Ab-initio calculations and STM observations on tetrapyridyl and Fe(II)-tetrapyridyl-porphyrin molecules on Ag(1 1 1)

We modelled the adsorption of tetra-pyridyl-porphyrin (TPyP) and Fe(II)-tetra-pyridyl- porphyrin (Fe-TPyP) molecules on Ag(1 1 1). TPyP adsorbs in a flat geometry at a distance of 5.6 Å from the surface. The dihedral angle of the pyridyl rings is found to be 70°. The molecular structure remains largely unaffected by the adsorption. The structure of the molecular adlayer should thus be determined mainly by lateral intermolecular interactions. These conclusions are confirmed by scanning tunnelling microscopy observations. Upon metalation spin-polarized states with strong Fe d-character appear in Fe-TPyP near the centre of the gap between the highest occupied and the lowest unoccupied states of a TPyP molecule. We find also that the gap is widened in the presence of Fe. This implies a shift of 0.3 eV of unoccupied states as identified by scanning tunnelling spectroscopy simulations and confirmed by experimental data.     

Structural, optical and electrochromic properties of nickel oxide thin films grown from electrodeposited nickel sulphide

Nickel oxide thin films were grown onto FTO-coated glass substrates by a two-step process: electrodeposition of nickel sulphide and their thermal oxidation at 425, 475 and 525 °C. The influence of thermal oxidation temperature on structural, optical, morphological and electrochromic properties was studied. The structural properties undoubtedly revealed NiO formation. The electrochromic properties were studied by means of cyclic voltammetry. The films exhibited anodic electrochromism, changing from a transparent state to a coloured state at +0.75 V versus SCE, i.e. by simultaneous ion and electron ejection. The transmittance in the coloured and bleached states was recorded to access electrochromic quality of the films. Colouration efficiency and electrochromic reversibility were found to be maximum (21 mC/cm² and 89%, respectively) for the films oxidized at 425 °C. The optical band gap energy of nickel oxide slightly varies with increase in annealing temperature.     

Scanning tunneling microscopy luminescence from nanoscale surface of GaAs(1 1 0)

Scanning tunneling microscopy luminescence (STML) was induced from the nanometer scale surfaces of cleaved n-type and p-type GaAs(1 1 0) wafers by using of an ITO-coated optical fiber probe in an ultrahigh-vacuum chamber. The STML from n-type GaAs(1 1 0) surface was induced under negative sample bias when the applied bias exceeds a threshold voltage around −1.5 V. Whereas the STML from p-type GaAs(1 1 0) surface was induced under positive sample bias when the applied bias exceeds a threshold voltage around +1.5 V. The excitation energies at the threshold voltages are consistent with the band gap of GaAs (1.42 eV) at 295 K. The typical quantum efficiencies for n-type and p-type GaAs are about 3 × 10⁻⁵ and 2 × 10⁻⁴ photons/electron, respectively. The observed STML from are attributed to a radiative recombination of electron-hole pairs generated by a hole injection for n-type GaAs under negative sample bias and an electron injection for p-type GaAs under positive sample bias, respectively.     

Growth and morphology of the epitaxial Fe(1 1 0)/MgO(1 1 1)/Fe(1 1 0) Trilayers

Growth and surface morphology of epitaxial Fe(1 1 0)/MgO(1 1 1)/Fe(1 1 0) trilayers constituting a magnetic tunnel junction were investigated by low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM). STM reveals a grain-like growth mode of MgO on Fe(1 1 0) resulting in dense MgO(1 1 1) films at room temperature as well as at 250 °C. As observed by STM, initial deposition of MgO leads to a partial oxidation of the Fe(1 1 0) surface which is confirmed by Auger electron spectroscopy. The top Fe layer deposited on MgO(1 1 1) at room temperature is relatively rough consisting of clusters which can be transformed by annealing to an atomically flat epitaxial Fe(1 1 0) film.     

Scanning tunneling microscopy investigation of clean (2 1 1) surface of Ta and Mo

Scanning tunneling microscopy was used to obtain images from clean (2 1 1) surfaces of Ta and Mo under the same ultrahigh vacuum conditions. In the case of tantalum the surface is very rough, and single extending atomic chains reach distances up to 100 Å. Those furrows are a surface reconstruction based on creation of (1 1 0) “micro-facets” along the [1 1 1] direction or (1 1 1)fcc micro-facets with a more dense structure than (1 1 0)bcc plane. In contrast, the (2 1 1) surface of Mo is smooth, and single atomic rows are visible on high resolution STM images. Step bunching occurs on the Mo surface, reducing the number of terrace edges.     

