Layer-resolved electronic behavior in a Kondo lattice system, CeAgAs2.

We investigate the electronic structure of an antiferromagnetic Kondo lattice system CeAgAs2employing hardx-ray photoemission spectroscopy. CeAgAs2, an orthorhombic variant of HfCuSi2structure, exhibits antiferromagnetic ground state, Kondo like resistivity upturn and compensation of magnetic moments at low temperatures. The photoemission spectra obtained at different photon energies suggest termination of the cleaved surface at cis-trans-As layers. The depth-resolved data show significant surface-bulk differences in the As and Ce core level spectra. The As 2pbulk spectrum shows distinct two peaks corresponding to two different As layers. The peak at higher binding energy correspond to cis-trans-As layers and is weakly hybridized with the adjacent Ce layers. The As layers between Ce and Ag-layers possess close to trivalent configuration due to strong hybridization with the neighboring atoms and the corresponding feature appear at lower binding energy. Ce 3dcore level spectra show multiple features reflecting strong Ce-As hybridization and strong correlation. Intensef0peak is observed in the surface spectrum while it is insignificant in the bulk. In addition, we observe a features at binding energy lower than the well-screened feature indicating the presence of additional interactions. This feature becomes more intense in the bulk spectra suggesting it to be a bulk property. Increase in temperature leads to a spectral weight transfer to higher binding energies in the core level spectra and a depletion of spectral intensity at the Fermi level as expected in a Kondo material. These results reveal interesting surface-bulk differences, complex interplay of intra- and inter-layer covalency, and electron correlation in the electronic structure of this novel Kondo lattice system.

X-ray photoemission and absorption study of the pyrochlore iridates (Eu1-xBix)2Ir2O7, 0 ⩽x ⩽ 1.

The pyrochlore iridates (Eu1-xBix)2Ir2O7(0⩽x⩽1) undergo an anomalous negative lattice expansion for small Bi-doping (x⩽0.035) (region I) and a normal lattice expansion forx⩾0.1(region II); this is accompanied by a transition from an insulating (and magnetically ordered) to a metallic (and with no magnetic ordering) ground state. Here, we investigate (Eu1-xBix)2Ir2O7(0⩽x⩽1) using hard x-ray photoemission spectroscopy and x-ray absorption fine structure (XAFS) spectroscopy. By analyzing the Eu-L3, Ir-L3and Bi-L2&L3edges x-ray absorption near edge structure spectra and Eu-3dcore-level XPS spectra, we show that the metal cations retain their nominal valence, namely, Ir4+, Bi3+and Eu3+, respectively, throughout the series. The Ir-4fand Bi-4fcore-level XPS spectra consist of screened and unscreened doublets. The unscreened component is dominant In the insulating range (x⩽0.035), and in the metallic region (x⩾0.1), the screened component dominates the spectra. The Eu-3dcore-level spectra remain invariant under Bi doping. The extended XAFS data show that the coordination around the Ir remains well preserved throughout the series. The evolution of the valence band spectra near the Fermi energy with increasing Bi doping indicates the presence of strong Ir(5d)-Bi(6p) hybridization which drives the metal-to-insulator transition.

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.

Antiferromagnetic Correlations in Strongly Valence Fluctuating CeIrSn.

CeIrSn with a quasikagome Ce lattice in the hexagonal basal plane is a strongly valence fluctuating compound, as we confirm by hard x-ray photoelectron spectroscopy and inelastic neutron scattering, with a high Kondo temperature of T_{K}∼480 K. We report a negative in-plane thermal expansion α/T below 2 K, which passes through a broad minimum near 0.75 K. Volume and a-axis magnetostriction for B∥a are markedly negative at low fields and change sign before a sharp metamagnetic anomaly at 6 T. These behaviors are unexpected for Ce-based intermediate valence systems, which should feature positive expansivity. Rather they point towards antiferromagnetic correlations at very low temperatures. This is supported by muon spin relaxation measurements down to 0.1 K, which provide microscopic evidence for a broad distribution of internal magnetic fields. Comparison with isostructural CeRhSn suggests that these antiferromagnetic correlations emerging at T≪T_{K} result from geometrical frustration.

