Fluorescence Yield Detection Research Articles

In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction.

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film.

Inducing molecular orientation in solution-processed thin films of fluorene-bithiophene-based copolymer: thermal annealing vs. solvent additive.

A deep understanding of the factors influencing the morphology of thin films based on conjugated polymers is essential to boost their performance in optoelectronic devices. Herein, we investigated the electronic structure and morphology of thin films of the copolymer poly(9,9-dioctyl-fluorenyl-co-bithiophene) (F8T2) in its pristine form as well as samples processed with the solvent additive 1,8-diiodooctane (DIO) or post-processed through thermal annealing treatment. Measurements were carried out using angle-resolved S K-edge NEXAFS (near-edge X-ray absorption fine structure) in total electron yield (TEY) and fluorescence yield (FY) detection modes. Two main transitions were observed at the S 1s NEXAFS spectra: S 1s → π* and S 1s → σ* (S-C). The observed dichroism pointed to a face-on orientation of the conjugated backbone, which was significantly increased for F8T2 films processed with DIO. Resonant Auger decay spectra were obtained and analyzed using the core-hole clock (CHC) method. An enhancement in the charge transfer process was observed for thermally annealed films, especially for samples processed with DIO, corresponding to an increase in film ordering. Furthermore, the investigated films were characterized using X-ray photoelectron spectroscopy, attesting to the presence of the thiophene unit in the samples and demonstrating that some of its sulfur atoms were positively polarized in the F8T2 films. All these experimental findings were compared with molecular dynamics (MD) simulations of film evaporation with and without DIO. The use of MD, together with mathematical modeling, was able to explain the major effects found in the experiments, including the polarization of sulfur atoms. The simultaneous use of powerful spectroscopic techniques and theoretical methods shed light on key aspects linking film morphology with fabrication procedures.

The rise of electrochemical NAPXPS operated in the soft X-ray regime exemplified by the oxygen evolution reaction on IrOx electrocatalysts.

Photoelectron spectroscopy offers detailed information about the electronic structure and chemical composition of surfaces, owing to the short distance that the photoelectrons can escape from a dense medium. Unfortunately, photoelectron based spectroscopies are not directly compatible with the liquids required to investigate electrochemical processes, especially in the soft X-ray regime. To overcome this issue, different approaches based on photoelectron spectroscopy have been developed in our group over the last few years. The performance and the degree of information provided by these approaches are compared with those of the well established bulk sensitive spectroscopic approach of total fluorescence yield detection, where the surface information gained from this approach is enhanced using samples with large surface to bulk ratios. The operation of these approaches is exemplified and compared using the oxygen evolution reaction on IrOx catalysts. We found that all the approaches, if properly applied, provide similar information about surface oxygen speciation. However, using resonant photoemission spectroscopy, we were able to prove that speciation is more involved and complex than previously thought during the oxygen evolution reaction on IrOx based electrocatalysts. We found that the electrified solid-liquid interface is composed of different oxygen species, where the terminal oxygen atoms on iridium are the active species, yielding the formation of peroxo species and, finally, dioxygen as the reaction product. Thus, the oxygen-oxygen bond formation is dominated by peroxo species formation along the reaction pathway. Furthermore, the methodologies discussed here open up opportunities to investigate electrified solid-liquid interfaces in a multitude of electrochemical processes with unprecedented speciation capabilities, which are not accessible by one-dimensional X-ray spectroscopies.

A Combined Study of Tc Redox Speciation in Complex Aqueous Systems: Wet-Chemistry, Tc K-/L3-Edge X-ray Absorption Fine Structure, and Ab Initio Calculations

The combination of wet-chemistry experiments (measurements of pH, Eh, and [Tc]) and advanced spectroscopic techniques (K- and L3-edge X-ray absorption fine structure spectroscopy) confirms the formation of a very stable Tc(V)-gluconate complex under anoxic conditions. In the presence of gluconate and an excess of Sn(II) (at pe + pH ≈ 2), technetium forms a very stable Tc(IV)-gluconate complex significantly enhancing the solubility defined by TcO2(s) in hyperalkaline gluconate-free systems. A new setup for "tender" X-ray spectroscopy (spectral range, ∼2-5 keV) in transmission or total fluorescence yield detection mode based on a He flow cell has been developed at the INE Beamline for radionuclide science (KIT light source). This setup allows handling of radioactive specimens with total activities up to one million times the exemption limit. For the first time, Tc L3-edge measurements (∼2.677 keV) of Tc species in liquid (aqueous) media are reported, clearly outperforming conventional K-edge spectroscopy as a tool to differentiate Tc oxidation states and coordination environments. The coupling of L3-edge X-ray absorption near-edge spectroscopy measurements and relativistic multireference ab initio methods opens new perspectives in the definition of chemical and thermodynamic models for systems of relevance in the context of nuclear waste disposal, environmental, and pharmaceutical applications.

