Alloy formation at the Ni–Al interface for nickel films deposited on Al(110) surfaces

Alloy formation at the Ni–Al interface for thin nickel films deposited on Al(110) surfaces has been studied using high-energy ion scattering/channeling (HEIS) and X-ray photoelectron spectroscopy (XPS). For nickel atoms deposited at room temperature on Al(110), a large amount of nickel–aluminum intermixing occurs at the interface. For the first two monolayers (ML) of deposited nickel, an NiAl-like compound is formed. The intermixing continues with a different rate, forming an Ni₃Al-like compound for nickel coverages from 2 to 8 ML, at which point a nickel metal film begins to grow on the surface. Nickel atoms deposited at 250°C on the Al(110) surface exhibit no surface compound formation, but diffuse up to 400 Å into the aluminum substrate. Interatomic potentials based on the embedded-atom method (EAM) are used in a Monte Carlo approach to simulate the evolution of the Ni–Al(110) interface as a function of the nickel coverage. The calculated ion-scattering yields and X-ray photoelectron intensities from nickel and aluminum atoms in these simulated interfaces are in good quantitative agreement with the experimental results. The simulations show a high-density Ni–Al alloy forming at the Al(110) surface which apparently inhibits outward diffusion of aluminum, leading to the more nickel-rich alloy and finally nickel film growth. The ion-scattering simulations show an unusually large amount of backscattering occurring below the Ni–Al(110) interface, apparently associated with defocusing of the incident ion beam.     

The interaction of ultrathin films of Ni and Pd with W(110): an XPS study

The interaction of ultrathin films of Ni and Pd with W(110) has been examined using X-ray photoelectron spectroscopy (XPS) and the effects of annealing temperature and adsorbate coverage (film thickness) are investigated. The XPS data show that the atoms in a monolayer of Pd or Ni supported on W(110) are electronically perturbed with respect to the surface atoms of Pd(100) and Ni(100). The magnitude of the electronic perturbations is larger for Pd than for Ni adatoms. Our results indicate that the difference in Pd(3d_5/2) XPS binding energies between a pseudomorphic monolayer of Pd on W(110) and the surface atoms of Pd(100) correlates with the variations observed for the desorption temperature of CO (i.e., the strength of the Pd---CO bond) on these surfaces. A similar correlation is seen for the Ni(2p_3/2) XPS binding energies of Ni/W(110) and Ni(100) and the CO desorption temperatures from the surfaces. The shifts in XPS binding energies and CO desorption temperatures can be explained in terms of: (1) variations that occur in the Ni---Ni and Pd---Pd interactions when Ni and Pd adopt the lattice parameters of W(110) in a pseudomorphic adlayer; and (2) transfer of electron density from the metal overlayer to the W(110) substrate upon adsorption. Measurements of the Pd(3d_5/2) XP binding energy of Pd/W(110) as a function of film thickness indicate that the Pd---W interaction affects the electronic properties of several layers of Pd atoms.     

The growth of Au/Pd/alumina/Cu-Al system studied by SRPES

An ultra-thin alumina layer grown on Cu-9at.%Al (1 1 1) surface was studied using synchrotron radiation photoelectron spectroscopy (SRPES), X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). By deconvolving SRPES spectra of the Al 2p doublet, four components belonging to metallic as well as oxide phases were recognized. Pd-Au alloy formation was confirmed by SRPES measurement during Pd and Au deposition. The study of the system's thermal stability reveals diffusion of Pd and Au atoms through the alumina layer. While Au atoms start to diffuse under the alumina layer at 670 K, Pd atoms are forming Pd-Al surface alloy at this temperature. The diffusion of Pd atoms through alumina occurs when sample was heated over 770 K. Alumina layer was stable even after heating the sample at 870 K, but its structure was corrupted probably due to the diffusion of metal atoms.     

