The thermal attenuation of elastic scattering of helium from copper single crystal surfaces

The dependence of diffraction peak intensities upon temperature for the scattering of helium from various copper surfaces: Cu (111), (100), (110), (113), (115) and (117), has been experimentally determined for two incident energies (21–63 meV) and a large range of incidence angles. For the close-packed faces (111) and (100), the data are consistent with a Debye-Waller formalism involving an effective surface mean square displacement <u²_eff〉. The quantitative fit with the data is good if anharmonic effects are properly taken into account. This result establishes that a generalized Debye-Waller formalism is, at least as a first approximation, relevant to the helium-surface diffraction. For the rougher surfaces the agreement remains good up to a threshold temperature above which the intensities are always lower than predicted by the model. It is proposed that this may be due to some kind of thermal roughening of the surface.     

Surface-melting induced faceting of aluminium

Medium-energy ion scattering measurements have been used to study the temperature dependent behaviour of aluminium surfaces with surface orientations in the (11&#x0304;0) zone. The ion-scattering measurements show that surface-melting induced faceting occurs between the melting (110) and the non-melting (111) orientations. The dry and melted facet orientations Θ_d and Θ_d have been determined up to 0.3 K from the bulk melting point. Close to the melting point these orientations are almost independent of temperature, and amount to Θ_d = 7 ± 2° and Θ_m = 29 ± 2° with respect to the (111) plane.     

Study of the structural and magnetic characteristics of epitaxial Fe3Si/Si(111) films

The results of the structural and magnetic studies of the epitaxial structure prepared during the simultaneous evaporation from two iron and silicon sources on an atomically pure Si(111)7 × 7 surface at a substrate temperature of 150°C have been presented. The epitaxial structure has been identified as a single-crystal Fe₃Si silicide film with the orientation Si[111]‖Fe₃Si[111] using methods of the X-ray structural analysis, transmission electron microscopy, and reflection high-energy electron diffraction. It has been established that the epitaxial Fe₃Si film at room temperature has magnetic uniaxial anisotropy (H _a = 26 Oe) and a relatively narrow uniform ferromagnetic resonance line (ΔH = 11.57 Oe) measured at a pump frequency of 2.274 GHz.     

Scanning tunneling microscopy observation of ultrathin epitaxial CoSi<Subscript>2</Subscript>(111) films grown at a high temperature

Scanning tunneling microscopy (STM) is used to study the basic laws of growth of ultrathin epitaxial CoSi₂(111) films with Co coverages up to 4 ML formed upon sequential deposition of Co and Si atoms taken in a stoichiometric ratio onto the Co–Si(111) surface at room temperature and subsequent annealing at 600–700°C. When the coverage of Co atoms is lower than ~2.7 ML, flat CoSi₂ islands up to ~3 nm high with surface structure 2 × 2 or 1 × 1 grow. It is shown that continuous epitaxial CoSi₂ films containing 3–4 triple Si–Co–Si layers grow provided precise control of deposition. CoSi₂ films can contain inclusions of the local regions with (2 × 1)Si reconstruction. At a temperature above 700°C, a multilevel CoSi₂ film with pinholes grows because of vertical growth caused by the difference between the free energies of the CoSi₂(111) and Si(111) surfaces. According to theoretical calculations, structures of A or B type with a coordination number of 8 of Co atoms are most favorable for the CoSi₂(111)2 × 2 interface.     

Adsorption of carbon monoxide,oxygen, hydrogen,nitrogen, ethylene and benzene on an iridium (110) surface; Correlation with other iridium crystal faces

