Olefin metathesis reaction on GaN (0 0 0 1) surfaces

Proof-of-concept reactions were performed on GaN (0 0 0 1) surfaces to demonstrate surface termination with desired chemical groups using an olefin cross-metathesis reaction. To prepare the GaN surfaces for olefin metathesis, the surfaces were hydrogen terminated with hydrogen plasma, chlorine terminated with phosphorous pentachloride, and then terminated with an alkene group via a Grignard reaction. The olefin metathesis reaction then bound 7-bromo-1-heptene. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements following each step in the reaction scheme. The XPS data was used to qualitatively identify surface chemical species and to quantitatively determine molecular surface coverage. The bromine atom in 7-bromo-1-heptene served as a heteroatom for identification with XPS. The reaction scheme resulted in GaN substrates with a surface coverage of 0.10 monolayers and excellent stability towards oxidation when exposed to oxygen plasma.     

Thin PTCDA films on Si(0 0 1): 1. Growth mode

We have studied the interface and thin film formation of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA) on clean and on hydrogen passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), near edge X-ray absorption fine structure (NEXAFS), low energy electron diffraction (LEED), and atomic force microscopy (AFM). On the passivated surface the LEED pattern is somewhat diffuse but reveals that the molecules grow in several ordered domains with equivalent orientations to the substrate. NEXAFS shows that the molecules are lying flat on the substrate. The Si 2p XPS line shape is not affected when the film is deposited so it can be concluded that the interaction at the interface between PTCDA and the substrate is weak. The evolution of the film formation appears to be homogeneous for the first monolayer with a nearly complete coverage of flat lying molecules based on the XPS attenuation. For layer thickness of 0.5-2 monolayers (ML) the molecules start to form islands, attracting the molecules in between, leaving the substrate partly uncovered. For thicker films there is a Stranski-Krastanov growth mode with thick islands and a monolayer thick film in between. For the clean surface the ordering of the film is much lower and angle resolved photoelectron spectroscopy (ARPES) of the molecular orbitals have only a small dependence of the emission angle. NEXAFS shows that the molecules do not lie flat on the surface and also reveal a chemical interaction at the interface.     

Co growth on Si(0 0 1) and Si(1 1 1) surfaces: Interfacial interaction and growth dynamics

In situ X-ray photoelectron spectroscopy (XPS) and ex situ atomic force microscopy (AFM) were used to study the growth of thin cobalt films at room temperature (RT) on both clean and H-terminated Si(0 0 1) and Si(1 1 1) surfaces. The growth proceeds by first forming an initial CoSi₂-like phase at the growth front of the Si substrate. With increasing Co coverage the interfacial layer composition becomes richer in Co and eventually a metallic Co film is formed on top. Hydrogen termination of the Si surface did not suppress the reaction of Co and Si. A pseudo-layer-by-layer growth mode is proposed to describe the growth of Co on H-terminated Si surfaces, while closed-packed small island growth occurs on clean Si surfaces. The difference in growth mode can be attributed to the increase in the surface mobility of Co adatoms in the presence of hydrogen.     

Composition and structure of chemically prepared GaAs(1 1 1)A and (1 1 1)B surfaces

The (1 1 1)A and (1 1 1)B surfaces of GaAs chemically treated in HCl-isopropanol solution (HCl-iPA) and annealed in vacuum were studied by means of X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED) and electron energy loss spectroscopy (EELS). To avoid uncontrolled contamination, chemical treatment and sample transfer into UHV were performed under pure nitrogen atmosphere. The HCl-iPA treatment removes gallium and arsenic oxides, with about 0.5-3 ML of elemental arsenic being left on the surface, depending on the crystallographic orientation. With the increase of the annealing temperature, a sequence of reconstructions were identified by LEED: (1 × 1) and (2 × 2) on the (1 1 1)A surface and (1 × 1), (2 × 2), (1 × 1), (3 × 3), (√19 × √19) on the (1 1 1)B surface. These sequences of reconstructions correspond to the decrease of surface As concentration. The structural properties of chemically prepared GaAs(1 1 1) surfaces were found to be similar to those obtained by decapping of As-capped epitaxial layers.     

