AES investigations of growth of very thin silver films deposited on the copper and nickel (110) faces

Growth of very thin silver films deposited under UHV conditions on the Ni(110) and Cu(110) faces was studied with the Auger Electron Spectroscopy. Silver 360eV and nickel 61eV Auger peaks kinetics show the Stranski-Krastanov growth mechanism. Two stages of the first ML growth at room temperature was observed. During annealing of 2 ML layer (the rate of temperature increase of 4 K/s) the silver Auger peak increases by about 10% atT 620 K. This indicates that reconstruction of silver islands takes place. The first monolayer desorbs atT=840 K. The Cu-Ag system was studied with silver 360eV and copper 62eV Auger peaks. The adsorption kinetics, up to 440 K, show the Stranski-Krastanov growth mechanism. After 1 ML deposition, the increase of the substrate temperature leads to the slope decrease of the adsorption kinetics. Adsorption kinetics forT=560–620 K show that after 1.5 ML deposition the silver dissolution occurs and the surface alloy is formed. Above 770 K the shape of kinetics drastically changes due to the decrease of a sticking coefficient.Presented at the Seminar on Secondary Electrons in Electron Spectroscopy, Microscopy, and Microanalysis, Chlum (The Czech Republic), 21–24 September, 1993.The authors would like to thank B. Stachnik and Z. Jankowski for the preparation of the measuring system.The work was supported by the Polish Committee for Scientific Research under Grant Nr. 20119 91 01.     

The chemisorption of sulphur on W(100)

The interaction of sulphur vapour with a W(100) surface is studied in detail with Auger Electron Spectroscopy (AES), LEED, work function difference (Δ?) measurements and thermal desorption spectroscopy (TDS). The dissociative adsorption of S occurs on the W surface without reconstruction. Several LEED structures are observed which indicate repulsive adatom interactions. TDS shows that the desorption energy of atomic S decreases from about 8 eV at θ = 0.1 ML to about 3 eV near saturation in close vicinity of 1 ML. Above $\text{θ =}\text{3}\text{4}$ ML, S₂ desorbs in addition to S in a high temperature peak which saturates at about 1 ML. Sulphur in excess of about 1 ML is desorbed in two low temperature peaks of which the lower one consists not only of S and S₂ but also of S₃ and S₄.     

Interaction of atomic oxygen (N2O) with a clean Si(001) surface: O adsorption geometries as derived from the O KVV Auger lineshape

The room temperature adsorption of N₂O on the clean Si(001)2 × 1 surface was used as a model system in an Auger electron spectroscopy (AES) study presented in this paper. Earlier experimental and recent theoretical work have provided evidence that this reaction evolves in discernible stages each exhibiting different adsorption geometries for the oxygen atom. In this AES study the intensity ratio of the KL₁L₁ and KL_2,3L_2,3 O Auger transitions, , was measured as a function of the fractional oxygen coverage, θ, and compared with our calculated intensity ratios and binding energy measurements of the O 1s photoelectron from literature. As a result we have found, for the first time, that (θ) can be related to a specific adsorption geometry in the submonolayer range. Moreover, we have found experimental evidence for an intermediate stable O adsorption state on the dimer at low coverage (θ 0.2 monolayer), as proposed earlier from theoretical studies.     

Distinct binding states in adsorption on a homogeneous surface: Te on W(100)

The adsorption of Te on a W(100) surface is studied by thermal desorption spectroscopy (TDS), Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and work function change (Δ?) measurements. Three distinct binding states are observed in the first monolayer corresponding the coverages from 0 to $\text{1}\text{2}$ monolayers (ML), $\text{1}\text{2}$ to $\text{2}\text{3}$ ML and$\text{2}\text{3}$ to 1 ML. Within each state a coverage dependence of the desorption parameters is found. The three binding states are discussed in terms of heterogeneity induced by lateral interactions and in terms of inherently different adsorption sites.     

