Chemically prepared well-ordered InP(0 0 1) surfaces

In the present work HCl-isopropanol treated and vacuum annealed InP(0 0 1) surfaces were studied by means of low-energy electron diffraction (LEED), soft X-ray photoemission (SXPS), and reflectance anisotropy (RAS) spectroscopies. The treatment removes the natural oxide and leaves on the surface a physisorbed overlayer containing InCl_x and phosphorus. Annealing at 230 °C induces desorption of InCl_x overlayer and reveals a P-rich (2 × 1) surface. Subsequent annealing at higher temperature induces In-rich (2 × 4) surface. The structural properties of chemically prepared InP(0 0 1) surfaces were found to be similar to those obtained by decapping of As/P-capped epitaxial layers.     

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.     

Me-PTCDI thin film deposition on InSb(1 1 1)A

The evolution of N,N′-dimethylperylene-3,4,9,10-dicarboxyimide (Me-PTCDI) thin films formed by vapour deposition on InSb(1 1 1)A substrates has been studied by X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS) and low energy electron diffraction (LEED). XPS studies of the Me-PTCDI covered surface indicate that no significant interaction occurs at sub-monolayer coverage when compared to multilayer Me-PTCDI films. HREELS studies suggest only a weak interaction as evidenced by very small changes in the frequencies of several molecular vibrational modes. LEED patterns show the Me-PTCDI overlayer adopts a structure commensurate with the underlying InSb(1 1 1)A substrate surface and that can be rationalised by van der Waals intermolecular energy calculations for the Me-PTCDI unit cell. The results are consistent with a weak interaction at the Me-PTCDI/InSb interface, the formation of the commensurate structure being sufficient to overcome the small energetic penalty associated with deviation from the calculated intermolecular interaction energy minimum.     

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.     

Structure and electronic properties of gold adsorbed on Ti(0 0 0 1)

The Au/Ti(0 0 0 1) adsorption system was studied by low energy electron diffraction (LEED) and photoemission spectroscopy with synchrotron radiation after step-wise Au evaporation onto the Ti(0 0 0 1) surface. For adsorption of Au at 300 K, no additional superstructures were observed and the (1 × 1) pattern of the clean surface simply became diffuse. Annealing of gold layers more than 1 ML thick resulted in the formation of an ordered Au-Ti surface alloy. Depending on the temperature and annealing time, three surface reconstructions were observed by LEED: (√3 × √3) R30°, (2 × 2) and a one-dimensional incommensurate (√3 × √3) rectangular pattern. The Au 4f core level and valence band photoemission spectra provided evidence of a strong chemical interaction between gold and titanium. The data indicated formation of an intermetallic interface and associated valence orbital hybridization, together with diffusion of gold into the bulk. Au core-level shifts were found to be dependent on the surface alloy stoichiometry.     

Phase mixing and phase separation accompanying the catalytic oxidation of CO on Ir{1 0 0}

The co-adsorption of CO and O on the unreconstructed (1 × 1) phase of Ir{1 0 0} was examined by low energy electron diffraction (LEED) and temperature programmed desorption (TPD). When CO is adsorbed at 188 K onto the Ir{1 0 0} surface precovered with 0.5 ML O, a mixed c(4 × 2)-(2O + CO) overlayer is formed. All CO is oxidised upon heating and desorbs as CO₂ in three distinct stages at 230 K, 330 K and 430 K in a 2:1:2 ratio. The excess oxygen left on the surface after all CO has reacted forms an overlayer with a LEED pattern with p(2 × 10) periodicity. This overlayer consists of stripes with a local p(2 × 1)-O arrangement of oxygen atoms separated by stripes of uncovered Ir. When CO is adsorbed at 300 K onto the surface precovered with 0.5 ML O an apparent (2 × 2) LEED pattern is observed. LEED IV analysis reveals that this pattern is a superposition of diffraction patterns from islands of c(2 × 2)-CO and p(2  × 1)-O structures on the surface. Heating this co-adsorbed overlayer leads to the desorption of CO₂ in two stages at 330 K and 430 K; the excess CO (0.1 ML) desorbs at 590 K.LEED IV structural analysis of the mixed c(4 × 2) O and CO overlayer shows that both the CO molecules and the O atoms occupy bridge sites. The O atoms show significant lateral displacements of 0.14 Å away from the CO molecules; the C-O bond is slightly expanded with respect to the gas phase (1.19 Å); the modifications of the Ir substrate with respect to the bulk-terminated surface are very small.     

