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.     

High resolution electron energy loss spectroscopy of fatty acids prepared by langmuir-blodgett techniques on polycrystalline silver

The surface of monomolecular layers of fatty acids prepared by Langmuir-Blodgett methods on polycrystalline silver has been studied by High Resolution Electron Energy Loss Spectroscopy (HREELS). Results demonstrate HREELS sensitivity to large molecules in molecular organizates on polycrystalline substrates. Spectra are interpreted in comparison with infrared vibrational data; results allow differentiation of degrees of unsaturation. The carbonyl vibration loss is observed as a weak feature, explained as due to the orientation of the fatty acid heads “down” on the subtrate surface approximately 20 Å from the scattering interaction.     

Low frequency surface resonance modes in electron energy loss spectroscopy

Electron energy loss spectroscopy has proved a powerful probe of vibrational modes of a wide variety of adsorbed species. Here the primary focus has been on modes with frequency well above the maximum phonon frequency of the substrate. Examples are internal vibration modes of adsorbed molecules, possibly shifted significantly in frequency from their gas phase analogues, and high frequency vibrations of an adsorbed molecule or atom against the substrate. Recent experiments explore features in the energy loss spectrum with frequency below the maximum phonon frequency of the substrate, for ordered overlayers of atoms adsorbed on low index metal surfaces. We shall summarize our theoretical studies of such spectra for several adsorbate/substrate combinations, with emphasis oh the physical origin of the features which appear in the calculations. We obtain a good account of the existing data, within the framework of a rather simple lattice dynamical model, and the calculations show that the features which appear are quite sensitive to the symmetry of the adsorption sits, and other details of the surface geometry. We shall illustrate this with several specific examples.     

The hydrogen chemisorption on TiC(111) surface studied by high resolution electron energy loss spectroscopy

At room temperature, hydrogen chemisorbs dissociatively on the three-fold hollow site of the TiC(111) surface with a sticking probability of ～ 0.5. The frequency of the stretching vibration of H is 1009 cm^-1, and the effective charge e¹ of hydrogen has been estimated to be 0.08 from the cross section of dipole scattering.     

Comparison of cross sections in high resolution electron energy loss spectroscopy and infrared reflection spectroscopy

Electron energy losses and absorption of infrared radiation are both caused by the dipole moment of the surface vibration. A comparison of absolute intensities between both techniques should therefore be possible. In this paper the appropriate formulas are derived. For the adsorption system CO on Pt(111) which has been investigated by both techniques a perfect agreement is found. For a number of adsorbate systems the effective ionic charge is calculated from previously published electron energy loss data.     

Practical spatial resolution of electron energy loss spectroscopy in aberration corrected scanning transmission electron microscopy

The resolution of electron energy loss spectroscopy (EELS) is limited by delocalization of inelastic electron scattering rather than probe size in an aberration corrected scanning transmission electron microscope (STEM). In this study, we present an experimental quantification of EELS spatial resolution using chemically modulated 2×(LaMnO(3))/2×(SrTiO(3)) and 2×(SrVO(3))/2×(SrTiO(3)) superlattices by measuring the full width at half maxima (FWHM) of integrated Ti M(2,3), Ti L(2,3), V L(2,3), Mn L(2,3), La N(4,5), La N(2,3) La M(4,5) and Sr L(3) edges over the superlattices. The EELS signals recorded using large collection angles are peaked at atomic columns. The FWHM of the EELS profile, obtained by curve-fitting, reveals a systematic trend with the energy loss for the Ti, V, and Mn edges. However, the experimental FWHM of the Sr and La edges deviates significantly from the observed experimental tendency.     

Reflection electron energy loss spectroscopy of aluminum

Reflection electron energy loss spectra (REELS) of Al(111) single crystal and of the aluminum polycrystalline (poly Al) film were measured at 200 eV and 1000 eV electron energies for a variety of experimental geometries and were mutually compared. No anisotropy was found for the poly Al, as expected. Polar intensity plots evaluated from the elastic (no loss) and inelastic first surface plasmon- and first bulk plasmon-loss intensities of the Al(111) surface show clearly discernable peaks for both considered electron energies. Their positions on the angular axis are the same for the elastic as well as for the inelastic, surface and bulk plasmon-loss peaks. The polar plots of intensities of the elastically and inelastically reflected electrons were compared to calculated intensities of photoelectrons emitted from the Al 2s core level to the same kinetic energy. Peak positions in the theoretically determined polar plots of electron intensities agree with those obtained experimentally in REELS.     

