Cu,Zn-SOD在银电极上的原位表面增强Raman光谱

本文应用原位共焦拉曼光谱技术观察了Cu ,Zn -SOD分子在经表面增强处理后的银电极上 ,吸附状态随电位跃迁变化的过程。结果表明在 -0 2V～ 0 1V的电位区间内 ,Cu,Zn -SOD分子经由羧酸根离子吸附于银电极表面 ,而在 0 2～ 0 4V电位区间内发生脱附 ,表面吸附的物种改变为缓冲溶液中的磷酸根离子。上述结果为SOD分子在固体电极表面电子传递机制的探索提供了依据。     

Magnetic and magnetoresistive properties of epitaxial Co/Cu/Co trilayers on Si(111)

Giant magnetoresistance of the epitaxial Co/Cu/Co trilayers grown on vicinal Si(111) was determined as a function of Cu spacer coverage in the range from 0 to 7 ML. The first maximum of giant magnetoresistance and antiferromagnetic coupling was detected at 3.0 ML coverage of the Cu spacer. The portion of antiferromagnetic coupling in the first antiferromagnetic maximum was estimated as 17%. 3D growth mode of the Cu spacer leads to the simultaneous occurrence of the ferromagnetically and antiferromagnetically coupled areas between the Co layers.     

Ordered growth of nanodots on a pre-structured metallic template: Au/N/Cu(0 0 1)

We have studied by Spot Profile Analysis Low Energy Electron Diffraction (SPA-LEED) the growth of gold particles on the N/Cu(0 0 1) self-organized surface. This template consists of nitrogen islands separated by bare Cu lines and forming a regular 2D array of period 5 nm. When Au is evaporated onto this surface, it mainly grows at the intersections between the Cu lines. The islands organization reproduces then the substrate 2D ordering.However, if the substrate temperature is too low, islands form everywhere. On the contrary, if the substrate temperature is too high, some nucleation sites are empty. By following the intensity of the diffraction satellites during the growth, we have observed that the ordering of the Au particles is optimum when the substrate temperature is between 210 and 290 K. Using both an analytical treatment based on the rate equations and kinetic Monte-Carlo simulations, we have determined the activation energy for the diffusion process and the energy of the traps.     

The synthesis of methanol and the reverse water-gas shift reaction over Zn-deposited Cu(100) and Cu(110) surfaces: comparison with Zn/Cu(111)

The catalytic activity of Zn vapor-deposited Cu(100) and Cu(110) surfaces for methanol synthesis by the hydrogenation of CO₂ and the reverse water-gas shift reaction were studied using an XPS apparatus combined with a high-pressure flow reactor (18 atm). At a reaction temperature of 523 K, no promotional effect of Zn was observed for the methanol synthesis on both Zn/Cu(100) and Zn/Cu(110). The results were quite different from those for Zn/Cu(111), on which a significant promotion of methanol synthesis activity appeared to be due to the deposition of Zn, indicating that the promotional effect of Zn was sensitive to the surface structure of Cu. However, hysteresis was observed in the catalytic activity for methanol synthesis over the Zn/Cu(110) surface upon heating above 543 K in the reaction mixture. The activity became twice that measured before heating, which was close to the methanol synthesis activity of Zn/Cu(111) at the same Zn coverage. On the other hand, no such hysteresis was observed for the reverse water-gas shift reaction on Zn/Cu(110), indicating that the active site for methanol synthesis was not identical to that for the reverse water-gas shift reaction. In the post-reaction surface analysis, formate species was detected on both Zn/Cu(100) and Zn/Cu(110), whose coverage increased with increasing Zn coverage at 0<Θ_Zn<0.2. No correlation between the formate coverage and the methanol synthesis activity was obtained, which was in contrast to the results for Zn/Cu(111). Thus, the structure sensitivity observed in the catalytic activity of methanol synthesis over Zn-deposited Cu surfaces is ascribed to the significant difference in the reactivity of the formate intermediate.     

