Modulated photoemission spectroscopy: Application to Au

We describe modulated photoemission spectroscopy, in which an internal (sample) parameter such as temperature, or an external (apparatus) parameter such as wavelength is varied. A general formalism is developed for modulated photoemission spectroscopy and then illustrated using temperature modulated photoemission spectra and yields for Au obtained in the ～ 6 to 11.6 eV photon energy range. Modulated s-p band photoemission data are described in terms of photoemission critical points in order to explain the nature of the modulated structures in the s-p band region and relate experiment to energy band thresholds obtained from a recent band calculation for Au. Application of the formalism to modulated d-band emission leads to a method for extracting d-band deformation potentials. For example, we find that the upper d band edge moves upward with respect to E_F at a rate of 2 to 6 × 10^?4 eV/K. Modulation of the quantum yield is described and our measurements are compared with modulated optical data.     

The 2π-derived level in the adsorption system CO/Cu(110)

The bremsstrahlung isochromat (or inverse photoemission) spectrum of CO chemisorbed on a Cu(110) surface has been investigated. An empty level derived from the CO 2 π orbital was found at an energy of 0.9 eV below the vacuum level E_vac and to have a halfwidth varying from 1.9 to 2.6 eV as a function of increasing coverage. The energetic position of the empty level is discussed in connection with photoemission data for occupied bands and excitation energies from electron energy loss measurements.     

Franck-condon-broadened angle-resolved photoemission spectra predicted in LaMnO3

The sudden photohole of least energy created in the photoemission process is a vibrationally excited state of a small polaron. Therefore the photoemission spectrum in LaMnO3 is predicted to have multiple Franck-Condon vibrational sidebands. This generates an intrinsic line broadening approximately 0.5 eV. The photoemission spectral function has two peaks whose central energies disperse with bandwidth approximately 1.2 eV. Signatures of these phenomena are predicted to appear in angle-resolved photoemission spectra.     

Ultraviolet photoemission from polymeric sulfur nitride polycrystalline films and single crystals

The (SN)_x valence band structure, for polycrystalline films as well as for single crystal samples, has been studied using He I and He II resonance radiation. In angle-resolved photoemission energy distributions from single crystals, structure in the spectra is selectively enhanced offering a possibility of assigning the photoemission as originating from particular regions of the Brillouin Zone. The observed onset of photoemission 0.2 eV below the Fermi edge is discussed.     

Synchrotron radiation measurements and calculation of core to conduction level transitions in lead chalcogenides

New high resolution reflectivity measurements on PbSe and PbTe using synchrotron radiation (18–26 eV) are studied using an OPW formalism based on recent improved EPM band structure models to determine the angular momentum character of the final conduction band states. Detailed analysis reveals that the reflectivity threshold is shifted to lower energies by 0.8 eV compared to results derived from photoemission and low energy reflectivity data. Electron-hole interactions are suggested as a possible explanation for this shift.     

Parameter-free quasiparticle calculations for YH3

Electronic structure calculations for YH3 within the local density approximation result in a metallic ground state with the bands at the Fermi energy overlapping by more than 1 eV, whereas a band gap of 2.8 eV is deduced from optical experiments. Here, we report the results of parameter-free GW calculations which predict a fundamental gap of 1 eV. When we take into account electric dipole matrix elements a large optical gap of almost 3 eV is obtained. A combination of photoemission and inverse photoemission spectroscopy could test the prediction of a small fundamental band gap.     

Hole lifetime and chemical shift of the 4f levels in Yb metal

UHV photoemission studies of Yb metal are reported using synchrotron radiation in the photon energy range 25 < hv < 180 eV, whereby maximum surface sensitivity can be reached. The 4f photoemission spectrum shows a quadruplet structure owing to a superposition of two 4f spin—orbit doublets. One doublet has a very asymmetric lineshape and an extremely narrow lifetime linewidth 2γ? 0.013 eV; this is attributed to bulk emission. The other doublet exhibits almost symmetric lines with a much larger linewidth (0.43 eV FWHM); it has also a larger binding energy by 0.6 ± 0.03 eV. This is attributed as being due to chemically bound Yb atoms located at the surface. The implications of these findings on recent high-resolution photoemission studies of rare earth (RE) metals and their analysis are considered.     

