O. Fuchs

Soft X-ray-induced decomposition of amino acids: an XPS, mass spectrometry, and NEXAFS study.

Abstract Zubavichus, Y., Fuchs, O., Weinhardt, L., Heske, C., Umbach, E., Denlinger, J. D. and Grunze, M. Soft X-Ray-Induced Decomposition of Amino Acids: An XPS, Mass Spectrometry, and NEXAFS Study. Radiat. Res. 161, 346–358 (2004). Decomposition of five amino acids, alanine, serine, cysteine, aspartic acid, and asparagine, under irradiation with soft X rays (magnesium KαX-ray source) in ultra-high vacuum was studied by means of X-ray photoelectron spectrometry (XPS) and mass spectrometry. A comparative analysis of changes in XPS line shapes, stoichiometry and residual gas composition indicates that the molecules decompose by several pathways. Dehydration, decarboxylation, decarbonylation, deamination and desulfurization of pristine molecules accompanied by desorption of H2, H2O, CO2, CO, NH3and H2S are observed with rates depending on the specific amino acid. NEXAFS spectra of cysteine at the carbon, oxygen and nitrogen K-shell and sulfur L2,3edges complement the XPS and mass spectrometry data and show that the exposure of the sample to an intense soft X-ray synchrotron beam results in the formation of C-C and C-N double and triple bonds. Qualitatively, the amino acids studied can be arranged in the following ascending order of radiation stability: serine < alanine < aspartic acid < cysteine < asparagine.

CdS and Cd(OH)2 formation during Cd treatments of Cu(In,Ga)(S,Se)2 thin-film solar cell absorbers

The surface modifications induced by treating Cu(In,Ga)(S,Se)2 films in an aqueous ammonia hydroxide-based solution of Cd2+ ions—as used in record Cu(In,Ga)(S,Se)2 solar cells without a CdS buffer layer—have been investigated for different Cd2+ concentrations. Employing a combination of x-ray photoelectron spectroscopy, Auger electron spectroscopy, and x-ray emission spectroscopy, it is possible to distinguish two different surface modifications. For Cd2+ concentrations below 4.5 mM in the solution we observe the formation of a CdS monolayer, while higher Cd2+ concentrations lead to the additional deposition of a cadmium hydroxide film on the CdS/Cu(In,Ga)(S,Se)2 surface.

Depth-resolved band gap in Cu(In,Ga)(S,Se)2 thin films

The surface composition of Cu(In,Ga)(S,Se)2 (“CIGSSe”) thin films intrinsically deviates from the corresponding bulk composition, which also modifies the electronic structure and thus the optical properties. We used a combination of photon and electron spectroscopies with different information depths to gain depth-resolved information on the band gap energy (Eg) in CIG(S)Se thin films. We find an increasing Eg with decreasing information depth, indicating the formation of a surface region with significantly higher Eg. This Eg-widened surface region extends further into the bulk of the sulfur-free CIGSe thin film compared to the CIGSSe thin film.

High-resolution, high-transmission soft x-ray spectrometer for the study of biological samples

We present a variable line-space grating spectrometer for soft x-rays that covers the photon energy range between 130 and 650 eV. The optical design is based on the Hettrick-Underwood principle and tailored to synchrotron-based studies of radiation-sensitive biological samples. The spectrometer is able to record the entire spectral range in one shot, i.e., without any mechanical motion, at a resolving power of 1200 or better. Despite its slitless design, such a resolving power can be achieved for a source spot as large as (30 x 3000) microm2, which is important for keeping beam damage effects in radiation-sensitive samples low. The high spectrometer efficiency allows recording of comprehensive two-dimensional resonant inelastic soft x-ray scattering (RIXS) maps with good statistics within several minutes. This is exemplarily demonstrated for a RIXS map of highly oriented pyrolytic graphite, which was taken within 10 min.

Band alignment at the CdS∕Cu(In,Ga)S2 interface in thin-film solar cells

The band alignment at the CdS∕Cu(In,Ga)S2 interface in thin-film solar cells on a stainless steel substrate was investigated using photoelectron spectroscopy and inverse photoemission. By combining both techniques, the conduction and valence band offsets were independently determined. We find an unfavorable conduction band offset of −0.45 (±0.15) eV, accounting for the generally observed low open-circuit voltage and indicating the great importance of the buffer∕absorber conduction band offset for such devices. The surface band gap of the Cu(In,Ga)S2 absorber is 1.76 (±0.15) eV, being increased with respect to the expected bulk value by a copper depletion near the surface.