Investigation of InSb(1 1 0) and InSb(1 1 1) surfaces by means of target current (VLEED) spectroscopy and LEED

In this paper, we present experimental results of target current (TCS) and LEED investigation of well-oriented InSb(1 1 0) and InSb(1 1 1)-A and InSb(1 1 1)-B crystals. TCS results are interpreted in terms of very low electron diffraction (VLEED) and empty band signatures. To examine to which extent the TCS spectra reflect the bulk or surface electronic properties of InSb(1 1 0), thin layers of indium have been evaporated and the corresponding spectrum changes have been investigated.     

Clean reconstructed InAs(1 1 1) A and B surfaces using chemical treatments and annealing

Well-ordered clean InAs(1 1 1) A and B surfaces have been prepared using HCl-isopropanol solutions and characterized using low-energy electron diffraction and photoemission spectroscopy. The as-treated surfaces are covered by a layer containing arsenic and small amounts of InCl_x. Annealing induces desorption of the overlayer and reveals (2 × 2) and (1 × 1) structures on the A and B surfaces, respectively. For both surfaces, the surface components of the In 4d and As 3d reveal a charge transfer from the electropositive surface indium to the electronegative surface arsenic. The major advantage of this preparation method over conventional thermal cleaning is a significant reduction in the annealing temperature (≈250 °C) thereby avoiding anion evaporation.     

(2 × 1)-Na surface reconstruction induced by NaCl dissociation on Ag(1 1 0) during LEED analysis

This study first reports the initial growth stages of sodium chloride (NaCl) on Ag(1 1 0) at room temperature. NaCl grows in bi-layer mode along its [1 0 0] axis and gives rise to (4 × 1) and (1 × 2) reconstructed domains for coverages lower than two monolayers (ML), a minimal thickness inducing a bi-dimensional closed film. In addition, a 10 ML NaCl film has been examined by low energy electron diffraction (LEED). LEED analysis leads to the dissociation of the NaCl deposit in a few minutes. The NaCl dissociation implies Cl desorption from the surface and Na remaining on it. The residual Na is arranged in the form of a (2 × 1) surface reconstruction and is found to be strongly bounded to the Ag substrate. These findings have been established by using the X-ray photoelectron spectroscopy technique.     

Nitrogen plasma cleaning of Ge(1 0 0) surfaces

We propose a dry method of cleaning Ge(1 0 0) surfaces based on nitrogen plasma treatment. Our in situ Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED) analyses demonstrate that surface contamination remaining after wet treatment was effectively removed by nitrogen radical irradiation at low substrate temperatures. The nitrogen plasma cleaned Ge(1 0 0) surface shows a well-ordered 2 × 1 reconstruction, which indicates the formation of a contamination-free Ge(1 0 0) surface with good crystallinity. We discuss the possible reaction mechanism considering how chemisorbed carbon impurities are removed by selective C-N bond formation and subsequent thermal desorption. These findings imply the advantage of plasma nitridation of Ge surfaces for fabricating nitride gate dielectrics, in which we can expect surface pre-cleaning at the initial stage of the plasma treatment.     

Combined EELS, LEED and SR-XPS study of ultra-thin crystalline layers of indium nitride on InP(1 0 0)—Effect of annealing at 450 °C

In this study, InP(1 0 0) surfaces were bombarded by argon ions in ultra high vacuum. Indium metallic droplets were created in well controlled quantities and played the role of precursors for the nitridation process. A glow discharge cell was used to produce a continuous plasma with a majority of N atomic species. X-ray photoelectron spectroscopy (XPS) studies indicated that the nitrogen combined with indium surface atoms to create InN thin films (two monolayers) on an In rich-InP(1 0 0) surface. This process occurred at low temperature: 250 °C. Synchrotron radiation photoemission (SR-XPS) studies of the valence band spectra, LEED and EELS measurements show an evolution of surface species and the effect of a 450 °C annealing of the InN/InP structures. The results reveal that annealing allows the crystallization of the thin InN layers, while the LEED pattern shows a (4 × 1) reconstruction. As a consequence, InN related structures in EELS and valence bands spectra are different before and after the annealing. According to SR-XPS measurements, the Fermi level is found to be pinned at 1.6 eV above the valence band maximum (VBM).     

One-dimensional atomic and electronic structures of submonolayer potassium deposited on stepped Ni(7 5 5) surface

We deposited 0.01-0.16 ML (monolayer) of potassium on stepped (7 5 5) [=6(1 1 1) × (1 0 0)] surface of nickel in order to fabricate and to understand the growth process of one-dimensional (1D) potassium atomic-chain structure by observing the low-energy-electron-diffraction (LEED) patterns. The LEED patterns from potassium adsorbates exhibit a distinct coverage dependence that 1× streaks first appeared at low coverages up to 0.04 ML and later 2× streaks appeared at around 0.09 ML. The streaks become spotty at the higher coverage. We explained these coverage-dependent changes in LEED patterns in a thorough comparison with kinematically calculated LEED patterns constructing a reasonable growth model.     