Growth of silver structures on silicon surfaces observed in vivo by scanning tunneling microscopy

Early stages of growth of silver thin films on oriented silicon surfaces Si(1 0 0)2 × 1 and Si(1 1 1)7 × 7 were studied directly during deposition at room temperature by the scanning tunneling microscopy. Single Ag atoms deposited on the Si(1 0 0)2 × 1 surface diffuse too fast on the surface to be imaged by the microscope. Nucleation on C-type defects of the Si(1 0 0)2 × 1 reconstruction has been observed. During further growth, the defects represent stable terminations of silver chains. Ag nanoclusters growing on the Si(1 1 1)7 × 7 surface have been studied as a system with low diffusivity at room temperature. On this surface, presence of effective interaction between Ag clusters and individual Ag atoms in neighboring cells of the reconstruction has been identified. The interaction results in lowering the barrier for Ag atom hopping to an adjacent unit cell occupied by an Ag cluster. Unique possibilities arising from scanning the surface directly during growth are demonstrated.     

Interaction of 2,2,6,6-tetramethyl-3,5-heptanedione with the Si(1 0 0)-2 × 1 surface: Scanning tunneling microscopy and density functional theory study

Room temperature adsorption and reaction of 2,2,6,6-tetramethyl-3,5-heptanedione (dpmH) on the Si(1 0 0)-2 × 1 surface has been studied with ultra-high vacuum scanning tunneling microscopy (UHV-STM) and temperature programmed desorption (TPD). The molecule is found to chemisorb as a mixture of at least five distinct species. Density functional theory (DFT) was used to calculate the structures and adsorption energies of 12 possible addition products. Unique bonding assignments for each experimental feature are proposed by consideration of a common intermediate reaction network, and a comparison of possible reaction pathways leading to the final products. These assignments are: OH inter-dimer dissociation, OH intra-dimer dissociation, 1,5 intra-dimer addition, 1,5 inter-dimer addition, and intra-dimer [2 + 2]CO addition with OH dissociation on an adjacent dimer. TPD and STM results show that the molecule dissociates completely upon annealing to 700 °C with formation of the c(4 × 4) phase at low exposures, and SiC islands for exposures exceeding 0.15 L.     

Morphology and electronic structure of bcc Co(1 1 0) and fcc/hcp Co(1 1 1) on Fe(1 1 0) investigated by STM and STS

We report on the growth of ultrathin epitaxial Co films on Fe(1 1 0) examined by scanning tunneling microscopy and spectroscopy (STM and STS). At room temperature Co forms pseudomorphic, ideally ordered body-centered cubic (bcc) layers for the first two monolayers as confirmed by atomically resolved STM images. This is in contrast to the related case of Co/Cr(1 1 0) where a superstructure occurs in the second layer. The third monolayer forms a close-packed structure and causes a transformation of the buried second monolayer into a close-packed structure. The Fe(1 1 0) substrate strongly influences the electronic structure of the first Co monolayer as concluded from the dI/dU spectra. This influence is less important for the second monolayer. The measured local density-of-states function for the bcc Co double layer is in agreement with theoretical predictions for bcc Co.     

Atomic surface structure of Si(1 0 0) substrates prepared in a chemical vapor environment

Subsequent III-V integration by metal-organic vapor phase epitaxy (MOVPE) or chemical vapor deposition (CVD) necessitates elaborate preparation of Si(1 0 0) substrates in chemical vapor environments characterized by the presence of hydrogen used as process gas and of various precursor molecules. The atomic structure of Si(1 0 0) surfaces prepared in a MOVPE reactor was investigated by low energy electron diffraction (LEED) and scanning tunnelling microscopy (STM) available through a dedicated, contamination-free sample transfer to ultra high vacuum (UHV). Since the substrate misorientation has a fundamental impact on the atomic surface structure, we selected a representative set consisting of Si(1 0 0) with 0.1°, 2° and 6° off-cut in [0 1 1] direction for our study. Similar to standard UHV preparation, the LEED and STM results of the CVD-prepared Si(1 0 0) surfaces indicated two-domain (2 × 1)/(1 × 2) reconstructions for lower misorientations implying a predominance of single-layer steps undesirable for subsequent III-V layers. However, double-layer steps developed on 6° misoriented Si(1 0 0) substrates, but STM also showed odd-numbered step heights and LEED confirmed the presence of minority surface reconstruction domains. Strongly depending on misorientation, the STM images revealed complex step structures correlated to the relative dimer orientation on the terraces.     

Self-assembly of zwitterionic molecules on a Au(23 23 21) surface at low temperature

The adsorption of zwitterionic (E) 4-methoxy-4′-(3-n-sulfonatopropyl)stilbazolium (MSPS) molecules on the stepped vicinal Au(23 23 21) surface was studied by scanning tunneling microscopy (STM) at low temperature as a function of the molecular coverage. At the sub-half monolayer, a supramolecular network based on MSPS is preferentially adsorbed onto face-centered cubic stacking regions. At the monolayer, a complete periodic supramolecular film is obtained.     

