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Photoemission from CsI - Experiment.

Considerable attention in the investigation was given to the resolution maximization of details in the spectra. Very thin films were used in the measurements, which were conducted at 300 and 77 C with the aid of an improved photoemission apparatus. It was found that the principal features of the photoemission spectra from CsI cannot be explained on the basis of simple transitions from localized ionic states because such a model would predict a doublet instead of the triplet observed in the photoemission data.

Distefano, T. H.↗

Two-photon photoemission from metals induced by picosecond laser pulses

We have measured the two-photon photoemission current density from tungsten, tantalum, and molybdenum when irradiated by 532-nm wavelength radiation. This wavelength was produced by the second-harmonic radiation of single picosecond laser pulses from a mode-locked neodymium-doped yttrium-aluminum-garnet laser. The results are interpreted in terms of both a simple temperature-independent two-photon photoemission effect and a generalization of the Fowler-DuBridge theory of photoemission. The laser polarization dependence of the emitted current is also reported.

Bechtel, J. H.↗

Photoemission Experiments for Charge Characteristics of Individual Dust Grains

Photoemission experiments with UV radiation have been performed to investigate the microphysics and charge characteristics of individual isolated dust grains of various compositions and sizes by using the electrodynamic balance facility at NASA Marshall Space Flight Center. Dust particles of 2-10 gm diameter are levitated in a vacuum chamber at pressures approximately 10(exp-5) torr and exposed to a collimated beam of UV radiation in the 120-200 nm spectral range from a deuterium lamp source with a MgF2 window. A monochromator is used to select the UV wavelength with a spectral resolution of 8 nm. The electrodynamic facility permits measurements of the charge and diameters of particles of known composition, and monitoring of photoemission rates with the incident UV radiation. Experiments have been conducted on test particles of silica and polystyrene to determine the photoelectric yields and surface equilibrium potentials when exposed to UV radiation. A brief description of an experimental procedure for photoemission studies is given and some preliminary laboratory measurements of the photoelectric yields of individual dust particles are presented.

Abbas, M. M.↗

Photoemission Experiments for Charge Characteristics of Individual Dust Grains

Photoemission experiments with UV radiation have been performed to investigate the microphysics and charge characteristics of individual isolated dust grains of various compositions and sizes by using the electrodynamic balance facility at NASA Marshall Space Flight Center. Dust particles of 1 - 100 micrometer diameter are levitated in a vacuum chamber at pressures approx. 10(exp -5) torr and exposed to a collimated beam of UV radiation in the 120-300 nanometers spectral range from a deuterium lamp source with a MgF2 window. A monochromator is used to select the UV radiation wavelength with a spectral resolution of 8 nanometers. The electrodynamic facility permits measurements of the charge and diameters of particles of known composition, and monitoring of photoemission rates with the incident UV radiation. Experiments have been conducted on Al2O3 and silicate particles, and in particular on JSC-1 Mars regolith simulants, to determine the photoelectron yields and surface equilibrium potentials of dust particles when exposed to UV radiation in the 120-250 micrometers spectral range. A brief discussion of the experimental procedure, the results of photoemission experiments, and comparisons with theoretical models will be presented.

Abbas, M. M.↗

Ultraviolet Photoemission Spectroscopy and Kelvin Probe Measurements on Metal Halide Perovskites: Advantages and Pitfalls

In this essay, a case study is presented on the electronic structure of several metal halide perovskites (MHP) using Kelvin probe (KP)-based surface photovoltage (SPV) measurements and ultraviolet photoemission spectroscopy (UPS) to demonstrate the advantages, but also the pitfalls, of using these techniques to characterize the surfaces of these materials. The first part addresses the loss of halide species from perovskite surfaces upon supragap illumination in vacuum. This has the potential to cause both a long-term alteration of the sample work function and a modification of the KP tip during SPV measurements. If undetected, this leads to a misinterpretation of the MHP surface potential. The second part illustrates the difficulties in determining the valence band maximum (VBM) of MHP surfaces with UPS and stresses the importance of taking into account the low density of states at the VBM edge. Given this circumstance, specific care must be taken to eliminate measurement artifacts in order to ascertain the presence or absence of low densities of electronic gap states above the VBM. This essay also highlights issues such as film degradation, nonequilibrium situations (e.g., SPV), and satellite emissions, which occur during photoemission spectroscopy.

