A versatile setup for nanosecond laser polishing processes with in situ analysis capabilities.

Laser polishing of material surfaces is a complex process depending on many variable parameters, such as, e.g., the properties of the used laser and optics (wavelength, pulse duration, fluence, and profile), as well as the processing (spot size, feed rate, and line or point overlap), and the thermodynamical properties of the material to be polished (heat capacity, heat conduction, etc.). For the successful laser polishing of any material, a systematic variation of all the process parameters is required to obtain satisfactorily polished surfaces with an appropriate set of parameters for the material of interest. In order to allow systematic studies of laser polishing processes, a new setup employing a highly stable nanosecond laser with an adjustable wavelength has been realized. The sample is located in a small high-vacuum chamber with the capability of introducing additional gases in a controlled manner, and the entire chamber is scanned in the beam to allow laser polishing of selected spots, lines, or larger areas. The setup is fully remote-controlled and allows in situ inspection of the initiated processes by means of a long-range microscope, electrical measurements, reflected laser light from the sample surface, and an analysis of the vacuum within the process chamber. The main properties of the setup will be presented, and some exemplary results on niobium and molybdenum metal samples will be discussed.

Advanced field emission measurement techniques for research on modern cold cathode materials and their applications for transmission-type x-ray sources.

We report on the functional capabilities of our field emission (FE) measurement systems. The samples are prepared and inserted under clean room conditions and can be precisely xyz-positioned, heat-treated, and investigated in different vacuum environments and temperatures. The FE scanning microscope is a unique microscope being used for the localization of FE sites with high lateral resolution by means of extraction voltage U(x, y) or emission current I(x, y) maps over the cathode area of 25 × 25 mm2 and measuring the FE properties of localized emission sites or individual emitters. In contrast, the integral measurement system with the luminescent screen provides real-time integral information about the distribution of emission sites over the whole cathode during long- and short-term current stability measurements, thus allowing us to investigate the properties of various materials and their applications. Commissioning results with the upgraded systems using a silicon emitter array and a point-type graphene emitter will be given to demonstrate that both FE measurement techniques are very useful for an improved understanding and tailoring of materials for applications. The results showed that point-type graphene emitters are more preferable for practical applications. Using simulation software, a suitable triode configuration for point emitters was designed, and a current transmission ratio of ∼100% was obtained. The FE current stability of graphene emitters at pressures >10-3 Pa can be improved by heating the cathode at 100 °C-300 °C for 1 min-30 min. Finally, point-type graphene film emitters were used for transmission-type x-ray sources, and their applications in imaging and fluorescence spectroscopy are presented.

Quick scanning monochromator for millisecond in situ and in operando X-ray absorption spectroscopy.

The design and capabilities of a novel Quick scanning Extended X-ray Absorption Fine Structure (QEXAFS) monochromator are presented. The oscillatory movement of the crystal stage is realized by means of a unique open-loop driving scheme operating a direct drive torque motor. The entire drive mechanics are installed inside of a goniometer located on the atmospheric side of the vacuum chamber. This design allows remote adjustment of the oscillation frequency and spectral range, giving complete control of QEXAFS measurements. It also features a real step-scanning mode, which operates without a control loop to prevent induced vibrations. Equipped with Si(111) and Si(311) crystals on a single stage, it facilitates an energy range from 4.0 keV to 43 keV. Extended X-ray absorption fine structure spectra up to k = 14.4 Å(-1) have been acquired within 17 ms and X-ray absorption near edge structure spectra covering more than 200 eV within 10 ms. The achieved data quality is excellent as shown by the presented measurements.

Sensitive fast electron spectrometer in adjustable triode configuration with pulsed tunable laser for research on photo-induced field emission cathodes.

We have completed an ultra-high vacuum system for sensitive fast electron spectroscopy from cold cathodes in triode configuration under high electric fields E (<100 MV/m) and pulsed tunable laser illumination (3.5 ns, 10 Hz, hν = 0.5-5.9 eV, and 0.3-17 mJ). The cathodes are prepared and inserted under clean room conditions and can be precisely 3D-positioned, cooled or heated (77-400 K). Commissioning results with the upgraded system are presented. Field emission measurements with a W tip yielded an energy resolution of 14 meV at 4 eV pass energy and a precise determination of the emitter work function, size, and temperature. Photoemission spectroscopy of short electron bunches from a virgin and laser-ablated S-GaP crystal and quantum efficiency measurements revealed surface states, energy relaxation, and band structure effects. In conclusion, this novel system is ready now for the development and characterization of photo-induced field emission cathodes.