Silicon surface passivation by aluminium oxide studied with electron energy loss spectroscopy

The origin behind crystalline silicon surface passivation by Al₂O₃ films is studied in detail by means of spatially‐resolved electron energy loss spectroscopy. The bonding configurations of Al and O are studied in as‐deposited and annealed Al₂O₃ films grown on c‐Si substrates by plasma‐assisted and thermal atomic layer deposition. The results confirm the presence of an interfacial SiO₂‐like film and demonstrate changes in the ratio between tetrahedrally and octahedrally coordinated Al in the films after annealing. These observations reveal the underlying origin of c‐Si surface passivation by Al₂O₃. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Image simulation for electron energy loss spectroscopy

Aberration correction of the probe forming optics of the scanning transmission electron microscope has allowed the probe-forming aperture to be increased in size, resulting in probes of the order of 1 A in diameter. The next generation of correctors promise even smaller probes. Improved spectrometer optics also offers the possibility of larger electron energy loss spectrometry detectors. The localization of images based on core-loss electron energy loss spectroscopy is examined as function of both probe-forming aperture and detector size. The effective ionization is nonlocal in nature, and two common local approximations are compared to full nonlocal calculations. The affect of the channelling of the electron probe within the sample is also discussed.     

High resolution Auger electron spectroscopy of metallic copper

Part of the LMM Auger spectrum from metallic copper has been studied in a high resolution X-ray photoelectron spectrometer. Fine structure not earlier reported has been observed. The main L₃M_4,5M_4,5 peak is very narrow, 1.0 eV, although the valence band is involved in the transition. The agreement between experimental and calculated Auger electron energies is very good. Since fine structure is found to be an intrinsic property in Auger spectra the interpretation of “satellite” peaks as due to electron—plasmon interactions should be used with care. The L₃M_4,5M_4,5 peak is very sensitive to the copper surface conditions. Surface oxygen affects the peak in a characteristic way.     

The surface relaxation of Al as determined by electron energy loss spectroscopy on plasmons

Electron energy loss spectroscopy (EELS) on plasmons has been applied to determine the thermal expansion coefficient on the surface and to estimate the density of conduction electrons in the surface layer of aluminium. Using the data on the temperature dependence of the surface plasmon energy shift, the value of thermal expansion coefficient on the surface was calculated to be α_s=1.3 × 10^?4K^?1 that is about two times higher than the bulk value. A simple model is proposed which takes account of the influence of electron density non-uniformity in the surface layer on the dispersion of plasma oscillations. An estimation of the density of conduction electrons in the surface layer based on the observed dependence of the surface plasmon energy on the energy of primary electrons gave a value about 5% lower than the bulk value. The thickness of altered surface layer is about 10 Å.     

High-detective-quantum-efficiency fast-electron detector for electron energy loss spectroscopy

In order to increase the sensitivity of the parallel electron detector used in electron energy loss spectroscopy (EELS), we have developed a direct electron exposed detector, based on a photodiode array (PDA). This work investigates the performance of this detector at 100 keV incident electrons in terms of the detective quantum efficiency (DQE), the modulation transfer function (MTF) and radiation damage.     

K-shell excitation of HCN by electron energy loss spectroscopy

Small angle inelastic scattering of fast electrons has been used to study carbon and nitrogen K-shell excitation and ionization of HCN. The K→π* transitions in HCN have been investigated with high resolution.     

A novel electron spectroscopy for surface studies

The method makes use of the decrease in the elastically backscattered electron current at characteristic excitation thresholds of surface atoms, when the primary energy is scanned. By means of electronic differentiation the structures in the energy dependence of the coefficient of elastic reflection are made visible. They can give information on the elemental composition and electronic structure of the surface layer.     

