ABSTRACT
We present a laser-driven, bright, and broadband (50 to 1500 eV) soft-x-ray plasma source with <10 ps pulse duration. This source is employed in two complementary, laboratory-scale beamlines for time-resolved, magnetic resonant scattering and spectroscopy, as well as near-edge x-ray absorption fine-structure (NEXAFS) spectroscopy. In both beamlines, dedicated reflection zone plates (RZPs) are used as single optical elements to capture, disperse, and focus the soft x rays, reaching resolving powers up to E/ΔE > 1000, with hybrid RZPs at the NEXAFS beamline retaining a consistent E/ΔE > 500 throughout the full spectral range, allowing for time-efficient data acquisition. We demonstrate the versatility and performance of our setup by a selection of soft-x-ray spectroscopy and scattering experiments, which so far have not been possible on a laboratory scale. Excellent data quality, combined with experimental flexibility, renders our approach a true alternative to large-scale facilities, such as synchrotron-radiation sources and free-electron lasers.
ABSTRACT
Scan-free grazing-emission X-ray fluorescence spectroscopy (GEXRF) is an established technique for the investigation of the elemental depth-profiles of various samples. Recently it has been applied to investigating structured nanosamples in the tender X-ray range. However, lighter elements such as oxygen, nitrogen or carbon cannot be efficiently investigated in this energy range, because of the ineffective excitation. Moreover, common CCD detectors are not able to discriminate between fluorescence lines below 1 keV. Oxygen and nitrogen are important components of insulation and passivation layers, for example, in silicon oxide or silicon nitride. In this work, scan-free GEXRF is applied in proof-of-concept measurements for the investigation of lateral ordered 2D nanostructures in the soft X-ray range. The sample investigated is a Si3N4 lamellar grating, which represents 2D periodic nanostructures as used in the semiconductor industry. The emerging two-dimensional fluorescence patterns are recorded with a CMOS detector. To this end, energy-dispersive spectra are obtained via single-photon event evaluation. In this way, spatial and therefore angular information is obtained, while discrimination between different photon energies is enabled. The results are compared to calculations of the sample model performed by a Maxwell solver based on the finite-elements method. A first measurement is carried out at the UE56-2 PGM-2 beamline at the BESSY II synchrotron radiation facility to demonstrate the feasibility of the method in the soft X-ray range. Furthermore, a laser-produced plasma source (LPP) is utilized to investigate the feasibility of this technique in the laboratory. The results from the BESSY II measurements are in good agreement with the simulations and prove the applicability of scan-free GEXRF in the soft X-ray range for quality control and process engineering of 2D nanostructures. The LPP results illustrate the chances and challenges concerning a transfer of the methodology to the laboratory.
ABSTRACT
The extension of the pump-probe approach known from UV/VIS spectroscopy to very short wavelengths together with advanced simulation techniques allows a detailed analysis of excited-state dynamics in organic molecules or biomolecular structures on a nanosecond to femtosecond time level. Optical pump soft X-ray probe spectroscopy is a relatively new approach to detect and characterize optically dark states in organic molecules, exciton dynamics or transient ligand-to-metal charge transfer states. In this paper, we describe two experimental setups for transient soft X-ray absorption spectroscopy based on an LPP emitting picosecond and sub-nanosecond soft X-ray pulses in the photon energy range between 50 and 1500 eV. We apply these setups for near-edge X-ray absorption fine structure (NEXAFS) investigations of thin films of a metal-free porphyrin, an aggregate forming carbocyanine and a nickel oxide molecule. NEXAFS investigations have been carried out at the carbon, nitrogen and oxygen K-edge as well as on the Ni L-edge. From time-resolved NEXAFS carbon, K-edge measurements of the metal-free porphyrin first insights into a long-lived trap state are gained. Our findings are discussed and compared with density functional theory calculations.
Subject(s)
Organic Chemicals/chemistry , X-Ray Absorption Spectroscopy/methods , Density Functional Theory , Electrons , Molecular Structure , Porphyrins/chemistry , Quantum Theory , Quinolines/chemistry , X-RaysABSTRACT
We provide corrections for our previous publication [Opt. Express27, 36524 (2019)10.1364/OE.27.036524].