Hard disk drive based microsecond X-ray chopper for characterization of ionization chambers and photodiodes.

A fast X-ray chopper capable of producing ms long X-ray pulses with a typical rise time of few µs was realized. It is ideally suited to investigate the temporal response of X-ray detectors with response times of the order of µs to ms, in particular, any kind of ionization chambers and large area photo diodes. The drive mechanism consists of a brushless DC motor and driver electronics from a common hard disk drive, keeping the cost at an absolute minimum. Due to its simple construction and small dimensions, this chopper operates at home lab based X-ray tubes and synchrotron radiation sources as well. The dynamics of the most important detectors used in time resolved X-ray absorption spectroscopy, namely, ionization chambers and Passivated Implanted Planar Silicon photodiodes, were investigated in detail. The results emphasize the applicability of this X-ray chopper.

Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study.

Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or L-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5(+) species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.

The multi-purpose hard X-ray beamline BL10 at the DELTA storage ring.

The layout and the characteristics of the hard X-ray beamline BL10 at the superconducting asymmetric wiggler at the 1.5 GeV Dortmund Electron Accelerator DELTA are described. This beamline is equipped with a Si(111) channel-cut monochromator and is dedicated to X-ray studies in the spectral range from ∼4 keV to ∼16 keV photon energy. There are two different endstations available. While X-ray absorption studies in different detection modes (transmission, fluorescence, reflectivity) can be performed on a designated table, a six-axis kappa diffractometer is installed for X-ray scattering and reflectivity experiments. Different detector set-ups are integrated into the beamline control software, i.e. gas-filled ionization chambers, different photodiodes, as well as a Pilatus 2D-detector are permanently available. The performance of the beamline is illustrated by high-quality X-ray absorption spectra from several reference compounds. First applications include temperature-dependent EXAFS experiments from liquid-nitrogen temperature in a bath cryostat up to ∼660 K by using a dedicated furnace. Besides transmission measurements, fluorescence detection for dilute sample systems as well as surface-sensitive reflection-mode experiments are presented.

New developments for the investigation of hard X-rays emitted by peeling adhesive tapes.

We realized an advanced apparatus for the investigation of emitted X-rays produced by peeling adhesive tape rolls under vacuum conditions. Two stepper motors can unwind and rewind a tape roll, and an additional roller with an optical encoder provides measurement and control of the tape speed. This way reproducible and consecutive experiments are feasible without having to change the tape or break the vacuum. The dependence of the X-ray emission on tape speed, gas pressure, type of adhesive tape, and detector angle has been investigated. The resulting spectra are continuous and span an X-ray energy range of typically 2-60 keV with high intensity. Furthermore, the new apparatus allows the in situ metalization of adhesive tape rolls by a gold sputter source. A significantly increased X-ray emission was observed for adhesive tapes with a metal coating. Thin metal foils have been placed between the tape and the detector, different K- and L-absorption edges could be measured. A considerable enhancement of the emission was achieved under the influence of the magnetic field of an NdFeB permanent magnet.

Electron spectrometer in adjustable triode configuration for photo-induced field emission measurements.

We have constructed a new ultrahigh vacuum apparatus with a triode configuration for the systematic investigation of photo-induced field emission (PFE) from metallic or semiconducting cathodes. These are exposed to electric fields up to 400 MV∕m and laser irradiation by means of hole or mesh gates. Cathodes and gates are in situ exchangeable and adjustable with high precision to ensure a homogeneous extraction of electrons which are partially transmitted to the fixed electron spectrometer. Its hemispherical sector analyzer provides an energy resolution limit of 8 meV. The commissioning of the measurement system has been performed with a tungsten needle. Its temperature showed up in the high-energy tail of the electron spectrum, while its work function was derived from the spectral low-energy part combined with the integral current-voltage curve. First PFE measurements on B-doped Si-tip arrays yielded a small field emission current increase under green laser illumination. A shift and splitting of the energy spectra was observed which revealed different emission regimes as well as the photosensitivity of the cathode due to carrier excitation into the conduction band. For the full exploitation of the PFE system, a tunable laser over a wide eV-range is required.

Structural properties of fluorozirconate-based glass ceramics doped with multivalent europium.

