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.     

CF interaction with Si(1 0 0)-(2 × 1): Molecular dynamics simulation

In this study, the interaction of CF with the clean Si(1 0 0)-(2 × 1) surface at normal incidence and room temperature was investigated using molecular dynamics simulation. Incident energies of 2, 12 and 50 eV were simulated. C atoms, arising from dissociation, preferentially react with Si to form Si-C bonds. A Si_xC_yF_z interfacial layer is formed, but no etching is observed. The interfacial layer thickness increases with increasing incident energy, mainly through enhanced penetration of the silicon lattice. Silicon carbide and fluorosilyl species are formed at 50 eV, which is in good agreement with available experimental data. The level of agreement between the simulated and experimental results is discussed.     

Ultra-thin Si overlayers on the TiO2 (1 1 0)-(1 × 2) surface: Growth mode and electronic properties

The growth of thin subnanometric silicon films on TiO₂ (1 1 0)-(1 × 2) reconstructed surfaces at room temperature (RT) has been studied in situ by X-ray and ultra-violet photoelectron spectroscopies (XPS and UPS), Auger electron and electron-energy-loss spectroscopies (AES and ELS), quantitative low energy electron diffraction (LEED-IV), and scanning tunneling microscopy (STM). For Si coverage up to one monolayer, a heterogeneous layer is formed. Its composition consists of a mixture of different suboxides SiO_x (1 < x ? 2) on top of a further reduced TiO₂ surface. Upon Si coverage, the characteristic (1 × 2) LEED pattern from the substrate is completely attenuated, indicating absence of long-range order. Annealing the SiO_x overlayer results in the formation of suboxides with different stoichiometry. The LEED pattern recovers the characteristic TiO₂ (1 1 0)-(1 × 2) diagram. LEED I-V curves from both, substrate and overlayer, indicate the formation of nanometric sized SiO_x clusters.     

CO2 adsorption on Cr(1 1 0) and Cr2O3(0 0 0 1)/Cr(1 1 0)

We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr₂O₃(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO₂ adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of E_i = 0.1-1.1 eV and adsorption temperatures of T_s = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy E_d = 33.3 kJ/mol, first order pre-exponential 1 × 10¹³ s⁻¹). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (E_d = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S₀, is independent of T_s for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing E_i, with S₀ smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low E_i is approx. independent of coverage (Kisliuk-shape) and increases initially at large E_i with coverage (adsorbate-assisted adsorption). CO₂ physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of E_d has been obtained by means of a Redhead analysis of the TDS curves.     

A DFT + U description of oxygen vacancies at the TiO2 rutile (1 1 0) surface

Experimental observations indicate that removing bridging oxygen atoms from the TiO₂ rutile (1 1 0) surface produces a localised state approximately 0.7 eV below the conduction band. The corresponding excess electron density is thought to localise on the pair of Ti atoms neighbouring the vacancy; formally giving two Ti³⁺ sites. We consider the electronic structure and geometry of the oxygen deficient TiO₂ rutile (1 1 0) surface using both gradient-corrected density functional theory (GGA DFT) and DFT corrected for on-site Coulomb interactions (GGA + U) to allow a direct comparison of the two methods. We show that GGA fails to predict the experimentally observed electronic structure, in agreement with previous uncorrected DFT calculations on this system. Introducing the +U term encourages localisation of the excess electronic charge, with the qualitative distribution depending on the value of U. For low values of U (?4.0 eV) the charge localises in the sub-surface layers occupied in the GGA solution at arbitrary Ti sites, whereas higher values of U (?4.2 eV) predict strong localisation with the excess electronic charge mainly on the two Ti atoms neighbouring the vacancy. The precise charge distribution for these larger U values is found to differ from that predicted by previous hybrid-DFT calculations.     