ABSTRACT
In laboratory based x-ray absorption fine structure (XAFS) spectroscopy, the slow readout speed of conventional CCD cameras can prolong the measuring times by multiple orders of magnitude. Using pulsed sources, e.g., laser-based x-ray sources, the pulse repetition rate often exceeds the frame rate of the CCD camera. We report the use of a scientific CMOS (sCMOS) camera for XAFS spectroscopy with a laser-produced plasma source facilitating measurements at 100 Hz. With this technological improvement, a new class of experiments becomes possible, starting from the time consuming analysis of samples with small absorption to pump-probe investigations. Furthermore, laboratory quick soft x-ray absorption fine structure (QXAFS) measurements with 10 ms time resolution are rendered feasible. We present the characterization of the sCMOS camera concerning noise characteristics and a comparison to conventional CCD camera performance. The feasibility of time resolved QXAFS measurements is shown by analyzing the statistical uncertainty of single shot spectra. Finally, XAFS spectroscopy on a complex sandwich structure with minute amounts of NiO exemplifies the additional merits of fast detectors.
ABSTRACT
We demonstrate visible pump soft X-ray probe near-edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements at the carbon K edge on thin molecular films in the laboratory. This opens new opportunities through the use of laboratory equipment for chemical speciation. We investigate the metal-free porphyrin derivative tetra(tert-butyl)porphyrazine as an ideal model system to elucidate electronic properties of tetrapyrroles like chlorophyll or heme. In contrast to measurements in gas or liquid state, the investigation of thin films is of high interest in the field of optoelectronic and photovoltaic devices though challenging due to the low damage thresholds of the samples upon excitation. With a careful pre-characterization using optical techniques, successful measurements were performed using a NEXAFS spectrometer based on a laser-produced plasma source and reflection zone plates with a resolving power of 1000 and a time resolution of 0.5 ns. In combination with density functional theory calculations, first insights into a long-lived excitonic state are gained and discussed.
ABSTRACT
Laboratory transmission soft X-ray microscopy (L-TXM) has emerged as a complementary tool to synchrotron-based TXM and high-resolution biomedical 3D imaging in general in recent years. However, two major operational challenges in L-TXM still need to be addressed: a small field of view and a potentially misaligned rotation stage. As it is not possible to alter the magnification during operation, the field of view in L-TXM is usually limited to a few tens of micrometers. This complicates locating areas and objects of interest in the sample. Additionally, if the rotation axis of the sample stage cannot be adjusted prior to the experiments, an efficient workflow for tomographic imaging cannot be established, as refocusing and sample repositioning will become necessary after each recorded projection. Both these limitations have been overcome with the integration of a visible-light microscope (VLM) into the L-TXM system. Here, we describe the calibration procedure of the goniometer sample stage and the integrated VLM and present the resulting 3D imaging of a test sample. In addition, utilizing this newly integrated VLM, the extracellular matrix of cryofixed THP-1 cells (human acute monocytic leukemia cells) was visualized by L-TXM for the first time in the context of an ongoing biomedical research project.
Subject(s)
Laboratories , Microscopy , Humans , Imaging, Three-Dimensional , Synchrotrons , Workflow , X-RaysABSTRACT
We developed a high power optical parametric chirped-pulse amplification (OPCPA) system at 2.1 µm harnessing a 500 W Yb:YAG thin disk laser as the only pump and signal generation source. The OPCPA system operates at 10 kHz with a single pulse energy of up to 2.7 mJ and pulse duration of 30 fs. The maximum average output power of 27 W sets a new record for an OPCPA system in the 2 µm wavelength region. The soft X-ray continuum generated through high harmonic generation with this driver laser can extend to around 0.55 keV, thus covering the entire water window (284 eV - 543 eV). With a repetition rate still enabling pump-probe experiments on solid samples, the system can be used for many applications.
