Chiral surfaces and metal/ceramic heteroepitaxy in the Pt/SrTiO3(621) system

Low-energy electron diffraction (LEED), atomic force microscopy (AFM), and X-ray diffraction (XRD) have been used to investigate the structural and morphological character of a naturally chiral ceramic SrTiO₃(621) substrate and of Pt and Cu thin films deposited on its surface. AFM experiments showed that as-received chirally-oriented SrTiO₃(621) substrates display atomically smooth surface morphologies, while LEED patterns revealed that the surface structure has a net chirality. Pt(621) and Cu(621) thin films were grown heteroepitaxially on SrTiO₃(621) substrates, as confirmed by XRD. AFM showed that the film surfaces were atomically smooth and LEED illustrated that the Pt films exhibit surface chirality, and by implication that the atomically-flat chirally-oriented Cu films also have chiral surfaces. The characteristics of the observed LEED patterns, where splitting of diffraction spots is considered to arise from the kinked step features of naturally chiral fcc metal surfaces, are discussed with respect to existing models. These results indicate that the chiral SrTiO₃(621) ceramic surface drives the growth of single-enantiomer, chiral, metal (621) thin films.     

The growth and chemisorptive propertles of Ag and Au monolayers on platinum single crystal surfaces: An AES,TDS and LEED study

The growth and chemisorptive properties of monolayer films of Ag and Au deposited on both the Pt(111) and the stepped Pt(553) surfaces were studied using Auger electron spectroscopy (AES), thermal desorption spectroscopy (TDS), and low energy electron diffraction (LEED). AES studies indicate that the growth of Au on Pt(111) and Pt(553) and Ag on Pt(111) proceeds via a Stranski-Krastanov mechanism, whereas the growth of Ag on the Pt(553) surface follows a Volmer-Weber mechanism. Au dissolves into the Pt crystal bulk at temperatures > 800 K, whereas Ag desorbs at temperatures > 900 K. TDS studies of Ag-covered Pt surfaces indicate that the AgPt bond (283 kJ mol^?1) is ～25 kJ mol^?1 stronger than the AgAg bond (254 kJ mol^?1). On the Pt(553) surface the Au atoms are uniformly distributed between terrace and step sites, but Ag preferentially segregates to the terraces. The decrease in CO adsorption on the Pt crystal surfaces is in direct proportion to the Ag or Au coverage. No CO adsorption could be detected for Ag or Au coverages above one monolayer at 300 K and 10^?8 Torr. The heat of adsorption of CO on Pt is unaltered by the presence of Ag or Au.     

Structure investigations on single-crystal gold films

Structure of epitaxially grown gold films of varying thickness (10–1000Å) has been investigated using LEED, AES, resistivity measurements and X-ray diffraction analysis. Silicon 111-oriented crystals, which are prehandled to exhibit \(\sqrt 3 \times \sqrt 3 R 30^\circ \) -supersctructure in the LEED pattern, serve as substrates. The gold films show a homogeneous structure with smooth surfaces and a marked (111)-orientation. The use of silicon substrates, however, is complicated by the fact, that silicon diffuses through the gold films to a small extent even at room temperature.     

Potassium and potassium oxide monolayers on the platinum (111) and stepped (755) crystal surfaces: A LEED,AES, and TDS study

The adsorption of potassium and the coadsorption of potassium and oxygen on the Pt(111) and stepped Pt(755) crystal surfaces were studied by AES, LEED, and TDS. Pure potassium adlayers were found by LEED to be hexagonally ordered on Pt(111) at coverages of θ = _K0.9–;1. The monolayer coverage was 5.4 × 10¹⁴K atoms/cm² (0.36 times the atomic density of the Pt(111) surface). Orientational reordering of the adlayers, similar to the behavior of noble gas phase transitions on metals, was observed. The heat of desorption of K decreased, due to depolarization effects, from 60 kcal/mole at θ_K <0.1, to 25 kcal/mole at θ_K = 1 on both Pt(111) and Pt(755). Exposure to oxygen thermally stabilizes a potassium monolayer, increasing the heat of desorption from 25 to 50 kcal/mole. Both potassium and oxygen were found to desorb simultaneously indicating strong interactions in the adsorbed overlayer. LEED results on Pt(111) further indicate that a planar K₂O layer may be formed by annealing coadsorbed potassium and oxygen to 750 K.     