Al原子在Pb基底上的沉积过程研究

利用分子动力学方法模拟了Al原子在Pb基底上的沉积过程. 对Al原子在Pb基底(001)面上沉积的形态与Pb原子在Al(001)基底上沉积的形态做了比较. 由于界面间势垒的不同, 两个体系界面间的形态有明显的差异. 分析了基底温度、基底晶面指向、沉积原子的入射动能对界面间原子混合的影响. 模拟结果显示: 随着基底温度升高, 基底原子的可移动性大大增加, 与沉积原子发生较大程度的混合; 入射能的改变对界面间原子的混合影响很小; 基底表面取不同的晶格指向时, 基底与沉积原子间的混合行为也有明显的不同. 利用径向分布函数分析了沉积原子的入射能对薄膜中原子排列有序性的影响. 较高入射能对应更有序的薄膜结构; 由径向分布函数的结构可以推测Al原子在Pb(001)基底表面沉积时界面间可能有金属间化合物生成. 关键词： Pb/Al体系 沉积过程 分子动力学 入射能     

Characterization of a Pd-Fe bimetallic model catalyst

Small bimetallic Pd-Fe particles supported on a well ordered alumina film grown on NiAl (1 1 0) were studied focusing on the geometric, electronic, adsorption, as well as magnetic properties. The morphology, growth mode and surface composition were investigated by combining scanning tunneling microscopy (STM), temperature-programmed desorption (TPD) and infrared spectroscopy (IRAS) using CO as a probe molecule. Information on the electronic properties of the bimetallic systems was obtained by means of X-ray photoelectron spectroscopy (XPS). These measurements were amended by in situ ferromagnetic resonance spectroscopy to address the magnetic properties of the bimetallic particles. The subsequent deposition of the metals at 300 K varying the order of metal deposition resulted in two distinct bimetallic systems. Pd deposited on existing Fe particles forms a shell, however, FMR and XPS suggest that intermixing of Pd and Fe occurs to some extent. For the reverse order, a larger amount of Fe is required to coat Pd particles, due to the strong tendency of Pd to segregate to the surface of the particles.     

Model of electroless Ni deposition on SiCp/Al composites and study of the interfacial interaction of coatings with substrate surface

Metallization techniques based on electroless plating are used to coat SiC_p/Al composite materials. The directly palladium chloride (PdCl₂) solutions in HCl is used to render the surface of such non-conductive substrates catalytically active towards metal deposition in the electroless plating solution. The microstructures of Ni-coated composites provided by scanning electron microscope (SEM) bring light into the palladium activation and electroless coating process. Also, X-ray photoelectron spectroscopy (XPS) and Line-scan have allowed to monitor the chemical and compositional surface modifications of activated and coated SiC_p/Al composites, as well as to understand the mechanisms of the catalyst (palladium species) chemisorption on the composites surface and the interaction mechanisms of Ni layer with the SiC_p/Al composites. The experimental results show that a nickel-substrate bonding action takes place during plating. Ni atom existing on the surface of the composites can partially obtain electrons from metals Al of the SiC_p/Al composites when the substrate is embedded in the Ni layers, that is, the orbital interaction through the mutual overlap of the electronic orbits does exist in the interfacial regions between the coated Ni atoms and composites substrate instead of the mechanical-interlocked form. On the basis of the evidence, a model of electroless Ni deposition on SiC_p/Al composites is submitted including Pd activation and Ni deposition processes to describe the formation of catalytic centers and the growth of deposited layer. The deposition model reveals that metal-substrate bond plays an important role in the high adhesion strength between the Ni coatings and the composites.     