Adsorption and decomposition of H2S on the Ge(100) surface

The adsorption and decomposition of H₂S on the Ge(100) surface is investigated. H₂S is a simple sulfur containing molecule that eventually decomposes to yield hydrogen gas and deposits sulfur on the germanium surface. The surface reactions of H₂S are investigated by ultraviolet photoelectron spectroscopy, Auger electron spectroscopy, and temperature programmed desorption. Room temperature exposure of H₂S to Ge(100) results in dissociative adsorption which can be followed easily by ultraviolet photoelectron spectroscopy. Warming the H₂S exposed surface results in some molecular desorption and further decomposition of the adsorbed species. At saturation, 0.25 ML of H₂S decomposes generating 0.5 ML of atomic hydrogen. Above the hydrogen desorption temperature some etching of the germanium surface is observed by sulfur. The etch product, GeS, is subsequently observed in temperature programmed desorption experiments. Exposure of H₂S to the Ge surface at elevated temperatures leads to higher sulfur coverages. A sulfur coverage approaching 0.5 ML can be deposited at the higher exposure temperatures.     

Interaction of oxygen with the Pt(1 1 1) surface in wide conditions range. A DFT-based thermodynamical simulation

We present the results of ab initio calculations of oxygen atomic adsorption in a wide range of coverage on Pt(1 1 1). At θ = 0.25 ML, the O adsorption at fcc hollow site is clearly favoured over the hcp site. At θ = 0.5 ML, the O adsorption energy decreases but the same site is favoured. When experimental or theoretical previously reported data are available, the calculated adsorption energies and site preferences are in good agreement. Among the various configurations and coverages investigated in the present work, no adsorption is stable beyond θ = 0.5 ML, except by occupation of a subsurface tetrahedral site. In that case, a total O coverage of 0.75 ML could be achieved, which is only slightly less stable than the θ = 0.5 ML configuration.

The use of thermodynamics permitted to explore the temperature–pressure stability domain corresponding to 0.25 ML, 0.5 ML and 0.75 ML. From this, we conclude that subsurface O species could be stable at temperatures lower than 700 K, with O₂ pressures of 1 bar or less.     

Growth and alloy formation of ultrathin Ni films on Co/Pt(1 1 1)

Low-energy electron diffraction (LEED) and Auger electron spectroscopy (AES) were used to study the growth and the structural evolution of Ni/Co/Pt(1 1 1) following high-temperature annealing. From the oscillation of the specular beam of the LEED and Auger uptake curve, we concluded that the growth mode of thin Ni films on 1 ML Co/Pt(1 1 1) is at least 2 ML layer-by-layer growth before three-dimensional island growth begins. The alloy formation of Ni/1 ML Co/Pt(1 1 1) was analyzed by AES. The temperature for the intermixing of Ni and Co layers in the upper interface without diffusing into the bulk of Pt is independent of the thickness of Ni when a Co buffer is one atomic monolayer. After the temperature was increased, formations of Ni-Co-Pt alloy, Ni-Pt alloy and Co-Pt alloy were observed. The temperature required for the Ni-Co intermixing layer to diffuse into Pt bulk increases with the thickness of Ni. The interlayer distance as a function of annealing temperature for 1 ML Ni/1 ML Co/Pt(1 1 1) was calculated from the I-V LEED. The evolution of LEED patterns was also observed at different annealing temperatures.     

Effect of surface reconstruction on the adsorption of Ge on clean Si(111)

The effect of ultrahigh vacuum deposition of Ge below and at monolayer (ML) coverage onto a 7 × 7 reconstructed clean Si(111) surface held at room temperature is studied by low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and photoemission yield spectroscopy (PYS). The results are compared to those obtained on 2 × 1 reconstructed clean Si(111) : (i) the Si dangling bond states are replaced by Ge dangling bond states at submonolayer coverages in both cases; (ii) the 7 × 7 reconstruction persists below 1 ML, it is not replaced by a ? 3 × ? 3 R30° at 1/3ML as it was on the 2 × 1; and (iii) the coverage below 1 ML is not homogeneous on the 7 × 7 reconstruction. This behaviour can be explained by the influence of the inhomogeneties associated with the 7 × 7 reconstruction.     