Growth,structure, and thermal stability of epitaxial BaTiO3 films on Pt(111)

The growth of epitaxial ultrathin BaTiO₃ films upon rf magnetron sputter deposition on a Pt(111) substrate has been studied by scanning tunnelling microscopy, low-energy electron diffraction, and X-ray photoelectron spectroscopy. The BaTiO₃ films have been characterized from the initial stages of growth up to a film thickness of 4 unit cells. The deposited films develop a long-range order upon annealing at 1050 K in UHV. In the submonolayer regime a wetting layer is formed on Pt(111). Thicker films reveal a Stranski–Krastanov-like structure as observed with STM. By XPS a good agreement of the thin film stoichiometry with BaTiO₃ single crystal data is determined. Due to annealing at 1150 K BaTiO₃ forms large two-dimensional islands on the Pt(111) substrate. Different surface structures develop on the islands depending on the O₂ partial pressure during annealing.     

IR absorption enhancement for ionized p -nitrobenzoic acid on silver island films epitaxially grown on the 7 × 7 reconstructed Si(111) surface

An enhanced infrared absorption is reported for p-nitrobenzoic acid (PNBA) adsorbed on molecular-beam-epitaxially grown silver films at room temperature on 7×7 reconstructed Si(111) substrates. Reflection high-energy electron diffraction reveals the formation of Ag(111) islands even for 82-monolayer-thick silver deposition on the substrate. The NO₂ symmetric stretch of the surface-ionized species (PNBA^-) is a maximum in intensity at a thickness of 64 monolayers and is one order of magnitude stronger than the same mode of PNBA deposited at a thickness of 5 nm on a Si wafer. Based on the change in film morphology and in light transmittance with silver film thickness, this absorption enhancement is ascribed to the excitation of transverse collective electron resonance of the silver islands. The thickness dependence of the enhancement and of the film morphology will be compared with those observed for silver films deposited on oxidized Si(111) substrates. PACS 61.14.Hg; 68.37.Hk; 78.30.-J     

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.     

Stoichiometry and surface reconstruction of epitaxial CuInSe2(112) films

CuInSe₂(112) films were grown on GaAs(111)A substrates by molecular beam epitaxy. The resulting surface stoichiometry was deduced by consideration of results from various surface analytic techniques. The obtainable Cu/In stoichiometry range in XPS was 0.4–1.2, where 1.2 marks the onset of Cu_2 ? xSe phase segregation at the surface and 0.4 corresponds to the copper-depleted surface with ordered defect compound (ODC) composition. For the stoichiometric CuInSe₂(112) surface, a c(4 × 2) reconstruction of the zinc blende surface periodicity is observed in the LEED pattern, with three rotational domains present on the flat GaAs(111) substrate. With the use of stepped (111) substrates, domain formation could be suppressed. By comparison of the LEED data and concentration depth profiles from angle-resolved XPS, two types of surface reconstructions could be distinguished. According to surface energy calculations in the literature, these correspond to surfaces stabilized by either Cu_In or 2V_Cu defects. The surface of copper-poor CuIn₃Se₅ shows no reconstruction of the zinc blende order.     

Cu adsorption on Pt(111) and its effects on Chemisorption: A comparison with electrochemistry

The growth modes and interaction of vapor-deposited Cu on a clean Pt(111) surface have been monitored by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and work function measurements. The LEED data indicate that below 475 K Cu grows in p(1 × 1) islands in the first monolayer with the interatomic Cu spacing the same as the Pt(111) substrate. The second monolayer of Cu grows in epitaxial, rotationally commensurate Cu(111) planes with the CuCu distance the same as bulk Cu. For substrate temperatures below ～ 475 K, the variation of work function and “cross-over beam voltage” with Cu coverage show characteristic features at one monolayer that are quite useful for calibration of θ_Cu. Above 525 K, Cu-Pt alloy formation was observed in AES and LEED data. Thermal desorption spectroscopy of H₂ and CO has demonstrated that simple site blocking of the Pt(111) surface by vapor-deposited Cu occurs linearly with chemisorption being essentially eliminated at θ_Cu = 1.0–1.15. Conclusions drawn from this work correlate very favorably with the well-known effects of under potentially deposited copper on the electrochemistry of the H₂2H⁺ couple at platinum electrodes.     

The growth and alloy formation of copper on the platinum (111) and stepped (553) crystal surfaces; characterization by Leed,AES, and CO thermal desorption

Epitaxial layers of copper were formed on Pt(111) and Pt(553) single crystal surfaces by condensation of copper atoms from the vapor. Surface alloys were formed by diffusing the copper atoms into the platinum substrate at temperatures above 550 K. The activation energy for this process was found to be ~ 120 $\text{kJ}\text{mol}$. These Pt/Cu surfaces were characterized by LEED, AES, and TDS of CO. The copper grows in islands on the Pt(111) surface and one monolayer is completed before another begins. There is an apparent repulsive interaction between the copper atoms and the step sites of the Pt(553) surface which causes a second layer of copper to begin forming before the first layer is complete. Epitaxial copper atoms block CO adsorption sites on the platinum surface without affecting the CO desorption energy. When the copper is alloyed with the platinum however, the energy of desorption of CO from the platinum was reduced by as much as 20 $\text{kJ}\text{mol}$. This reduction in the desorption energy suggests an electronic modification that weakens the Pt-CO bond.     