Formation and characterization of the Cu2O overlayer on Zn-terminated ZnO(0 0 0 1)

Low-energy electron diffraction, X-ray photoelectron spectroscopy and synchrotron-radiation-excited angle-resolved photoelectron spectroscopy have been used to characterize Cu-oxide overlayers on the Zn-terminated ZnO(0 0 0 1) surface. Deposition of Cu on the ZnO(0 0 0 1)-Zn surface results in the formation of Cu clusters with (1 1 1) top terraces. Oxidation of these clusters by annealing at 650 K in O₂ atmosphere (1.3 × 10⁻⁴ Pa) leads to an ordered Cu₂O overlayer with (1 1 1) orientation. Good crystallinity of the Cu₂O(1 1 1) overlayer is proved by energy dispersion of one of Cu₂O valence bands. The Cu₂O(1 1 1) film exhibits a strong p-type semiconducting nature with the valence band maximum (VBM) of 0.1 eV below the Fermi level. The VBM of ZnO at the Cu₂O(1 1 1)/ZnO(0 0 0 1)-Zn interface is estimated to be 2.4 eV, yielding the valence-band offset of 2.3 eV.     

Core-level shifts at the Pt/W(1 1 0) monolayer bimetallic interface

We have measured W and Pt 4f_7/2 core-level photoemission spectra from interfaces formed by ultrathin Pt layers on W(1 1 0), completing our core-level measurements of W(1 1 0)-based bimetallic interfaces involving the group-10 metals Ni, Pd, and Pt. With increasing Pt coverage the sequence of W spectra can be described using three interfacial core-level peaks with binding-energy (BE) shifts (compared to the bulk) of −0.220 ± 0.015, −0.060 ± 0.015, and +0.110 ± 0.010 eV. We assign these features to 1D, 2D pseudomorphic (ps), and 2D closed-packed (cp) Pt phases, respectively. For ∼1 ps ML the Pt 4f_7/2 BE is 71.40 ± 0.02 eV, a shift of +0.46 ± 0.09 eV with respect to the BE of bulk Pt metal. The W 4f_7/2 core-level shifts induced by all three adsorbates are semiquantitatively described by the Born-Haber-cycle based partial-shift model of Nilsson et al. [39]. As with Ni/W(1 1 0), the difference in W 4f_7/2 binding energies between ps and cp Pt phases has a large structural contribution. The Pt 4f lineshape is consistent with a small density of states at the Fermi level, reflective of the Pt monolayer having noble-metal-like electronic structure.     

Vertical bonding distances of PTCDA on Au(1 1 1) and Ag(1 1 1): Relation to the bonding type

The vertical bonding distance of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) above the Au(1 1 1) surface has been measured by the normal incidence X-ray standing wave (NIXSW) technique. The carbon skeleton of PTCDA has a vertical distance of D = (3.27 ± 0.02) Å to the Au(1 1 1) substrate. This distance corresponds very nearly to the sum of the van der Waals radii of carbon and gold, suggesting the adsorption to be a physisorptive one. In contrast, the PTCDA/Ag(1 1 1) interface which according to spectroscopic data follows the standard model of chemisorption very closely, shows a considerably smaller bonding distance of D = (2.86 ± 0.01) Å [A. Hauschild, K. Karki, B.C.C. Cowie, M. Rohlfing, F.S. Tautz, M. Sokolowski, Phys. Rev. Lett. 94 (2005) 036106, comment: Rurali et al., Phys. Lett. 95 (2005) 209205, reply: Phys. Rev. Lett. 95 (2005) 209206]. The different vertical adsorption heights of PTCDA on gold and silver are discussed in relation to the different bonding mechanisms on both noble metal surfaces.     

