Gating the charge state of a single molecule by local electric fields

The electron acceptor molecule TCNQ is found in either of two distinct integer charge states when embedded into a monolayer of a charge transfer-complex on a gold surface. Scanning tun- neling spectroscopy measurements identify these states through the presence/absence of a zero-bias Kondo resonance. Increasing the (tip-induced) electric field allows us to reversibly induce the ox- idation/reduction of TCNQ species from their anionic or neutral ground state, respectively. We show that the different ground states arise from slight variations in the underlying surface potential, pictured here as the gate of a three-terminal device.Comment: 5 pages, 4 figure

Rubidium Fluoride Post-Deposition Treatment: Impact on the Chemical Structure of the Cu(In,Ga)Se2 Surface and CdS/Cu(In,Ga)Se2 Interface in Thin-Film Solar Cells.

We present a detailed characterization of the chemical structure of the Cu(In,Ga)Se2 thin-film surface and the CdS/Cu(In,Ga)Se2 interface, both with and without a RbF post-deposition treatment (RbF-PDT). For this purpose, X-ray photoelectron and Auger electron spectroscopy, as well as synchrotron-based soft X-ray emission spectroscopy have been employed. Although some similarities with the reported impacts of light-element alkali PDT (i.e., NaF- and KF-PDT) are found, we observe some distinct differences, which might be the reason for the further improved conversion efficiency with heavy-element alkali PDT. In particular, we find that the RbF-PDT reduces, but not fully removes, the copper content at the absorber surface and does not induce a significant change in the Ga/(Ga + In) ratio. Additionally, we observe an increased amount of indium and gallium oxides at the surface of the treated absorber. These oxides are partly (in the case of indium) and completely (in the case of gallium) removed from the CdS/Cu(In,Ga)Se2 interface by the chemical bath deposition of the CdS buffer

X-SPEC: a 70 eV to 15 keV undulator beamline for X-ray and electron spectroscopies

X-SPEC is a high-flux spectroscopy beamline at the KIT (Karlsruhe Institute of Technology) Synchrotron for electron and X-ray spectroscopy featuring a wide photon energy range. The beamline is equipped with a permanent magnet undulator with two magnetic structures of different period lengths, a focusing variable-line-space plane-grating monochromator, a double-crystal monochromator and three Kirkpatrick–Baez mirror pairs. By selectively moving these elements in or out of the beam, X-SPEC is capable of covering an energy range from 70 eV up to 15 keV. The flux of the beamline is maximized by optimizing the magnetic design of the undulator, minimizing the number of optical elements and optimizing their parameters. The beam can be focused into two experimental stations while maintaining the same spot position throughout the entire energy range. The first experimental station is optimized for measuring solid samples under ultra-high-vacuum conditions, while the second experimental station allows in situ and operando studies under ambient conditions. Measurement techniques include X-ray absorption spectroscopy (XAS), extended X-ray absorption fine structure (EXAFS), photoelectron spectroscopy (PES) and hard X-ray PES (HAXPES), as well as X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS)

X‐SPEC: a 70 eV to 15 keV undulator beamline for X‐ray and electron spectroscopies

X‐SPEC is a high‐flux spectroscopy beamline at the KIT (Karlsruhe Institute of Technology) Synchrotron for electron and X‐ray spectroscopy featuring a wide photon energy range. The beamline is equipped with a permanent magnet undulator with two magnetic structures of different period lengths, a focusing variable‐line‐space plane‐grating monochromator, a double‐crystal monochromator and three Kirkpatrick–Baez mirror pairs. By selectively moving these elements in or out of the beam, X‐SPEC is capable of covering an energy range from 70 eV up to 15 keV. The flux of the beamline is maximized by optimizing the magnetic design of the undulator, minimizing the number of optical elements and optimizing their parameters. The beam can be focused into two experimental stations while maintaining the same spot position throughout the entire energy range. The first experimental station is optimized for measuring solid samples under ultra‐high‐vacuum conditions, while the second experimental station allows in situ and operando studies under ambient conditions. Measurement techniques include X‐ray absorption spectroscopy (XAS), extended X‐ray absorption fine structure (EXAFS), photoelectron spectroscopy (PES) and hard X‐ray PES (HAXPES), as well as X‐ray emission spectroscopy (XES) and resonant inelastic X‐ray scattering (RIXS).X‐SPEC is a high‐flux undulator beamline for electron and X‐ray spectroscopy with an energy range from 70 eV to 15 keV. It offers X‐ray absorption spectroscopy (XAS), extended X‐ray absorption fine structure (EXAFS), photoelectron spectroscopy (PES) and hard X‐ray PES (HAXPES), as well as X‐ray emission spectroscopy (XES) and resonant inelastic X‐ray scattering (RIXS) for in vacuo, in situ and operando sample environments. imag

Direct Observation of Reactant, Intermediate, and Product Species for Nitrogen Oxide-Selective Catalytic Reduction on Cu-SSZ-13 Using <i>In Situ</i> Soft X‑ray Spectroscopy

Catalytic processes have supported the development of myriad beneficial technologies, yet our fundamental understanding of the complex interactions between reaction intermediates and catalyst surfaces is still largely undefined for many reactions. Experimental analyses have generally been limited to investigation of catalyst materials or a subset of functional groups as indirect probes of the critical surface-bound intermediate species and reaction mechanisms. A more direct approach is to probe the intermediate species themselves, but this requires direct study of the local chemical environment of light elements. In this work, we use soft X-ray emission spectroscopy (XES) and a custom-designed in situ reactor cell to directly observe and characterize the electronic structure of reactant, intermediate, and product species under reaction conditions. Specifically, we employ N K XES to probe the interaction of various nitrogen species with a Cu-SSZ-13 catalyst during selective catalytic reduction of nitrogen oxides (NO and NO2) by ammonia (NH3-SCR), a reaction that is critical for the removal of NOx pollutants formed in combustion reactions. This work reveals a novel spectral feature for all spectra measured with flowing NO gas present, which we attribute to the interaction of NO with the catalyst. We find that introducing both NO and O2 gases (compared to only NO) increases the interaction of NO with Cu-SSZ-13. Adsorption of NH3 leads to a more pronounced spectral signal compared to NO adsorption. For the standard NH3-SCR reaction, we observe a strong N2 signal, comprising 30% of the total spectral intensity. These results demonstrate the vast potential of this technique to provide direct, novel insights into the complex interactions between reaction intermediates and the active sites of catalysts, which may guide advanced knowledge-based optimization of these processes

Formation of a KInSe Surface Species by NaF/KF Postdeposition Treatment of Cu(In,Ga)Se₂ Thin-Film Solar Cell Absorbers

A NaF/KF postdeposition treatment (PDT) has recently been employed to achieve new record efficiencies of Cu­(In,Ga)­Se₂ (CIGSe) thin film solar cells. We have used a combination of depth-dependent soft and hard X-ray photoelectron spectroscopy as well as soft X-ray absorption and emission spectroscopy to gain detailed insight into the chemical structure of the CIGSe surface and how it is changed by different PDTs. Alkali-free CIGSe, NaF-PDT CIGSe, and NaF/KF-PDT CIGSe absorbers grown by low-temperature coevaporation have been interrogated. We find that the alkali-free and NaF-PDT CIGSe surfaces both display the well-known Cu-poor CIGSe chemical surface structure. The NaF/KF-PDT, however, leads to the formation of bilayer structure in which a KInSe species covers the CIGSe compound that in composition is identical to the chalcopyrite structure of the alkali-free and NaF-PDT absorber