Large Distortion of Fused Aromatics on Dielectric Interlayers Quantified by Photoemission Orbital Tomography.

Polycyclic aromatic compounds with fused benzene rings offer an extraordinary versatility as next-generation organic semiconducting materials for nanoelectronics and optoelectronics due to their tunable characteristics, including charge-carrier mobility and optical absorption. Nonplanarity can be an additional parameter to customize their electronic and optical properties without changing the aromatic core. In this work, we report a combined experimental and theoretical study in which we directly observe large, geometry-induced modifications in the frontier orbitals of a prototypical dye molecule when adsorbed on an atomically thin dielectric interlayer on a metallic substrate.

Momentum space imaging of σ orbitals for chemical analysis.

Tracing the modifications of molecules in surface chemical reactions benefits from the possibility to image their orbitals. While delocalized frontier orbitals with π character are imaged routinely with photoemission orbital tomography, they are not always sensitive to local chemical modifications, particularly the making and breaking of bonds at the molecular periphery. For such bonds, σ orbitals would be far more revealing.

Hexacene on Cu(110) and Ag(110): Influence of the Substrate on Molecular Orientation and Interfacial Charge Transfer.

Hexacene, composed of six linearly fused benzene rings, is an organic semiconductor material with superior electronic properties. The fundamental understanding of the electronic and chemical properties is prerequisite to any possible application in devices. We investigate the orientation and interface properties of highly ordered hexacene monolayers on Ag(110) and Cu(110) with X-ray photoemission spectroscopy (XPS), photoemission orbital tomography (POT), X-ray absorption spectroscopy (XAS), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT).

Going beyond Pentacene: Photoemission Tomography of a Heptacene Monolayer on Ag(110).

Longer acenes such as heptacene are promising candidates for optoelectronic applications but are unstable in their bulk structure as they tend to dimerize. This makes the growth of well-defined monolayers and films problematic. In this article, we report the successful preparation of a highly oriented monolayer of heptacene on Ag(110) by thermal cycloreversion of diheptacenes.

Charge-Promoted Self-Metalation of Porphyrins on an Oxide Surface.

Metalation and self-metalation reactions of porphyrins on oxide surfaces have recently gained interest. The mechanism of porphyrin self-metalation on oxides is, however, far from being understood. Herein, we show by a combination of results obtained with scanning tunneling microscopy, photoemission spectroscopy, and DFT computations, that the self-metalation of 2H-tetraphenylporphyrin on the surface of ultrathin MgO(001) films is promoted by charge transfer.

Kekulene: On-Surface Synthesis, Orbital Structure, and Aromatic Stabilization.

We revisit the question of kekulene's aromaticity by focusing on the electronic structure of its frontier orbitals as determined by angle-resolved photoemission spectroscopy. To this end, we have developed a specially designed precursor, 1,4,7(2,7)-triphenanthrenacyclononaphane-2,5,8-triene, which allows us to prepare sufficient quantities of kekulene of high purity directly on a Cu(111) surface, as confirmed by scanning tunneling microscopy. Supported by density functional calculations, we determine the orbital structure of kekulene's highest occupied molecular orbital by photoemission tomography.

Controlling the electronic and physical coupling on dielectric thin films.

Ultrathin dielectric/insulating films on metals are often used as decoupling layers to allow for the study of the electronic properties of adsorbed molecules without electronic interference from the underlying metal substrate. However, the presence of such decoupling layers may effectively change the electron donating properties of the substrate, for example, by lowering its work function and thus enhancing the charging of the molecular adsorbate layer through electron tunneling. Here, an experimental study of the charging of -sexiphenyl (6P) on ultrathin MgO(100) films supported on Ag(100) is reported.

Identifying surface reaction intermediates with photoemission tomography.

The determination of reaction pathways and the identification of reaction intermediates are key issues in chemistry. Surface reactions are particularly challenging, since many methods of analytical chemistry are inapplicable at surfaces. Recently, atomic force microscopy has been employed to identify surface reaction intermediates.

An X-ray gas monitor for free-electron lasers.