Core-level spectroscopy of the Pd/W(1 1 0) interface: Evidence of long-range Pd-island-W interactions at submonolayer Pd coverages

We have measured W 4f_7/2 core-level photoemission spectra from W(1 1 0) in the presence of Pd overlayers for coverages up to ∼1 pseudomorphic monolayer (ML). At coverages close to 0.05 ML a striking change in the W core-level spectrum is observed, which we interpret as indicating a long-range lateral effect of 2D Pd islands upon the W electronic structure in both the first and second W layers. As the coverage increases the long-range effect weakens and finally vanishes near 0.85 ML. Above this coverage the W spectra are typical for a W-based bimetallic interface, with the first-layer W atoms exhibiting a small interfacial core-level shift (−95 ± 5 meV) compared to the bulk atoms.     

Scanning tunnelling microscopy and spectroscopy of the reduced TiO2(1 0 0) surface

Scanning tunnelling microscopy and current imaging tunnelling spectroscopy were used to study the topographic and electronic structure of a reduced TiO₂(1 0 0) surface. The STM results showed that the TiO₂(1 0 0) surface is capable to form (1 × 7) reconstruction which can transform to (1 × 3) reconstruction due to reoxidation of the surface. The CITS results showed that the (1 × 7) reconstruction is much more metallic in compared to the (1 × 3) reconstruction showing pronounced surface states at energy 1.3 eV and 0.8 eV below the Fermi level and at energy 1.0-1.2 eV above the Fermi level.     

Formation and characterization of Rh-Mo bimetallic layers on the TiO2(1 1 0) surface

The investigation of Rh, Mo and Rh-Mo nanosized clusters formed by physical vapor deposition on TiO₂(1 1 0) single crystal was performed by X-ray Photoelectron Spectroscopy (XPS), Low Energy Ion Scattering (LEIS) and Auger Electron Spectroscopy (AES). There was no sign for site-exchange between Mo and Rh atoms during deposition of Mo onto Rh particles at 330 K. Mixing between Ti and Mo ions was facilitated at the Mo particle-titania interface due to reaction at 550-700 K. The redox process between titania and Mo deposit was hindered at 330 K by forming predeposited rhodium layer (Θ_Rh = 2.0 ML), but reached nearly the same extent as without Rh after moderate heating to 600 K. The encapsulation of Rh by titania was complete by about 700 K in the presence of 1.2 ML Mo, in case of Mo-predeposition and Mo-postdeposition as well. Elevating the temperature of TiO₂/Rh-Mo layers above 700 K, these metals form alloy at the Mo-Rh interface irrespective of deposition sequences.     

Formation of strontium template on Si(1 0 0) by atomic layer deposition

The formation of ordered Sr overlayers on Si(1 0 0) by Atomic Layer Deposition (ALD) from bis(triisopropylcyclopentadienyl) Strontium (Sr(C₅ⁱPr₃H₂)₂) and H₂O has been investigated. SrO overlayers were deposited on a 1-2 nm SiO₂/Si(1 0 0) substrate, followed by a deoxidation process to remove the SiO₂ layer at high temperatures. Auger electron spectroscopy, Rutherford backscattering spectrometry, spectroscopic ellipsometry, and low-energy electron diffraction were used to investigate the progress of both ALD and deoxidation processes. Results show that an ordered Sr/Si(1 0 0) surface with 2 × 1 pattern can be obtained after depositing several monolayers of SrO on Si using ALD followed by an anneal at 800-850 °C. The (2 × 1) ordered Sr/Si(1 0 0) surface is known to be an excellent template for the epitaxial growth of SrTiO₃ (STO) oxide. The present results demonstrate that ALD is a potential alternative to molecular beam epitaxy methods for the fabrication of epitaxial oxides on semiconductor substrates.     