The interaction of CO, O₂, H₂, N₂, C₂H₄ and C₆H₆ with an Ir(110) surface has been studied using LEED, Auger electron spectroscopy and flash desorption mass spectroscopy. Adsorption of oxygen at 30°C produces a (1× 2) structure, while a c(2 × 2) structure is formed at 400°C. Two peaks have been detected in the thermal desorption spectrum of oxygen following adsorption at 30°C. The heat of adsorption of hydrogen is slightly higher on Ir(110) than on Ir(111). Adsorption of carbon monoxide at 30°C produces a (2 × 1) surface structure. The main CO desorption peak is found around 230, while two other desorption peaks are observed around 340 and 160°C. At exposures between 250 and 500°C carbon monoxide adsorption yields a c(2 × 2) structure and a desorption peak around 600°C. Carbon monoxide is adsorbed on an Ir(110) surface partly covered with oxygen or carbon in a new binding state with a significantly higher desorption temperature than on the clean surface. Adsorption of nitrogen could not be detected on either clean or on carbon covered Ir(110) surfaces. The hydrocarbon molecules do not form ordered surface structures on Ir(110). The thermal desorption spectra obtained after adsorption of C₆H₆ or C₂H₄ are similar to those reported previously for Ir(111) consisting mostly of hydrogen. Heating the (110) surface above 700°C in the presence of C₆H₆ or C₂H₄ results in the formation of an ordered carbonaceous overlayer with (1 × 1) structure. The results are compared with those obtained previously on the Ir(111) and Ir(755) or stepped [6(111) × (100)] surfaces. The CO adsorption results are discussed in relation to data on similar surfaces of other Group VIII metals.     

LEED,AES and thermal desorption studies of chemisorbed Hydrogen and hydrocarbons (C2H2, C2H4, C6H6, C6H12) on the (111) and stepped [6(111) × (100)] iridium crystal surfaces; comparison with platinum

The adsorption of hydrogen, ethylene, acetylene, cyclohexane and benzene was studied on both the (111) and stepped [6(111) × (100)] crystal surfaces of iridium. The techniques used were low energy electron diffraction, Auger electron spectroscopy, and thermal desorption mass spectrometry. At 30°C, acetylene, ethylene and benzene are adsorbed with a sticking probability near unity. The sticking probability of cyclohexane is less than 0.1 on both surfaces. Heating the (111) surface above 800°C, in the presence of the hydrocarbons, results in the formation of an ordered carbonaceous overlayer with a diffraction pattern corresponding to a (9 × 9) surface structure. No indication for ordering of the carbonaceous residue was found on the stepped iridium surface in these experimental conditions. The hydrocarbon molecules form only poorly ordered surface structures on both iridium surfaces when the adsorption is carried out at 30°C. Benzene is the only gas that can be desorbed from the surfaces in large amounts by heating. Ethylene remains largely on the surface, only a few percent is removed by heating while acetylene and cyclohexane cannot be desorbed at all. When adsorption is carried out at 30°C and the crystal is subsequently flashed to high temperature, hydrogen is liberated from the surface. The hydrogen desorption spectra from the iridium surfaces exposed to C₂H₄, C₂H₂, or C₆H₆ exhibit two hydrogen desorption peaks, one around 200°C and the second around 350°C. The temperatures where these peaks appear vary slightly with the type of hydrocarbon. The relative intensities of these two peaks depend strongly on the surface used. Arguments are presented that decomposition of the hydrocarbon molecules (C-H bond breaking nd possibly also C-C bond breaking) occurs easier on the stepped iridium surface than on the (111) surface. Hydrogen is desorbed at a higher temperature from an iridium surface possessing a high density of surface imperfections than from a perfect iridium (111) surface. The results are compared with those obtained previously on similar crystal surfaces of platinum. It appears that C-H bond breaking occurs more easily on iridium than on platinum.     

Study of the surface cleaning of GOI and SGOI substrates for Ge epitaxial growth

An effective wet cleaning process, optimized for low temperature Ge epitaxial growth on thin Ge or SiGe structures with reduced surface roughening, is proposed. It is found that HF + HCl cleaning is the most effective wet cleaning method that is applicable to the low temperature thermal cleaning. It is also found that temperature of the thermal cleaning appropriate to 25-30 nm thick germanium on insulator (GOI) or silicon-germanium on insulator (SGOI) substrates is approximately 450 °C. Moreover, it is also found that the temperatures of Ge epitaxial growth even in lattice-matched systems must be reduced to around 400 °C to prevent surface roughening and those in lattice-mismatched systems also must be reduced sufficiently (300 °C for strained Ge growth on SGOI (X_eff = 0.6)) to prevent lattice relaxation as well as surface roughening. Finally, the successful formation of the compressively strained GOI structures is demonstrated by applying these wet cleaning and low temperature thermal cleaning processes and low temperature Ge epitaxy to thin SGOI substrates.     