Fe/Al混合膜的PLD法制备及表面分析

 采用脉冲激光气相沉积（PLD）技术制备了Fe/Al混合膜,测量了该混合膜的光电子能谱（XPS）,并采用原子力显微镜（AFM）、扫描电子显微镜（SEM）对Fe/Al混合膜作了表面分析。结果表明：Fe/Al混合膜的表面粗糙度对衬底温度有明显的依赖性, 随着衬底温度的升高,薄膜的表面逐渐变得平滑,膜层变得致密,在200 ℃衬底温度下制得了均方根（rms）粗糙度为0.154 nm、具有原子尺度光滑性的Fe/Al混合膜, 膜中Fe和Al分布比较均匀,其成分比约为1∶3,同时XPS分析也表明Fe/Al混合膜暴露在空气中后表面形成了Al₂O₃和FeO氧化层。     

强流脉冲离子束辐照混合双层靶的Monte Carlo模拟

采用Monte Carlo方法模拟强流脉冲离子束与铝基钛膜双层靶的相互作用.强流脉冲离子束与双层靶材相互作用过程中,随着离子的注入,高能离子束引起涂层原子与基体材料原子之间相互渗透和混合,同时离子能量沉积到靶材内一定深度,并呈规律性的空间分布.这种能量分布影响靶内两种材料的熔化或气化过程,并导致界面物质结合强度发生变化.利用建立的束流模型,计算束流在靶材内的能量沉积和分布状况及界面处级联碰撞对双层靶界面混合区的影响,得出强流脉冲离子束混合双层靶时级联碰撞不起主要作用的结论,离子流密度在100A·cm^-2~150A·cm^-2时对离子束混合最为有利.     

AlCl3-induced crystallization of amorphous silicon thin films

It is reported that the direct contact between Al and amorphous silicon (a-Si) enhances the crystallization of a-Si films. But the polycrystalline silicon (poly-Si) films crystallized by the direct contact of Al metal film suffer the problems of rough surface. In our study, we utilized the AlCl₃ vapor during the a-Si films deposition instead of Al metal film to enhance crystallization. X-ray diffraction (XRD) shows that the AlCl₃ vapor so successfully enhanced the crystallization of a-Si films that the crystallization was completed in 5 h at 540 °C. And the orientation of the poly-Si film deposited with AlCl₃ vapor is much more random than that of annealed with Al metal under layer. But the average grain size is much larger than that. Moreover, the surface of the AlCl₃-induced crystallized poly-Si film was much smoother than that of the Al-induced poly-Si film. The Al and Cl incorporation into the poly-Si film was confirmed using X-ray photoelectron spectroscopy (XPS) and found that the quantity of Al and Cl incorporated into the Si film was below the detection limit of XPS.     

Influence of a heterogeneous Al2O3 surface on the electronic properties of single Pd atoms

Electronic properties of single Pd atoms, deposited on Al(2)O(3)/NiAl(110), have been characterized by scanning tunneling spectroscopy at 12 K. The spectra reveal distinct conductivity resonances, assigned to discrete electronic levels in the atom. The energy position of the resonances reflects adsorption properties of Pd atoms on different sites of the oxide support. Mapping the spatial extent of conductivity channels in the Pd atoms yields the symmetry of the underlying electronic states. The results demonstrate the effect of a heterogeneous oxide surface on the electronic structure of adsorbed metal atoms.     

Photoinduced formation and aggregation of silver nanoparticles at the surface of carboxymethylcellulose films

Formation and aggregation of photolytic silver nanoparticles at the surface of silver salt of carboxymethylcellulose films (CMCAg films) have been investigated. Detailed X-ray photoelectron spectroscopy (XPS) study and field emission type scanning electron microscopy (FE-SEM) observation have been carried out to characterize silver nanoparticles at the film surface. When the CMCAg films were irradiated with UV light in wet air at room temperature for 30–60 min, silver nanoparticles of ca. 10 nm size were formed at the irradiated surface. According to the FE-SEM observation, the growth of the particle diameter and aggregation of nanoparticles took place after prolonged irradiation, and finally, the irradiated side of the film surface was densely covered with the silver nanoparticles of ca. 35 nm size. Chemical composition analysis by the XPS measurements has confirmed the increase in the atomic concentration of silver with irradiation time. It is suggested that silver atoms and clusters can move in the film and precipitate at the irradiated surface.     

