Tl/Ge(1 0 0) system: Phase formation and phase transitions

Using scanning tunneling microscopy, phase formation and temperature-driven phase transitions in Tl/Ge(1 0 0) system have been studied. Evolution of Tl overlayer structure has been considered for three temperature ranges, including around room temperature (RT), high-temperature (HT) (350-450 K) and low-temperature (LT) (20-100 K) ranges. Upon RT growth, a 2 × 1-Tl phase develops in submonolayer range and is completed at around 1 ML of Tl. Cooling of the RT-deposited Tl overlayer results in formation of a set of various LT structures. These are 1D chains, 5 × 4-Tl and “stroked” phases observed in submonolayer range and a long-period c(12 × 14)-Tl phase developed at around 1 ML. All transitions between these RT and LT structures are reversible. At doses beyond 1 ML, RT deposition of Tl onto Ge(1 0 0) leads to the growth of second-layer Tl stripes, forming arrays with a 1 × 4 periodicity. Meanwhile, structure of the first layer also changes and it displays a set of various reconstructions, c(2 × 8), c(10 × 6) and c(10 × 7). All these structures remain unchanged upon cooling to LT. Growth at HT as well as heating of RT-deposited Tl overlayer irreversibly produces 3 × 2-Tl phase whose rows become decorated by second-layer Tl stripes at prolonged Tl deposition.     

Surface alloying and anomalous diffusion of Bi on Cu(1 1 1)

We have used Low-Energy Electron Microscopy (LEEM) to study the formation and structure of the surface alloy of Bi on the Cu(1 1 1) surface. As a function of Bi coverage we find a progression from a dilute surface alloy to a structure, which coexists with a Bi overlayer when the Bi coverage exceeds 1/3 ML. At a temperature of 401 K, an unusual formation of alloy domains is observed. The origin of this effect is traced down to the mobility of Bi adatoms, which is found to strongly depend on the Bi coverage of the surface alloy on which they reside.     

Morphology of Ni ultrathin films on Mo(1 1 0) and W(1 0 0) studied by LEED and STM

The morphology of ultrathin Ni films on Mo(1 1 0) and W(1 0 0) has been studied by low-energy electron diffraction and scanning tunneling microscopy. Ni films grow pseudomorphically on Mo(1 1 0) at 300 K for a coverage of 0.15 ML. A (8 × 1) structure is found at 0.4 ML, which develops into a (7 × 1) structure by 0.8 ML. The film undergoes a structural change to fcc Ni(1 1 1) at 6 ML. The growth mode switches from layer-by-layer to Stranski-Krastanov between 4 ML and 6 ML. Annealing at around 850 K results in alloying of submonolayer films with the substrate, while for higher coverages the Ni agglomerates into nanowedge islands. Ni films grow pseudomorphically on W(1 0 0) up to a coverage of around 2 ML at 300 K, above which there is a structural change from bcc to hcp Ni with the epitaxial relationship . This is accompanied by the formation of orthogonal domains of uniaxial strain-relieving dislocations from the third layer of the film. For coverages up to 1 ML the growth proceeds by formation of two-dimensional islands, but shifts to three-dimensional growth by 2 ML with rectangular islands aligned along the 〈0 1 1〉 substrate directions. Annealing at around 550 K results in agglomeration of Ni into larger islands and increasing film roughness.     

Surface alloys, overlayer and incommensurate structures of Bi on Cu(1 1 1)

Using surface X-ray diffraction, we have determined the structure of three different sub-monolayer phases of Bi on Cu(1 1 1). In contrast to an early report, we find that at a coverage of 1/3 monolayer a substitutional surface alloy is formed with a (√3 × √3)R30° unit cell. For increasing coverage, de-alloying occurs, leading to an overlayer structure at a coverage of 0.5 ML in which the Bi atoms form zigzag chains. The surface contains three domains of this phase. Finally, at a slightly higher coverage of 0.53 ML, the unit cell is compressed in one direction, leading to a uniaxial-incommensurate phase with three rotational domains.The structure determination includes relaxations in the topmost layers and therefore allows a detailed comparison of the most important bond distances. This shows that an increased charge density of the Cu(1 1 1) surface is the main driving force for the different phases.     