ABSTRACT
We present a laboratory setup for near edge X-ray absorption spectroscopy (NEXAFS) in the soft X-ray regime between 284 eV to 1303 eV with a resolving power of up to 1370. Based on a laser-produced plasma source, a pair of identical reflection zone plates and an X-ray CCD camera, the setup is intended for optical pump X-ray probe NEXAFS measurements with a detectable change in absorption of the excited sample down to 10-4 and 500 ps time resolution. Because of the high stability of the source the statistical error only depends on the detector response and the number of photons detected and can reach the detector noise limit after a couple of thousands single shots. Thus, structure-function relationship investigations of bio-molecules are rendered feasible in the laboratory.
ABSTRACT
A sub-pixel 16 bit charge coupled device camera featuring superresolution for the soft X-ray regime is presented. Superresolution images (SRIs) are reconstructed from a set of 4 × 4 individual low-resolution images that are recorded for different sub-pixel shifts of the detector. SRIs have a 1.3 times higher resolution than individual low-resolution images which is close to the maximum achievable enhancement factor of about 1.5 in the X-ray regime under ideal conditions. To characterize this camera and demonstrate its potential, an X-ray microscope setup is used to image different objects at different photon energies.
ABSTRACT
Using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, the carbon backbone of sodium copper chlorophyllin (SCC), a widely used chlorophyll derivative, and its breakdown products are analyzed to elucidate their electronic structure and physicochemical properties. Using various sample preparation methods and complementary spectroscopic methods (including UV/Vis, X-ray photoelectron spectroscopy), a comprehensive insight into the SCC breakdown process is presented. The experimental results are supported by density functional theory calculations, allowing a detailed assignment of characteristic NEXAFS features to specific C bonds. SCC can be seen as a model system for the large group of porphyrins; thus, this work provides a novel and detailed description of the electronic structure of the carbon backbone of those molecules and their breakdown products. The achieved results also promise prospective optical pump/X-ray probe investigations of dynamic processes in chlorophyll-containing photosynthetic complexes to be analyzed more precisely.
Subject(s)
Chlorophyll/chemistry , Copper/chemistry , X-Ray Absorption Spectroscopy , Electrons , Molecular Structure , Quantum TheoryABSTRACT
The interaction of the central magnesium atom of chlorophyll a (Chl a) with the carbon and nitrogen backbone was investigated by magnesium K near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in fluorescence detection mode. A crude extract of Chl a was measured as a 1 × 10-2 mol/L ethanol solution (which represents an upper limit of concentration without aggregation) and as dried droplets. For the first time, the investigation of Mg bound to Chl a in a liquid environment by means of X-ray absorption spectroscopy is demonstrated. A pre-edge feature in the dissolved as well as in dried Chl a NEXFAS spectra has been identified as a characteristic transition originating from Mg in the Chl a molecule. This result is confirmed by theoretical DFT calculations leading to molecular orbitals (MO) which are mainly situated on the magnesium atom and nitrogen and carbon atoms from the pyrrole rings. The description is the first referring to the MO distribution with respect to the central Mg ion of Chl a and the surrounding atoms. On this basis, new approaches for the investigations of dynamic processes of molecules in solution and structure-function relationships of photosynthetic pigments and pigment-protein complexes in their native environment can be developed.
Subject(s)
Chlorophyll/analogs & derivatives , Ethanol/chemistry , Magnesium/chemistry , Chlorophyll/chemistry , Solutions , X-Ray Absorption SpectroscopyABSTRACT
In this work, a novel laser-produced plasma source is presented which delivers pulsed broadband soft X-radiation in the range between 100 and 1200 eV. The source was designed in view of long operating hours, high stability, and cost effectiveness. It relies on a rotating and translating metal target and achieves high stability through an on-line monitoring device using a four quadrant extreme ultraviolet diode in a pinhole camera arrangement. The source can be operated with three different laser pulse durations and various target materials and is equipped with two beamlines for simultaneous experiments. Characterization measurements are presented with special emphasis on the source position and emission stability of the source. As a first application, a near edge X-ray absorption fine structure measurement on a thin polyimide foil shows the potential of the source for soft X-ray spectroscopy.