Morphological and chemical study of the initial growth of CdS thin films deposited using an ammonia-free chemical process

We study the initial growth stages of CdS thin films deposited by an ammonia-free chemical bath deposition process. This ammonia-free process is more environmentally benign because it reduces potential ammonia release to the environment due to its high volatility. Instead of ammonia, sodium citrate was used as the complexing agent. We used atomic force microscopy (AFM), Rutherford backscattering (RBS) and X-ray photoelectron spectroscopy (XPS) to investigate the morphological and chemical modifications at the substrate surface during the first initial stages of the CdS deposition process. Additionally, X-ray diffraction (XRD) and optical transmission spectroscopy measurements were carried out to compliment the study. XPS results show that the first nucleation centers are composed by Cd(OH)₂ which agglomerate in patterns of bands, as demonstrated by AFM results. It is also observed that the conversion to CdS (by anionic exchange) of the first nucleus begins before the substrate surface is completely covered by a homogenous film.     

Properties of the interaction of europium with Si(111) surface

Formation of the Eu/Si(111) system as the metal layer thickness gradually increases from 0.5 to 60 monolayers (ML) deposited on the silicon surface at room temperature, and after heating at up to 900 °C, has been studied by Auger electron spectroscopy, electron-energy-loss spectroscopy, and low-energy-electron diffraction. It is shown that room-temperature film growth passes through three stages, depending on the Eu layer thickness: metal chemisorption, interdiffusion of the metal and substrate atoms, and buildup of the metal on the surface of the system. Heating of ultrathin (about one ML) Eu films deposited at room temperature results in ordering of metal atoms on the silicon surface with only weak interaction. Heating thick (above 15 ML) Eu layers on the silicon surface produces silicides whose structure depends on the heating temperature. Fiz. Tverd. Tela (St. Petersburg) 40, 562–567 (March 1998)     

Formation, stability and CO adsorption properties of PdAg/Pd(1 1 1) surface alloys

The formation, stability and CO adsorption properties of PdAg/Pd(1 1 1) surface alloys were investigated by X-ray photoelectron spectroscopy (XPS) and by adsorption of CO probe molecules, which was characterized by temperature-programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The PdAg/Pd(1 1 1) surface alloys were prepared by annealing (partly) Ag film covered Pd(1 1 1) surfaces, where the Ag films were deposited at room temperature. Surface alloy formation leads to a modification of the electronic properties, evidenced by core-level shifts (CLSs) of both the Pd(3d) and Ag(3d) signal, with the extent of the CLSs depending on both initial Ag coverage and annealing temperature. The role of Ag pre-coverage and annealing temperature on surface alloy formation is elucidated. For a monolayer Ag covered Pd(1 1 1) surface, surface alloy formation starts at ∼450 K, and the resulting surface alloy is stable upon annealing at temperatures between 600 and 800 K. CO TPD and HREELS measurements demonstrate that at 120 K CO is exclusively adsorbed on Pd surface atoms/Pd sites of the bimetallic surfaces, and that the CO adsorption behavior is dominated by geometric ensemble effects, with adsorption on threefold hollow Pd₃ sites being more stable than on Pd₂ bridge sites and finally Pd₁ a-top sites.     

Adsorption of thiophene on Al(1 1 1) and deposition of aluminum on condensed thiophene

The adsorption of thiophene on clean Al(1 1 1) at 90 and 130 K has been studied with X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) and work function measurements. Relatively weak chemisorption compared to adsorption on transition metals is indicated by minor changes in the valence spectrum in progressing from monolayer to multilayer thiophene, a modest work function change of −0.50 eV due to saturation dosing, and return of the work function and valence spectrum to that of clean Al(1 1 1) upon annealing at 210 K. The complementary experiment in which aluminum is thermally deposited on multilayer thiophene condensed on gold at 130 K has also been performed. XPS peak area analysis shows that metal doses less than 14×10¹⁵ atoms/cm² result in penetration through the physisorbed thiophene, but higher doses lead to the gradual build up of metal throughout the organic layer. Persistence of the thiophene UPS valence features for metal doses of 50×10¹⁵ atoms/cm² is consistent with penetration and aluminum island formation. For aluminum deposition on thiophene, charge transfer from aluminum is evidenced by metal-induced low binding energy components in the C 1s and S 2p spectra at 282.6 and 162.5 eV, respectively, and a shift in the Al 2p spectrum of 0.5 eV to higher binding energy compared to metallic aluminum. UPS also indicates progression of the frontier orbital toward the Fermi level as aluminum is deposited.     