The structure/property relationships of fluorochlorozirconate glass ceramics as a function of divalent and trivalent europium (Eu) co-doping and thermal processing have been investigated; the influence of doping ratio on the formation of barium chloride (BaCl(2)) nanocrystals therein was elucidated. X-ray absorption near-edge structure spectroscopy shows that the post-thermal annealing changes the Eu valence of the as-poured glass slightly, but during the melting process Eu(3+) is more strongly reduced to Eu(2+), in particular, when doped as a chloride instead of fluoride compound. The Eu(2+)-to-Eu(3+) doping ratio also plays a significant role in chemical equilibrium in the melt. X-ray diffraction measurements indicate that a higher Eu(2+) fraction leads to a BaCl(2) phase transition from hexagonal to orthorhombic structure at a lower temperature.

A new flexible monochromator setup for quick scanning x-ray absorption spectroscopy.

A new monochromator setup for quick scanning x-ray absorption spectroscopy in the subsecond time regime is presented. Novel driving mechanics allow changing the energy range of the acquired spectra by remote control during data acquisition for the first time, thus dramatically increasing the flexibility and convenience of this method. Completely new experiments are feasible due to the fact that time resolution, edge energy, and energy range of the acquired spectra can be changed continuously within seconds without breaking the vacuum of the monochromator vessel and even without interrupting the measurements. The advanced mechanics are explained in detail and the performance is characterized with x-ray absorption spectra of pure metal foils. The energy scale was determined by a fast and accurate angular encoder system measuring the Bragg angle of the monochromator crystal with subarcsecond resolution. The Bragg angle range covered by the oscillating crystal can currently be changed from 0 degrees to 3.0 degrees within 20 s, while the mechanics are capable to move with frequencies of up to ca. 35 Hz, leading to ca. 14 ms/spectrum time resolution. A new software package allows performing programmed scan sequences, which enable the user to measure stepwise with alternating parameters in predefined time segments. Thus, e.g., switching between edges scanned with the same energy range is possible within one in situ experiment, while also the time resolution can be varied simultaneously. This progress makes the new system extremely user friendly and efficient to use for time resolved x-ray absorption spectroscopy at synchrotron radiation beamlines.

The electronic structure and ionic diffusion of nanoscale LiTiO2 anatase.

Upon lithium insertion in the pristine TiO2 anatase phase the theoretical maximum of LiTiO2 can be reached in crystallite sizes less than approximately 10 nm, whereas bulk compositions appear limited to Li(x) approximately 0.6TiO2 at room temperature. Both X-ray absorption spectroscopy (XAS) and ab initio calculations have been applied to probe the electronic structure of the newly formed LiTiO2 phase. These results indicate that a large majority of the Li-2s electrons reside at the Ti-3d(t2g)/4s hybridized site. About 10% of these electrons are transferred to non-localized states which makes this compound a good electronic conductor. Ionic conductivity is probed by nuclear magnetic resonance (NMR) relaxation experiments indicating relatively small hopping rates between the Li-ion sites in LiTiO2. Formation of the poor ionic-conducting LiTiO2 at the surface of the particles explains why micro-anatase Li(x)TiO2 is not able to reach the theoretical maximum capacity at room temperature, and why this theoretical maximum capacity reached in nano-sized materials cannot be (dis)charged at high rates.

Surface-sensitive reflection-mode EXAFS from layered sample systems: the influence of surface and interface roughness.

The calculation of reflection-mode grazing-incidence X-ray absorption spectra from single surfaces and (multi-)layered systems is studied here. In particular, the influence of the surface and interface roughness was investigated in detail. Simulations of grazing-incidence reflection-mode EXAFS spectra using a simple Fresnel theory neglecting any effect of roughness are compared with the Névot-Croce model and the elaborated distorted-wave Born approximation which both include surface and interface roughness. Data are presented for clean gold surfaces, where the strong influence of the surface roughness on the resulting spectra is demonstrated. Furthermore, in the case of layered systems, the influence of both the outer (air or vacuum side) surface roughness and the inner interface roughness on the reflection-mode EXAFS spectra is evaluated. The practical consequences of the observed correlations are discussed, and a quantitative data analysis of a copper sample that was oxidized in ambient air for several months is shown, including the evaluation of specular reflectivity profiles at fixed energy.

Novel angular encoder for a quick-extended x-ray absorption fine structure monochromator.