A novel X-ray gas monitor (XGM) has been developed which allows the measurement of absolute photon pulse energy and photon beam position at all existing and upcoming free-electron lasers (FELs) over a broad spectral range covering vacuum ultraviolet (VUV), extreme ultraviolet (EUV) and soft and hard X-rays. The XGM covers a wide dynamic range from spontaneous undulator radiation to FEL radiation and provides a temporal resolution of better than 200 ns. The XGM consists of two X-ray gas-monitor detectors (XGMDs) and two huge-aperture open electron multipliers (HAMPs).

The U125 insertion device beamline at the Metrology Light Source.

At the Metrology Light Source, an electron storage ring dedicated to metrological applications, the U125 insertion device beamline utilizes undulator radiation for various applications over a broad spectral range. Using a hybrid normal-incidence and grazing-incidence in-vacuum switchable plane-grating monochromator, a spectral region ranging from the near-infrared to soft X-ray is covered. The beamline is dedicated to surface-analytical methods, e.

Optical properties of a Cr/4H-SiC photodetector in the spectral range from ultraviolet to extreme ultraviolet.

This work examines the electrical and radiometric characteristics of a photodiode based on a 4H-SiC semiconductor material with a semitransparent Cr Schottky barrier of about 7 nm thickness. The device had a photosensitive area 10 mm in diameter. The spectral responsivity was determined in the wavelength range from 40 nm to 400 nm, thus particularly extending the characterization into the vacuum- and extreme ultraviolet spectral ranges.

Uncertainty analysis for the determination of BC optical constants by angle-dependent reflectance measurement for 40 nm to 80 nm wavelength.

The index of refraction and the extinction coefficient for thin films of boron carbide were determined by angle-dependent reflectance measurements in the vacuum-ultraviolet spectral range. The numerical approximation was done using transfer-matrix formalism in combination with particle swarm optimization for the fitting algorithm. By this, not only for the reflectance measurement but also for the numerical approximation, a profound uncertainty budget was developed.

Irradiation-induced degradation of PTB7 investigated by valence band and S 2p photoelectron spectroscopy.

Monochromatic radiation with known absolute radiant power from an undulator at the electron storage ring Metrology Light Source (MLS) was used to irradiate PTB7 (a thieno[3, 4-b]thiophene-alt-benzodithiophene polymer) thin films at wavelengths (photon energies) of 185 nm (6.70 eV), 220 nm (5.64 eV), 300 nm (4.

Polarization-dependent vacuum-ultraviolet reflectometry using elliptically polarized synchrotron radiation.

In the laboratory of the Physikalisch-Technische Bundesanstalt (PTB) at the Berlin electron-storage ring BESSY II, a procedure has been developed to investigate the dependence of vacuum-ultraviolet reflection on polarization. It is based on characterizing the elliptically polarized synchrotron radiation at PTB's normal-incidence monochromator beamline for reflectometry by means of polarization-sensitive photodetectors. For this purpose, the polarization dependency in the detector responsivity was determined at a small, low, solid angle of acceptance for the synchrotron radiation, i.

Absolute measurement of F2-laser power at 157 nm.

We report a comparison of laser power measurements at the F2-laser wavelength of 157 nm made at two facilities of the Physikalisch-Technische Bundesanstalt (PTB), the German national metrology institute. At the PTB laboratory at the electron storage ring BESSY II in Berlin, the scale for laser power was directly traced to a cryogenic radiometer operating at 157 nm, whereas at the PTB laser radiometry facility in Braunschweig the calibration of transfer detectors was performed with a newly developed standard for laser power at 157 nm, which is traceable in several steps to a cryogenic radiometer operating at 633 nm. The comparison was performed under vacuum conditions with laser pulse energies of approximately 10 microJ, however with different average powers because different primary standard radiometers were used.

Metrology of pulsed radiation for 157-nm lithography.

In the framework of current development in 157-nm lithography we have investigated the performance of photodetectors with emphasis to their stability and linearity. The measurements were performed in the radiometry laboratories of the Physikalisch-Technische Bundesanstalt at the Berlin electron-storage rings BESSY I and BESSY II with spectrally dispersed synchrotron radiation as well as with highly pulsed F2 laser radiation at 157 nm in combination with a cryogenic radiometer as the primary detector standard. Relative standard uncertainties of as little as 1% were achieved for the calibration of photodetectors in the spectral range of ultraviolet and vacuum-ultraviolet radiation.