Molecular adsorption and growth of naphthalene films on Ag(1 0 0)

The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.     

Specific features of the formation of ytterbium films on the Si(111) surface at room temperature

The processes accompanying the formation of ytterbium films on the Si(111) surface at room temperature are investigated by the contact potential difference method, Auger electron spectroscopy, low-energy electron diffraction, and thermal desorption spectroscopy. It is shown that the grown metal films are uniform in thickness and that Si atoms virtually do not dissolve in the films. The atoms of the silicon substrate can diffuse in limited amounts into the Yb metal film only when the surface is bombarded by high-energy primary electron beams employed in Auger electron spectroscopy. The results obtained permit the conclusion that the previously observed oscillations of the work function in Yb-Si(111) thin-film structures cannot originate from dissolution of silicon atoms in the ytterbium film.     

XPS and LEED study of Pd and Au growth on alumina/Cu-Al surface

Metal-insulator-metal system was prepared using the single-crystalline Cu-9at.% Al(1 1 1) support. Oxidation of the substrate under well-controlled conditions at elevated temperature leads to the formation of well-ordered aluminium oxide layer. The Pd-Au topmost layer was prepared by a step-by-step deposition of both metals afterwards on the oxide layer at room temperature. Low energy electron diffraction (LEED) measurement did not confirm epitaxial growth of the metal overlayer and gave only a rise of diffuse background after each deposition step. The growth of Pd-Au overlayer exhibited Stranski-Krastanov mode influenced by intermetallic interaction between those metals. No binding energy shifts were visible for the core-level photoelectron peaks of the substrate and the oxide using X-ray photoelectron spectroscopy (XPS). In contrast, the binding energy shifts of Pd 3d and Au 4f photoelectron levels in both directions were observed during all depositions. Bimetallic interactions between the metals as well as size effects are further discussed.     

The cytocompatibility investigation of Ti6Al4V modified with a fluorine-contained copolymer thin film

The objective of the present study is to preliminarily explore the effect of surface chemistry modification of Ti6Al4V with a fluorine-contained copolymer thin film on the cellular behavior of osteoblasts. A fluorine-contained random copolymer thin film was fabricated on Ti6Al4V substrate, and then characterized by X-ray photoelectron spectroscopy (XPS), contact angle meter and surface profiler. The results showed that the surface modification of Ti6Al4V alloy could simultaneously transform the surface chemical constitution and reduce the surface energy evidently. However, the surface morphology and roughness of the Ti6Al4V substrate were hardly changed after the modification. By immersion process with simulated body fluid (SBF) and then by in vitro cytotoxicity test with MC3T3-E1 osteoblasts, the fluorine-contained copolymer thin film exhibited desirable stability and admirable cytocompatibility. In conclusion, the fluorine-contained copolymer thin film could be easily applied in modifying various solid surfaces, and the as-fabricated film also has potential applications in biomedical field.     

Charging of metal adatoms on ultrathin oxide films: Au and Pd on FeO/Pt(111)

We present a combined experimental (STM/scanning tunneling spectroscopy) and theoretical (density functional theory) study on the deposition of Au and Pd metal atoms on FeO/Pt(111) ultrathin films. We show that while the Pd atoms are only slightly oxidized, the Au atoms form positive ions upon deposition, at variance to a charge transfer into the Au atoms as observed for MgO/Ag(100). The modulation of the adsorption properties within the surface Moiré cell and the charging induce the formation a self-assembled array of gold adatoms on FeO/Pt(111), whereas Pd atoms are randomly distributed.