Many-electron effect in the Fe L3-M4,5M4,5 Auger electron spectrum of ultrathin Fe films grown on Cu(1 0 0)

D’Addato et al. [S. D’Addato, P. Luches, R. Gotter, L. Floreano, D. Cvetko, A. Morgante, A. Newton, D. Martin, P. Unsworth, P. Weightman, Surf. Rev. Lett. 9 (2002) 709] studied the variation with Fe coverages in the relative Fe L₃-M_4,5M_4,5 Auger electron spectroscopy (AES) spectral satellite intensity of ultrathin Fe films grown on Cu(1 0 0) by sweeping photon excitation energy through the Fe L₂-level ionization threshold. They interpreted that the M_4,5 hole in the L₃M_4,5 double-hole state created by the L₂-L₃M_4,5 Coster–Kronig (CK) decay remains localized for longer than the L₃-hole lifetime for the 0.3 and 10 ML coverages but has a lifetime comparable to the L₃-hole lifetime for the 1 ML coverages. The present many-body theory shows that when the M_4,5 hole created either by the CK decay or by the L₃M_4,5 shakeoff hops away from the ionized atomic site and becomes completely screened out prior to the L₃-hole decay, the Fe L₂-L₃M_4,5-L₃-M_4,5M_4,5 AES main line as well as the Fe L₃ M_4,5 (satellite)-L₃-M_4,5M_4,5 one, both of which are identical in line shape to the Fe L₃-M_4,5M_4,5 one, dominate in the Fe CK preceded AES spectrum. The present analysis shows that the delocalization time of the M_4,5 hole created in the 1 ML Fe/Cu(1 0 0) system by the L₂-L₃M_4,5 CK decay is much shorter than the L₃-hole lifetime so that the Fe L₃-M_4,5M_4,5 AES spectral line shape hardly changes, except for the presence of a very weak spectator L₂-L₃M_4,5-M_4,5M_4,5M_4,5 AES satellite, when the photon excitation energy is swept through the Fe L₂-level ionization threshold. For the 0.3 ML coverages the M_4,5-hole delocalization time is still shorter than the L₃-hole lifetime.     

The effect of relaxation on the epitope mapping by saturation transfer difference NMR

The effect of longitudinal relaxation of ligand protons on saturation transfer difference (STD) was investigated by using a known binding system, dihydrofolate reductase and trimethoprim. The results indicate that T1 relaxation of ligand protons has a severe interference on the epitope map derived from a STD measurement. When the T1s of individual ligand protons are distinctly different, STD experiments may not give an accurate epitope map for the ligand-target interactions. Measuring the relaxation times prior to mapping is strongly advised. A saturation time shorter than T1s is suggested for improving the potential epitope map. Reduction in temperature was seen to enhance the saturation efficiency in small to medium size targets.     

Observation of triangular terraces and triangular craters of CaF2 film on Si(1 1 1) substrate

We have investigated the growth mode and surface morphology of CaF₂ film on Si(1 1 1)7×7 substrate by reflection high-energy electron diffraction (RHEED) using very weak electron beam and atomic force microscopy (AFM). It was found by RHEED intensity oscillation measurements and AFM observations that three-dimensional (3D) islands grow at RT; however, rather flat surface appears with two-dimensional (2D) islands around 300 °C. Especially, at high temperature of 700 °C, characteristic equilateral triangular terraces (or islands) with flat and wide shape grow with the tops directed toward [1 1 −2] of substrate Si(1 1 1). On the other hand, the desorption process of the CaF₂ film due to electron stimulated desorption (ESD) was also examined. It was found that the ESD process at 300 °C forms characteristic equilateral triangular craters on the film surface with the tops (or corners) directed toward [−1 −1 2] of substrate Si(1 1 1), provided that the film was grown at 700 °C.     

蓝宝石衬底上GaN/AlxGa1-xN超晶格插入层对AlxGa1-xN外延薄膜应变及缺陷密度的影响

室温300K下,由于Al_xGa_1-xN的带隙宽度可以从GaN的3.42eV到AlN的6.2eV之间变化,所以Al_xGa_1-xN是紫外光探测器和深紫外LED所必需的外延材料.高质量高铝组分Al_xGa_1-xN材料生长的一大困难就是Al_xGa_1-xN与常用的蓝宝石衬底之间大的晶格失配和热失配.因而采用MOCVD在GaN/蓝宝石上生长的Al_xGa_1-xN薄膜由于受张应力作用非常容易发生龟裂.GaN/Al_xGa_1-xN超晶格插入层技术是释放应力和减少Al_xGa_1-xN薄膜中缺陷的有效方法.研究了GaN/Al_xGa_1-xN超晶格插入层对GaN/蓝宝石上Al_xGa_1-xN外延薄膜应变状态和缺陷密度的影响.通过拉曼散射探测声子频率从而得到材料中的残余应力是一种简便常用的方法,Al_xGa_1-xN外延薄膜的应变状态可通过拉曼光谱测量得到.Al_xGa_1-xN外延薄膜的缺陷密度通过测量X射线衍射得到.对于具有相同阱垒厚度的超晶格,例如4nm/4nm,5nm/5nm,8nm/8nm的GaN/Al_0.3Ga_0.7N超晶格,研究发现随着超晶格周期厚度的增加Al_xGa_1-xN外延薄膜缺陷密度降低,Al_xGa_1-xN外延薄膜处于张应变状态,且5nm/5nmGaN/Al_0.3Ga_0.7N超晶格插入层Al_xGa_1-xN外延薄膜的张应变最小.在保持5nm阱宽不变的情况下,将垒宽增大到8nm,即十个周期的5nm/8nmGaN/Al_0.3Ga_0.7N超晶格插入层使Al_xGa_1-xN外延层应变状态由张应变变为压应变.由X射线衍射结果计算了Al_xGa_1-xN外延薄膜的刃型位错和螺型位错密度,结果表明超晶格插入层对螺型位错和刃型位错都有一定的抑制效果.透射电镜图像表明超晶格插入层使位错发生合并、转向或是使位错终止,且5nm/8nmGaN/Al_0.3Ga_0.7N超晶格插入层导致Al_xGa_1-xN外延薄膜中的刃型位错倾斜30°左右,释放一部分压应变.     

