dark spots for empty and bright spots for filled states (DB). We relate the BB spots to the interstitial structures and the DB spots to substitutional structures.     

Simulations of iodine adsorbed Ge(0 0 1) surface and its STM images

A layer of iodine at Ge(0 0 1) surface develops an ordered structure of iodine atoms bound to Ge dimers. Here are discussed atomic structures of Ge(0 0 1) surface covered by 0.25 monolayer of iodine. The p(2×4), p(2×2), c(2×4) and p(1×4) surface structures are found in calculations. The structure with two iodine atoms of the dissociated I₂ molecule adsorbed at both ends of the same germanium dimer is found to be energetically favourable over iodine adsorption at neighbouring dimers. Simulated STM images of the obtained surface structures are presented and compared with experimental data.     

SrTiO3(0 0 1) reconstructions: the (2 × 2) to c(4 × 4) transition

Scanning tunneling microscopy (STM) is used to investigate the (0 0 1) surface structure of Nb doped SrTiO₃ single crystals annealed in ultra high vacuum (UHV). Atomically resolved images of the (2 × 2) reconstructed surface are obtained after annealing a chemically etched sample. With further annealing dotted row domains appear, which coexist with the (2 × 2) reconstruction. The expansion of these domains with further annealing gives rise to the formation of a TiO₂ enriched c(4 × 4) reconstruction.     

The Na-adsorbed Ge(0 0 1) surface: Structure and STM image simulations

Sodium adsorbed on the Ge(0 0 1) surface causes reconstruction of the surface with the type of reconstruction depending on the amount of the adsorbate. We present theoretical investigations of the structure and electronic properties of Na-adsorbed Ge(0 0 1) for the coverage of 0.5 monolayer using the combination of two methods: a plane-wave basis method and a local-orbital minimal-basis method. Two possible minimum-total-energy atomic configurations have been found, namely, the Na/Ge(0 0 1)-p(2 ×1) and Na/Ge(0 0 1)-p(4 × 1) reconstructions. The surface electronic structure for all calculated configurations occurs to be metallic. Our investigations are completed by a simulation of STM images for the obtained atomic structures.     

(6 × 2) Reconstruction of the Ag/Si(1 1 1) surface at 77 K

The ground state of the Ag/Si(1 1 1)-(3 × 1) has been investigated by low temperature scanning tunneling microscopy (STM) and density-functional theory. The Fourier transform of the STM image reveals a (6 × 2) reconstruction, which is theoretically found to yield a reconstruction with lower energy than the (3 × 1). The most stable (6 × 2) structural model leads to excellent correspondence between experimental and simulated STM images, and reveals a dimerization of the silver atoms in the channels formed by neighbouring honeycomb Si chains.     

Structural fluctuation of dimers on Ge(0 0 1) surface near transition temperature

The structural fluctuation of the orientational arrangement of buckled dimers on a Ge(0 0 1) surface near the transition temperature of the order-disorder phase transition is investigated by time-resolving dynamical Monte Carlo simulations. STM images averaged in a finite period are derived from the simulation. The coexistence of the c(4 × 2) and the apparent (2 × 1) domains in the STM images observed by experiments is reproduced in the simulated STM images. We show that the coexistence on the Ge(0 0 1) surface can be attributed to the critical slowing down near the transition temperature.     

Room temperature observation of nitric oxide on Ir(1 1 1) by scanning tunneling microscopy

Room temperature (RT) adsorption of nitric oxide (NO) on Ir(1 1 1) was studied by scanning tunneling microscopy (STM). At low exposures, NO molecules can not be imaged by STM, because at RT the diffusion of NO is much faster than the STM scanning speed. At high exposures near the saturation coverage, however, a well-ordered 2 × 2 structure is observed. The coverage of the major 2 × 2 species is 0.25 and they can be assigned to the NO molecules adsorbed on the Ir ontop sites. A small number of less bright spots are assigned to nitrogen atoms produced by dissociation. Their number increases by annealing the NO-saturated surface at 380 K. A small number of another dissociation product, oxygen, are observed as black lines, indicating that the diffusion of oxygen atoms is fast. Scratch-like noise features were also detected by the STM, which suggests that a mobile precursor state exists, which was clearly shown by the effects of electron irradiation from the STM tip. These results are consistent with the previous molecular beam studies. Hopping of the 2 × 2 ordered NO species was frequently observed at the anti-phase domain boundaries and edges of the 2 × 2 islands.     

