新型高分辨率电子能量损失谱仪与表面元激发研究

高分辨率电子能量损失谱仪利用单色平行电子束入射样品表面,与表面吸附基团的化学键振动、表面声子、电子及其集体激发模式等相互作用而被散射,通过分析散射电子的能量和动量,可以测量表面化学键、晶格动力学、电子态占据以及表面等离激元等的精确信息,是表面科学研究的有力工具.最近,能够对电子能量、动量做二维成像探测分析的半球形电子能量分析器被引入电子能量损失谱仪,实现了高能量、动量分辨率的高效率测量.在对FeSe/SrTiO_3界面超导增强物理机制的研究中,不同厚度的FeSe膜表面的电子能量损失谱表明衬底光学声子产生的偶极电场能够穿透到薄膜内部,诱导较强的电子-声子耦合作用,从而增强薄膜中电子的配对作用,进而使超导转变温度显著提高.三维拓扑绝缘体Bi_2Se_3表面大动量范围的电子能量损失谱还显示出一支奇异的电子集体激发模式,其色散特征不受晶格周期性的限制,而且其寿命和强度几乎不随动量的增加而衰减.这说明在拓扑绝缘体表面,不仅是狄拉克电子态本身,其集体激发也受到拓扑保护.充分发挥新型电子能量损失谱仪观测表面元激发分辨率高、动态范围大的优势,将有力地推动表面界面凝聚态物理问题研究的深入和发展.     

RF溅射的SiO_2和SiO_2/Al/SiO_2薄膜的喇曼散射光谱研究

用射频溅射(RF Sputtering)法制成了SiO_2和SiO_2/Al/SiO_2薄膜。应用喇曼光谱研究了薄膜结构。结果表明:RF溅射制成的SiO_2薄膜是含有大量环结构缺陷的玻璃态;SiO_2/Al/SiO_2层状薄膜的喇曼光谱中观察到Al_2O_3的特征峰,证实了Al/SiO_2薄膜界面确有氧化还原反应发生;从喇曼光谱中Al_2O_3的特性峰的位置和相对强度可推断出,SiO_2/Al/SiO_2薄膜界面处的Al_2O_3是非晶γ-Al_2O_3。     

The angular behaviour of electrons inelastically scattered from the shape resonance for CO chemisorbed on Ni(110)

Recent vibrational high resolution electron energy loss experiments (HREELS) have shown evidence for molecular shape resonances in the inelastic scattering of electrons from chemisorbed molecules. Such resonances arise from the capture of the incident electron in a quasibound state of the molecule, leading to the formation of a temporary negative ion. They are manifest as an enhancement in the intensity of a specific vibrational mode at a characteristic incident electron energy. In contrast to gaseous species, the alignment which the surface provides for the chemisorbed species, can be exploited to determine the angular characteristics of the resonant state. In this work, we show evidence for a shape resonance, centred at an incident energy of 18 eV, for CO/Ni(110). The angular dependence of the scattered electron intensity has been measured for the CO stretching vibration. The results are discussed in terms of the spherical harmonic components of the resonant state, modified by vibrational broadening caused by low frequency bending modes associated with the bonding of the CO molecule to the surface.     

The threshold electron impact spectrum of H2O

The threshold electron spectrum of H2 O was obtained using a high resolution electron impact spectrometer combined with the penetrating field method for scattered electrons with energies close to zero eV. The valence, triplet Rydberg states, as well as the resonances were identified and are discussed in the energy region 5.2–14.3 eV. The threshold spectrum confirms the influence of resonances on the enhancement of the intensity of some Rydberg states above 10 eV. The vibrational spacing of the observed transitions of the Rydberg states indicates that the water molecule is excited in the symmetric stretching mode.     

Depth dependence of the anomalous thermal behavior of Cu(110)

We report the results of a mirror electron microscope low energy electron diffraction (MEM-LEED) study of anomalous thermal behavior caused by enhanced thermal vibrational motion on a clean Cu(110) surface. The enhanced vibrational amplitudes cause diffracted intensities to deviate from simple Debye-Waller behavior. These deviations become apparent between 550 K and 600 K; i.e. at about 0.45 of the bulk melting temperature. Because of the finite penetration of low energy electrons, LEED intensities contain information about both surface and subsurface order. Our LEED results are analyzed to extract this information using a kinematical model in which the electron attenuation and the depth and temperature dependent vibrational amplitudes are parametrized. For a large range of model parameters, we conclude that by 850 K large anharmonic vibrations are present in several layers and at least two subsurface layers may have melted.     