Temperature-dependent change of the electronic structure in the Kondo lattice system YbRh2Si2.

The heavy-fermion behavior in intermetallic compounds manifests itself in a quenching of local magnetic moments by developing Kondo spin-singlet many-body states combined with a drastic increase of the effective mass of conduction electrons, which occurs below the lattice Kondo temperatureTK. This behavior is caused by interactions between the strongly localized 4felectrons and itinerant electrons. A controversially discussed question in this context is how the localized electronic states contribute to the Fermi surface upon changing the temperature. One expects that hybridization between the local moments and the itinerant electrons leads to a transition from a small Fermi surface in a non-coherent regime at high temperatures to a large Fermi surface once the coherent Kondo lattice regime is realized belowTK. We demonstrate, using hard x-ray angle-resolved photoemission spectroscopy that the electronic structure of the prototypical heavy fermion compound YbRh2Si2changes with temperature between 100 and 200 K, i.e. far above the Kondo temperature,TK= 25 K, of this system. Our results suggest a transition from a small to a large Fermi surface with decreasing temperature. This result is inconsistent with the prediction of the dynamical mean-field periodic Anderson model and supports the idea of an independent energy scale governing the change of band dispersion.

3D Porous Polymeric-Foam-Supported Pd Nanocrystal as a Highly Efficient and Recyclable Catalyst for Organic Transformations.

The efficient recovery of noble metal nanocrystals used in heterogeneous organic transformations has remained a significant challenge, hindering their use in industry. Herein, highly catalytic Pd nanoparticles (NPs) were first prepared having a yield of >98% by a novel hydrothermal method using PVP as the reducing cum stabilizing agent that exhibited excellent turnover frequencies of ∼38,000 h-1 for Suzuki-Miyaura cross-coupling and ∼1200 h-1 for catalytic reduction of nitroarene compounds in a benign aqueous reaction medium. The Pd NPs were more efficient for cross-coupling of aryl compounds with electron-donating substituents than with electron-donating ones. Further, to improve their recyclability, a strategy was developed to embed these Pd NPs on mechanically robust polyurethane foam (PUF) for the first time and a "dip-catalyst" (Pd-PUF) containing 3D interconnected 100-500 µm pores was constructed. The PUF was chosen as the support with an expectation to reduce the fabrication cost of the "dip-catalyst" as the production of PUF is already commercialized. Pd-PUF could be easily separated from the reaction aliquot and reused without any loss of activity because the leaching of Pd NPs was found to be negligible in the various reaction mixtures. We show that the Pd-PUF could be reused for over 50 catalytic cycles maintaining a similar activity. We further demonstrate a scale-up reaction with a single-reaction 1.5 g yield for the Suzuki-Miyaura cross-coupling reaction.

Néel Vector Induced Manipulation of Valence States in the Collinear Antiferromagnet Mn2Au.

The coupling of real and momentum space is utilized to tailor electronic properties of the collinear metallic antiferromagnet Mn2Au by aligning the real space Néel vector indicating the direction of the staggered magnetization. Pulsed magnetic fields of 60 T were used to orient the sublattice magnetizations of capped epitaxial Mn2Au(001) thin films perpendicular to the applied field direction by a spin-flop transition. The electronic structure and its corresponding changes were investigated by angular-resolved photoemission spectroscopy with photon energies in the vacuum-ultraviolet, soft, and hard X-ray range. The results reveal an energetic rearrangement of conduction electrons propagating perpendicular to the Néel vector. They confirm previous predictions on the origin of the Néel spin-orbit torque and anisotropic magnetoresistance in Mn2Au and reflect the combined antiferromagnetic and spin-orbit interaction in this compound leading to inversion symmetry breaking.

Progress in HAXPES performance combining full-field k-imaging with time-of-flight recording.