Supramolecular assembly of biphenyl dicarboxylic acid on Au(1 1 1)

We investigate the structure of submonolayer film of 4,4′-biphenyl dicarboxylic acid (BDA) molecules on Au(1 1 1)-22 × √3 reconstructed surface with the use of scanning tunneling microscopy (STM). The BDA molecules form ordered structures on Au(1 1 1) surface which are commensurate with the substrate. We have concluded that the molecule-molecule interaction is mainly through hydrogen bonding formed by a straight dimer of BDA molecules. The straight dimer can be expressed as 4s + 2t or its six crystallographic equivalents using the unit vectors of the gold substrate of s and t. The length of hydrogen bonding (O-H-O) is estimated to be 0.31 nm assuming nearest neighbor distance of gold atoms of 0.275 nm. The ordering shows a clear contrast with the case of BDA on Cu(1 0 0) surface [S. Stepanow, N. Lin, F. Vidal, A. Landa, M. Ruben, J.V. Barth, K. Kern, Nanoletters 5 (2005) 901] in which a square type of ordering of molecules is observed by the formation of hydrogen bonding between a carboxylate (COO) and a benzene ring. The clear difference of the ordered structure on Cu(1 0 0) and Au(1 1 1) surface demonstrates that the absence (presence) of deprotonation of carboxyl group of BDA molecule on Au(1 1 1) (Cu(1 0 0)) switches the straight and square type ordering of BDA molecules.     

Sulphur overlayers on the Au(1 1 0) surface: LEED and TPD study

The adsorption and desorption of sulphur on the clean reconstructed Au(1 1 0)-(1 × 2) surface has been studied by low energy electron diffraction, Auger electron spectroscopy and temperature programmed desorption. The results obtained show a complex behaviour of the S/Au(1 1 0) system during sulphur desorption at different temperatures. Two structures of the stable ordered sulphur overlayer on the Au(1 1 0) surface, p(4 × 2) and c(4 × 4), were found after annealing the S/Au(1 1 0) system at 630 K and 463 K, respectively. The corresponding sulphur coverage for these overlayers was estimated by AES signal intensity analysis of the Au NOO and S LMM Auger lines to be equal to 0.13 ML and 0.2 ML, respectively. Both sulphur structures appear after removing an excess of sulphur, which mainly desorbs at 358 K as determined from TPD spectra. Furthermore, it was not possible to produce the lower coverage p(4 × 2) sulphur structure by annealing the c(4 × 4) surface. In the case of the p(4 × 2) S overlayer on the Au(1 1 0)-(1 × 2) surface it is proposed that the sulphur is attached to “missing row” sites only. The c(4 × 4) S overlayer arises via desorption of S₂ molecules that are formed on the surface due to mobility of sulphur atoms after a prolonged anneal.     

Au-induced nanofaceting and the stoichiometry of the Si(7 7 5)-Au surface

The Au-induced changes in the surface morphology of a Si(1 1 1) sample miscut 8° towards have been measured using room temperature scanning tunneling microscopy and low energy electron diffraction. Au coverages of less than 0.06 ML up to 0.43 ML have been investigated. In all cases Au adsorption produces dramatic changes in surface morphology. The Au-induced surface exhibits nanofacets with orientations that depend critically on the amount of Au deposited. Below 0.32 ML, the restructured surface always includes (7 7 5)-Au nanofacets suggesting that the (7 7 5)-Au facet is energetically preferred on this surface. The (7 7 5)-Au facet is oriented 8.5° from [1 1 1] towards and is characterized by 1-d chains spaced 21.3 Å apart that run along the direction. By maximizing the surface area of the (7 7 5) facets and optimizing the associated diffraction pattern we determine that the (7 7 5)-Au reconstruction is optimized at 0.24 ML and corresponds to a stoichiometry of 1.5 Au atoms per 1 × 1 unit cell. We believe that the local Au coverage on the (7 7 5) facet is 0.24 ML, and that the deficit/extra of Au at any particular coverage is accommodated by non-(7 7 5) facets. For example at 0.06 ML the regions of step bunching observed on the clean surface are eliminated and Au-induced (7 7 5) and Au-free (1 1 1)7 × 7 facets are already visible. Up to 0.18 ML the non-(7 7 5) facet is Au free. Beyond 0.32 ML, the (7 7 5)-Au reconstruction is no longer stable and the extra Au is accommodated by the formation of higher angle facets with smaller chain spacings.     