Observation of double- to single-domain transition on the Eu/Si(1 0 0) surface by LEED and STM

The orientational phase diagram and morphology of the Eu-adsorbed Si(1 0 0) surface miscut by 0.4° have been studied by low-energy electron diffraction and scanning tunneling microscopy. We demonstrate that the original double-domain configuration with single-layer steps on the Si(1 0 0) substrate can be drastically broken at 0.4 monolayer (ML) of Eu. At this coverage, the ordered domain pattern formed by topographically non-equivalent terraces with Eu-induced 2 × 3 and “2 × 1” (so-called “wavy” structure) reconstructions is found, while no orthogonal 3 × 2 and “1 × 2” domains are observed. A model of the single-domain surface is proposed. The origin of the double- to single-domain transition found for the Eu/Si(1 0 0) system is discussed.     

Halogen chemisorption, the pairwise diffusion of I, and trapping by defects on Si(1 0 0)

Halogen molecules dissociatively chemisorb on Si(1 0 0)-(2 × 1), and the bonding structures that they adopt can be elucidated with scanning tunneling microscopy. Of the Cl, Br, and I group, Cl has the highest single atom diffusion barrier, and both single and paired adatoms are observed at 295 K. The barrier is smaller for Br, and the adatoms can interrogate the surface until they form pairs, which are then immobile, or are trapped at C-type defects. The barrier is smallest for I, allowing the formation of pairs and trapped states, but the pairs are mobile at ambient temperature. Their motion is thermally activated, the events are random, and the diffusivities along and across the dimer row are ∼0.42 and ∼0.17 Å²/s at 295 K. The respective energy barriers for pairwise diffusion are ∼0.76 and ∼0.82 eV, assuming an attempt frequency of 10¹² s⁻¹. Studies over long times reveal that pairwise diffusion at low coverage is ultimately quenched by the increasing density of C-type defects, i.e. the increasing amounts of dissociated H₂O.     

Germanium growth on Br-terminated Si(1 0 0)

The consequences of Ge deposition on Br-terminated Si(1 0 0) were studied with scanning tunneling microscopy at ambient temperature after annealing at 650 K. One monolayer of Br was sufficient to prevent the formation of Ge huts beyond the critical thickness of 3 ML. This is possible because Br acts as a surfactant whose presence lowered the diffusivity of Ge adatoms. Hindered mobility was manifest at low coverage through the formation of short Ge chains. Further deposition resulted in the extension and connection of the Ge chains and gave rise to the buildup of incomplete layers. The deposition of 7 ML of Ge resulted in a rough surface characterized by irregularly shaped clusters. A short 800 K anneal desorbed the Br and allowed Ge atoms to reorganize into the more energetically favorable “hut” structures produced by conventional Ge overlayer growth on Si(1 0 0).     

Ge quantum dots growth on nanopatterned Si(0 0 1) surface: Morphology and stress relaxation study

The self-organized growth of germanium quantum dots on square nanopatterned Si(0 0 1) substrates is investigated by scanning tunnelling microscopy (STM) and grazing incidence X-ray diffraction (GIXRD) techniques. A regular surface patterning in the 10-100 nm period range is obtained by etching an interface dislocation network obtained by the controlled molecular bonding of Si substrates. The depth of the silicon surface profile is increased by a double etching process. Growth experiments are performed by solid source molecular beam epitaxy (MBE), and for deep trenches, germanium growth conditions are optimized to obtain one Ge dot per Si mesa. It is shown that the trench depth and the mesa profile strongly affect the dot size and its coincidence with the initial regular surface network. Anomalous GIXRD measurements are performed to highlight the Ge elastic relaxation and intermixing during heteroepitaxial growth. We report a significant modification in the stress state of Ge dots as a function of thermal annealing after growth.     

The surface structure of BaO on Pt(1 1 1): (2 × 2)-reconstructed BaO(1 1 1)

The surface structure of BaO(1 1 1) has been determined using STM and computer modelling. The BaO(1 1 1) surface was prepared in thin film form on Pt(1 1 1) and presents a surface with twice the lattice parameter expected for that of the bulk termination, i.e. a (2 × 2) reconstruction. Computer modelling indicates that the bulk termination is unstable, but that the (2 × 2) reconstructed BaO(1 1 1) surface has a low surface energy and is hence a stable surface reconstruction. The (2 × 2) reconstruction consists of small, three-sided pyramids with (1 0 0) oriented sides and either oxygen or barium ions at the apices. Less regular surface reconstructions containing the same pyramids are almost equally stable, indicating that we may also expect less regular regions to appear with a fairly random distribution of these surface species. The simulations further suggest that a regular (4 × 4) reconstruction built up of bigger pyramids is even more energetically favourable, and some evidence is found for such a structure in the STM.     