New concepts for time-resolved x-ray absorption spectroscopy using the quick-extended x-ray absorption fine structure (QEXAFS) method are presented. QEXAFS is a powerful tool to gain structural information about, e.g., fast chemical reactions or phase transitions on a subsecond scale. This can be achieved with a monochromator design that employs a channel-cut crystal on a cam driven tilt table for rapid angular oscillations of the Bragg angle. A new angular encoder system and a new data acquisition were described and characterized that were applied to a QEXAFS monochromator to get spectra with a directly measured accurate energy scale. New electronics were designed to allow a fast acquisition of the Bragg angle values and the absorption data during the measurements simultaneously.

A new cell for temperature-dependent X-ray absorption spectroscopy of liquid solutions: application to PbBr2 solutions in diethylene glycol.

An in situ cell has been constructed for temperature-dependent X-ray absorption experiments (EXAFS and XANES) of lead bromine (PbBr2) solutions in diethylene glycol in the temperature range from room temperature up to about 433 K. The solution is kept in a thermostated container made of carbon-reinforced teflon between two thin chemically inert quartz glass windows with a high transmission for hard X-rays. The construction of the cell ensures that these X-ray windows are thermalized so that any possible precipitation of solid products from the solution is inhibited. The cell consists mainly of two hermetically sealed teflon containers for the thermostating fluid (silicon oil) that were fitted together in such a way that a small and variable volume (approximately 2-4 cm3) for the liquid under investigation was achieved. A small thermocouple in a glass enclosure was placed in the solution to maintain temperature control and feedback to the thermostat. The cell design and its performance for temperature-dependent in situ investigations with X-rays are reported. Some preliminary results obtained for PbBr2 solutions in diethylene glycol are given.

Time-resolved study of the oxidation of ethanol by cerium(IV) using combined quick-XANES, UV-vis, and Raman spectroscopies.

Time-resolved X-ray absorption spectroscopy (Quick-XANES) has been combined with UV-vis and Raman spectroscopies to study the in situ reduction of Ce4+ to Ce3+ in ethanolic solution with a time resolution of ca. 4-5 s. For this purpose, a cam-driven oscillating double-crystal monochromator with a channel-cut crystal was combined with two spectrometers for UV-vis and Raman spectroscopies in a specialized cell which allows one to fit the optical pathways for all three spectroscopies individually. The results show that high-quality results can be obtained simultaneously, thus giving a detailed insight into the mechanisms of the investigated chemical reaction. The continuous release of nitrate and ethanol ligands from the initial Ce4+ into the solution finally leads to a trivalent cerium species which is only coordinated with water molecules after about 1800 s of reaction time.

Piezo-QEXAFS: advances in time-resolved X-ray absorption spectroscopy.

The Piezo-QEXAFS technique is a novel tool for time-resolved X-ray absorption spectroscopy in the hard X-ray range. Monochromator components consisting of specialized tilt stages to perform fast energy scans, lightweight crystal holders, bending mechanics, and control electronics are being installed and commissioned. It is planned to perform fast EXAFS scans with time resolution in the millisecond range. With Piezo-QEXAFS all typical X-ray absorption experiments will be possible as it retains the standard linear geometry. The achieved time resolution opens interesting insights into the dynamics of phase transitions and chemical reactions.

Reflection mode XAFS investigations of reactively sputtered thin films.

Amorphous Ta-oxide and Sn-nitride thin films were prepared by reactive sputter deposition on smooth float glass substrates and investigated ex situ using reflection mode XAFS. The absorption coefficient mu and its fine structure were extracted from the measured reflection mode XAFS spectra with a method based on the Kramers-Kronig transform. Bond distances, coordination numbers and Debye-Waller factors were determined by a detailed XAFS data analysis and compared to those of reference compounds. In addition, changes of the atomic short range order of the sputter deposited Ta2O5-films induced by a thermal heat treatment in ambient air were examined as a function of the annealing temperature.

XAFS investigations of tin nitrides.

Tin nitrides (Sn3N4) prepared by the reaction of Sn-halides with KNH2 in liquid ammonia and a subsequent vacuum annealing procedure were investigated with transmission mode XAFS experiments. While the near edge data suggest the presence of a univalent Sn-compound with a valency close to +4, the analysis of the extended X-ray absorption fine structure proves the presence of two different local Sn sites in this crystal structure: While Sn(1) is surrounded by 4 nitrogen in a distance of 2.06 A, each Sn(2) ion is coordinated with 6 nitrogen at about 2.17 A radial distance.