80 research outputs found
A new charge-transfer complex in UHV co-deposited tetramethoxypyrene and tetracyanoquinodimethane
UHV-deposited films of the mixed phase of tetramethoxypyrene and
tetracyanoquinodimethane (TMP1-TCNQ1) on gold have been studied using
ultraviolet photoelectron spectroscopy (UPS), X-ray-diffraction (XRD), infrared
(IR) spectroscopy and scanning tunnelling spectroscopy (STS). The formation of
an intermolecular charge-transfer (CT) compound is evident from the appearance
of new reflexes in XRD (d1= 0.894 nm, d2= 0.677 nm). A softening of the CN
stretching vibration (red-shift by 7 cm-1) of TCNQ is visible in the IR
spectra, being indicative of a CT of the order of 0.3e from TMP to TCNQ in the
complex. Characteristic shifts of the electronic level positions occur in UPS
and STS that are in reasonable agreement with the prediction of from DFT
calculations (Gaussian03 with hybrid functional B3LYP). STS reveals a HOMO-LUMO
gap of the CT complex of about 1.25 eV being much smaller than the gaps (>3.0
eV) of the pure moieties. The electron-injection and hole-injection barriers
are 0.3 eV and 0.5 eV, respectively. Systematic differences in the positions of
the HOMOs determined by UPS and STS are discussed in terms of the different
information content of the two methods.Comment: 20 pages, 6 figure
Asymmetric Electrostatic Dodecapole: Compact Bandpass Filter with Low Aberrations for Momentum Microscopy
Imaging energy filters in photoelectron microscopes and momentum microscopes
employ spherical fields with deflection angles of 90{\deg}, 180{\deg} and even
2 x 180{\deg}. These instruments are optimized for high energy resolution, yet
they come along with image aberrations when they are operated in high
transmission mode with medium energy resolution. Here we present a new approach
for bandpass-filtered imaging in real or reciprocal space, using an asymmetric
electrostatic dodecapole. This multipole enables energy-dispersive beam
deflection and correction of image aberrations up to the 3rd order. Owing to a
deflection angle of only 4{\deg}, the total beam displacement in the filter is
just ~10 mm. Hence, the entire instrument is compact and just requires a
straight vacuum tube. The multipole is framed by transfer lenses in the
entrance and exit branch. Two sets of 16 entrance and exit apertures with
different sizes on piezomotor-driven holders allow selecting the desired
resolution. The combination of apertures and dodecapole acts as a bandpass
pre-selector in a high-energy time-of-flight momentum microscope at the hard
X-ray beamline P22 at PETRA-III (DESY, Hamburg). At pass energies between 400
and 600 eV it transmits electrons with kinetic energies in the range of 20-40
eV and thus effectively eliminates unwanted intensity from higher-energy
electrons in the ToF analyzer. At low pass energies, the instrument allows
energy-filtered imaging without subsequent ToF analysis. In a laboratory
experiment the 4{\deg} prototype reached < 500 meV resolution, which is
sufficient for fast survey studies in the X-ray range.Comment: 16 pages, 6 figures, 26 reference
Near-Edge X‐ray Absorption Fine Structure Investigation of the Quasi-One-Dimensional Organic Conductor (TMTSF)2PF6
We present high-resolution near-edge X-ray absorption fine structure (NEXAFS) measurements at the P L2/3 edges, F K edge, C K edge, and Se M2/3 edges of the quasi-one-dimensional (1D) conductor and superconductor (TMTSF)2PF6. NEXAFS allows probing the donor and acceptor moieties separately; spectra were recorded between room temperature (RT) and 30 K at normal incidence. Spectra taken around RT were also studied as a function of the angle (θ) between the electric field of the X-ray beam and the 1D conducting direction. In contrast with a previous study of the S L2/3-edges spectra in (TMTTF)2AsF6, the Se M2/3 edges of (TMTSF)2PF6 do not exhibit a well-resolved spectrum. Surprisingly, the C K-edge spectra contain three well-defined peaks exhibiting strong and nontrivial θ and temperature dependence. The nature of these peaks as well as those of the F K-edge spectra could be rationalized on the basis of first-principles DFT calculations. Despite the structural similarity, the NEXAFS spectra of (TMTSF)2PF6 and (TMTTF)2AsF6 exhibit important differences. In contrast with the case of (TMTTF)2AsF6, the F K-edge spectra of (TMTSF)2PF6 do not change with temperature despite stronger donor−anion interactions. All these features reveal subtle differences in the electronic structure of the TMTSF and TMTTF families of salts
Time- and momentum-resolved photoemission studies using time-of-flight momentum microscopy at a free-electron laser
Time-resolved photoemission with ultrafast pump and probe pulses is an emerging technique with wide application potential. Real-time recording of nonequilibrium electronic processes, transient states in chemical reactions, or the interplay of electronic and structural dynamics offers fascinating opportunities for future research. Combining valence-band and core-level spectroscopy with photoelectron diffraction for electronic, chemical, and structural analyses requires few 10 fs soft X-ray pulses with some 10 meV spectral resolution, which are currently available at high repetition rate free-electron lasers. We have constructed and optimized a versatile setup commissioned at FLASH/PG2 that combines free-electron laser capabilities together with a multidimensional recording scheme for photoemission studies. We use a full-field imaging momentum microscope with time-of-flight energy recording as the detector for mapping of 3D band structures in (kx, ky, E) parameter space with unprecedented efficiency. Our instrument can image full surface Brillouin zones with up to 7 Å−1 diameter in a binding-energy range of several eV, resolving about 2.5 × 105 data voxels simultaneously. Using the ultrafast excited state dynamics in the van der Waals semiconductor WSe2 measured at photon energies of 36.5 eV and 109.5 eV, we demonstrate an experimental energy resolution of 130 meV, a momentum resolution of 0.06 Å−1, and a system response function of 150 fs
Suppression of the vacuum space-charge effect in fs-photoemission by a retarding electrostatic front lens
The performance of time-resolved photoemission experiments at fs-pulsed photon sources is ultimately limited by the e–e Coulomb interaction, downgrading energy and momentum resolution. Here, we present an approach to effectively suppress space-charge artifacts in momentum microscopes and photoemission microscopes. A retarding electrostatic field generated by a special objective lens repels slow electrons, retaining the k-image of the fast photoelectrons. The suppression of space-charge effects scales with the ratio of the photoelectron velocities of fast and slow electrons. Fields in the range from −20 to −1100 V/mm for Ekin = 100 eV to 4 keV direct secondaries and pump-induced slow electrons back to the sample surface. Ray tracing simulations reveal that this happens within the first 40 to 3 μm above the sample surface for Ekin = 100 eV to 4 keV. An optimized front-lens design allows switching between the conventional accelerating and the new retarding mode. Time-resolved experiments at Ekin = 107 eV using fs extreme ultraviolet probe pulses from the free-electron laser FLASH reveal that the width of the Fermi edge increases by just 30 meV at an incident pump fluence of 22 mJ/cm2 (retarding field −21 V/mm). For an accelerating field of +2 kV/mm and a pump fluence of only 5 mJ/cm2, it increases by 0.5 eV (pump wavelength 1030 nm). At the given conditions, the suppression mode permits increasing the slow-electron yield by three to four orders of magnitude. The feasibility of the method at high energies is demonstrated without a pump beam at Ekin = 3830 eV using hard x rays from the storage ring PETRA III. The approach opens up a previously inaccessible regime of pump fluences for photoemission experiments
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