Growth and crystalline structure of Co layers on Cu(0 0 1)

The crystalline structure of Co layers deposited on the Cu(0 0 1) surface was investigated with the use of the directional elastic peak electron spectroscopy (DEPES). For clean Cu(0 0 1) the experimental DEPES profiles obtained for different energies of the primary electron beam exhibit intensity maxima corresponding to the close packed rows of atoms. The Auger peak kinetics recorded during continuous Co deposition suggest the layer-by-layer growth mode. The DEPES profiles recorded for 10 monolayers (ML) of Co on Cu(0 0 1) reflect a short-range order in the adsorbate. Intensity maxima observed in the DEPES profiles for Co along [1 0 0], [0 1 0], and [1 1 0] azimuths of Cu(0 0 1) are characteristic of the face centered cubic (fcc) Co(0 0 1) layers. Low-intensity reflections and considerable background intensities were found in the low energy electron diffraction (LEED) patterns recorded from 10 ML of Co, which indicates a weak long-range order in the adsorbate. The adsorption of about 20 ML of Co results in considerable background contribution to DEPES. No reflections but a large background were observed with the use of LEED for this layer. The heating of the Co/Cu(0 0 1) system at T = 770 K leads to an increase of the short- and long-range order in the overlayer, observed in the DEPES profiles and LEED patterns, respectively. The theoretical DEPES profiles were obtained with the use of a multiple scattering approximation. A very good agreement between experimental and theoretical scans was found for the clean and covered copper substrate. The latter proves the epitaxial growth of Co layers on Cu(0 0 1).     

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.     

Structural and electrical analysis of S ion bombarded p-InP(1 0 0)

The chemical state of sulfur and surface structure on low-energy S⁺ ion-treated p-InP(1 0 0) surface have been investigated by high-resolution X-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED). S⁺ ion energy over the range of 10-100 eV was used to study the effect of ion energy on surface damage and the process of sulfur passivation on p-InP(1 0 0) by S⁺ ion beam bombardment. It was found that sulfur species formed on the S⁺ ion-treated surface. The S⁺ ions with energy above 50 eV were more effective in formation of In-S species, which assisted the InP surface in reconstruction into an ordered (1 × 1) structure upon annealing. After taking into account physical damage due to the process of ion bombardment, we found that 50 eV was the optimal ion energy to form In-S species in the sulfur passivation of p-InP(1 0 0). The subsequent annealing process removed donor states that were introduced during the ion bombardment of p-InP(1 0 0). Results of theoretical simulations by Transport of Ions in Materials (TRIM) are in accordance with those of experiments.     

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.     

Growth of Ce on Rh(1 1 1)

We have studied the growth of cerium films on Rh(1 1 1) using STM (scanning tunneling microscopy), LEED (low energy electron diffraction), XPS (X-ray photoelectron spectroscopy) and AES (Auger electron spectroscopy). Measurements of the Ce films after room temperature deposition showed that Ce is initially forming nanoclusters in the low coverage regime. These clusters consist of 12 Ce atoms and have the shape of pinwheels. At a coverage of 0.25 ML (monolayer, ML) an adatom layer with a (2 × 2) superstructure is observed. Above 0.4 ML, Rh is diffusing through pinholes into the film, forming an unstructured mixed layer. Annealing at 250 °C leads to the formation of ordered Ce-Rh compounds based on the bulk compound CeRh₃. At a coverage of 0.1 ML, small ordered (2 × 2) surface alloy domains are observed. The exchanged Rh atoms form additional alloy islands situated on the pure Rh(1 1 1) surface, showing the same (2 × 2) superstructure as the surface alloy. At a coverage of 0.25 ML, the surface is completely covered by the surface alloy and alloy islands. The (2 × 2) structure is equivalent to a (1 1 1)-plane of CeRh₃, contracted by 6%. Annealing a 1 ML thick Ce layer leads to a flat surface consisting of different rotational domains of CeRh₃(1 0 0). The Rh needed for alloy formation comes from 50 Å deep pits in the substrate. Finally we show that LEIS (low energy ion scattering) is not suitable for the characterization of Ce and CeRh films due to strong effects of neutralization.     

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.     

Gd adsorption on the Mo(2 1 1) surface

The adsorption of Gd thin layers on the Mo(2 1 1) face was investigated by using Auger electron spectroscopy (AES), low electron energy diffraction (LEED), scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS) and measurements of the work function changes (Δφ). It was found that at 300 K Gd does not form any dilute chain structures and from the very beginning of the adsorption process Gd forms a densely packed layer. The dilute p(4 × 1) chain structure was observed by LEED after annealing thin layers (θ < 1 ML) to temperatures above 770 K. STM images confirm the existence of the p(4 × 1) structure islands. The intermixing of the substrate and adsorbate atoms takes place.     

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.