Combined spectroscopy and microscopy of supported MoS2 nanoparticles

Supported molybdenum-sulfide nanoparticles are known catalysts for petroleum hydrodesulfurization as well as for electrochemical hydrogen evolution. In this study, we investigate molybdenum-sulfide nanoparticles supported on Au(1 1 1) using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), aiming to correlate spectroscopically determined chemical states with atomically resolved nanostructure. The results of this study allow us to conclude the following: (1) the XPS results from our model system are in good agreement with previously published results on supported MoS₂ for industrial applications, validating in part the fidelity of the model system; (2) STM reveals that catalytically active, crystalline MoS₂ nanoparticles exhibiting the well-known metallic edge state are only present after a post-deposition annealing step in the synthesis procedure, without which the particles exhibit amorphous shapes and incomplete sulfidation; and (3) the sulfided nanoparticles are found to be stable in air at room temperature.     

Ordered arrangement of 9-aminoanthracene on Au(1 1 1) surfaces: A scanning tunneling microscopy study

We present a scanning tunneling microscopy (STM) investigation of 9-aminoanthracene (AA) on the reconstructed Au(1 1 1) surface. The bare Au(1 1 1) surface shows the herringbone reconstruction which is conserved upon deposition of the organic molecules. Most of the AA molecules are found to decorate the regions of fcc-stacking of the gold surface where a periodic linear arrangement is observed. The orientation of the long molecule axis of individual molecules is along the -directions of the Au substrate. In addition, for individual domains of the surface reconstruction, one of the three possible orientations is preferred. On substrate areas which exhibit a high step density, the steps are completely decorated by AA molecules. A detailed analysis of the STM images reveals that the molecules are located on top terrace levels. The fine structure of individual molecules on the terrace shows a clear dependence on the tunneling voltage and resembles the molecular orbitals of the free AA molecule.     

Formation of single layer h-BN on Pd(1 1 1)

The structure of hexagonal boron nitride (h-BN) on Pd(1 1 1) was studied with low energy electron diffraction (LEED), photoelectron spectroscopy and scanning tunnelling microscopy (STM). h-BN forms flat monolayers on the Pd(1 1 1) surface in contrast to Rh(1 1 1) where a complex self-assembled double layer structure, the nanomesh [M. Corso, W. Auwärter, M. Muntwiler, A. Tamai, T. Greber, J. Osterwalder, Science 303 (2004) 217], appears. The LEED patterns reveal a dominating 10 × 10 h-BN superstructure, with a second, distinct structure rotated by 30° and further azimuthally randomly oriented h-BN overlayers. This is consistent with STM images which show several different Moiré patterns associated with different rotation angles of the overlayer. Additionally the use of thin Pd(1 1 1) films instead of single crystal substrates was studied. No significant differences in the h-BN film quality were found.     

Structural analysis of the c(4 × 2) reconstruction in Si(0 0 1) and Ge(0 0 1) surfaces by low-energy electron diffraction

The c(4 × 2) structures in (0 0 1) surfaces of Si and Ge have been studied by low-energy electron diffraction (LEED). Using a proper cleaning method for the Si surface, we were able to observe clear c(4 × 2) LEED patterns up to incident energy of ∼400 eV as well as the Ge surface. Extensive experimental intensity-voltage curves allowed us to optimize the asymmetric dimer model up to the eighth layer (including the dimer layer) in depth in the dynamical LEED calculation. Optimized structural parameters are almost the same for the Si and Ge except for the height of the buckled-up atom of the asymmetric dimer. For the Ge surface, the structural parameters are in excellent agreement with those obtained by a previous theoretical calculation. The tilt angle and bond length of the dimer are 18 ± 1 (19 ± 1)° and 2.4 ± 0.1 (2.5 ± 0.1) Å for the Si(0 0 1) (Ge(0 0 1)), respectively.     

Highly sintered nickel oxide: surface morphology and FTIR investigation of CO adsorbed at low temperature

The monolayer of CO molecules adsorbed at low temperature on highly sintered nickel oxide, gives rise to a very symmetric IR absorption band at 2136 cm⁻¹ (θ_max) with a full-width at half-maximum (FWHM) of 3.7 cm⁻¹. This band shifts to higher frequenc upon decreasing the coverage, reaching the 2152 cm⁻¹ value for θ→0. The observed shift is due to changes in the lateral interactions (dynamic and static) among the adsorbed molecules. The observed spectral simplicity implies that most of the adsorbed CO molecules occupy crystallographically identical sites with a similar environment. Moreover, the remarkably small half-width indicates that inhomogeneous broadening effects, due to surface defects, are very small and that NiO microcrystals behave as single crystals. The morphology of microcrystals has been studied by SEM, AFM and HRTEM techniques: it was concluded that the surface termination of the sample is mainly represented by the (100) and (111) faces.