Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F430 and P450nor co-factors, with their reduced NiI - and FeIII -containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature. The interpretation of the measurements is far from being straightforward due to the high reactivity of the different nitrogen oxides species (eventually present in the residual gas background) and of the possible reaction intermediates. The picture is detailed in order to disentangle the challenging complexity of the system, where even a small fraction of contamination can change the scenario.

Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F430 and P450nor co-factors, with their reduced NiI- and FeIII-containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature. The interpretation of the measurements is far from being straightforward due to the high reactivity of the different nitrogen oxides species (eventually present in the residual gas background) and of the possible reaction intermediates. The picture is detailed in order to disentangle the challenging complexity of the system, where even a small fraction of contamination can change the scenario.

Room-Temperature On-Spin-Switching and Tuning in a Porphyrin-Based Multifunctional Interface.

Molecular interfaces formed between metals and molecular compounds offer a great potential as building blocks for future opto-electronics and spintronics devices. Here, a combined theoretical and experimental spectro-microscopy approach is used to show that the charge transfer occurring at the interface between nickel tetraphenyl porphyrins and copper changes both spin and oxidation states of the Ni ion from [Ni(II), S = 0] to [Ni(I), S = 1/2]. The chemically active Ni(I), even in a buried multilayer system, can be functionalized with nitrogen dioxide, allowing a selective tuning of the electronic properties of the Ni center that is switched to a [Ni(II), S = 1] state. While Ni acts as a reversible spin switch, it is found that the electronic structure of the macrocycle backbone, where the frontier orbitals are mainly localized, remains unaffected. These findings pave the way for using the present porphyrin-based system as a platform for the realization of multifunctional devices where the magnetism and the optical/transport properties can be controlled simultaneously by independent stimuli.

Extremely low-energy ARPES of quantum well states in cubic-GaN/AlN and GaAs/AlGaAs heterostructures.

Quantum well (QW) heterostructures have been extensively used for the realization of a wide range of optical and electronic devices. Exploiting their potential for further improvement and development requires a fundamental understanding of their electronic structure. So far, the most commonly used experimental techniques for this purpose have been all-optical spectroscopy methods that, however, are generally averaging in momentum space. Additional information can be gained by angle-resolved photoelectron spectroscopy (ARPES), which measures the electronic structure with momentum resolution. Here we report on the use of extremely low-energy ARPES (photon energy ~ 7 eV) to increase depth sensitivity and access buried QW states, located at 3 nm and 6 nm below the surface of cubic-GaN/AlN and GaAs/AlGaAs heterostructures, respectively. We find that the QW states in cubic-GaN/AlN can indeed be observed, but not their energy dispersion, because of the high surface roughness. The GaAs/AlGaAs QW states, on the other hand, are buried too deep to be detected by extremely low-energy ARPES. Since the sample surface is much flatter, the ARPES spectra of the GaAs/AlGaAs show distinct features in momentum space, which can be reconducted to the band structure of the topmost surface layer of the QW structure. Our results provide important information about the samples' properties required to perform extremely low-energy ARPES experiments on electronic states buried in semiconductor heterostructures.

Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO2 Exposure.

Due to its unique magnetic properties offered by the open-shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d-states of FePc and the sp-band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The FeII ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO2 dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO2 at room temperature.

A scanning reflection X-ray microscope for magnetic imaging in the EUV range.

The mechanical setup of a novel scanning reflection X-ray microscope is presented. It is based on zone plate optics optimized for reflection mode in the EUV spectral range. The microscope can operate at synchrotron radiation beamlines as well as at laboratory-based plasma light sources. In contrast to established X-ray transmission microscopes that use thin foil samples, the new microscope design presented here allows the investigation of any type of bulk materials. Importantly, this permits the investigation of magnetic materials by employing experimental techniques based on X-ray magnetic circular dichroism, X-ray linear magnetic dichroism or the transversal magneto-optical Kerr effect (T-MOKE). The reliable functionality of the new microscope design has been demonstrated by T-MOKE microscopy spectra of Fe/Cr-wedge/Fe trilayer samples. The spectra were recorded at various photon energies across the Fe 3p edge revealing the orientation of magnetic domains in the sample.

Fast and easy fabrication methodology of Fresnel zone plates for the extreme ultraviolet and soft x-ray regions.