Enhanced reactivity and selectivity in oxidation of Cu(1 0 0) and α-Cu-Al(5 at.%)(1 0 0) surfaces studied by electron and ion spectroscopies

In this study we investigate the influence of alloying on the reactivity and bonding of oxygen on α-Cu-Al(5 at.%)(1 0 0) oriented single crystal surfaces by X-ray photoelectron spectroscopy (XPS), ultra-violet spectroscopy (UPS) and low energy ion scattering (LEIS) spectroscopy, at room temperature. It was found that alloying results in an enhanced reactivity of both Cu and Al sites in comparison with the pure metals. According to adsorption curves calculated from XPS, saturation of the alloy surface occurs for exposures of ∼15 L. At saturation the total amount of adsorbed oxygen is similar for the alloy and pure copper surfaces. It was determined that first mostly Al sites are oxidized, followed by simultaneous oxidation of Cu and Al sites. At saturation the amount of oxygen bonded to Cu sites is ∼1.7 larger then that bonded to Al sites. From a comparison of the XPS and LEIS data analysis as a function of oxygen exposure it was found that oxidation of α-Cu-Al(5 at.%)(1 0 0) alloy is a multi-stage process with fast and slow stages. These stages involve an interplay of chemisorption, sub-surface diffusion of oxygen and Al segregation. UPS measurements show an increase in the work function of the alloy surface with oxygen adsorption. This is a contrast to pure Cu surfaces where the work function decreases at the initial stages of oxidation followed by an increase with oxygen exposure. Annealing to 400 °C drives the oxidized alloy surface into its thermodynamic state resulting in the formation of an aluminum oxide layer. Possible mechanisms to explain the enhanced reactivity of the alloy surface compared to that of pure copper are suggested and discussed.     

Coordination-dependent valence state of Sm adsorbed on Cu(1 0 0) and (1 1 0) studied by STM and XPS

Geometric and electronic structures of Sm adlayers on Cu(1 0 0) and (1 1 0) were studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The present results, in addition to the previous results for Sm/Cu(1 1 1) [Y. Nakayama, H. Kondoh, T. Ohta, Surf. Sci. 552 (2004) 53], indicate that the valence state of Sm adsorbed on Cu surfaces is determined by Sm-Sm and Sm-Cu coordination numbers. We propose that the valence state of the adsorbed Sm atoms can be explained by a simple thermodynamic equation including the coordination numbers.     

Fabrication of nanostructures on Si(1 0 0) and GaAs(1 0 0) by local anodic oxidation

Atomic force microscopes have become useful tools not only for observing surface morphology and nanostructure topography but also for fabrication of various nanostructures itself. In this paper, the application of AFM for fabrication of nanostructures by local anodic oxidation (LAO) of Si(1 0 0) and GaAs(1 0 0) surfaces is presented. A special attention is paid to finding relations between the size of oxide nanolines (height and half-width) and operational parameters as tip-sample voltage and tip writing speed. It was demonstrated that the formation of silicon oxide lines obeys the Cabrera-Mott theory, i.e. the height of the lines grow, linearly with tip-sample voltage and is inversely proportional to logarithm of tip writing speed. As for GaAs substrates, the oxide line height grows linearly with tip-sample voltage as well but LAO exhibits a certain deviation from this theory. It is shown that the selective chemical etching of Si or GaAs ultrathin films processed by LAO makes it possible to use these films as nanolithographic masks for further nanotechnologies, e.g. fabrication of metallic nanostructures by ion-beam bombardment. The ability to control LAO and tip motion can be utilized in fabrication of complex nanostructures finding their applications in nanoelectronic devices, nanophotonics and other high-tech areas.     

