Electronic structures of imidazolium-based ionic liquids

Electronic structures of ionic liquids formed by 1-buthyl-3-alkylimidazolium ion [C_nmim]⁺ (n = 4 and 8) with various inorganic and organic anions have been investigated by ultraviolet photoemission, X-ray photoemission, inverse photoemission and soft X-ray emission spectroscopies (SXES). The comparison of the calculated density of states with the observed spectra revealed that the molecular orbital energies of these ionic liquids are significantly affected by the electrostatic Madelung potential among the ions. The SXES results clearly show that the both highest occupied and lowest unoccupied states of [C₄mim]⁺PF₆⁻ are derived from the cation as a result of strong Madelung potential. On the other hand, the SXES results show the valence electronic structures of ionic liquids with larger anion molecules, [C_nmim]⁺Tf₂N⁻ and [C_nmim]⁺OTf⁻ are contributed from the both cation and anion.     

High-precision sample stage for photoemission microscopy of organic films

A high-precision sample stage for photoemission microscopy has been constructed to translate the sample by ±3 mm with accuracy better than 100 nm. The stage is actuated by step motors settled outside the vacuum. The accuracies of the translations were measured by observing a standard patterned sample with a photoemission electron microscope (PEEM) of 50 nm resolution. The accuracy was nearly independent of the distance of each translation step and the error was not accumulated by repeated steps. After round-trip translations up to 0.2 mm, the sample came back to the original position with accuracy of ±50 nm. The performance of the stage was demonstrated by observing growth processes of lead phthalocyanine (PbPc) films formed on graphite.     

Surface transfer doping of semiconductors

Surface transfer doping relies on charge separation at interfaces, and represents a valuable tool for the controlled and nondestructive doping of nanostructured materials or organic semiconductors at the nanometer-scale. It cannot be easily achieved by the conventional implantation process with energetic ions. Surface transfer doping can effectively dope semiconductors and nanostructures at relatively low cost, thereby facilitating the development of organic and nanoelectronics. The aim of this review is to highlight recent advances of surface transfer doping of semiconductors. Special focus is given to the effective doping of diamond, epitaxial graphene thermally grown on SiC, and organic semiconductors. The doping mechanism of various semiconductors and their possible applications in nanoelectronic devices will be discussed, including the interfacial charge transfer and the energy level alignment mechanisms.     

Photoemission study of glycine adsorption on Cu/Au(1 1 1) interfaces

The adsorption of glycine on Au(1 1 1) pre-deposited with different amounts of Cu was investigated with both conventional X-ray photoelectron spectroscopy (XPS) and synchrotron-based photoemission. In the Cu submonolayer range, glycine physically adsorbs on the Cu/Au(1 1 1) surfaces in its zwitterionic form and completely desorbs at 350 K. The C 1s, O 1s and N 1s core level binding energies monotonically increase with Cu coverage. This indicates that, in the Cu submonolayer range, the admetal is alloyed with Au rather than forming overlayers on the Au(1 1 1) substrate, consistent with our recent experimental and theoretical results [X. Zhao, P. Liu, J. Hrbek, J.A. Rodriguez, M. Pérez, Surf. Sci. 592 (2005) 25]. Upon increasing the amount of deposited Cu over 1 ML, part of the glycine overlayer transforms from the zwitterionic form to the anionic form (NH₂CH₂COO⁻) and adsorbs chemically on the Cu/Au(1 1 1) surface with the N 1s binding energy shifted by −2.3 eV. When the amount of deposited Cu is at 3.0 or 6.0 ML, the intensity of the N 1s chemisorption peak increases with aging time at 300 K. It indicates that glycine adsorption induces Cu segregation from the subsurface region onto the top layer of the substrate. Judging from the initial N 1s peak intensities, it is concluded that 64% and 36% of the top layer are still occupied by Au atoms before glycine adsorption even when the amounts of deposited Cu are 3.0 and 6.0 ML, respectively. On the Au(1 1 1) surface pre-dosed with 6.0 ML of Cu, part of the chemisorbed glycine will desorb and part will decompose upon heating to 450-500 K. In addition, about 20% of the glycine exists in the neutral form when the glycine overlayer was dosed on Cu/Au(1 1 1) held at 100 K.     

Role of electron correlation effects in δ-Pu and “115”-Pu-based unconventional superconductors

Electronic structure calculations combining the local density approximation with an exact diagonalization of the Anderson impurity model show intermediate 5f⁵–5f⁶-valence ground state and delocalization of the 5f⁵ multiplet of the Pu atom 5f-shell in PuCoGa₅, and δ-Pu. The 5f-local magnetic moment is compensated by a moment formed in the surrounding cloud of conduction electrons. For PuCoGa₅ and δ-Pu the compensation is complete and the Anderson impurity ground state is a singlet. This can be important for analyses of the superconducting pairing mechanism in PuCoGa₅. It is likely that in PuCoGa₅ unconventional d-wave superconductivity is mediated by the 5f-states valence fluctuations, rather than antiferromagnetic fluctuations.     