Surface phase diagram and temperature induced phase transitions of Sn/Cu(1 0 0)

Room temperature deposition of Sn on Cu(1 0 0) gives rise to a rich variety of surface reconstructions in the submonolayer coverage range. In this work, we report a detailed investigation on the phases appearing and their temperature stability range by using low-energy electron diffraction and surface X-ray diffraction. Previously reported reconstructions in the submonolayer range are p(2 × 2) (for 0.2 ML), p(2 × 6) (for 0.33 ML), ()R45° (for 0.5 ML), and c(4 × 4) (for 0.65 ML). We find a new phase with a structure for a coverage of 0.45 ML. Furthermore, we analyze the temperature stability of all phases. We find that two phases exhibit a temperature induced reversible phase transition: the ()R45° phase becomes ()R45° phase above 360 K, and the new phase becomes p(2 × 2) also above 360 K. The origin of these two-phase transitions is discussed.     

Direct STM evidence for Cu-benzoate surface complexes on Cu(1 1 0)

The chemisorption of benzoate on a Cu(1 1 0) crystal at room temperature was studied using low temperature scanning tunneling microscopy. STM images, obtained at 5 K for low benzoate coverage, show isolated surface species that consist of a single Cu adatom stabilizing two benzoate molecules in a flat orientation. These species are discussed in relation to other known metal-organic surface compounds. At higher coverage the overlayer, called the α-phase, was also observed at 5 K and found to contain features attributable to two Cu adatoms associated with two pairs of non-equivalent benzoate species. The observed topographic features are used to suggest refinements of the structural model of the ordered α-phase overlayer.     

The growth of ultrathin Au films on Ni{1 1 1}: A study with medium energy ion scattering

The initial growth of Au on Ni{1 1 1} is strongly influenced by the 15.7% difference in bulk lattice parameter between the two fcc metals. At 400 K, the first monolayer of Au grows on the Ni{1 1 1} surface as a (9 × 9) overlayer with 8 Au-Au spacings being equivalent to 9 Ni-Ni spacings. Umezawa et al. [Physical Review B 57 (1998) 8842; Surface Science 426 (1999) 225] reported that the growth of Au overlayers can occur either via a reverse (R)-mode (i.e., incorporating a stacking fault at the Au-Ni interface) or a normal (N)-mode—the relative proportion of each mode being strongly sensitive to growth temperature. Using the technique of medium energy ion scattering, we examine the growth of Au on Ni{1 1 1} at 400 K. We conclude that, at this deposition temperature, there is a preference for growth via the R-mode (74 ± 9%). In addition, we find that the Au overlayer has a considerably higher density than bulk Au being contracted isotropically by 3.1% in the {1 1 1} plane and also by ∼7% perpendicular to the {1 1 1} plane. We discuss possible explanations for our findings.     

Photoelectron spectroscopy study of Pb/Ag(1 1 1) in the submonolayer range

The vacuum deposition of Pb onto Ag(1 1 1) gives rise to two different surface structures depending on coverage and deposition temperature. At room temperature (RT), low energy electron diffraction (LEED) reveals a sharp reconstruction completed at 1/3 Pb monolayer (ML). Beyond, a close-packed Pb(1 1 1) incommensurate overlayer develops. At low temperature (LT, ∼100 K) the incommensurate structure is directly observed whatever the coverage, corresponding to the growth of close-packed two-dimensional Pb(1 1 1) islands. Synchrotron radiation Pb 5d core-level spectra clearly demonstrate that in each surface structure all Pb atoms have essentially a unique, but different, environment. This reflects the surface alloy formation between the two immiscible metals in the reconstruction and a clear signature of the de-alloying process at RT beyond 1/3 ML coverage.     