An alternative approach to hard-X-ray photoelectron spectroscopy (HAXPES) has been established. The instrumental key feature is an increase of the dimensionality of the recording scheme from 2D to 3D. A high-energy momentum microscope detects electrons with initial kinetic energies up to 8 keV with a k-resolution of 0.025 Å-1, equivalent to an angular resolution of 0.034°. A special objective lens with k-space acceptance up to 25 Å-1 allows for simultaneous full-field imaging of many Brillouin zones. Combined with time-of-flight (ToF) parallel energy recording this yields maximum parallelization. Thanks to the high brilliance (1013 hν s-1 in a spot of <20 µm diameter) of beamline P22 at PETRA III (Hamburg, Germany), the microscope set a benchmark in HAXPES recording speed, i.e. several million counts per second for core-level signals and one million for d-bands of transition metals. The concept of tomographic k-space mapping established using soft X-rays works equally well in the hard X-ray range. Sharp valence band k-patterns of Re, collected at an excitation energy of 6 keV, correspond to direct transitions to the 28th repeated Brillouin zone. Measured total energy resolutions (photon bandwidth plus ToF-resolution) are 62 meV and 180 meV FWHM at 5.977 keV for monochromator crystals Si(333) and Si(311) and 450 meV at 4.0 keV for Si(111). Hard X-ray photoelectron diffraction (hXPD) patterns with rich fine structure are recorded within minutes. The short photoelectron wavelength (10% of the interatomic distance) `amplifies' phase differences, making full-field hXPD a sensitive structural tool.

Self-immobilized Pd nanowires as an excellent platform for a continuous flow reactor: efficiency, stability and regeneration.

Despite extensive use of Pd nanocrystals as catalysts, the realization of a Pd-based continuous flow reactor remains a challenge. Difficulties arise due to ill-defined anchoring of the nanocrystals on a substrate and reactivity of the substrate under different reaction conditions. We demonstrate the first metal (Pd) nanowire-based catalytic flow reactor that can be used across different filtration platforms, wherein, reactants flow through a porous network of nanowires (10-1000 nm pore sizes) and the product can be collected as filtrate. Controlling the growth parameters and obtaining high aspect ratio of the nanowires (diameter = ∼13 nm and length > 8000 nm) is necessary for successful fabrication of this flow reactor. The reactor performance is similar to a conventional reactor, but without requiring energy-expensive mechanical stirring. Synchrotron-based EXAFS studies were used to examine the catalyst microstructure and Operando FT-IR spectroscopic studies were used to devise a regenerative strategy. We show that after prolonged use, the catalyst performance can be regenerated up to 99% by a simple wash-off process without disturbing the catalyst bed. Thus, collection, regeneration and redispersion processes of the catalyst in conventional industrial reactors can be avoided. Another important advantage is avoiding specific catalyst-anchoring substrates, which are not only expensive, but also non-universal in nature.

Interface Engineering to Create a Strong Spin Filter Contact to Silicon.

Integrating epitaxial and ferromagnetic Europium Oxide (EuO) directly on silicon is a perfect route to enrich silicon nanotechnology with spin filter functionality. To date, the inherent chemical reactivity between EuO and Si has prevented a heteroepitaxial integration without significant contaminations of the interface with Eu silicides and Si oxides. We present a solution to this long-standing problem by applying two complementary passivation techniques for the reactive EuO/Si interface: (i) an in situ hydrogen-Si (001) passivation and (ii) the application of oxygen-protective Eu monolayers-without using any additional buffer layers. By careful chemical depth profiling of the oxide-semiconductor interface via hard x-ray photoemission spectroscopy, we show how to systematically minimize both Eu silicide and Si oxide formation to the sub-monolayer regime-and how to ultimately interface-engineer chemically clean, heteroepitaxial and ferromagnetic EuO/Si (001) in order to create a strong spin filter contact to silicon.

Bulk sensitive hard x-ray photoemission electron microscopy.

Hard x-ray photoelectron spectroscopy (HAXPES) has now matured into a well-established technique as a bulk sensitive probe of the electronic structure due to the larger escape depth of the highly energetic electrons. In order to enable HAXPES studies with high lateral resolution, we have set up a dedicated energy-filtered hard x-ray photoemission electron microscope (HAXPEEM) working with electron kinetic energies up to 10 keV. It is based on the NanoESCA design and also preserves the performance of the instrument in the low and medium energy range. In this way, spectromicroscopy can be performed from threshold to hard x-ray photoemission. The high potential of the HAXPEEM approach for the investigation of buried layers and structures has been shown already on a layered and structured SrTiO3 sample. Here, we present results of experiments with test structures to elaborate the imaging and spectroscopic performance of the instrument and show the capabilities of the method to image bulk properties. Additionally, we introduce a method to determine the effective attenuation length of photoelectrons in a direct photoemission experiment.