Thermal roughening of FEM-clean Pt{110} and its vicinal areas

After heat treatment at ∼1600 K and rapid quenching, thermal roughening through kink formation could be observed on “FEM-clean” Pt{110} and on all its vicinal areas (which are made up of {110} terraces). Noticeable exceptions were the areas between {771} and {331} (including {771}), which are located on the [1&#x0304;10] zone. These areas may remain topographically unchanged, or, more likely, may form {111}-microfacets during heat treatment. Upon annealing, the high-temperature roughness on {110} started to decrease at 830 K (formation of an 1 × 2 structure) and reached a minimum at 960 ± 25 K (≡ transition temperature, T_c). Thereafter, it increased precipitously until 1030 K was reached (surface roughening/deconstruction). Surface roughening could be suppressed readily by gas phase and/or bulk impurities (surface segregation). Vapour deposited Si, P, SiO, TiO₂, Al₂O₃ and C (graphite) prevented surface roughening on Pt{110}. All investigations were carried out by FEM.     

Effect of the chromium layer thickness on the morphology and optical properties of heterostructures Si(111)/(CrSi<Subscript>2</Subscript> nanocrystallites)/Si(111)

Growth and the optical properties of epitaxial heterostructures Si(111)/(CrSi₂ nanocrystallites)/Si(111) based on nanosized islands of chromium disilicide (CrSi₂) on Si(111) were studied using low-energy electron diffraction, atomic-force microscopy, and optical reflection and transmission spectroscopy. The heterostructures with thicknesses of 0.1, 0.3, 0.6, 1.0, and 1.5 nm were formed by reactive epitaxy at a temperature of 500°C followed by the epitaxial growth of silicon at 750°C. The specific features of changes in the density and sizes of CrSi₂ islands on the silicon surface were determined at T = 750°C as the chromium layer thickness was increased. It was established that, in the heterostructures with chromium layer thicknesses exceeding 0.6 nm, a small part of faceted Cr₂Si₂ nanocrystallites (NCs) emerge into near-surface region of the silicon, which is confirmed by the data from optical reflectance spectroscopy and an analysis of the spectral dependence of the absorption coefficient. A critical size of NCs is shown to exist above which their shift to the silicon surface is hampered. The decreased density of emerging NCs at chromium layer thicknesses of 1.0–1.5 nm is associated with the formation of coarser NCs within a silicon layer, which is confirmed by the data from differential reflection spectroscopy.     

Helium scattering and work function investigation of co adsorption on Pt(111) and vicinal surfaces

CO adsorption on Pt(111) and vicinal Pt(111) surfaces has been studied by means of work function variation and He scattering measurements. AES and LEED were used mainly for correlations with other work. Special attention has been paid to the low coverage regime (θ_co < 0.1) with emphasis on surface structural dependencies. The minimum of the work function versus CO exposure curve occurs at a coverage less than 11% on “kink-free” surfaces. This is much lower than the hitherto commonly accepted value of 33%, and does not relate to any observed LEED superstructure. The value of Δφ_min depends strongly on the surface structure. For an “ideal” Pt(111) surface with a step density less than 10^?3 at a temperature of 300 K, Δφ_min = ?240 meV. The scattering cross section Σ of CO adsorbed on Pt(111) for 63 meV He is typically > 250 Ų, i.e. much larger than expected from the Van der Waals radii of He and CO. For two nominal Pt(111) surfaces with step densities of 10^?2 and less than 10^?3, respectively, the measured Σ values varied by a factor of three. This can be explained by preferential CO occupation of defect sites, which are already not “seen” by thermal helium. By comparing results on a stepped (997) and a kinked (12 11 9) Pt surface with similar defect densities, the kinks are proven to play a decisive role. They probably form saddles in the recently proposed activation barrier for migration between terrace and step sites.     