Dynamics of inner- and outer-sphere electron transfer in a polar solvent

In this paper, inner-sphere electron transfer reactions in a solvent are studied in the framework of multidimensional transition state theory. It is demonstrated that the preexponential factor essentially depends upon the interaction with the inner-sphere vibrational mode, increasing the rate of electron transfer as much as one order of magnitude. The prefactor is shown to be strongly dependent on the frequency of this vibration. At high frequencies the rate constant increases with the reorganization energy of this inner-sphere mode while at small frequencies, electron transfer is inhibited. Estimations of inner mode reorganization energies have been performed for system where it is necessary to account nonequilibrium solvent relaxation. Finally it is shown that the equilibrium approximation fails when the reaction is close to an activationless regime.     

Vibration spectroscopy of benzene adsorbed on Pt(111) and Ni(111)

High resolution electron energy loss spectroscopy has been applied to study the adsorption of benzene (C₆H₆ and C₆D₆) on Pt(111) and Ni(111) single crystal surfaces between 140 and 320 K. The vibrational spectra provide evidence that benzene is chemisorbed with its ring parallel to the surface, predominantly π bonded to the platinum and nickel surface respectively. A significant frequency increase of the CH-out-of-plane bending mode, largest in the case of platinum, is observed compared to the free molecule. On both metals two phases of benzene exist simultaneously, characterized by a different frequency shift. The shifts are explained by electronic interaction between the metal d-orbitals and molecules adsorbed in on top and threefold hollow sites respectively. The vibrational spectra of the multilayer condensed phase of benzene exhibit the infrared active modes of the gasphase molecule as expected.     

Dynamics of Si-H vibrations in an amorphous environment

We present results of the first vibrational photon-echo, transient-grating, and temperature dependent transient-bleaching experiments on a-Si:H. Using these techniques, and the infrared light of a free electron laser, the vibrational population decay and phase relaxation of the Si-H stretching mode were investigated. Careful analysis of the data indicates that the vibrational energy relaxes directly into Si-H bending modes and Si phonons, with a distribution of rates determined by the amorphous host. Conversely, the pure dephasing appears to be single exponential, and can be modeled by dephasing via two-phonon interactions.     

Vibrational characterization of carbon monoxide oxidation on the Pt(111) surface

The surface reaction between coadsorbed carbon monoxide and atomic oxygen has been characterized using high resolution electron energy loss spectroscopy, coupled with temperature programmed reaction spectroscopy on a Pt(111) surface characterized using Auger electron spectroscopy and low energy electron diffraction. Preferential oxidation of bridge bonded CO is not observed despite the fact that bridge bonded CO is adsorbed less vigorously than linearly bound CO. Saturation of the Pt(111) surface with one quarter of a monolayer of atomic oxygen completely suppresses the adsorption of bridge bonded CO. However, substantial coverages of bridge bonded CO can be coadsorbed if the Pt(111) surface is only partially saturated with atomic oxygen. The vibrational data for reaction of coadsorbed CO and atomic oxygen is consistent with a reaction mechanism involving reaction of mobile CO along oxygen island perimeters.     

Adsorption of CO on a pseudomorphic palladium monolayer on Mo(110)

Adsorption of CO on a Pd monolayer (ML) supported on Mo(110) has been studied using low energy electron diffraction (LEED), temperature programmed desorption (TPD), and high resolution electron energy loss spectroscopy (HREELS). Three ordered CO substructures denoted as are observed with LEED. The binding energy of C0 on the 1.0 ML Pd/Mo(110) surface is reduced by 12 kcal/mol relative to the Pd(111) surface, consistent with previous results for supported palladium monolayers on other substrates. Two vibrational states of C0 are observed near 1950 and 2050 cm⁻¹, with the feature at the lower wavenumber having the smaller binding energy.