Direct observation of half-metallicity in the Heusler compound Co2MnSi.

Ferromagnetic thin films of Heusler compounds are highly relevant for spintronic applications owing to their predicted half-metallicity, that is, 100% spin polarization at the Fermi energy. However, experimental evidence for this property is scarce. Here we investigate epitaxial thin films of the compound Co2MnSi in situ by ultraviolet-photoemission spectroscopy, taking advantage of a novel multi-channel spin filter. By this surface sensitive method, an exceptionally large spin polarization of (93(-11)(+7)) % at room temperature is observed directly. As a more bulk sensitive method, additional ex situ spin-integrated high energy X-ray photoemission spectroscopy experiments are performed. All experimental results are compared with advanced band structure and photoemission calculations which include surface effects. Excellent agreement is obtained with calculations, which show a highly spin polarized bulk-like surface resonance ingrained in a half metallic bulk band structure.

Bulk electronic structure of quasicrystals.

We use hard x-ray photoemission to resolve a controversial issue regarding the mechanism for the formation of quasicrystalline solids, i.e., the existence of a pseudogap at the Fermi level. Our data from icosahedral fivefold Al-Pd-Mn and Al-Cu-Fe quasicrystals demonstrate the presence of a pseudogap, which is not observed in surface sensitive low energy photoemission because the spectrum is affected by a metallic phase near the surface. In contrast to Al-Pd-Mn, we find that in Al-Cu-Fe the pseudogap is fully formed; i.e., the density of states reaches zero at E(F) indicating that it is close to the metal-insulator phase boundary.

Electronic structure changes across the metamagnetic transition in FeRh via hard X-ray photoemission.

Stoichiometric FeRh undergoes a temperature-induced antiferromagnetic (AFM) to ferromagnetic (FM) transition at ~350 K. In this Letter, changes in the electronic structure accompanying this transition are investigated in epitaxial FeRh thin films via bulk-sensitive valence-band and core-level hard x-ray photoelectron spectroscopy with a photon energy of 5.95 keV. Clear differences between the AFM and FM states are observed across the entire valence-band spectrum and these are well reproduced using density-functional theory. Changes in the 2p core levels of Fe are also observed and interpreted using Anderson impurity model calculations. These results indicate that significant electronic structure changes over the entire valence-band region are involved in this AFM-FM transition.

Photoemission electron microscopy as a tool for the investigation of optical near fields.

Photoemission electron microscopy was used to image the electrons photoemitted from specially tailored Ag nanoparticles deposited on a Si substrate (with its native oxide SiO(x)). Photoemission was induced by illumination with a Hg UV lamp (photon energy cutoff homega(UV) = 5.0 eV, wavelength lambda(UV) = 250 nm) and with a Ti:sapphire femtosecond laser (homega(l) = 3.1 eV, lambda(l) = 400 nm, pulse width below 200 fs), respectively. While homogeneous photoelectron emission from the metal is observed upon illumination at energies above the silver plasmon frequency, at lower photon energies the emission is localized at tips of the structure. This is interpreted as a signature of the local electrical field therefore providing a tool to map the optical near field with the resolution of emission electron microscopy.

Measurement of the electric field distribution and potentials on the object surface in an emission electron microscope without restriction of the electron beams.

An emission electron microscope without restriction of the electron beams was used to visualize and measure the distribution of electric fields and potentials on the surface under study. Investigations of this kind can be performed in an emission electron microscope without any aperture diaphragm. The potentialities of this method have been demonstrated using measurements with a silicon p-n junction to which a voltage has been applied in the reverse direction. The quantitative analysis becomes more complicated if the specimen is characterized by a heterogeneous intensity distribution of the electron emission from different areas of its surface. In the latter case two images obtained at different accelerating voltages (i.e. different voltages of the microscope extractor) provide the information necessary for an analysis of electric field and potential distributions.