High resolution analysis of the rotational levels of the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states of SO2

A high resolution (0.0018 cm⁻¹) Fourier transform instrument has been used to record the spectrum of an enriched ³⁴S (95.3%) sample of sulfur dioxide. A thorough analysis of the ν₂, 2ν₂ − ν₂, ν₁, ν₁ + ν₂ − ν₂, ν₃, ν₂ + ν₃ − ν₂, ν₁ + ν₂ and ν₂ + ν₃ bands has been carried out leading to a large set of assigned lines. From these lines ground state combination differences were obtained and fit together with the existing microwave, millimeter, and terahertz rotational lines. An improved set of ground state rotational constants were obtained. Next, the upper state rotational levels were fit. For the (0 1 0), (1 1 0) and (0 1 1) states, a simple Watson-type Hamiltonian sufficed. However, it was necessary to include explicitly interacting terms in the Hamiltonian matrix in order to fit the rotational levels of the (0 2 0), (1 0 0) and (1 0 1) states to within their experimental accuracy. More explicitly, it was necessary to use a ΔK = 2 term to model the Fermi interaction between the (0 2 0) and (1 0 0) levels and a ΔK = 3 term to model the Coriolis interaction between the (1 0 0) and (0 0 1) levels. Precise Hamiltonian constants were derived for the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states.     

The growth and structure of titanium dioxide films on a Re(1 0 −1 0) surface: Rutile(0 1 1)-(2 × 1)

Titanium dioxide films were grown on Re(1 0 −1 0) by Ti vapor deposition in oxygen at T = 830 K and studied by means of low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS) and X-ray diffraction (XRD). The Ti oxide stoichiometry was determined by XPS as Ti:O = 1:2, with the Ti oxidation state (4+). The TiO₂ growth was monitored by means of LEED as a function of film thickness. Extending the coverage from the submonolayer into the multilayer regime gives rise to a p(2 × 2) pattern, a (poorly ordered) (1 × 1), and, finally, a stable (2 × 2) structure, the latter being associated with a homogeneous TiO₂ phase. For normal electron incidence, the (2 × 2) LEED pattern exhibits systematically extinguished beams at (n ± 1/2, 0) positions, indicating a glide mirror plane. The pg(2 × 2) structure could be explained by both a rutile(0 1 1)-(2 × 1) reconstructed surface and a bulk truncated brookite(0 0 1) surface. Faceting phenomena, i.e. running LEED spots, observed with thin TiO₂ films point to the formation of a rutile(0 1 1)-(2 × 1) surface with two domains and {0 1 1}-(2 × 1) facets and rule out the brookite alternative. Confirmation of this assignment was obtained by an XRD analysis performed at the Berlin synchrotron facility BESSY.     

The small unit cell reconstructions of SrTiO3(1 1 1)

We analyze the basic structural units of simple reconstructions of the (1 1 1) surface of SrTiO₃ using density functional calculations. The prime focus is to answer three questions: what is the most appropriate functional to use; how accurate are the energies; what are the dominant low-energy structures and where do they lie on the surface phase diagram. Using test calculations of representative small molecules we compare conventional PBE-GGA with higher-order methods such as the TPSS meta-GGA and on-site hybrid methods PBE0 and TPSSh, the later being the most accurate. There are large effects due to reduction of the metal d oxygen sp hybridization when using the hybrid methods which are equivalent to a dynamical GGA + U, which leads to rather substantial improvements in the atomization energies of simple calibration molecules, even though the d-electron density for titanium compounds is rather small. By comparing the errors of the different methods we are able to generate an estimate of the theoretical error, which is about 0.25 eV per 1 × 1 unit cell, with changes of 0.5-1.0 eV per 1 × 1 cell with the more accurate method relative to conventional GGA. An analysis of the plausible structures reveals a new low-energy TiO₂-rich configuration with octahedral co-ordination. This structure can act as a template for layers of either TiO or Ti₂O₃, consistent with experimental results. The results also suggest that both the fracture surface and the stoichiometric SrTiO₃(1 1 1) surface should spontaneously disproportionate into SrO and TiO₂ rich domains.     