Electron and lattice structure of ultra thin Ag films on Si(1 1 1) and Si(0 0 1)

We studied the low temperature (T ? 130 K) growth of Ag on Si(0 0 1) and Si(1 1 1) flat surfaces prepared by Si homo epitaxy with the aim to achieve thin metallic films. The band structure and morphology of the Ag overlayers have been investigated by means of XPS, UPS, LEED, STM and STS. Surprisingly a (√3 × √3)R30° LEED structure for Ag films has been observed after deposition of 2-6 ML Ag onto a Si(1 1 1)(√3 × √3)R30°Ag surface at low temperatures. XPS investigations showed that these films are solid, and UPS measurements indicate that they are metallic. However, after closer STM studies we found that these films consists of sharp Ag islands and (√3 × √3)R30°Ag flat terraces in between. On Si(0 0 1) the low-temperature deposition yields an epitaxial growth of Ag on clean Si(0 0 1)-2 × 1 with a twinned Ag(1 1 1) structure at coverage’s as low as 10 ML. Furthermore the conductivity of few monolayer Ag films on Si(1 0 0) surfaces has been studied as a function of temperature (40-300 K).     

The interaction of carbon with Si(1 1 1):As and Si(1 1 1):H surfaces, a theoretical study

Density functional theory calculations have been performed to determine the adsorption site of carbon at the Si(1 1 1):As and Si(1 1 1):H surfaces at different coverages. The As- and H-passivated surfaces were simulated by replacing the topmost Si layer by As or by saturating the Si dangling bonds with hydrogen atoms, respectively. Different high symmetry sites were considered. Carbon was placed successively in the fourfold (T₄) or threefold coordinated (H₃), the ontop (T₁) sites or substituted for a Si atom in the S₅ position located underneath the Si adatom in the T₄ site. We found that the preferred carbon adsorption site depends on the coverage of the passivated surfaces. At low coverages i.e. at 1/16 ML and 1/3 ML, it prefers a distorted T₄ position whereas at 1 ML, it occupies an H₃ site. This contrasts with the clean surface where the most energetically favored site is the S₅ at all coverages. Carbon adsorption induces a significant change in the structural geometry of the surface atoms, leading to a charge re-arrangement in the surface layers.     

Adsorption of water on TiN (1 0 0), (1 1 0) and (1 1 1) surfaces: A first-principles study

We use first-principles density functional theory-based calculations in the analysis of the interaction of H₂O with (1 0 0), (1 1 0) and (1 1 1) surfaces of TiN, and develop understanding in terms of surface energies, polarity of the surface and chemistry of the cation, through comparison with H₂O adsorption on ZrN. While water molecule physisorbs preferentially at Ti site of (1 0 0) and (1 1 1) surfaces, it adsorbs dissociatively on (1 1 0) surface of TiN with binding stronger than almost 1.32 eV/molecule. Our analysis reveals the following general trends: (a) surfaces with higher energies typically lead to stronger adsorption, (b) dissociative adsorption of H₂O necessarily occurs on a charge neutral high energy surface and (c) lower symmetry of the (1 1 0) plane results in many configurations of comparable stability, as opposed to the higher symmetry (1 0 0) and (1 1 1) surfaces, which also consistently explain the results of H₂O adsorption on MgO available in literature. Finally, weaker adsorption of H₂O on TiN than on ZrN can be rationalized in terms of greater chemical stability of Ti arising from its ability to be in mixed valence.     