Superlattices formed by electrodeposition of silver on iodine-pretreated Pt(111); studies by LEED,Auger spectroscopy and electrochemistry

Reported are studies by LEED and Auger spectroscopy of silver layers electrodeposited on well-characterized Pt(111) surfaces from aqueous solution. Prior to electrodeposition. the Pt(111) surface was treated with I₂ vapor to form the Pt(111) ($\text{7}\text{×}\text{7}$)R19.1°-I superlattice which protected the Pt and Ag surfaces from attack by the electrolyte and residual gases. Electrodeposition of silver occurred in four distinct ranges of electrode potential. Ordered layers having (3 × 3) and (18 × 18) (coincidence lattice) LEED patterns were formed at all coverages from the onset of deposition to the highest coverages studied, about twenty equivalent atomic layers. Formation of ordered Ag layers has therefore been demonstrated, at least for deposits of limited thickness. Auger spectra revealed that for deposits of a few atomic layers. The iodine layer remained attached to the surface during multiple cycles of electrodeposition and dissolution of silver from iodine-free solution. Each peak of the voltammetric current-potential scan produced a change in the LEED pattern.     

Comparative AES and RHEED study of the formation of Pd silicide on clean and oxide covered Si(100) and (111) surfaces

The formation and epitaxial orientation of Pd silicide on clean and native oxide covered Si(100) and (111) surfaces was studied by Auger electron spectroscopy (AES) and reflection high energy electron diffraction (RHEED). Pd was vapor deposited in UHV on to the substrates up to thicknesses of about 6 nm. On clean Si substrates, ultra-thin Pd deposits reacted to form Pd₂Si already at room temperature, as detected by a characteristic splitting of the Si LVV Auger peak. However, a polycrystalline structure with very small crystallite sizes was indicated by diffuse ring patterns in RHEED. When the initial thickness of the Pd deposit exceeded about 3 nm, the diffraction ring pattern of unreacted metal developed. During annealing of room temperature deposits of Pd, the (100) and (111) substrates behaved differently. Larger crystallites formed on Si(100), but the films remained polycrystalline, though textured. On Si(111), virtually perfect epitaxial re-orientation of the silicide was found. When the substrates were initially covered with native oxide of about 2 nm thickness, silicide formation started at about 200°C, resulting in polycrystalline, but strongly textured Pd₂Si. Upon further annealing at temperatures up to 600°C, an additional phase of epitaxially oriented Pd₂Si developed on Si(111), similar to that on clean Si(100). In all experiments, extended annealing at temperatures above 250°C caused segregation of Si to the surface. This was accompanied by the development of an additional peak in the Auger electron spectra at about 313 eV, which we assign to a plasmon loss of δE = 17 eV in the Si overlayer, being excited by Pd Auger electrons of energy 330 eV.     

Leed and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 AND C) chemisorbed on the rhodium (111) and (100) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₄, C₂H₂ and C has been studied on the clean Rh(111) and (100) surfaces. LEED, AES and thermal desorption were used to determine the surface structures, disordering and desorption temperatures, displacement and decomposition characteristics for each species. All of the molecules studied readily chemisorbed on both surfaces. A large variety of ordered structures was observed, especially on the (111) surface. The disordering temperatures of most ordered surface structures on the (111) surface were below 100°C. It was necessary to adsorb the gases at 25° C or below in order to obtain well-ordered surface structures. Chemisorbed oxygen was readily removed from the surface by H₂ or CO gas at crystal temperatures above 50°C. CO₂ appears to dissociate to CO upon adsorption on both rhodium surfaces as indicated by the identical ordering and desorption characteristics of these two molecules. C₂H₄ and C₂H₂ also had very similar ordering and desorption characteristics and it is likely that the adsorbed species formed by both molecules is the same. Decomposition of ethylene produced a sequence of ordered carbon surface structures on the (111) face as a result of a bulk-surface carbon equilibrium. The chemisorption properties of rhodium appear to be generally similar to those of iridium, nickel and palladium.     

