Dirk Lützenkirchen-Hecht

Determination of secondary phases in kesterite Cu2ZnSnS4 thin films by x-ray absorption near edge structure analysis

Secondary phases in Cu2ZnSnS4 (CZTS) are investigated by x-ray absorption spectroscopy. Evaluating the x-ray absorption near edge structure at the sulfur K-edge, we show that secondary phases exhibit sufficiently distinct features to allow their quantitative determination with high accuracy. We are able to quantify the ZnS fraction with an absolute accuracy of ±3%, by applying linear combination analysis using reference spectra. We find that even in CZTS thin films with [Sn]/[Zn] ≈ 1, a significant amount of ZnS can be present. A strong correlation of the ZnS-content with the degradation of the electrical performance of solar cells is observed.

Mapping the chemical states of an element inside a sample using tomographic x-ray absorption spectroscopy

Hard x-ray absorption spectroscopy is combined with scanning microtomography to reconstruct full near-edge spectra of an elemental species at each location on an arbitrary virtual section through a sample. These spectra reveal the local concentrations of different chemical compounds of the absorbing element inside the sample and give insight into the oxidation state, the local atomic structure, and the local projected free density of states. The method is implemented by combining a quick scanning monochromator and data acquisition system with a scanning microprobe setup based on refractive x-ray lenses.

Investigation of Room Temperature Oxidation of Cu in Air by Yoneda‐XAFS

The structure of thin copper oxide layers which are formed on metallic Cu due to the exposure to air are investigated with Yoneda‐XAFS and ReflEXAFS. The measured Yoneda‐XAFS data were compared to quantitative model calculations in the framework of the distorted wave Born approximation (DWBA) assuming different model structures for the oxide layer. Yoneda‐XAFS fine structure spectra measured for various different grazing angles show that the experimental data are best described by a model structure consisting of a duplex type oxide layer with an outer layer of CuO (tenorite) in direct contact with the gas atmosphere and an inner Cu2O (cuprite) layer at the interface to the underlying Cu metal.

Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution

A new quick-scanning EXAFS (QEXAFS) monochromator, ionization chambers and data acquisition system have been developed and installed at the SuperXAS beamline at the Swiss Light Source to reach a temporal resolution of 10 ms.

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.

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.

Piezo-XAFS–time-resolved x-ray absorption spectroscopy

The piezo-x-ray absorption spectroscopy technique is a novel tool for time-resolved x-ray absorption spectroscopy in the hard x-ray range. It makes use of piezo tilt tables mounted below the crystals in a double crystal or channel cut crystal monochromator. Repetitive energy scans are performed by applying an oscillatory high voltage to the piezo translators of the tilt tables. Currently, this allows one to scan an energy range of several hundred eV in the hard x-ray range with repetition frequencies of typically 10 Hz. The capability to record full extended x-ray absorption fine structure spectra on a subsecond time scale is demonstrated.

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.

A new approach for QEXAFS data acquisition.

Quick-scanning EXAFS (QEXAFS) data were recorded by direct readout of the ionization chambers by means of current amplifiers and a high speed analog to digital converter (ADC) which enables the simultaneous measurement of 4 individual cllannels with sampling rates of up to 200 kHz. QEXAFS spectra covering an energy range of more than 2000 eV as well as XANES data are presented. The results show that near edge spectra of metal foils can be measured in about 5 ms with an excellent reproducibility. First applications of this setup in catalysis research will be discussed.

Structural investigations of sputter deposited thin films: reflection mode EXAFS, specular and non specular X-ray scattering

Abstract The extended X-ray absorption fine structure technique (EXAFS) in the reflection mode was used for the ex situ investigation of sputter deposited thin films on float glass substrates. We show that a detailed analysis of the reflectivity fine structure enables the extraction of short-range order structural information such as bond distances, coordination numbers and Debye–Waller factors. The surface roughness and the density of the thin films were determined from specular and non-specular X-ray scattering experiments. Polycrystalline Ag and Au films prepared by DC-sputtering in Ar atmospheres were investigated to show the potential of the technique. Both systems reveal a polycrystalline short-range order structure similar to that of the respective bulk materials. In contrast, amorphous structures with significantly reduced densities were found for Ta 2 O 5 thin films prepared by reactive sputtering in pure O 2 -atmospheres.