Azimuthal dependence of impact scattering in electron energy loss spectroscopy

The azimuthal dependence of electron energy loss spectroscopy (EELS) dipole and impact scattering intensity has been measured. Spectra for a saturation coverage of H adsorbed on W(110) exhibit loss peaks due to impact scattering from adsorbate vibrational modes. The intensity of the 160 meV loss peak has been measured as a function of the azimuthal angle between the scattering plane and a mirror plane of the $\text{s}$urface. The angular pattern has strong maxima oriented perpendicular to the <111 > rows of atoms on the surface, and has the C_2v symmetry of the W(110) surface. This azimuthal dependence is strikingly different from the nearly isotropic angular dependence of dipole scattering from Cl adsorbed on W(110). Selection rules for impact scattering account for the general features of the angular pattern based on asymmetric stretch modes associated with bridge site H atoms.We have shown that the azimuthal dependence of the 36 meV Cl/W(110) dipole scattering loss peak is isotropic and that the 160 meV H/W(110) impact scattering loss peak exhibits a striking azimuthal pattern with C_2v symmetry. The symmetry and deep minima suggest that selection rules play a central role in determining the azimuthal pattern. Application of these rules to two orthogonal directions (as in ref. 6) may be misleading, as is clear from Fig. 2, because essential features of the pattern will not be observed. Our analysis of the full pattern has suggested two bridge sites may be occupied at saturation coverage, but has still not resolved certain questions about the H/W(110) system.

1. Impact scattering selection rules for potential adsorbate sites. The listed directions are the intersections of the planes with the (110) surface for the mirror planes and the scattering planes, and the displacement directions for the adsorbate vibrational modes. Modes are assumed to be strictly parallel to the surface. The long bridge site is between two W atoms along the <001 > direction, the short bridge site is between two W atoms along the <$\text{111}\text{-}$ > direction, and the distorted bridge site is displaced from the long bridge site along the <$\text{110}\text{-}$ > direction (ref. 6) The asterisks (*) denote that the scattering amplitude is zero for all directions in the scattering plane, otherwise it is zero only in the specular direction. The <$\text{110}\text{-}$ > mode of the distorted bridge is not covered by the selection rules of ref. 2.

     

20.

Exciton coherence and electron energy loss spectroscopy of conjugated molecules     

Chernyak V  Volkov SN  Mukamel S 《Physical review letters》2001,86(6):995-998

Signatures of the exciton coherence size, which controls the nonlinear optical response and luminescence of conjugated systems, in the electronic dynamic structure factor S(q,omega) are calculated. We find that for small molecules the momentum dependence of the lowest exciton resonance is purely geometric, reflecting the molecular size rather than a universal exciton size, as suggested recently. For long chains the q dependence is determined by the interplay of the exciton size and the bond-alternation length scales.     

SITE	LONG BRIDGE	SHORT BRIDGE	DISTORTED BRIDGE
MIRROR PLANES	[001], [1$\text{1}\text{-}$0]	NONE	[1$\text{1}\text{-}$0]
2-FOLD ABOUT Z	YES	YES	NO
PARALLEL MODES	[001]	[1$\text{1}\text{-}$0]	[1$\text{1}\text{-}$1]	[$\text{1}\text{-}$12]	[001]	[1$\text{1}\text{-}$0]
DIRECTIONS OF ZERO SCATTERING	[001] * [1$\text{1}\text{-}$0]	[001] * [1$\text{1}\text{-}$0]	[1$\text{1}\text{-}$1] [$\text{1}\text{-}$12]	[1$\text{1}\text{-}$1] [$\text{1}\text{-}$12]	[001] * [1$\text{1}\text{-}$0]	NA

Exciton coherence and electron energy loss spectroscopy of conjugated molecules

Signatures of the exciton coherence size, which controls the nonlinear optical response and luminescence of conjugated systems, in the electronic dynamic structure factor S(q,omega) are calculated. We find that for small molecules the momentum dependence of the lowest exciton resonance is purely geometric, reflecting the molecular size rather than a universal exciton size, as suggested recently. For long chains the q dependence is determined by the interplay of the exciton size and the bond-alternation length scales.