36 MATERIALS SCIENCE↗

Crystal structure and X-ray photoemission spectroscopic study of A{sub 2}LaMO{sub 6} [A=Ba, Ca; M=Nb, Ta]

The X-ray photoemission spectroscopic (XPS) study of the double perovskite oxides A{sub 2}LaMO{sub 6} [A=Ba, Ca; M=Nb, Ta] synthesized by the solid-state reaction technique has been carried out to investigate the nature of the chemical state of the constituent ions and the bonding between them. The Rietveld refinement of the X-ray diffraction patterns suggests the monoclinic crystal structure of all the materials at room temperature. The negative and positive chemical shifts of the core level XPS spectrum of O-1s and Nb-3d{sub 3/2}/Ta-4f{sub 5/2} respectively suggest the covalent bonding between Nb/Ta cations and O ion. The change of the bonding strength between the anion and the cations from one material to another has been analyzed. The vibrational property of the materials is investigated using the room temperature Raman spectra. A large covalency of Ta-based compound than Nb compound is confirmed from the relative shifting of the Raman modes of the materials. - Graphical abstract: Crystal structure of two perovskite oxides CLN and CLT is investigated. XPS study confirms the two different co-ordination environments of Ca and covalent bonding between B-site cations and O-ion. - Highlights: • Ordered perovskite structure obtained by Rietveld refinement of XRD patterns. • Study of nature of chemical bonding by X-ray photoemission spectroscopy. • Opposite chemical shift of d-states of Nb/Ta with respect to O. • Covalent bonding between d-states of Nb/Ta and O. • Relative Raman shifts of CLN and CLT substantiate the more covalent character of Ta than Nb.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic structure of superconducting nickelates probed by resonant photoemission spectroscopy

We report the discovery of infinite-layer nickelate superconductors has spurred enormous interest. While the Ni 1+ cations possess nominally the same 3d 9 configuration as Cu 2+ in cuprates, the electronic structure variances remain elusive. Here, we present a soft X-ray photoemission spectroscopy study on parent and doped infinite-layer Pr-nickelate thin films with a doped perovskite reference. By identifying the Ni character with resonant photoemission and comparison with density functional theory + U (on-site Coulomb repulsion energy) calculations, we estimate U ~5 eV, smaller than the charge transfer energy Δ ~8 eV, confirming the Mott-Hubbard electronic structure in contrast to charge-transfer cuprates. Near the Fermi level (E F ), we observe a signature of occupied rare-earth states in the parent compound, which is consistent with a self-doping picture. Our results demonstrate a correlation between the superconducting transition temperature and the oxygen 2p hybridization near E F when comparing hole-doped nickelates and cuprates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effects of Defects on Band Structure and Excitons in WS 2 Revealed by Nanoscale Photoemission Spectroscopy

Two-dimensional materials with engineered composition and structure will provide designer materials beyond conventional semiconductors. Yet, the potentials of defect engineering remain largely untapped, because it hinges on a precise understanding of electronic structure and excitonic properties, which are not yet predictable by theory alone. In this report, we use correlative, nanoscale photoemission spectroscopy to visualize how local introduction of defects modifies electronic and excitonic properties of two-dimensional materials at the nanoscale. As a model system, we study chemical vapor deposition grown monolayer WS 2 , a prototypical, direct gap, two-dimensional semiconductor. By cross-correlating nanoscale angle-resolved photoemission spectroscopy, core level spectroscopy, and photoluminescence, we unravel how local variations in defect density influence electronic structure, lateral band alignment, and excitonic phenomena in synthetic WS 2 monolayers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Through such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.

36 MATERIALS SCIENCE↗

Chemical potential shift and gap-state formation in SrTiO{sub 3−δ} revealed by photoemission spectroscopy