Atom geometry of nanostructured Fe films grown on c(2 × 2)-N/Cu(1 0 0) surface: An investigation by X-ray absorption spectroscopy with multishell analysis

We investigated the growth of Fe nanostructured films on c(2 × 2)-N/Cu(1 0 0) surface with Fe K-edge X-ray absorption fine structure (XAFS) in the near edge and in the extended energy region. The high photon flux of the incident X-rays allowed us to perform multishell analysis of the XAFS oscillations for Fe coverage Θ_Fe < 1 ML. This data analysis yields a detailed investigation of the atom geometry and some insights in the film morphology. At Θ_N < 0.5 ML (N saturation coverage) there is absence of contribution to XAFS from N atoms. First shell analysis of linearly polarized XAFS gives Fe-Fe (or Fe-Cu) bond length values varying between R₁ = 2.526 ± 0.006 Å at the highest Fe coverage (3 ML ) and R₁ = 2.58 ± 0.01 Å at Θ_Fe = 0.5 ML, Θ_N = 0.3 ML, with incidence angle Θ = 35°. These values are different from the case of bcc Fe (R = 2.48 Å), and compatible with fcc Fe (R₁ = 2.52 Å) and fcc Cu (R₁ = 2.55 Å). At the Fe lowest coverage (Θ_Fe = 0.5 ML) the dependence of R₁ on the incidence angle indicates expansion of the outmost layer. Near edge spectra and multishell analysis can be well reproduced by fcc geometry with high degree of static disorder. At N saturation pre-coverage (Θ_N = 0.5 ML) the XAFS analysis has to keep into account the Fe-N bonding. The results suggest two different adsorption sites: one with Fe in a fcc hollow site, surrounded by other metal atoms as nearest neighbours, and one resulting from an exchange with a Cu atom underneath the N layer.     

Scanning tunneling microscopy study of growth of Pt nanoclusters on thin film Al2O3/NiAl(1 0 0)

The growth of Pt nanoclusters on thin film Al₂O₃ grown on NiAl(1 0 0) was studied by using scanning tunneling microscopy (STM). The samples were prepared by vapor depositing various amounts of Pt onto the Al₂O₃/NiAl(1 0 0) at different substrate temperatures in ultra high vacuum (UHV). The STM images show that sizeable Pt nanoclusters grow solely on crystalline Al₂O₃ surface. These Pt clusters appear to be randomly distributed and only a few form evident alignment patterns, contrasting with Co clusters that are highly aligned on the crystalline Al₂O₃. The size distributions of these Pt clusters are rather broader than those of the Co clusters on the same surface and the sizes are evidently smaller. With increasing coverage or deposition temperature, the number of larger clusters is enhanced, while the size of the majority number of the clusters remains around the same (0.4 nm as height and 2.25 nm as diameter), which differs drastically from the Pt clusters on γ-Al₂O₃/NiAl(1 1 0) observed earlier. These Pt cluster growth features are mostly attributed to smaller diffusion length and ease to form stable nucleus, arising from strong Pt-Pt and Pt-oxide interactions and the peculiar protrusion structures on the ordered Al₂O₃/NiAl(1 0 0). The thermal stability of Pt nanoclusters was also examined. The cluster density decreased monotonically with annealing temperature up to 1000 K at the expense of smaller clusters but coalescence is not observed.     