A study of the (00) LEED beam intensity at normal incidence from CdS(0001), Cu(001), Cu(111), and Ni(111)

A Faraday cage apparatus is used for the measurement of the (00) LEED beam intensity, I₍₀₀₎, and the total secondary emission coefficient, δ(E_k), for angles of incidence from 0° ± 2° to 8° ± 2°, with an energy resolution of ± 0.037 of the incident beam energy, in the energy range 1 to 200 eV. The data are normalized and expressed as a fraction of the incident beam intensity. The basic principle of operation is the separation of the incident and specularly diffracted beams in a uniform magnetic field. Monolayer, or in-plane, resonances associated with the emergence of nonspecular beams, as well as beam threshold minima, are observed in I₍₀₀₎ at normal incidence from clean CdS(0001), Cu(111), and Ni(111). Some major differences are observed in the I₍₀₀₎ profiles for the clean (111) surfaces of nickel and copper. All secondary Bragg peaks, except the 2$\text{2}\text{3}$ order, have greater intensities for Ni(111) in the energy range 50–150 eV, thus indicating that the atomic scattering cross-section for electrons in this energy range is larger for nickel than for copper. For the (111) surface of nickel, the (11) resonance is missing, but the (10) resonance and all $\text{1}\text{3}$ order secondary Bragg peaks between the second and fifth orders are observed. For Cu(111) both the (10) and (11) resonances are observed, but the $\text{1}\text{3}$, $\text{2}\text{3}$, 1$\text{2}\text{3}$, and 3$\text{1}\text{3}$ order secondary Bragg peaks are missing in this energy range. These data indicate that multiple scattering with evanescent intermediate waves, or “shadowing”, is predominate on the (111) surfaces on nickel and copper for energies above 30 eV, and that below 30 eV multiple scattering with propagating intermediate waves is predominate on Cu(111). Correlation of the (00) beam intensity profiles from clean Ni(111) at 0°, 2°, and 6° with the intensity profiles of the (10). (1&#x0304;0), and (11) non-specular beams is nearly one-to-one from 30 eV to 100 eV, thus supporting the dynamical theories of LEED in which peaks in the (00) beam are expected to occur at nearly the same energies as peaks in the non-specular beams.     

Elastic leed intensity-energy studies of clean (001), (110) and (111) nickel surfaces

Elastic low energy electron diffraction (LEED) intensity-energy (I-E) measurements for clean (001), (110), and (111) nickel surfaces were obtained at room temperature. Surface composition was monitored by Auger spectroscopy. I-E data from 15 to 220 eV were obtained at normal incidence for the non specular beams and for the specular beams at incidence angles from 4° to 20° on the 0° and 45° azimuths of (001), on the 0° and 90° azimuths of (110), and on the 0° azimuth of (111) nickel. Normalization of the data was performed electronically during data acquisition. Intensities were calibrated with the use of a shielded, biased Faraday collector. The effects of instrumental and experimental uncertainties were examined and minimized to obtain intensities accurate to ± 15 %, energy scales accurate to ± 0.35 eV, and incident and azimuthal angles accurate to ± 0.25° and ± 1.0° respectively.All nickel surfaces have I-E spectra which are characteristic of strong multiple scattering. Angular evolution features for (001) and (110) spectra may be correlated with intraplanar resonances associated with the onset of propagating beams. Only the (001) surfaces were found to have pronounced, sharp resonance features associated with surface barrier resonances and inelastic loss processes. Kinematic analysis of the Lorenzian-shaped I-E peaks on all surfaces in consistent with surface expansion using either an energy-dependent or a constant inner potential of 10.75 ± 0.5 eV. The widths of these same peaks on all surfaces were found to vary as $\text{E}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ above 40 eV and $\text{E}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}$ below.     

Methanol decomposition on platinum (111)

The interaction of methanol with clean and oxygen-covered Pt(111) surfaces has been examined with high resolution electron loss spectroscopy (EELS) and thermal desorption spectroscopy (TDS). On the clean Pt(111) surface, methanol dehydrogenated above 140 K to form adsorbed carbon monoxide and hydrogen. On a Pt(111)-p(2 × 2)O surface, methanol formed a methoxy species (CH₃O) and adsorbed water. The methoxy species was unstable above 170 K and decomposed to form adsorbed CO and hydrogen. Above room temperature, hydrogen and carbon monoxide desorbed near 360 and 470 K, respectively. The instability of methanol and methoxy groups on the Pt surface is in agreement with the dehydrogenation reaction observed on W, Ru, Pd and Ni surfaces at low pressures. This is in contrast with the higher stability of methoxy groups on silver and copper surfaces, where decomposition to formaldehyde and hydrogen occurs. The hypothesis is proposed that metals with low heats of adsorption of CO and H₂ (Ag, Cu) may selectively form formaldehyde via the methoxy intermediate, whereas other metals with high CO and H₂ chemisorption heats rapidly dehydrogenate methoxy species below room temperature.     

