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.

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.

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.

The surface hydro-oxidation of LaNiO(3-delta) thin films.

The chemical structure and possible hydro-oxidation of LaNiO(3-delta) films were studied by means of tuneable high-energy X-ray photoelectron spectroscopy using synchrotron radiation. It was shown that the hydroxyl-containing phase, located near the film surface, may be attributed to the lanthanum and nickel hydroxide species. The thickness of a hydroxide-enriched layer was estimated from the oxide/hydroxide ratio measured at normal and grazing conditions. The hydroxide layer thickness was about 2 nm for step and/or exponential hydroxide spatial distribution.

Electronic structure of Pd nanoparticles on carbon nanotubes.

The effect of the oxygen plasma treatment on the electronic states of multi-wall carbon nanotubes (MWCNTs) is analyzed by X-ray photoemission measurements (XPS) and UPS, both using synchrotron radiation. It is found that the plasma treatment effectively grafts oxygen at the CNT-surface. Thereafter, the interaction between evaporated Pd and pristine or oxygen plasma-treated MWCNTs is investigated. Pd is found to nucleate at defective sites, whether initially present or introduced by oxygen plasma treatment. The plasma treatment induced a uniform dispersion of Pd clusters at the CNT-surface. The absence of additional features in the Pd 3d and C 1s core levels spectra testifies that no Pd-C bond is formed. The shift of the Pd 3d core level towards high-binding energy for the smallest clusters is attributed to the Coulomb energy of the charged final state.

X-ray diffraction study of the ultrathin Al2O3 layer on NiAl110.

Ultrathin Al2O3 layers on alloys are used as templates for model catalysts, tunneling barriers in electronic devices, or corrosion-resistant layers. The complex atomic structure of well-ordered alumina overlayers on NiAl110 was solved by surface x-ray diffraction. The oxide layer is composed of a double layer of strongly distorted hexagonal oxygen ions that hosts aluminum ions on both octahedral and tetrahedral sites with equal probability. The alumina overlayer exhibits a domain structure that can be related to characteristic growth defects and is generated during the growth of a hexagonally ordered overlayer (Al2O3) on a body-centered cubic (110) substrate (NiAl).

Quadrupolar transitions evidenced by resonant auger spectroscopy.

From absorption spectra, the only way to bring to the fore the occurrence of quadrupolar transitions is to study their angular dependence. Resonant spectroscopies offer a new opportunity to obtain more insight into excited electronic states by studying lineshape and intensity of decay processes. We show here that resonantly excited Ti KL(2,3)L(2,3) Auger spectra of TiO2(110) carry a clear signature of quadrupolar transitions to localized e(g) and t(2g) d-like states, giving access to a direct measurement of crystal field splitting.

Backscattering X-ray standing waves in the XUV region.

It is demonstrated that Bragg reflection of XUV radiation can be used to study structural properties of crystalline materials with large unit cells. A standing-wave field is formed in a layered TiSe2 single crystal for a near-backscattering geometry (theta = 88.5 degrees). The partial electron yield is measured as a function of photon energy across the (001) Bragg reflection condition (hv approximately equal to 1033 eV) and its characteristic modulation is compared with the results derived from dynamical diffraction theory in the two-wave approximation. The data reveal a large amount of disorder along the c-axis.