多碱阴极光电发射机理研究

通过比较有Cs-Sb表面层多碱阴极和未有Cs-Sb表面层多碱阴极的荧光谱,发现有Cs-Sb表面层多碱阴极的荧光谱峰值波长向短波方向“蓝移”以及荧光峰增强的现象.这一现象表明在多碱阴极Na2KSb基层上制作Cs-Sb表面层之后,不仅多碱阴极的逸出功降低,而且 Na2KSb基层的结构也发生了变化.这意味着在相同功率和相同频率入射光照射下,经过表面Cs-Sb处理的Na2KSb基层能够产生更多的跃迁电子并且跃迁能级更高,逸出表面的机率更大,获得的阴极灵敏度更高.这表明Cs-Sb表面层既具有表面效应,又具有体效应.要进一步提高多碱阴极的灵敏度,除进一步降低多碱阴极的逸出功外,还需进一步提高Na2KSb基层的性能,使相同功率和频率的入射光能产生更多的跃迁电子,并且跃迁的能级更高,这就需要进一步改进工艺,提高Na2KSb材料的性能.     

Oxidation of Zn in UHV environment at low temperature

Thermal oxidation of polycrystalline Zn foils at 5 × 10⁻⁷ Torr oxygen pressure and at room temperature, 50 °C, 70 °C, 90 °C and 110 °C was studied. In situ photoemission spectroscopy using synchrotron light with photon energy of 57 eV was used to monitor the formation of ZnO and to determine the thickness of the oxide overlayer. At the initial oxidation, the oxidation rate follows a two-stage logarithmic equation and later trends to saturate at a certain thickness depending on the oxidation temperature. The saturated thickness was found to increase with the oxidation temperature. The two-stage oxidation process may be governed by two kinds of space charge presumably formed in the thin oxide overlayer.     

Band structure and cluster model calculations of LaNiO3 compared to photoemission,O 1s X-ray absorption,and optical absorption spectra

We studied the electronic structure of LaNiO₃ using band structure and cluster model calculations. This compound is a paramagnetic metal with a R3?c rhombohedral structure. The band structure was calculated using the generalized gradient approximation (GGA). The cluster model was solved using the configuration interactions (CI) many-body method. We present results for the density of states (DOS), the spectral weight, and the dielectric function ${\epsilon }_2$. The calculations are compared to previous photoemission (PES), O 1s X-ray absorption (XAS), as well as optical absorption spectra. Both band structure and cluster model results are in good agreement with the experimental data. We point out that this concordance is very rare and far from trivial; we argue that this may be due to the unusual characteristics of the ground state of LaNiO₃.     

Cobaltocene adsorption and dissociation on Cu(1 1 1)

Photoemission results indicate that the initial adsorption of cobaltocene on Cu(1 1 1) at 150 K leads to molecular fragmentation, but with subsequent cobaltocene exposures, molecular absorption occurs. The molecularly adsorbed species is either adsorbed with only a fraction of molecules adopting a preferential orientation along the surface normal or adsorbed with the molecular axis away from the surface normal. This adsorption behavior is compared to nickelocene and ferrocene adsorption.     

Structure and reactivity of GaAs surfaces

First the analytical tools, preparation methods and surface crystallography of clean GaAs surfaces are briefly reviewed. Besides the usual methods of cleaving, ion bombardment and annealing, molecular beam epitaxy is mainly used as a growth method under UHV conditions, and has brought a manifold of differently reconstructed structures on the same crystallographic surface, depending on the exact experimental conditions during growth. Quantitative analysis of the surface composition by AES gives the result that these structures differ only in the amount of As in the topmost layer. From the combination of theoretical LEED analysis, UPS results and arguments considering the different physicochemical nature of Ga and As atoms, rehybridisation of the surface atomic bonds emerges as the driving force for reconstruction: the surface Ga atoms try to assume a trivalent planarsp² and the As atoms a trivalentp³ configuration with three mutually perpendicularp-bonds. The better this rehybridised configuration can be achieved, the better is the chemical stability of the respective structure. The sticking coefficient for oxygen, although generally low, thus varies between ～10^-4 and <10^-9, depending on the crystallographic surface and, on the same surface, on the degree of surface bond saturation given by the respective structure. However, it emerges that, at least on As-depleted polar surfaces, adsorption proceeds via a mechanism of removal of Ga atoms during exposure and adsorption on the defect sites created in this way. The existence of such a complicated mechanism is consistent with the difficulties arising with the preparation of thick stoichiometric oxide layers, the preparation methods and properties of which are reviewed briefly in the last section.