Zone plate design and efficient methods for the fabrication of zone plates for extreme ultraviolet (EUV) and soft x-ray applications in a newly developed scanning reflection microscope are presented. Based on e-beam lithography, three types of transmission zone plates with focal lengths between 6 and 15 mm are reported: (i) phase-shifting zone plates made by 190 nm thick PMMA rings on Si3N4 membranes, (ii) absorbing zone plates made by 75 nm thick Au ring structures on Si3N4, and (iii) freestanding Au rings of 50 nm thickness and increased transmission in the EUV range. Experiments at the DELTA synchrotron facility reveal a minimum spot size and resulting spatial resolution of 9±3 µm, which is the theoretical limit resulting from the synchrotron beam parameters at 60 eV photon energy. Images of a Ti/Si chessboard test pattern are recorded exploiting the energy dependence of the element-specific reflectance.

Publisher Correction: Multi-orbital charge transfer at highly oriented organic/metal interfaces.

The original version of this Article contained an error in the spelling of the author Claus Michael Schneider, which was incorrectly given as Claus Michael Schneidery. This has now been corrected in both the PDF and HTML versions of the Article.

Multi-orbital charge transfer at highly oriented organic/metal interfaces.

The molecule-substrate interaction plays a key role in charge injection organic-based devices. Charge transfer at molecule-metal interfaces strongly affects the overall physical and magnetic properties of the system, and ultimately the device performance. Here, we report theoretical and experimental evidence of a pronounced charge transfer involving nickel tetraphenyl porphyrin molecules adsorbed on Cu(100). The exceptional charge transfer leads to filling of the higher unoccupied orbitals up to LUMO+3. As a consequence of this strong interaction with the substrate, the porphyrin's macrocycle sits very close to the surface, forcing the phenyl ligands to bend upwards. Due to this adsorption configuration, scanning tunneling microscopy cannot reliably probe the states related to the macrocycle. We demonstrate that photoemission tomography can instead access the Ni-TPP macrocycle electronic states and determine the reordering and filling of the LUMOs upon adsorption, thereby confirming the remarkable charge transfer predicted by density functional theory calculations.Charge transfer at molecule-metal interfaces affects the overall physical and magnetic properties of organic-based devices, and ultimately their performance. Here, the authors report evidence of a pronounced charge transfer involving nickel tetraphenyl porphyrin molecules adsorbed on copper.

Spatial coherence determination from the Fourier analysis of a resonant soft X-ray magnetic speckle pattern.

We present a method to determine the two-dimensional spatial coherence of synchrotron radiation in the soft X-ray regime by analyzing the Fourier transform of the magnetic speckle pattern from a ferromagnetic film in a multidomain state. To corroborate the results, a Young's double-pinhole experiment has been performed. The transverse coherence lengths in vertical and horizontal direction of both approaches are in a good agreement. The method presented here is simple and gives a direct access to the coherence properties of synchrotron radiation without nanostructured test objects.

Quantifying redox-induced Schottky barrier variations in memristive devices via in operando spectromicroscopy with graphene electrodes.

The continuing revolutionary success of mobile computing and smart devices calls for the development of novel, cost- and energy-efficient memories. Resistive switching is attractive because of, inter alia, increased switching speed and device density. On electrical stimulus, complex nanoscale redox processes are suspected to induce a resistance change in memristive devices. Quantitative information about these processes, which has been experimentally inaccessible so far, is essential for further advances. Here we use in operando spectromicroscopy to verify that redox reactions drive the resistance change. A remarkable agreement between experimental quantification of the redox state and device simulation reveals that changes in donor concentration by a factor of 2-3 at electrode-oxide interfaces cause a modulation of the effective Schottky barrier and lead to >2 orders of magnitude change in device resistance. These findings allow realistic device simulations, opening a route to less empirical and more predictive design of future memory cells.

Bulk mixed ion electron conduction in amorphous gallium oxide causes memristive behaviour.

In thin films of mixed ionic electronic conductors sandwiched by two ion-blocking electrodes, the homogeneous migration of ions and their polarization will modify the electronic carrier distribution across the conductor, thereby enabling homogeneous resistive switching. Here we report non-filamentary memristive switching based on the bulk oxide ion conductivity of amorphous GaOx (x~1.1) thin films. We directly observe reversible enrichment and depletion of oxygen ions at the blocking electrodes responding to the bias polarity by using photoemission and transmission electron microscopies, thus proving that oxygen ion mobility at room temperature causes memristive behaviour. The shape of the hysteresis I-V curves is tunable by the bias history, ranging from narrow counter figure-eight loops to wide hysteresis, triangle loops as found in the mathematically derived memristor model. This dynamical behaviour can be attributed to the coupled ion drift and diffusion motion and the oxygen concentration profile acting as a state function of the memristor.