Oxidation of Pt(1 0 0)-hex-R0.7° by gas-phase oxygen atoms

We utilized temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (ELS), and low energy electron diffraction (LEED) to investigate the oxidation of Pt(1 0 0)-hex-R0.7° at 450 K. Using an oxygen atom beam, we generated atomic oxygen coverages as high as 3.6 ML (monolayers) on Pt(1 0 0) in ultrahigh vacuum (UHV), almost 6 times the maximum coverage obtainable by dissociatively adsorbing O₂. The results show that oxidation occurs through the development of several chemisorbed phases prior to oxide growth above about 1 ML. A weakly bound oxygen state that populates as the coverage increases from approximately 0.50 ML to 1 ML appears to serve as a necessary precursor to Pt oxide growth. We find that increasing the coverage above about 1 ML causes Pt oxide particle growth and significant surface disordering. Decomposition of the Pt oxide particles produces explosive O₂ desorption characterized by a shift of the primary TPD feature to higher temperatures and a dramatic increase in the maximum desorption rate with increasing coverage. Based on thermodynamic considerations, we show that the thermal stability of the surface Pt oxide on Pt single crystal surfaces significantly exceeds that of bulk PtO₂. Furthermore, we attribute the high stability and the acceleratory decomposition rates of the surface oxide to large kinetic barriers that must be overcome during oxide formation and decomposition. Lastly, we present evidence that structurally similar oxides develop on both Pt(1 1 1) and Pt(1 0 0), therefore concluding that the properties of the surface Pt oxide are largely insensitive to the initial structure of the Pt single crystal surface.     

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.     

Surface and subsurface oxide formation on Ni(1 0 0) and Ni(1 1 1)

The oxidation of Ni(1 0 0) and Ni(1 1 1) at elevated temperatures and large oxygen exposures, typical of the methods used in the preparation of NiO(1 0 0) films for surface studies, has been investigated by medium energy ion scattering (MEIS) using 100 keV H⁺ incident ions. Oxide film growth proceeds significantly faster on Ni(1 1 1) than on Ni(1 0 0), but on both surfaces oxide penetration occurs to depths significantly greater than 100 Å with total exposures of 1200 and 6000 L respectively. The metal/oxide interface is extremely rough, with metallic Ni extending to the surface, even for much thicker oxide films on Ni(1 1 1). On Ni(1 1 1), NiO growth occurs with the (1 0 0) face parallel to the Ni(1 1 1) surface and the close-packed 〈1 1 0〉 directions parallel. On Ni(1 0 0) the MEIS blocking curves cannot be reconciled with a single orientation of NiO(1 0 0) (with the 〈1 1 0〉 directions parallel) on the surface, but is consistent with the substantial orientational disorder (including tilt) previously identified by spot-profile analysis LEED.     

Partial oxidation of higher olefins on Ag(1 1 1): Conversion of styrene to styrene oxide, benzene, and benzoic acid

Temperature programmed reaction spectroscopy (TPRS), X-ray photoelectron spectroscopy (XPS), and reflection absorption infrared spectroscopy (RAIRS) were used to study the partial oxidation of styrene on Ag(1 1 1). Styrene oxide, benzene, and benzoic acid were identified as partially oxidized reaction products. XPS and RAIRS provide evidence for the formation of a styrene-derived surface oxametallacycle that either forms styrene oxide or is further oxidized in a branching reaction to form benzoate, which is the intermediate responsible for the formation of both benzene and benzoic acid. The strong dependence of the product distribution on oxygen coverage suggests that O monomers adsorbed on Ag(1 1 1) provide a higher selectivity for partial oxidation than oxygen from the Ag(1 1 1)-p(4 × 4)-O reconstruction.     

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 plasma oxidation of Pd(1 0 0)

The oxidation of Pd(1 0 0) by an oxygen plasma was characterized using X-ray photoelectron spectroscopy (XPS), low energy ion scattering spectroscopy (ISS), temperature programmed desorption (TPD), and low energy electron diffraction (LEED). The oxygen uptake followed a typical parabolic profile with oxygen coverages reaching 32 ML after 1 h in the plasma; a factor of 40 higher than could be achieved by dosing molecular oxidants in ultra high vacuum. Even after adsorbing 32 ML of oxygen, XPS revealed both metallic Pd and PdO in the surface region. The R27^o LEED pattern previously attributed to a surface oxide monolayer, slowly attenuated with oxygen coverage indicating that the PdO formed poorly ordered three dimensional clusters that slowly covered the ordered surface oxide. While XPS revealed the formation of bulk PdO, only small changes in the ISS spectra were observed once the surface oxide layer was completed. The leading edges of the O₂ TPD curves showed only small shifts with increasing oxygen coverage that could be explained in terms of the lower thermodynamic stability of small oxide clusters. The desorption curves, however, could not be adequately described as simple zero order decomposition of PdO. There has been an ongoing debate in the literature about the relative catalytic activities of PdO and oxygen phases on Pd, the results indicate that any differences in the reactivity between bulk PdO and surface oxides are not associated with differences in the density of exposed Pd atoms or the decomposition kinetics of these two phases.     