In this study, we report on investigations of the electronic structure of SrTiO{sub 3} annealed at temperature ranging between 550 and 840 °C in an ultrahigh vacuum. Annealing induced oxygen vacancies (O{sub vac}) impart considerable changes in the electronic structure of SrTiO{sub 3}. Using core-level photoemission spectroscopy, we have studied the chemical potential shift (Δμ) as a function of annealing temperature. The result shows that the chemical potential monotonously increases with electron doping in SrTiO{sub 3−δ}. The monotonous increase of the chemical potential rules out the existence of electronic phase separation in the sample. Using valence band photoemission, we have demonstrated the formation of a low density of states at the near Fermi level electronic spectrum of SrTiO{sub 3−δ}. The gap-states were observed by spectral weight transfer over a large energy scale of the stoichiometric band gap of SrTiO{sub 3} system leading finally to an insulator-metal transition. We have interpreted our results from the point of structural distortions induced by oxygen vacancies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Femtosecond time-resolved photoemission electron microscopy for spatiotemporal imaging of photogenerated carrier dynamics in semiconductors

We constructed an instrument for time-resolved photoemission electron microscopy (TR-PEEM) utilizing femtosecond (fs) laser pulses to visualize the dynamics of photogenerated electrons in semiconductors on ultrasmall and ultrafast scales. The spatial distribution of the excited electrons and their relaxation and/or recombination processes were imaged by the proposed TR-PEEM method with a spatial resolution about 100 nm and an ultrafast temporal resolution defined by the cross-correlation of the fs laser pulses (240 fs). A direct observation of the dynamical behavior of electrons on higher resistivity samples, such as semiconductors, by TR-PEEM has still been facing difficulties because of space and/or sample charging effects originating from the high photon flux of the ultrashort pulsed laser utilized for the photoemission process. Here, a regenerative amplified fs laser with a widely tunable repetition rate has been utilized, and with careful optimization of laser parameters, such as fluence and repetition rate, and consideration for carrier lifetimes, the electron dynamics in semiconductors were visualized. For demonstrating our newly developed TR-PEEM method, the photogenerated carrier lifetimes around a nanoscale defect on a GaAs surface were observed. The obtained lifetimes were on a sub-picosecond time scale, which is much shorter than the lifetimes of carriers observed in the non-defective surrounding regions. Our findings are consistent with the fact that structural defects induce mid-gap states in the forbidden band, and that the electrons captured in these states promptly relax into the ground state.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Momentum resolution in inverse photoemission

We present a method to determine the electron beam divergence, and thus the momentum resolution, of an inverse-photoemission setup directly from a series of spectra measured on Cu(111). Simulating these spectra with different beam divergences shows a distinct influence of the divergence on the appearance of the Shockley surface state. Upon crossing the Fermi level, its rise in intensity can be directly linked with the beam divergence. A comparison of measurement and simulation enables us to quantify the momentum resolution independent of surface quality, energy resolution, and experimental geometry. With spin resolution, a single spectrum taken around the Fermi momentum of a spin-split surface state, e.g., on Au(111), is sufficient to derive the momentum resolution of an inverse-photoemission setup.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Ultrahigh-spatial-resolution chemical and magnetic imaging by laser-based photoemission electron microscopy

We report the first experiments carried out on a new chemical and magnetic imaging system, which combines the high spatial resolution of a photoemission electron microscope (PEEM) with a continuous-wave deep-ultraviolet laser. Threshold photoemission is sensitive to the chemical and magnetic structures of the surface of materials. The spatial resolution of PEEM is limited by space charging when using pulsed photon sources as well as aberrations in the electron optics. We show that the use of a continuous-wave laser enabled us to overcome such a limit by suppressing the space-charge effect, allowing us to obtain a resolution of approximately 2.6 nm. With this system, we demonstrated the imaging of surface reconstruction domains on Si(001) by linear dichroism with normal incidence of the laser beam. We also succeeded in magnetic imaging of thin films with the use of magnetic circular dichroism near the Fermi level. The unique features of the ultraviolet laser will give us fast switching of the incident angles and polarizations of the photon source, which will be useful for the characterization of antiferromagnetic materials as well as ferromagnetic materials.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Measurements of Schottky barrier at the low-k SiOC:H/Cu interface using vacuum ultraviolet photoemission spectroscopy