Magnetic ordering of Vn/Mo(0 0 1) systems: Ab-initio calculations

A density-functional theory (DFT) study is performed using a full-potential linearized-augmented-plane-waves (FP-LAPW) method to investigate the magnetic structure of vanadium-molybdenum systems (V_n/Mo(0 0 1), n = 1, 2). The topmost V layers relax inward in both systems with a larger contraction in V₂/Mo(0 0 1) system. A p(1 × 1) in-plane ferromagnetic ordering with appreciable magnetic moments is obtained on V overlayers, which is found to be the ground state in both systems. The layers below the surface exhibit induced magnetism with antiferromagnetic interlayer coupling.     

Photoemission study of the modification of the electronic structure of transition-metal overlayers on TiO2 surfaces II. Cr on TiO2(0 0 1)

The electronic states of the Cr overlayers on TiO₂(0 0 1) surfaces have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. At lower coverages, Cr deposition on TiO₂(0 0 1) creates two well separated in-gap emissions due to the formation of surface Ti³⁺ (3d¹) ions and Cr³⁺ (3d³) ions. At higher coverages, the in-gap emission is developed into the 2-peak-structure emission of Cr 3d character. The corresponding state is considered to be of metallic nature from the viewpoint of the high ability of oxygen adsorption, but has no Fermi edge, indicating a possibility of forming small Cr clusters on TiO₂(0 0 1) at this stage.     

Formation of oxygen vacancies on the TiO2(1 1 0) surfaces

Density functional theory was employed to investigate the formation and properties of the oxygen vacancies on the rutile TiO₂(1 1 0) surface. It is found that the formation of the positively charged bridging-oxygen vacancy (BOV⁺, 4.2 eV) is the most favored one, followed by the positively charged in-plane-oxygen vacancy (POV⁺, 4.5 eV). In contrast, the formation of the neutral bridging-oxygen and in-plane-oxygen vacancies (BOV and POV), and their dication oxygen vacancies (BOV²⁺ and POV²⁺) needs much higher energies (7.9 and 8.3 vs. 8.1 and 8.6 eV), respectively.     

Scanning tunneling microscopy and spectroscopy investigations of copper phthalocyanine adsorbed on Al2O3/Ni3Al(1 1 1)

Low temperature scanning tunneling microscopy (LT-STM) and scanning tunneling spectroscopy (STS) have been used to investigate adsorbed copper phthalocyanine (C₃₂H₁₆N₈Cu) molecules on an ordered ultrathin Al₂O₃ film on the Ni₃Al(1 1 1) surface as a function of coverage and annealing temperature. For sub-monolayer coverage and a deposition temperature of 140 K two different planar molecular adsorption configurations rotated by 30° with respect to each other were observed with submolecular resolution in the STM images. The template effect of the underlying oxide film on the CuPc orientation, however, is only weak and negligible at higher coverages. For θ_CuPc ≈ 1 ML, before completion of the first layer, the growth of a second layer was already observed. The measured spacing of 3.5 Å between first and second layer corresponds to the distance between the layers in the α-modification of crystalline CuPc. The molecules deposited at 140 K are thermally stable upon prolonged annealing to temperatures up to 250 K. By the use of STS the lowest unoccupied molecular orbital (LUMO) of the adsorbed copper phthalocyanine molecules has been identified at an energy of 1.2 eV above E_F. The lateral distribution of the electronic states of the CuPc has been analyzed and mapped by STS.     

Supramolecular architecture of organic molecules: PTCDA and CuPc on a Cu(1 1 1) substrate

We report on the molecular self-assembly of a highly ordered mixed molecular structure of copper-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) on Cu(1 1 1) starting from dense PTCDA domains. Low temperature scanning tunneling microscopy (LT-STM) data reveal the surface structure as the CuPc coverage is stepwise increased. A highly ordered mixed phase as well as a disordered mixed phase can be found, where the highly ordered mixed phase seems to be thermodynamically favored. Low energy electron diffraction (LEED) measurements aid the STM analysis. Tentative models for the formation of the highly ordered mixed phase are given.