Solid and liquid spectroscopic analysis (SALSA)--a soft x-ray spectroscopy endstation with a novel flow-through liquid cell.

We present a novel synchrotron endstation with a flow-through liquid cell designed to study the electronic structure of liquids using soft x-ray spectroscopies. In this cell, the liquid under study is separated from the vacuum by a thin window membrane, such that the sample liquid can be investigated at ambient pressure. The temperature of the probing volume can be varied in a broad range and with a fast temperature response. The optimized design of the cell significantly reduces the amount of required sample liquid and allows the use of different window membrane types necessary to cover a broad energy range. The liquid cell is integrated into the solid and liquid spectroscopic analysis (SALSA) endstation that includes a high-resolution, high-transmission x-ray spectrometer and a state-of-the-art electron analyzer. The modular design of SALSA also allows the measurement of solid-state samples. The capabilities of the liquid cell and the x-ray spectrometer are demonstrated using a resonant inelastic x-ray scattering map of a 25 wt % NaOD solution.

Monitoring chemical reactions at a liquid–solid interface: Water on CuIn(S,Se)2 thin film solar cell absorbers

The chemical and electronic structure of the interface between liquid water and a CuIn(S,Se)2 thin film surface was studied with synchrotron-based, high energy-resolution soft x-ray emission spectroscopy (XES). By probing the local environment around the sulfur atoms, an x-ray-induced sulfate formation at the CuIn(S,Se)2 surface can be monitored, correlated with a substantial enhancement of sodium impurity atoms from the CuIn(S,Se)2 film and its glass substrate. The results demonstrate that, with XES, an experimental probe is available to in situ study chemical reactions at liquid–solid interfaces or at surfaces in a high-pressure gas environment in a chemically sensitive and atom-specific way.

Damp-heat induced sulfate formation in Cu(In,Ga)(S,Se)2-based thin film solar cells

To investigate the impact of damp heat treatments on the electronic and chemical structure of Cu(In,Ga)(S,Se)2-based thin film solar cells, we have performed a detailed soft x-ray emission study of the ZnO/CuIn(S,Se)2 and ZnO/CdS/CuIn(S,Se)2 interfaces. By comparing the sulfur L2,3 emission spectra of pristine and damp-heat treated samples, we find a sulfate formation at the ZnO/CuIn(S,Se)2 and the ZnO/CdS interface. The intensity behavior as a function of ZnO film thickness further reveals a diffusion of sulfur atoms into the ZnO film, leading to the formation of zinc sulfate in the ZnO window layer of damp-heat-treated Cu(In,Ga)(S,Se)2-based solar cells.

Surface modifications of Cu(In,Ga)S2 thin film solar cell absorbers by KCN and H2O2∕H2SO4 treatments

KCN etching of the CuxS surface layer formed during the production process of Cu(In,Ga)S2 thin film solar cell absorbers as well as subsequent H2O2∕H2SO4 etching of the Cu(In,Ga)S2 surface have been investigated using x-ray photoelectron spectroscopy, x-ray excited Auger electron spectroscopy, and x-ray emission spectroscopy. We find that the KCN etching removes the CuxS layer—being identified as Cu2S—and that there is K deposited during this step, which is removed by the subsequent H2O2∕H2SO4 oxidation treatment. When a CdS buffer layer is deposited on the absorber directly after KCN etching, a K compound (KCO3) is observed at the CdS surface.

Inducing and monitoring photoelectrochemical reactions at surfaces and buried interfaces in Cu(In,Ga)(S,Se)2 thin-film solar cells

We report the direct observation of a photoinduced oxidation process at the buried buffer/absorber interface in high-efficiency Zn(O,OH)∕Cu(In,Ga)(S,Se)2 thin-film solar cell structures by means of x-ray emission and photoelectron spectroscopy. We propose a reaction mechanism that involves the decomposition of a hydroxide compound in the buffer layer into water and an oxide and present evidence that this process also occurs with visible light excitation and after accelerated lifetime tests of nonencapsulated devices. This suggests a possible photoinduced aging effect in solar cell devices with other hydroxide containing buffer layers or under humid conditions.