Ultra-thin films and surface alloying of Pd on Cu(1 1 1) investigated by medium energy ion scattering

The structure of Pd films on Cu(1 1 1) and the alloying between the films and the substrate have been investigated by medium energy ion scattering (MEIS) using 100 keV H⁺ ions. Data are presented for the and alignments (nominal one- and three-layer alignments, respectively). It is found that beyond 1 ML the Pd grows in a twinned fcc structure, the incommensurate nature of which increases the visibility of the Cu(1 1 1) substrate to MEIS. Deposition of 0.2 ML of Pd produces a structure in which Pd mostly occupies the top two layers which have interlayer distances d₁₂ = 208 ± 4 pm and d₂₃ = 211 ± 4 pm. Some twinning is also present in this structure. Upon annealing 1.6 ML of Pd to 600 K for 1 min, the copper and palladium interdiffuse leaving around 0.4 ML of visible palladium. Energy plots show that there are several layers with an altered structure present over at least part of the surface. This may be due to large scale interdiffusion or alloy island formation. Incremental annealing to successively higher temperatures shows that the structural transformation begins around 500 K.     

Adsorption structure of glycine on TiO2(1 1 0): A photoelectron diffraction determination

High-resolution core-level photoemission and scanned-energy mode photoelectron diffraction (PhD) of the O 1s and N 1s states have been used to investigate the interaction of glycine with the rutile TiO₂(1 1 0) surface. Whilst there is clear evidence for the presence of the zwitterion CH₂COO⁻ with multilayer deposition, at low coverage only the deprotonated glycinate species, NH₂CH₂COO is present. Multiple-scattering simulations of the O 1s PhD data show the glycinate is bonded to the surface through the two carboxylate O atoms which occupy near-atop sites above the five-fold-coordinated surface Ti atoms, with a Ti-O bondlength of 2.12 ± 0.06 Å. Atomic hydrogen arising from the deprotonation is coadsorbed to form hydroxyl species at the bridging oxygen sites with an associated Ti-O bondlength of 2.01 ± 0.03 Å. Absence of any significant PhD modulations of the N 1s emission is consistent with the amino N atom not being involved in the surface bonding, unlike the case of glycinate on Cu(1 1 0) and Cu(1 0 0).     

Formation and hydrogenation of p(2 × 2)-N on Pt(1 1 1)

The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N₂ TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm⁻¹) peak at 3322 cm⁻¹. The areas of the H₂ TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here.     

Quantitative determination of the local structure of thymine on Cu(1 1 0) using scanned-energy mode photoelectron diffraction

The local adsorption structures of the surface species formed by interaction of thymine with a Cu(1 1 0) surface at room temperature, and after heating to ∼530 K, have been investigated. Initial characterisation by soft-X-ray photoelectron spectroscopy and O K-edge near-edge X-ray absorption fine structure (NEXAFS) indicates the effect of sequential dehydrogenation of the NH species and provides information on the molecular orientation. O 1s and N 1s scanned-energy mode photoelectron diffraction shows the species at both temperatures bond to the surface through both carbonyl O atoms and the deprotonated N atom between them, each bonding atom adopting near-atop sites on the outermost Cu surface layer. The associated bondlengths are 1.96 ± 0.03 Å for Cu-N and 1.91 ± 0.03 Å and 2.03 ± 0.03 Å for the two inequivalent Cu--O bonds. The molecular plane lies almost exactly in the close-packed azimuth, but with a tilt relative to the surface normal of approximately 20°. Heating to ∼530 K, or deposition at this temperature, appears to lead to dehydrogenation of the second N atom in the ring, but no significant change in the adsorption geometry.     