The effect of Pt on Ni3Al surface oxidation at low-pressures

The fully-oxidized surface that forms on (1 1 1) oriented Ni₃Al single crystals, with and without Pt addition, at 300-900 K under oxygen pressures of ca. 10⁻⁷ Torr was studied using XPS, AES, and LEIS. Two main types of surfaces form, depending upon oxidation temperature. At low-temperature, the predominant oxide is NiO, capped by a thin layer of aluminum oxide, which we refer to generically as Al_xO_y. At high-temperature (i.e., 700-800 K), NiO is replaced by a thick layer of Al_xO_y. By comparing samples that contain 0, 10 and 20 at.% Pt in the bulk, we find that the effect of Pt is to: (1) reduce the maximum amount of both NiO and Al_xO_y; and (2) shift the establishment of the thick Al_xO_y layer to lower temperatures. Platinum also decreases the adsorption probability of oxygen on the clean surface.     

过渡族金属替代元素M对YFe11M系统的磁性质的影响

基于密度泛函理论(DFT),采用线性缀加平面波展式结合改进的局域轨道方法(APW+lo),对具有ThMn₁₂结构的永磁材料YFe₁₁M(M=Sc,V等)的结构和磁性进行了计算和分析.探讨了过渡族金属替代元素M在YFe₁₁M中系统的最佳可能占位.讨论了不同替代元素M对YFe₁₁M系统的磁性质的影响. 关键词： 11M')" href="#">YFe₁₁M 密度泛函 晶体结构 磁矩     

Effects of strain field in nitrogen-mediated Co film growth on Cu(0 0 1): Segregation and electronic structure change

Growth modes of Co thin films on the both N-saturated and partially N-adsorbed Cu(0 0 1) surfaces are studied in detail. From results of the STM and XPS measurements, segregation of N atoms depending on the Co island size is concluded. This new type of atom segregation is explained by means of a lattice strain of the substrate due to the small Co island formation. A novel core-level shift of N 1s during the Co film growth is also reported. A possible influence of the lattice strain to the electronic structure of the surfactant is discussed.     

The adsorption of 1,3-butadiene on Ag(1 1 1): A TPD/IRAS study and importance of lateral interactions

Temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRAS) have been used to study the adsorption, desorption, molecular orientation and conformation of 1,3-butadiene on Ag(1 1 1) at 80 K. Butadiene adsorbs weakly as an s-trans conformer with the first layer oriented parallel to the silver surface and desorbs without decomposition. A very narrow line shape of the out-of-plane modes at low submonolayer coverage indicates molecular ordering within the diluted adsorbed layer, presumably through weak π-bonding interaction with the surface and intermolecular repulsive interaction. Compression within the first layer at coverages above 0.5 ML is driven by repulsive interaction as seen in both TPD and IRAS data. The IR intensity rollover and peak broadening, together with a significant shift in the TPD peak to lower temperature, indicate a reorientation of the butadiene molecule. Adsorption in the second- and multilayer is characterized by distinct IR frequency shifts and crystal field splitting effects similar to those reported for solid butadiene.     

The growth of manganese layers on Si(1 0 0) at room temperature: A photoelectron spectroscopy study

The combination of spin-and charge based electronics in future devices requires the magnetic doping of group IV semiconductors, and the formation of ferromagnetic contacts. The doping of Mn with Si is one of the material systems which is discussed in this context. The present study focuses on the growth of Mn on a Si(100)(2x1) surface, and the evolution of the surface was observed as a function of Mn coverage with synchrotron-based photoelectron spectroscopy. The reaction of Mn with the Si(100) surface at room temperature leads the formation of silicide at the boundary between the Si substrate and the Mn-overlayer, presumably with MnSi stoichiometry. The residual sub-oxide reacts with the Mn and therefore incorporates a few percent of Mn-O-Si at the interface. The analysis of the sub-oxide composition indicates that the Si⁺¹ component is the most reactive oxidation state. The overlayer is dominated by Mn, either as Mn-metal or as a Mn-rich silicide phase, and the metallic layer introduces a band bending in Si. As a consequence of our observations, including information from a recent STM study, the formation of ferromagnetic contacts which require ideally a flat and compositionally homogenous overlayer, cannot be achieved through room temperature deposition of Mn on the Si(100) (2x1) surface. The influence of residual oxides and surface defects on the growth process will be further investigated.     