Subject(s)
Spectrum Analysis/instrumentation , Equipment Design , Feasibility Studies , Imides/chemistry , Lasers , Photons , Rotation , Spectrum Analysis/methods , Ultraviolet Rays , X-RaysABSTRACT
A pump scheme with one long and two short pump pulses is proposed, in a grazing incidence pumping x-ray laser (XRL) configuration. A 360 ps long pulse, prepares a plasma in a low charge state. Then, an initial short pulse ionizes the plasma to an optimal charge state, while the second short pulse induces strong collisional excitation in the gain region. With only 200 mJ of pump energy on target, a compact Ag XRL at 13.9 nm with a gain coefficient of 55 cm(-1) was achieved.
ABSTRACT
Peridinin-chlorophyll a protein (PCP) is a unique water soluble antenna complex that employs the carotenoid peridinin as the main light-harvesting pigment. In the present study the near edge X-ray absorption fine structure (NEXAFS) spectrum of PCP was recorded at the carbon K-edge. Additionally, the NEXAFS spectra of the constituent pigments, chlorophyll a and peridinin, were measured. The energies of the lowest unoccupied molecular levels of these pigments appearing in the carbon NEXAFS spectrum were resolved. Individual contributions of the pigments and the protein to the measured NEXAFS spectrum of PCP were determined using a "building block" approach combining NEXAFS spectra of the pigments and the amino acids constituting the PCP apoprotein. The results suggest that absorption changes of the pigments in the carbon near K-edge region can be resolved following excitation using a suitable visible pump laser pulse. Consequently, it may be possible to study excitation energy transfer processes involving "optically dark" states of carotenoids in pigment-protein complexes by soft X-ray probe optical pump double resonance spectroscopy (XODR).
Subject(s)
Carotenoids/chemistry , Light-Harvesting Protein Complexes/chemistry , Protozoan Proteins/chemistry , Amino Acids/chemistry , Animals , Dinoflagellida/chemistry , Multiprotein Complexes/chemistry , Spectrophotometry , Spectrophotometry, Ultraviolet , Spectrum Analysis/methods , X-RaysABSTRACT
Manifestation and extent of excitonic interactions in the red Chl-absorption region (Q(y) band) of trimeric LHC-II were investigated using two complementary nonlinear laser-spectroscopic techniques. Nonlinear absorption of 120-fs pulses indicates an increased absorption cross section in the red wing of the Q(y) band as compared to monomeric Chl a in organic solution. Additionally, the dependence of a nonlinear polarization response on the pump-field intensity was investigated. This approach reveals that one emitting spectral form, characterized by a 2.3(+/-0.8)-fold larger dipole strength than monomeric Chl a, dominates the fluorescence spectrum of LHC-II. Considering available structural and spectroscopic data, these results can be consistently explained assuming the existence of an excitonically coupled dimer located at Chl-bindings sites a2 and b2 (referring to the original notation of W. Nühlbrandt, D.N. Wang, and Y. Fujiyoshi, Nature, 1994, 367:614-621), which must not necessarily correspond to Chls a and b). This fluorescent dimer, terminating the excitation energy-transfer chain of the LHC-II monomeric subunit, is discussed with respect to its relevance for intra- and inter-antenna excitation energy transfer.
Subject(s)
Chlorophyll/chemistry , Photosynthetic Reaction Center Complex Proteins/chemistry , Biophysical Phenomena , Biophysics , Chlorophyll/metabolism , Light , Light-Harvesting Protein Complexes , Models, Statistical , Models, Theoretical , Pisum sativum/chemistry , Photons , Protein Binding , SpectrophotometryABSTRACT
We achieved a continuous, stable, ultrashort pulse hard x-ray point source by focusing 1.8-W, 1-kHz, 50-fs laser pulses onto a novel, 30-microm -diameter, high-velocity, liquid-metal gallium jet. This target geometry avoids most of the debris problems of solid targets and provides nearly 4pi illumination. Photon fluxes of 5x10(8) photons/s are generated in a two-component spectrum consisting of a broad continuum from 4 to 14 keV and strong K(alpha) and K(beta) emission lines at 9.25 and 10.26 keV. This source will find wide use in time-resolved x-ray diffraction studies and other applications.