氯原子在Cu(111)表面的吸附结构和电子态

密度泛函理论(DFT)总能计算研究了不同覆盖度下氯原子在Cu(111)表面的吸附结构和表面电子态。计算结果表明,清洁Cu(111)表面自由能 为15.72 ,表面功函数φ为4.753eV。在1/4ML和1/3ML覆盖度下,每个氯原子在Cu(111)表面fcc谷位的吸附能分别等于3.278eV/atom和3.284eV/atom。在1/2ML覆盖度下,两个紧邻氯原子分别吸附于fcc和hcp谷位,氯原子的平均吸附能为2.631eV/atom。在1/3ML覆盖度下,fcc和hcp两个位置每个氯原子吸附能的差值约为2meV/atom,与正入射X光驻波实验结合蒙特卡罗方法得到结果(<10meV/atom)基本一致。在1/4ML、1/3ML和1/2ML覆盖度下,吸附后Cu(111)表面的功函数依次为5.263eV、5.275eV和5.851eV。吸附原子和衬底价轨道杂化形成的局域表面电子态位于费米能级以下约1.2eV、3.6eV和4.5eV等处。吸附能和电子结构的计算结果表明,氯原子间的直接作用和表面铜原子紧邻氯原子数目是决定表面结构的两个重要因素。     

Adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface

The adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface has been studied with scanning tunneling microscopy (STM) and temperature programmed desorption (TPD). At 0.1 ML Cs coverage the whole surface exhibits a mixture of (1 × 2) and (1 × 3) reconstructed structures, indicating that Cs atoms exert a cooperative effect on the surface structures. Real-time STM observation shows that silver atoms on the Cs-covered surface are highly mobile on the nanometer scale at 300 K. The Cs-reconstructed Ag(1 1 0) surface alters the structure formed by dissociative adsorption of oxygen from p(2 × 1) or c(6 × 2) to a p(3 × 5) structure which incorporates 1/3 ML Ag atoms, resulting in the formation of nanometer-sized (10–20 nm) islands. The Cs-induced reconstruction facilitates the adsorption of CO₂, which does not adsorb on unreconstructed, clean Ag(1 1 0). CO₂ adsorption leads to the formation of locally ordered (2 × 1) structures and linear (2 × 2) structures distributed inhomogeneously on the surface. Adsorbed CO₂ desorbs from the Cs-covered surface without accompanied O₂ desorption, ruling out carbonate as an intermediate. As a possible alternative, an oxalate-type surface complex [OOC–COO] is suggested, supported by the occurrence of extensive isotope exchange between oxygen atoms among CO₂(a). Direct interaction between CO₂ and Cs may become significant at higher Cs coverage (>0.3 ML).     

Pd与CeO2(111)面的相互作用的第一性原理研究

采用基于广义梯度近似的投影缀加平面波(projector augmented wave) 赝势和具有三维周期性边界条件的超晶胞模型，用第一性原理计算方法，计算并分析了Pd在CeO₂(111)面上不同覆盖度时的吸附能，价键结构和局域电子结构. 考虑了单层Pd和1/4单层Pd两种覆盖度吸附的情况. 结果表明：1)在单层吸附时，Pd的最佳吸附位置是O的顶位偏向Ce的桥位；在1/4单层吸附时，Pd最易在O的桥位偏向次层O的顶位吸附.2) 单层覆盖度吸附时，吸附原子Pd之间的作用较强；1/4单 关键词： 三元催化剂 Pd 2')" href="#">CeO₂ 吸附 密度泛函理论     

Adsorption and reaction of oxygen and deuterium on a Pd(110) surface, studied by Δφ and TDS