The band alignment between copper interconnects and their low-k interlayer dielectrics is critical to understanding the fundamental mechanisms involved in electrical leakage in low-k/Cu interconnects. In this work, vacuum-ultraviolet (VUV) photoemission spectroscopy is utilized to determine the potential of the Schottky barrier present at low-k a-SiOC:H/Cu interfaces. By examining the photoemission spectra before and after VUV exposure of a low-k a-SiOC:H (k = 3.3) thin film fabricated by plasma-enhanced chemical-vapor deposition on a polished Cu substrate, it was found that photons with energies of 4.9 eV or greater can deplete accumulated charge in a-SiOC:H films, while VUV photons with energies of 4.7 eV or less, did not have this effect. These critical values were identified to relate the electric potential of the interface barrier between the a-SiOC:H and the Cu layers. Using this method, the Schottky barrier at the low-k a-SiOC:H (k = 3.3)/Cu interface was determined to be 4.8 ± 0.1 eV.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural and electronic properties of V{sub 2}O{sub 3} ultrathin film on Ag(001): LEED and photoemission study

V{sub 2}O{sub 3} ultrathin films were grown on Ag(001) substrate by reactive evaporation of vanadium (V) metal in presence of oxygen and their structural and electronic properties were studied by Low Energy Electron Diffraction (LEED), X-ray Photo Electron Spectroscopy (XPS) and Angle Resolved Photoemission Spectroscopic (ARPES) techniques, respectively. On top of square symmetry substrate Ag(001), hexagonal surface of V{sub 2}O{sub 3} (0001) is stabilized in the form of two domain structure, rotated by 30°(or 90°)to each other, has been observed by LEED. Rather than epitaxial flat monolayer, formation of well-ordered V{sub 2}O{sub 3} (0001) island has been confirmed from the LEED and the Photoemission Spectroscopic (PES) study. Stoichiometry of the grown film was confirmed by the XPS study. Evolution of valance band electronic structure of V{sub 2}O{sub 3} (0001) surface has been studied as a function of film thickness by ARPES.

36 MATERIALS SCIENCE↗

Thickness-dependent change in the valence band offset of the SiO{sub 2}/Si interface studied using synchrotron-radiation photoemission spectroscopy

We have studied the thickness-dependent change in the valence band offset (VBO) of the SiO{sub 2}/Si(001) interface using synchrotron-radiation photoemission spectroscopy with soft and hard X-rays. The SiO{sub 2}-film thickness (T{sub ox}) and X-ray irradiation time (t{sub irrad}) were systematically parameterized to distinguish between the “intrinsic” T{sub ox} effects in the VBOs and the “extrinsic” differential charging phenomena in SiO{sub 2} films on Si substrates. The results revealed that at a spontaneous time (t{sub irrad} ≈ 5 s) that suppresses the differential charging phenomena as much as possible, the experimental VBO abruptly increases as a function of T{sub ox} and gradually saturates to the traditional VBO value range determined by the internal photoemission and photoconduction measurements. This effect is not attributed to the differential charging phenomena, but rather it is attributed to the “intrinsic” T{sub ox}-dependent change in the VBO. The two possible physical behaviors include electronic polarization and image charge. We have derived the electronic polarization contribution from experimental data by carefully describing the effects of the long-range image charges based on the classical dielectric-screening model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Femtosecond photoemission electron microscopy of surface plasmon polariton beam steering via nanohole arrays

Directional control over surface plasmon polariton (SPP) waves is a prerequisite for the development of miniaturized optical circuitry. Here, the efficacy of single and dual component SPP steering elements is explored through photoemission electron microscopy. Our imaging scheme relies on two-color photoemission and counter-propagating SPP generation, which collectively allow SPPs to be visualized in real space. Wave-vector difference mixing between two-dimensional arrays of nanoholes and photon momenta enables SPP steering with directionality governed by the array lattice constant. The magnitude of grating momentum required to achieve counter-propagation guarantees efficient steering over the full range of the negative half-space. In our dual component configuration, separate SPP generation and Bragg diffraction based steering optics are employed. We find that array Bragg planes principally influence the SPP angles through the array band structure, which allows us to visualize both positive and negative refractory waves.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Polarization dependent photoemission as a probe of the magnetic ground state in the van der Waals ferromagnet VI 3

Van der Waals ferromagnets are thrilling materials from both a fundamental and technological point of view. VI 3 is an interesting example, with a complex magnetism that differentiates it from the first reported Cr based layered ferromagnets. In this work, we show in an indirect way through angle resolved photoemission spectroscopy experiments, the importance of spin–orbit coupling setting the electronic properties of this material. Our light polarized photoemission measurements point to a ground state with a half-filled $\mathcal{e}_{±}^{'}$ doublet, where a gap opening is triggered by spin–orbit coupling enhanced by electronic correlations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