A leed-aes study of thin Pd films on Si(111) and (100) substrates

A system Pd (deposit)-Si (substrate) has been studied by LEED and AES. Pd₂Si formed on Si(111) became epitaxial after a short time of annealing at a temperature between 300 and 700°C, while the Pd₂Si formed on Si(100) did not, in both cases the surfaces of the Pd₂Si being covered with a very thin Si layer. A sequence of superstructures (3√3 × 3√3), (1 × 1), and (2√3 × 2√3) was observed successively in Pd/Si(111) as the annealing temperature was increased. A (√3 × √3) structure was obtained by sputtering the 3√3 surface slightly. It was found that the √3 structure corresponds to Pd²Si(0001)-(1 × 1) grown epitaxially on Si(111), and that the 3√3 structure comes from the thin Si layer accumulated over the silicide surface, while the 2√3 and 1 structures arise from a submonolayer of Pd adsorbed on Si(111). Superstructures observed on a Pd/Si(100) system are also studied.     

Low-energy 3He+ ion scattering spectroscopy studies of D2 adsorption on W(211)

Direct physical evidence for occupation of a trough site by the β₂ state of deuterium adsorbed on W(211) has been obtained by angle-resolved ³He⁺/D(ads) ion-scattering spectroscopy (ISS) in combination with LEED/Auger. The W(211) surface is composed of close-packed 〈111〉 rows of W atoms separated by a wide channel. Previous thermal desorption studies have shown two clearly resolved hydrogen states: β₁ desorbing with a temperature maximum of ca. 60°C, and β₂ at ca. 400°C. Analyses of flash desorption, work-function, adsorption kinetics, stoichiometry and mixed adsorption further indicated that the more tightly bound β₂ form occupies a deep-trough position. In the present study, ISS polar-angle profiles were taken at an incident energy of 306 eV. With only the β₂ state populated, a ³He⁺ beam parallel to the close-packed 〈111〉 rows was found to scatter from D(ads) with a cutoff angle close to grazing incidence while for the perpendicular direction D(ads) scattering is observed only for angles greater than 18° away from grazing incidence. These measurements are consistent with the corrugated W(211) geometry and with the proposed β₂-D trough-site model.     

Surface nanostructure effects on optical properties of Pb(Zr x Ti1−x )O3 thin films

Optical scattering properties of nanostructured matter have crucial impact on performance efficiency of various photonic components, such as waveguides, display elements, and solar cells. In this paper, diffuse transmission properties of nanocrystalline Pb(Zr _x Ti_1?x )O₃ thin films with a high refractive index of ~2.5 and optical transmittance are presented. Thin films with a thicknesses ranging from 50 to 500 nm were studied using integrating sphere technique and results were compared to simulations performed by a scalar scattering theory. Thin films were deposited by pulsed laser deposition at room temperature on MgO(100) substrates and post-annealed at a temperature of 800 °C. Structural phase evolution-induced surface effects, which introduced periodicity on the film surface, cause the definite diffuse elements in transmission spectra of the films. Low and evenly distributed scattering amplitudes in k-space were seen for highly tetragonal- or trigonal-oriented films with non-textured surfaces, which led to low diffuse transmission values (T _D ≈ 5 %), while confined and increased scattering amplitudes in k-space were seen for tetragonal–trigonal-oriented films, with phase co-existence, which led to microstructure-induced textured surfaces and increased diffuse transmission values (T _D ≈ 50 %). For highly textured surfaces, scattering amplitudes distributed in tilted ellipsoid shape in k-space was observed. Difference between modeled and measured values was 3.8 % in maximum.