The co-adsorption of oxygen and deuterium at 100 K on a Pd(110) surface has been studied by measurements of the change in work function (Δφ) and by thermal desorption spectroscopy (TDS). When the surface with co-adsorbed species is heated, the adsorbates O and D react to form D₂O which desorbs from the surface at T > 200 K. The D₂O desorption peaks shift continuously to lower temperatures as the surface D coverage (θ_D) increases. The maximum production of D₂O is estimated to be 0.26 ML (1 ML = 9.5 × 10¹⁴ atoms cm⁻²), resulting from reaction in a layer containing 0.65 ML D and 0.3 ML O. The maximum work function increase caused by adsorption of D to saturation onto oxygen precovered Pd(110) decreases almost linearly with Δφ_O of the oxygen precovered surface. On a surface with pre-adsorbed D however, the maximum Δφ increase contributed by oxygen adsorption decreases abruptly at Δφ_D > 200 mV. This sharp change occurs at θ_D > 1 ML and is believed to be associated with the development of the reconstructed (1 × 2) phase of D/Pd(110).     

H2O在SrTiO3-(001)TiO2表面上吸附和解离的密度泛函理论研究

利用密度泛函理论研究了0.25单层(ML),0.5ML,0.75ML和1ML吸附率下H2O在SrTiO3-(001)TiO2表面上的吸附行为.比较了不同吸附率下分子吸附和解离吸附的稳定性,利用微动弹性带(nudged elastic band)方法计算了H2O的解离势垒.结果表明:在低吸附率(0.25ML和0.5ML)时,H2O表现为解离吸附;在0.75ML吸附率下,分子吸附和解离吸附同时存在;而在全吸附(吸附率为1ML)时,分子吸附更稳定.基于对H2O分子与表面之间以及H2O分子之间的电荷转移和相互作用的分析,讨论了吸附率对H2O吸附和解离的影响.     

用可调探测深度电子能量损失谱与俄歇电子能谱研究Pb/Ni(001)界面

本工作用可调探测深度电子能量损失谱(ELS)与俄歇电子能谱(AES)研究Pb在Ni(001)表面的生长过程。发现Pb是一层一层地在表面生长的,即按Franck-van der Merwe(F-M)模式生长。当Pb的覆盖度大于1单层(ML)时,Pb的6s能带对应的电子能量损失峰开始出现,当Pb的覆盖度为3ML时,Pb的体等离激元的损失峰已相当明显。在Pb的蒸镀过程及随后的整个退火过程中,Pb的体等离激元峰,6s能带峰和Ni的3p能带峰的峰位与峰宽均保持与纯金属相同的值,也没有出现新的体等离激元峰。由此说明P     

The Rh(100)-(3 × 1)-2O structure

The O adsorption on Rh(100) has been studied using high resolution core level spectroscopy, low energy electron diffraction and scanning tunnelling microscopy. In addition to the well known (2 × 2), (2 × 2)-pg and c(8 × 2) structures at coverages of 0.25, 0.5 and 1.75 ML respectively, an intermediate (3 × 1) structure with a coverage of 2/3 ML is identified.     

Growth and oxidation of aluminum thin films deposited on Ag(1 1 1)

Auger electron spectroscopy (AES) and low energy electron diffraction (LEED) were used to study the first steps of growth and oxidation of aluminum on Ag(1 1 1) substrate. We find that the growth of aluminum at room temperature (RT) shows the formation of a complete monolayer (ML) in epitaxy with the substrate. After deposition at RT of one aluminum ML, the dissolution kinetics is recorded at 200 °C and the bulk diffusion coefficient is deduced. We also show that the oxidation at RT of one aluminum ML is very rapid, and that both aluminum and oxygen do not dissolve in silver up to 500 °C. From the AES intensities variations, we deduce the composition profile of the oxide layer which corresponds probably to the stacking …/Ag/Ag/Al/O.     