Ultrathin Y2O3(111) films on Pt(111) substrates

The growth of ultrathin films of Y₂O₃(111) on Pt(111) has been studied using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS), and low energy electron diffraction (LEED). The films were grown by physical vapor deposition of yttrium in a 10^? 6 Torr oxygen atmosphere. Continuous Y₂O₃(111) films were obtained by post-growth annealing at 700 °C. LEED and STM indicate an ordered film with a bulk-truncated Y₂O₃(111)–1 × 1 structure exposed. Furthermore, despite the lattices of the substrate and the oxide film being incommensurate, the two lattices exhibit a strict in-plane orientation relationship with the [11?0] directions of the two cubic lattices aligning parallel to each other. XPS measurements suggest hydroxyls to be easily formed at the Y₂O₃ surface at room temperature even under ultra high vacuum conditions. The hydrogen desorbs from the yttria surface above ~ 200 °C.     

Electronic Relaxation in Indium Oxide Films Studied with Perturbed Angular Correlations

The electronic relaxation due to the ¹¹¹In → ¹¹¹Cd electron capture process was studied by measuring perturbed γγ-angular correlations after ¹¹¹In-ion implantation into indium oxide films of various compositions and thicknesses and deposited on different substrates. X-ray diffraction, Rutherford backscattering and secondary ion mass spectrometry were used to characterize the microstructure and composition of the samples. The film thickness and type of substrate were found to have much less influence on the after effect than the deposition parameters and impurities.     

Epitaxial Properties of Co-Doped ZnO Thin Films Grown by Plasma Assisted Molecular Beam Epitaxy

High quality Co-doped ZnO thin films are grown on single crystalline Al2O3（0001） and ZnO（0001） substrates by oxygen plasma assisted molecular beam epitaxy at a relatively lower substrate temperature of 450℃. The epitaxial conditions are examined with in-situ reflection high energy electron diffraction （RHEED） and ex-situ high resolution x-ray diffraction （HRXRD）. The epitaxial thin films are single crystal at film thickness smaller than 500nm and nominal concentration of Co dopant up to 20%. It is indicated that the Co cation is incorporated into the ZnO matrix as Co^2＋ substituting Zn^2＋ ions. Atomic force microscopy shows smooth surfaces with rms roughness of 1.9 nm. Room-temperature magnetization measurements reveal that the Co-doped ZnO thin films are ferromagnetic with Curie temperatures Tc above room temperature.     

Reactivities of ultrathin alumina films exposed to intermediate pressures of H2O: Substrate-mediated mechanism for growth and loss of surface order

The response of ordered ultrathin Al₂O₃ films on NiAl(1 1 0) and Ni₃Al(1 1 0) substrates to sequential exposures at varying pressures of H₂O between 10⁻⁷ Torr and 10⁻³ Torr, ambient temperature, was characterized by LEED, AES and density functional theory (DFT) calculations. In all cases, an increase in average oxide thickness, as determined by AES, was observed, consistent with a field-induced oxide growth mechanism. Ordered oxide films of initial average thicknesses of 7 Å and 12 Å grown on NiAl(1 1 0) achieved a limiting thickness of 17(1) Å, while films of initial thickness of 7 Å and 11 Å grown on Ni₃Al(1 1 0) achieved a limiting thickness of 12(1) Å. The LEED patterns for the thinner (7 Å) films were not observed after exposure to 10⁻⁵ Torr (NiAl(1 1 0)), or 10⁻⁴ Torr (Ni₃Al(1 1 0)). In contrast, LEED patterns for the films of greater initial thickness persisted after exposures to 10⁻³ Torr UHV. DFT calculations indicate an Al vacancy formation energy that is significantly greater (by ∼0.5 eV) on the surface that has the thicker oxide film, directly opposite to what may be naively expected. A simple coordination argument supports these numerical results. Therefore, the greater limiting oxide thickness observed on NiAl(1 1 0) demonstrates that the rate determining step in the oxide growth process is not Al removal from the metal substrate and transport across the oxide/metal interface. Instead, the results indicate that the determining factor in the oxide growth mechanism is the kinetic barrier to Al diffusion from the substrate bulk to the oxide/metal interface. The persistence of the LEED patterns observed for the films of greater initial oxide thickness indicates that the surface disorder generally observed for alumina films grown on aluminide substrates and exposed to intermediate pressures of H₂O is due to the growth of a disordered alumina layer over an ordered substrate, rather than to direct H₂O interaction with terrace sites.     