Growth process and surface structure of MnSi on Si(1 1 1)

The solid-phase epitaxial growth process and surface structure of MnSi on Si(1 1 1) were investigated by coaxial impact-collision ion scattering spectroscopy (CAICISS) and atomic force microscopy (AFM). For the Si(1 1 1) sample deposited with 30 monolayers (ML) of Mn at room temperature, the intermixing of Mn and Si gradually started at 100 °C and reached equilibrium at approximately 400 °C. At this equilibrium state, the Mn atoms were transformed into crystalline MnSi film. Further annealing caused the desorption of Mn atoms. We identified the structure of MnSi as cubic B20 and the crystallographic orientation relationships as Si(1 1 1)//MnSi(1 1 1) and Si[]//MnSi[]. The MnSi(1 1 1) surface was found to have a dense Si terminating layer on its topmost surface. On the other hand, 3 ML of Mn deposited on Si(1 1 1) reacted with Si even at room temperature and formed a pseudomorphic structure. This structure was transformed into MnSi after annealing. A filmlike morphology with protrusions was observed for the sample with 30 ML of Mn, while island growth occurred for the sample with 3 ML of Mn.     

Mixed layer formation of copper overlayers on Ni(1 1 0) surface

Copper overlayer formation on the Ni(1 1 0) surface was studied by scanning tunneling microscopy (STM) in an ultrahigh vacuum. Atom-resolved STM images showed that initially deposited Cu is replaced with surface Ni atoms forming atom-size depressions on the Ni(1 1 0) terraces and a Ni-rich quasi-one-dimensional island along the direction. Further Cu deposition yields a mosaic structure on the islands, indicating Cu/Ni mixed layer formation. From the quantitative measurement of the Cu/Ni ratio on the substrate and the islands, impinging Cu will be replaced with surface Ni whereas expelled Ni and directly impinging Cu to the island form the mixed island. The number of Cu atoms in the islands, however, more than the directly impinging Cu, indicate significant Cu/Ni replacement at the periphery of the island.     

Oxidation of ultrathin indium layers on W(1 1 0)--a core-level photoemission study

We have studied the reaction of ultrathin In overlayers on W(1 1 0) with molecular oxygen at 300 K. At a coverage of 0.25 monolayers (ML) oxygen first chemisorbs dissociatively at free tungsten sites and oxidation of In occurs with some delay. At an In coverage of 1.2 ML complete oxidation of the closed overlayer is observed. Layers of 3 ML thickness first show rapid transformation from In to an In₂O₃-like species until an oxide monolayer is formed. Further oxidation occurs at much reduced rate. No oxygen-induced restructuring is observed for In at 300 K, in contrast to the response of Ag monolayers deposited on W(1 1 0).     

Growth mode and electronic structure of Au nano-clusters on NiO(0 0 1) and TiO2(1 1 0)

The growth mode and electronic structure of Au nano-clusters grown on NiO and TiO₂ were analyzed by reflection high-energy electron diffraction, a field-emission type scanning electron microscope, medium energy ion scattering and photoelectron spectroscopy. Au was deposited on clean NiO(0 0 1)-1 × 1 and TiO₂(1 1 0)-1 × 1 surfaces at room temperature with a Knudsen cell at a rate of 0.25-0.35 ML/min (1 ML = 1.39 × 10¹⁵ atoms/cm²:Au(1 1 1)). Initially two-dimensional (2D) islands with thickness of one Au-atom layer grow epitaxially on NiO(0 0 1) and then neighboring 2D-islands link each other to form three-dimensional (3D)-islands with the c-axis oriented to the [1 1 1] direction. The critical size to form 3D-islands is estimated to be about 5 nm². The shape of the 3D-islands is well approximated by a partial sphere with a diameter d and height h ranging from 2.0 to 11.8 nm and from 0.95 to 4.2 nm, respectively for Au coverage from 0.13 to 4.6 ML. The valence band spectra show that the Au/NiO and Au/TiO₂ surfaces have metallic characters for Au coverage above 0.9 ML. We observed Au 4f spectra and found no binding energy shift for Au/NiO but significant higher binding energy shifts for Au/TiO₂ due to an electron charge transfer from Au to TiO₂. The work function of Au/NiO(0 0 1) gradually increases with increase in Au coverage from 4.4 eV (NiO(0 0 1)) to 5.36 eV (Au(1 1 1)). In contrast, a small Au deposition(0.15 to 1.5 ML) on TiO₂(1 1 0) leads to reduction of the work function, which is correlated with an electron charge transfer from Au to TiO₂ substrate.