Simulation of STM images of p(3 × 2)/Na/Ge(0 0 1) surface

Adsorption of Na on the Ge(0 0 1) surface is known to be a cause of surface reconstruction. It is expected to find one Na atom per unit cell of the reconstructed surface, however, the precise atomic configuration of this system is still a matter of controversy. Consequently, the aim of our present theoretical study is to examine the atomic structure of stable p(3 × 2)/Na/Ge(0 0 1) surfaces with and without the possible change of the number of Ge atoms in the surface layer (so-called mass transport). Structural and electronic properties of the considered system are investigated using the local-orbital density functional method. Our considerations are completed by a simulation of STM images of the structures following from molecular dynamics calculations.     

Theoretical STM images of alkaline-earth metal adsorbed Si(1 1 1)3 × 2 surfaces

We have performed total-energy calculations to study theoretical scanning tunneling microscopy (STM) images of the Si(1 1 1)3 × 2 surfaces induced by the adsorption of alkaline-earth metals (AEMs). Previously, in a series of works on Ba/Si(1 1 1) system, we have found that the observed Si(1 1 1)3 × 1-Ba LEED phase indeed has a 3 × 2 periodicity with a Ba coverage of 1/6 ML and the HCC substrate structure. Based on results of the Ba case, we proposed that the HCC structure is also adopted for other AEM atoms, which was confirmed by our recent work. In this paper, we mainly report the STM simulations for different AEM systems to compare with existing experimental data. We discuss the difference in the detailed STM images for different AEM adsorbates. Especially, the difference in filled-state images between Mg and other AEM atoms is attributed to the strong Mg-Si interaction.     

Non-contact atomic force microscopy studies of (2 × 4) InP(0 0 1) surface

A sputter-cleaned indium-rich (2 × 4) InP(0 0 1) surface was investigated by non-contact scanning atomic force microscopy (NCAFM). Atomically-resolved images of the surface exhibit two different patterns. The patterns can be interpreted within the mixed dimer model of (2 × 4) reconstructed InP(0 0 1) surface. It is shown that due to contrast formation mechanism in NCAFM the features resolved are in close correspondence to scanning tunnelling microscopy (STM) data. Due to chemical interaction a P-terminated tip gives the image similar to an empty-state STM image, whereas an In-terminated tip gives the image resembling a filled-state STM one. Moreover, it is shown that due to dipole-dipole interaction, NCAFM can be sensitive to orientation of In-P dimers.     

A new structural model for the SiC(0 0 0 1)(3 × 3) surface derived from first principles studies

A new structural model with fluctuant Si-trimers and missing Si-adatom is proposed for Si-terminated 6H-SiC(0 0 0 1)(3 × 3) reconstruction. The atomic and electronic structures of the model are studied using first principles pseudopotential density-functional approach. The calculated surface electronic density of states coincides quantitatively with the experimental results of photoemission and electron energy loss spectroscopy. Based on the calculations, the Patterson map and scanning tunneling microscopic (STM) images simulated for the new model agree more satisfactorily with the experimental X-ray diffraction and STM observations than that for previously proposed models. The calculations of formation energies suggest that the new structure would be formed under the environment of dilute Si vapor around the surface in the preparation process.     

Oxygen-induced p(3 × 1) reconstruction of the W(1 0 0) surface

The oxidation of the W(1 0 0) surface at elevated temperatures has been studied using room temperature STM and LEED. High exposure of the clean surface to O₂ at 1500 K followed by flash-annealing to 2300 K in UHV results in the formation of a novel p(3 × 1) reconstruction, which is imaged by STM as a missing-row structure on the surface. Upon further annealing in UHV, this surface develops a floreted LEED pattern characteristic of twinned microdomains of monoclinic WO_x, while maintaining the p(3 × 1) missing-row structure. Atomically resolved STM images of this surface show a complex domain structure with single and double W〈0 1 0〉 rows coexisting on the surface in different domains.     