Preparation of a Pd/ZnO (0001) model catalyst and its characterization by AES,LEED and UHV reaction studies

Supported Pd catalysts are prepared in UHV on ZnO (000$\text{1}$) (oxygen face). By repeated cycles consisting of Pd deposition and an annealing step total amounts from 0.3 to 130 monolayers (ML) are reached. The growth mode of Pd is deduced indirectly from an analysis of Auger peak heights as a function of deposition amount and annealing temperature. At 300 K substrate temperature Pd, deposited with a rate of 1.2 ML/min, weakens the zinc and oxygen Auger yields in such a way that up to a deposit of 10 ML a constant ratio is maintained. This is ascribed to an agglomeration of the Pd deposit into clusters much higher than the escape depth. A critical inititial height of the clusters is derived as 6 ML (14.6 Å). The height increases linearly with Pd deposit. Above a deposit of 10 ML the oxygen Auger yield decreases much faster than the zinc yield. The data can be fitted using the assumption of a homogeneous Pd film on the free areas between the clusters. Annealing of faces with up to 130 ML Pd deposit at temperatures up to 970 K reestablishes free substrate area between the clusters. No evidence is found for zinc or oxygen atoms on top of the clusters. Pd does not desorb but at constant substrate Auger signals the Pd signal is significantly reduced upon annealing above room temperature. Therefore, it is concluded that appreciable amounts of Pd diffuse into the bulk or react with the substrate. After Pd deposition at room temperature only a faint (1 × 1) LEED pattern appears but on annealed faces with less than 35 ML Pd deposit intense (1 × 1) LEED spots of the ZnO lattice prevail indicating epitaxial growth. At higher coverages additional spots with hexagonal symmetry show up, arising from a Pd (111) structure aligned parallel to the ZnO lattice. In addition, TDS results of ethanol decomposition are discussed: The presence of 5.2 ML Pd deposit on ZnO (000$\text{1}$) increases at low temperatures the rates of the products already known from the uncovered face. This implies that a part of the ZnO surface is still accessible for desorption. Above 10 ML Pd deposit also CO from a total oxidation appears     

The adsorption position of Hg on Ni(100): a transmission channeling study

The adsorption position of Hg on Ni(100) has been studied with transmission channeling. It is shown that for coverages up to 0.5 monolayer (ML), Hg adsorbs in the four-fold hollow site (FFHS) at a height of 2.25 ± 0.10 rA. This is at variance with an earlier report of adsorption in the bridge site. For a crystal temperature of 115 K and low coverage (θ_Hg t 0.18 ML), the two-dimensional vibration amplitude parallel to the surface, ρ_Hg, is 0.10 +- 0.03 rA, but at higher coverage, θ_Hg 0.45 ML, there is an apparent increase in the root-mean-square displacement of the Hg atoms from the FFHS. Possible origins of this increase are discussed.     

Adsorbate-oxide interactions during the NO + CO reaction on MgO(100) supported Pd monolayer films

The potential energy diagram for the NO+CO reaction on 1, 2, and 3 monolayer (ML) Pd films supported by MgO(100) is calculated using density functional theory. Thin Pd films are generally found to be more reactive than thick films, with a notable exception for nitrogen adsorption on 2 ML Pd/MgO(100). For this system an attractive through-the-metal adsorbate-oxide interaction of 0.5 eV is identified. Nitrogen adsorption is consequently estimated to provide a thermodynamic driving force for the reconstruction of MgO(100) supported 3 ML (or thicker) Pd clusters into thinner Pd clusters.     

The surface structure of Fe3O4(1 1 1) films as studied by CO adsorption

We have studied adsorption of CO on Fe₃O₄(1 1 1) films grown on a Pt(1 1 1) substrate by temperature programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS) and high resolution electron energy loss spectroscopy (HREELS). Three adsorption states are observed, from which CO desorbs at ∼110, 180, and 230 K. CO adsorbed in these states exhibits stretching frequencies at ∼2115-2140, 2080 and 2207 cm⁻¹, respectively. The adsorption results are discussed in terms of different structural models previously reported. We suggest that the Fe₃O₄(1 1 1) surface is terminated by 1/2 ML of iron, with an outermost 1/4 ML consisting of octahedral Fe²⁺ cations situated above an 1/4 ML of tetrahedral Fe³⁺ ions, in agreement with previous theoretical calculations. The most strongly bound CO is assigned to adsorption to Fe³⁺ cations present on the step edges.