Annealing effect on the structural and optical properties of a Cd1−xZnxS thin film for photovoltaic applications

Herein is a report of a study on a Cd_1−xZn_xS thin film grown on an ITO substrate using a chemical bath deposition technique. The as-deposited films were annealed in air at 400 °C for 30 min. The composition, surface morphology and structural properties of the as-deposited and annealed Cd_1−xZn_xS thin films were studied using EDX, SEM and X-ray diffraction techniques. The annealed films have been observed to possess a crystalline nature with a hexagonal structure. The optical absorption spectra were recorded within the range of 350-800 nm. The band gap of the as-deposited thin films varied from 2.46 to 2.62 eV, whereas in the annealed film these varied from 2.42 to 2.59 eV. The decreased band gap of the films after annealing was due to the improved crystalline nature of the material.     

The simulation study for the nanometer-scale selective growth of Si islands on Si(0 0 1) windows in ultrathin SiO2 films

The nanometer-scale selective growth of Si islands on Si(0 0 1) windows in ultrathin SiO₂ films are studied using the kinetic Monte Carlo simulation. The growth of Si islands is reproduced in simulation where we assume that the migration barrier energy for Si adatom on SiO₂ film is far lower than that on the Si surface at the window.     

Growth of Al2O3 thin films on NiAl(1 0 0) by gas-phase oxidation and electro-oxidation

The growth and structures of aluminum oxides on NiAl(1 0 0) have been investigated by RHEED (reflection high energy electron diffraction), complemented by LEED (low energy electron diffraction), AES (Auger electron spectroscopy) and STM (scanning tunneling microscopy). Crystalline θ-Al₂O₃ phase grows through gas-phase oxidation on the NiAl(1 0 0) substrate with its a and b-axes parallel to [0 −1 0] and [0 0 1] direction of the substrate, respectively, forming a (2 × 1) unit cell. Whilst, three-dimensional nano-sized NiAl(1 0 0) protrusions and Al₂O₃, NiAl(0 1 1) clusters were found to co-exit at the surface, evidenced by extraordinary transmission spots superposed to the substrate reflection rods in the RHEED patterns. Particularly, the NiAl(0 1 1) clusters develop with their (0 1 1) plane parallel to the NiAl(1 0 0) surface, and [1 0 0] axis parallel to the [0 −1 1] direction of the substrate surface. STM observation combined with information from AES and TPD (temperature programmed desorption) suggest the formation of these 3D structures is closely associated with partial decomposition of the crystalline oxides during annealing. On the other hand, smoother (2 × 1) oxide islands with thickness close to a complete monolayer of θ-Al₂O₃ can be formed on NiAl(1 0 0) by electro-oxidation, in contrast with the large crystalline films formed by gas-oxidation.     

The effect of PVA (Bi2O3-doped) interfacial layer and series resistance on electrical characteristics of Au/n-Si (110) Schottky barrier diodes (SBDs)

Two types of Schottky Barrier Diodes (SBDs) with and without PVA (Bi₂O₃-doped) polymeric interfacial layer, were fabricated and measured at room temperature in order to investigate the effects of the PVA (Bi₂O₃-doped) interfacial layer on the main electrical parameters such as the ideality factor (n), zero-bias barrier height (Φ_B0), series resistance (R_s) and interface-state density (N_ss). Electrical parameters of these two diodes were calculated from the current-voltage (I-V) characteristics and compared with each other. The values of Φ_B0, n and R_s for SBDs without polymeric interfacial layer are 0.71 eV, 1.44 and 4775 Ω, respectively. The values of Φ_B0, n and R_s for SBDs with PVA (Bi₂O₃-doped) polymeric interfacial layer are 0.74 eV, 3.49 and 10,030 Ω, respectively. For two SBDs, the energy density distribution profiles of interface states (N_ss) were obtained from forward-bias I-V measurements by taking the bias dependence of R_s of these devices into account. The values of N_ss obtained for the SBD with PVA (Bi₂O₃-doped) polymeric interfacial layer are smaller than those of the SBD without polymeric interfacial layer.     

The preparation of c-axis epitaxial Bi-2212 films on STO(1 0 0) by sol-gel method

Bi₂Sr₂Ca₁Cu₂O_8+δ (Bi-2212) films were grown on (1 0 0) oriented SrTiO₃ (STO) substrate using sol-gel spin-coating method. The effects of heat treatment conditions and coating times on the phase formation and surface morphology were investigated using thermal analysis, optical microscope, X-ray diffraction, and scanning electronic microscopy. Mixed phases were formed from 820 to 840 °C, and Bi-2212 single phase was obtained at 830 °C for 3 h. c-axis epitaxial films with smooth surfaces were obtained by drying at 600 °C and coating for 5 times.