Anomalous hybridization in the In-rich InAs(0 0 1) reconstruction

The surface bonding arrangement in nearly all the confirmed reconstructions of InAs(0 0 1) and GaAs(0 0 1) have only two types of hybridization present. Either the bonds are similar to those in the bulk and the surface atoms are sp³ hybridized or the surface atoms are in a tricoordinated bonding arrangement and are sp² hybridized. However, dicoordinated In atoms with sp hybridization are observed on the InAs(0 0 1), In-rich, room temperature and low temperature surfaces. Scanning tunneling microscopy (STM) images of the room temperature (300 K) InAs(0 0 1) surface reveal that the In-rich surface reconstruction consists of single-atom rows with areas of high electron density that are separated by ∼4.3 Å. The separation in electron density is consistent with rows of undimerized, sp hybridized, In atoms, denoted as the β3′(4 × 2) reconstruction. As the sample is cooled to 77 K, the reconstruction spontaneously changes. STM images of the low temperature surface reveal that the areas of high electron density are no longer separated by ∼4.3 Å but instead by ∼17 Å. In addition, the LEED pattern changes from a (4 × 2) pattern to a (4 × 4) pattern at 77 K. The 77 K reconstruction is consistent with two (4 × 2) subunit cells; one that contains In dimers on the row and another subunit cell that contains undimerized, sp hybridized, In atoms on the row. This combination of dimerized and undimerized subunit cells results in a new unit cell with (4 × 4) periodicity, denoted as the β3(4 × 4) reconstruction. Density functional theory (DFT) and STM simulations were used to confirm the experimental findings.     

STM study of Bi-on-Cu(1 0 0)

Scanning tunneling microscopy (STM) has been used to study the various possible structures of adsorbed Bi on the Cu(1 0 0) surface, after equilibration at a temperature of 520 K. All of the structures previously identified by X-ray diffraction (lattice gas, c(2 × 2), c(9√2 × √2)R45°, and p(10 × 10), in order of increasing Bi-coverage) were found to be present on a single sample produced by diffusing Bi onto the Cu(1 0 0) surface from a 3-d source. By investigating the possible coexistence of various pairs of phases, it was demonstrated that the c(2 × 2) phase transforms to the c(9√2 × √2)R45° phase by a first order transition, whereas the transition from c(9√2 × √2)R45° to p(10 × 10) is continuous. In addition, the structure of surface steps was studied as a function of Bi-coverage. The results showed that the presence of Bi changes the nature of the step-step interactions at the Cu(1 0 0) surface from repulsive to attractive. The attractive step-step interactions transform any small deviations from the nominal (1 0 0) orientation of the Cu substrate into (3 1 0) microfacets. When compared with the known equilibrium crystal shape (ECS) of Bi-saturated Cu, the observed microfaceting may imply that the ECS of Cu-Bi alloys is temperature dependent.     

The chemisorption of pentacene on Si(0 0 1)-2 × 1

Adsorption structures of the pentacene (C₂₂H₁₄) molecule on the clean Si(0 0 1)-2 × 1 surface were investigated by scanning tunneling microscopy (STM) in conjunction with density functional theory calculations and STM image simulations. The pentacene molecules were found to adsorb on four major sites and four minor sites. The adsorption structures of the pentacene molecules at the four major sites were determined by comparison between the experimental and the simulated STM images. Three out of the four theoretically identified adsorption structures are different from the previously proposed adsorption structures. They involve six to eight Si-C covalent chemical bonds. The adsorption energies of the major four structures are calculated to be in the range 67-128 kcal/mol. It was also found that the pentacene molecule hardly hopped on the surface when applying pulse bias voltages on the molecule, but was mostly decomposed.