Methanol adsorption on a CeO2(1 1 1)/Cu(1 1 1) thin film model catalyst

Adsorption and desorption of methanol on a CeO₂(1 1 1)/Cu(1 1 1) thin film surface was investigated by XPS and soft X-ray synchrotron radiation PES. Resonance PES was used to determine the occupancy of the Ce 4f states with high sensitivity. Methanol adsorbed at 110 K formed adsorbate multilayers, which were partially desorbed at 140 K. Low temperature desorption was accompanied by formation of chemisorbed methoxy groups. Methanol strongly reduced cerium oxide by forming hydroxyl groups at first, which with increasing temperature was followed by creation of oxygen vacancies in the topmost cerium oxide layer due to water desorption. Dissociative methanol adsorption and creation of oxygen vacancies was observed as a Ce⁴⁺ → Ce³⁺ transition and an increase of the Ce 4f electronic state occupancy.     

Initial growth of platinum on oxygen-covered Ni(1 1 0) surfaces

The initial growth of Pt on the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) surfaces has been studied by coaxial impact collision ion scattering spectroscopy (CAICISS), low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). Prior to Pt deposition, the atomic structure of the near-surface regions of the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) structures were studied using CAICISS, finding changes to the interlayer spacings due to the adsorption of oxygen. Deposition of Pt on the Ni(1 1 0)-(3 × 1)-O surface led to a random substitutional alloy in the near-surface region at Pt coverages both below and in excess of 1 ML. In contrast, when the surface was treated with 1800 L of atomic oxygen in order to form a NiO(1 1 0) surface, a thin Pt layer was formed upon room temperature Pt deposition. XPS and LEED data are presented throughout to support the CAICISS observations.     

SEM and XPS studies of nanohole arrays on InP(1 0 0) surfaces created by coupling AAO templates and low energy Ar ion sputtering

The aim of the present study is to demonstrate the feasibility to form well-ordered nanoholes on InP(1 0 0) surfaces by low Ar⁺ ion sputtering process in UHV conditions from anodized aluminum oxide (AAO) templates. This process is a promising approach in creating ordered arrays of surface nanostructures with controllable size and morphology. To follow the Ar⁺ ion sputtering effects on the AAO/InP surfaces, X-ray photoelectron spectroscopy (XPS) was used to determine the different surface species. In_4d and P_2p core level spectra were recorded on different InP(1 0 0) surfaces after ions bombardment. XPS results showed the presence of metallic indium on both smooth InP(1 0 0) and AAO/InP(1 0 0) surfaces. Finally, we showed that this experiment led to the formation of metallic In dropplets about 10 nm in diameter on nanoholes patterned InP surface while the as-received InP(1 0 0) surface generated metallic In about 60 nm in diameter.     

Density functional study of ethylamine and allylamine on Si(1 0 0)-2 × 1 and Ge(1 0 0)-2 × 1 surfaces

We have investigated the interactions of ethylamine and allylamine with models of the Si(1 0 0)-2 × 1 and Ge(1 0 0)-2 × 1 semiconductor surfaces. Ab initio molecular orbital calculations, along with density functional theory (DFT), are used to examine the interaction of these amines with cluster models of the semiconductor surfaces. The transition states and final adsorption products for adsorption of the molecules are predicted. The DFT calculations show the amines form N-dative bond states with Si(1 0 0)-2 × 1 or Ge(1 0 0)-2 × 1 as the initial adsorption product. The initial dative-bond products can be further activated, resulting in N-H bond cleavage on both surfaces. The overall reaction of a given amine on Si(1 0 0) via N-H dissociation is more exothermic than on the Ge(1 0 0) surface.