Electronic band structure of Cu3Au: An angle-resolved photoemission study along the [111]-direction

High-resolution normal photoemission (ARPE) spectra have been recorded for Cu₃Au(111) with the use of polarized synchrotron and rare-gas resonance radiation in the photon energy range from 9 to 27 eV. It is for the first time that dispersions of the gold-like bands have been found experimentally. Using a fully relativistic layer-KKR photoemission formalism, occupied and unoccupied bands as well as one-step-model photoemission spectra have been calculated. The comparison of calculated spectra with experimental ones and the observation of direct-transition resonances upon photon energy near the Brillouin zone-center reveal a shift of the unoccupied ground-state bands by about +2.5 eV (self-energy shift). The direct-transition structures in the experimental spectra have been exploited to determine the dispersions of the occupied bands along the [111] direction (A line in k space). In order to determine the wave vector of the experimental direct transitions we used as final state that calculated unoccupied band along [111], which also exists in pure copper and gold up to about 20 eV above the Fermi energy (“unfolded” band structure), shifted by + 2.5 eV. The experimental occupied bands with Cu character are in very good agreement with theory after shifting the latter by about 0.3 eV to lower energy, whereas somewhat bigger discrepancies exist for the gold-like bands.     

砷化镓上银和金膜的价带光电子谱

木文测量了光子能量为21.2eV,40.8eV和1486.6eV的光电子谱,得到了关于GaAs(110)解理面上银膜的价带能谱新数据,并得到金膜价带能谱的补充数据,蒸发的银膜和金膜的厚度范围为0.l?到1000?,实验上发现并讨论了下面的现象:GaAs(110)面上金膜和银膜的紫外价带光电子谱的强度与膜厚的关系曲线中出现极大峰。 关键词：     

The energy dependence of the electron inelastic scattering mean-free-path in gold

The relative electron inelastic scattering mean-free-path in gold in the energy range 60–140 eV has been determined by the overlayer technique using synchrotron radiation photoemission spectroscopy from the 4f core levels of a tantalum foil substrate. The mean-free-path falls rapidly from 60 to 80 eV but is essentially constant from 100 to 140 eV.     

Core level photoemission study of the adsorption of iodine on Ni{100}

Synchrotron radiation photoemission from the Ni 3p and I 4d core levels has been studied for iodine adsorbed on Ni{100} in a range of different phases. In the range of chemisorbed structures involving overlayer compression from coverages θ of about 0.3 to 0.4 the I 4d photoemission binding energies decrease by ~0.3 eV, while further compression to a c(2 × 2) structure leads to a further decrease by ~0.4 eV. Low temperature adsorption of molecular iodine shows a binding energy of 0.1 eV lower still. In the chemisorbed coverage range these core level shifts are found to be substantially less than the I-I repulsive energy interactions and are associated with the through-metal component of this interaction, while the residual component concealed from the photoemission experiments is attributed to through-space overlap interaction. Other processes which may contribute to the observed binding energy shifts, including Coulomb interactions in both initial and final states, are discussed in some detail.     

Electronic structure of Yb/H－Si (111) interface

Photoemission spectra are measured for Yb covered surface of wet-chemically-etched H－Si (111). The results reveal that the lattice structure of the H－Si (111) surface is stable against the deposition of Yb atoms. X-ray photoemission spectra indicate the formation of a polarized (dipole) surface layer, with the silicon negatively charged. Ultraviolet photoemission spectra exhibit the semiconducting property of the interface below one monolayer coverage. Work function variation during the formation of the Yb/H－Si (111) interface is measured by the secondary-electron cutoff in the ultraviolet photoemission spectral line. The largest decrease of work function is ～1.65eV. The contributions of the dipole surface layer and the band bending to the work function change are determined to be ～1.15eV and ～0.5eV, respectively. The work function of metal Yb is determined to be ～2.80±0.05eV.     

The surface electronic structure of Ag8Au4 superlattice

We present the calculations of electronic structure and photoemission spectra for a lattice-matched Ag-Au(111) superlattice. The selfconsistent band structure exhibits a superlattice gap at about 1 eV below the Fermi level. A surface state is found in this gap and its dispersion properties are investigated. Its energy location is varied with location of surface terminating plane within the superlattice period. The calculated normal photoemission spectra explain well available experimental data.     

Photoemission spectroscopy and microscopy of n-, p-GaAs(110) homostructures

Zinc-blend III–V semiconductors being cleaved along nonpolar (110) planes yield atomically clean surfaces due to their charge neutrality, which can be employed as mirror planes for optical resonators. As a result of the Ga3d core level photoemission measurements after the n-, p-GaAs (110) plane cleavage in situ of doped semiconductors with 14 nominally identical p-n homojunctions having optically flat cleaved surface under the optical microscope inspection, the estimate of the Fermilevel positions on energy scale were acquired for p- and n-epilayers. The two-dimentional photoemission image for p-n homojunction was studied as well, using the focused synchrotron radiation beam (diameter 0.7 μm, 95 eV, ～10¹⁰ phot./s) at the scanning photoemission microscope. The average value of surface band bending for p-epilayer measured from the energy position of ideal flat-band conditions, was equal to 0.12 ± 0.05 eV, and that for n-epilayer—0.16 ± 0.08 eV, the spectrometer energy resolution being <0.15 eV. The detailed analysis of the experimental data was carried out in order to clarify the deviation fsrom ideal flat band conditions characteristic for absence of surface cleavage defects. Comparison was done with the well-known literature data on theoretical and experimental investigations of cleavage defects. The experimental results leading to different deviations from ideal flat-band conditions for each cleavage are explained by extrinsic local microscopic defects of cleavage which can appear accidentally and unpredictably, since the system dynamics during cleavage is a highly nonlinear many-body process with many degrees of freedom.     