Effect of CoSi2 buffer layer on structure and magnetic properties of Co films grown on Si（001） substrate

Buffer layer provides an opportunity to enhance the quality of ultrathin magnetic films.In this paper,Co films with different thickness of Co Si2buffer layers were grown on Si(001)substrates.In order to investigate morphology,structure,and magnetic properties of films,scanning tunneling microscope(STM),low energy electron diffraction(LEED),high resolution transmission electron microscopy(HRTEM),and surface magneto-optical Kerr effect(SMOKE)were used.The results show that the crystal quality and magnetic anisotropies of the Co films are strongly affected by the thickness of Co Si2buffer layers.Few Co Si2monolayers can prevent the interdiffusion of Si substrate and Co film and enhance the Co film quality.Furthermore,the in-plane magnetic anisotropy of Co film with optimal buffer layer shows four-fold symmetry and exhibits the two-jumps of magnetization reversal process,which is the typical phenomenon in cubic(001)films.     

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.     

GaAs(100)衬底上ZnSe薄膜的热壁束外延生长

介绍热壁束外延法生长ZnSe/GaAs异质结工作。低能电子衍射和俄歇电子能谱对样品的原位检测表明,用此方法可以在GaAs(100)衬底上外延得到单晶的ZnSe(100)薄膜。当外延生长速率大时,Znse薄膜质量下降,样品的Raman谱中出现TO模。X射线衍射实验结果表明,这种外延膜质量的退化主要是由于在ZnSe(100)薄膜体内存在〈111〉方向的晶核。 关键词：     

Thickness-dependent orientation evolution in nickel thin films grown on yttria-stabilized zirconia single crystals

Microstructure evolution along with crystallographic orientation change as a function of film thickness was investigated in Ni thin films grown on (100) yttria-stabilized zirconia (YSZ) single crystal substrates. Texture development with two different orientation relationships, OR1: Ni {111}//YSZ {100} and OR2: Ni {100}//YSZ {100}, cube on cube orientation were identified by X-ray diffraction and transmission electron microscopy depending on the film thickness. The observed orientation transition reveals the existence of a critical thickness (～320?nm) favoring two different orientations in sputtered Ni films on YSZ (100) substrate.     

The chemisorption of O2, CO,D2 and C2H4 over epitaxially grown rhenium crystalline films

The adsorption and desorption of oxygen, carbon monoxide, deuterium and ethylene has been studied over rhenium films using thermal desorption spectroscopy, low energy electron diffraction and Auger electron spectroscopy. The films, obtained by evaporating rhenium onto a platinum (111) single crystal, grow over the substrate forming (0001) basal plane rhenium surfaces. Oxygen chemisorbs on this film, forming an ordered structure, consisting of three (2 × 1) overlayer domains and giving a saturation coverage of half a monolayer of atomic oxygen. CO chemisorption is mainly molecular, although some dissociation occurs at temperatures above about 700 K. A complicated LEED pattern is obtained when saturating the surface at 150 K with CO, but it changes to a (2 × 2) or (2 × 1) structure upon heating. Also, CO chemisorption can be modified by predissociated CO or preadsorbed oxygen on the rhenium surface. Deuterium desorbs in three peaks, starting at temperatures as low as 150 K. Ethylene desorbs partially intact at around 250 K, the rest decomposing and yielding hydrogen, that appears as two main peaks at 357 K and 460 K during thermal desorption. We conclude that epitaxially grown films may be an alternative to single crystals for studying chemisorption over well ordered surfaces.     

The effect of silicon-substrate orientation on the local piezoelectric characteristics of LiNbO<Subscript>3</Subscript> films

The domain structure of lithium-niobate thin films grown on Si(111) and Si(100) substrates coated with a native oxide layer with a thickness of no less than 2 nm is investigated by X-ray diffraction, scanning electron microscopy and piezoresponse force microscopy. The films are synthesized by the rf magnetron sputtering of a single-crystal lithium-niobate target. A high degree of grain orientation in the polycrystalline films is demonstrated. The piezoelectric coefficients d _zz of the lithium-niobate films on Si(111) and Si(100) substrates are calculated from the measured dependences of the amplitude of the piezoresponse signal on the ac voltage applied between the cantilever tip and the substrate. Piezoelectric hysteresis loops are obtained in the remanent piezoelectric response regime