Acceptors in Li doped NiO

The electronic structure of the Li doped large gap semiconductor (insulator) NiO is investigated by photoemission and inverse photoemission spectroscopy. Spectral weight is produced by the Li doping within the gap at 1.4 eV above the top of the valence band. It is interpreted as due to an acceptor level associated with a LiO complex.     

Excited states mapped by secondary photoemission

We report on angle-resolved photoemission (ARPES) experiments on Cu(110) using Mg K(alpha) radiation. The secondary emission (SE) fine structure of electrons below 50 eV is found to map the empty band structure relevant for absolute band mapping in ARPES. The finding is based on a direct comparison of our experiments with very low-energy electron diffraction data [Phys. Rev. Lett. 81, 4943 (1998)]] recently shown to map the unoccupied states representing the photoemission final-state. This suggests a new theoretical approach to the SE process treating the outgoing electron state as the time-reversed diffraction state.     

Properties of hydrogen terminated diamond as a photocathode

Electron emission from the negative electron affinity (NEA) surface of hydrogen terminated, boron doped diamond in the [100] orientation is investigated using angle resolved photoemission spectroscopy (ARPES). ARPES measurements using 16 eV synchrotron and 6 eV laser light are compared and found to show a catastrophic failure of the sudden approximation. While the high energy photoemission is found to yield little information regarding the NEA, low energy laser ARPES reveals for the first time that the NEA results from a novel Franck-Condon mechanism coupling electrons in the conduction band to the vacuum. The result opens the door to the development of a new class of NEA electron emitter based on this effect.     

Theory of resonant photoemission in black phosphorus

Resonant photoemission in black phosphorus is studied theoretically with a model of simplified energy bands. It is shown that a core exciton state plays an essentially important role both in the resonant enhancement of the photoemission peak at the binding energy 10.8eV and the Fano type interference at 2.7eV, which have recently been observed experimentally.     

Surface plasmon assisted photoemission from Au nanoparticles on graphite

The resonant multiple excitation of collective modes in metallic nanoparticles using ultrashort laser pulses leads to an enhanced multiphoton photoemission from the particles. This effect is here demonstrated for the surface-plasmon resonance of Au nanoparticles on graphite. The shape of the photoemission spectra is explained by multiphoton photo-assisted thermionic emission from the nanoparticles and resonant emission via the image-potential state on graphite. Tuning the photon energy between 1.7 eV and 3.2 eV allows the identification of an enhancement of the photoemission yield at 2.1±0.1-eV photon energy that is attributed to the resonant excitation of the surface plasmon in the Au nanoparticles. This identification of the surface-plasmon excitation in this energy range is also supported by electron energy loss spectroscopy. Received: 8 August 2001 / Revised version: 13 September 2001 / Published online: 10 October 2001     

Impedance-type measurements using XPS

An impedance type of measurement using X-ray photoelectron spectroscopy is applied for probing charging/discharging dynamics of a sample containing Rb deposited on a SiO₂/Si substrate containing an octadecyltrichlorosilane (OTS) bilayer coating. The OTS bilayer coatings have possible use as anti-relaxation wall coatings for alkali atom vapor cells in miniaturized instruments such as chip-scale atomic clocks, and/or magnetometers. The measurement consists of the application of bipolar square wave pulses of ±10.0 V amplitude to the sample with varying frequencies in the range of 10⁻² to 10² Hz while recording X-ray photoemission data. For a conducting sample this type of measurement twins all the photoemission peaks at −10.0 and +10.0 eV positions at all frequencies with exactly 20.0 eV difference between them. However, for samples amenable to charging, the difference between the twinned peaks is less than 20.0 eV, and gradually decreases at correspondingly lower frequencies. For the sample under consideration here at 0.01 Hz, the twinned O1s and Si2p peaks, representing the SiO₂ substrate, are separated by 18.2 eV, displaying a 1.8 eV charging shift. These positions differ from those of the C1s (18.0 eV) representing the OTS bilayer and the Rb3d peaks (18.1 eV). These results reveal that the Rb is electrically (perhaps also chemically) isolated from the OTS bilayer, which may be correlated with the improved performance of the OTS bilayers as anti-relaxation coatings in these alkali atom magnetometer cells.