Sum rule distortions in fluorescence-yield x-ray magnetic circular dichroism

The quantitative analysis of $3d$ transition metal ${\mathrm{L}}_{2,3}$ edge x-ray magnetic circular dichroism (XMCD) spectra and the related sum rules are compared for measurements with electron yield and fluorescence yield detection. Multiplet calculations on divalent ions show that fluorescence yield detected sum rule derived expectation values of ${\mathrm{L}}_{z}$ and ${\mathrm{S}}_{z}$ show noticeable deviations and detection angle dependence. We show that small deviations of the polarization dependent fluorescent decay values lead to significant deviations in the ${\mathrm{L}}_{z}$ and ${\mathrm{S}}_{z}$ sum rule values. Fe and Co experimental XMCD spectra of a supported 10 nm ${\mathrm{CoFe}}_{2}{\mathrm{O}}_{4}$ thin film are measured simultaneously by both electron and fluorescence yield. The deviations shown in the experimental data are well explained by the calculations and are shown to mainly depend on the polarization dependent total decay. We conclude that fluorescence yield detected x-ray magnetic circular dichroism is unsuitable for quantitative analysis of the ${\mathrm{L}}_{z}$ and ${\mathrm{S}}_{z}$ sum rule values.

Towards efficient time-resolved X-ray absorption studies of electron dynamics at photocatalytic interfaces.

We present a picosecond time-resolved X-ray absorption spectroscopy (tr-XAS) setup designed for synchrotron-based studies of interfacial photochemical dynamics. The apparatus combines a high power, variable repetition rate picosecond laser system with a time-resolved X-ray fluorescence yield detection technique. Time-tagging of the detected fluorescence signals enables the parallel acquisition of X-ray absorption spectra at a variety of pump-probe delays employing the well-defined time structure of the X-ray pulse trains. The viability of the setup is demonstrated by resolving dynamic changes in the fine structure near the O1s X-ray absorption edge of cuprous oxide (Cu2O) after photo-excitation with a 355 nm laser pulse. Two distinct responses are detected. A pronounced, quasi-static, reversible change of the Cu2O O1s X-ray absorption spectrum by up to ∼30% compared to its static line shape corresponds to a redshift of the absorption edge by ∼1 eV. This value is small compared to the 2.2 eV band gap of Cu2O but in agreement with previously published results. The lifetime of this effect exceeds the laser pulse-to-pulse period of 8 μs, resulting in a quasi-static spectral change that persists as long as the sample is exposed to the laser light, and completely vanishes once the laser is blocked. Additionally, a short-lived response corresponding to a laser-induced shift of the main absorption line by ∼2 eV to lower energies appears within <200 ps and decays with a characteristic timescale of 43 ± 5 ns. Both the picosecond rise and nanosecond decay of this X-ray response are simultaneously captured by making use of a time-tagging approach - highlighting the prospects of the experimental setup for efficient probing of the electronic and structural dynamics in photocatalytic systems on multiple timescales.

An ultra-high vacuum electrochemical flow cell for in situ/operando soft X-ray spectroscopy study.

An in situ flow electrochemical cell has been designed and fabricated to allow better seal under UHV chamber thus to achieve a good signal to noise ratio in fluorescence yield detection of X-ray absorption spectra for spectroelectrochemical study. The cell also stabilizes the thin silicon nitride membrane window in an effective manner so that the liquid cell remains intact during X-ray absorption experiments. With the improved design of the liquid cell, electrochemical experiments such as cyclic voltammetry have been performed for 10 cycles with a good stability of sample window. Also an operando electrochemical experiment during photoelectrochemistry has been performed on n-type hematite electrode deposited on silicon nitride window. The experiment allows us to observe the formation of two extra electronic transitions before pre edge of O K-edge spectra.

Electronic structure and O K-edge XAS spectroscopy of U3O8

Understanding the uranium 5f/6d orbital mixing with oxygen 2p valence orbitals in uranium oxides is important for advancing nuclear technology. Unfortunately, U–O orbital mixing is difficult to probe experimentally. In this manuscript, U–O bonding is evaluated in U3O8 using O K-edge X-ray absorption spectroscopy (XAS). To confirm that the O K-edge XAS spectra were correct and did not contain contributions from surface contamination, three different sample types were investigated using three unique detection methods. Specifically an epitaxial film of U3O8 deposited on Al2O3 (PAD-U3O8) was probed using grazing-incidence fluorescence yield (GIFY) detection, a bulk powder of α-phase U3O8 was analyzed with fluorescence yield (FY) detection at normal incidence, and particles of α-phase U3O8 were studied in transmission mode using a scanning transmission X-ray microscope (STXM). Experimental spectra have been presented in the context of previously published computational results from DFT using the Heyd–Scuseria–Ernzerhof (HSE) screened hybrid functional. Overall, the comparative analyses of PAD-U3O8 and α-phase U3O8 samples enabled identification of unique signatures associated with oxygen 2p orbital mixing with both UV and UVI 5f and 6d valence orbitals.

Application Ce L1 HERFD XAS to determine the atomic structure of CeO2 based nano-catalysts under working conditions

Ce L1-edge high-energy-resolution fluorescence detected (HERFD) X-ray absorption spectroscopy (XAS) was applied to unravel the electronic structure of Pt-promoted CeO2 nanoparticles under different redox conditions. The Ce Lγ3 emission line was chosen for partial fluorescence yield detection to improve the XAS spectral resolution. Oxygen vacancies were formed on the surface of ceria nanoparticles upon reducing in 5% CO in He. Theoretical Ce L1-edge simulations showed good agreement with the experimental data.

Reversible change in the oxidation state and magnetic circular dichroism of Fe driven by an electric field at the FeCo/MgO interface

The influence of an electric field on an ultrathin FeCo film was investigated by x-ray absorption spectroscopy and magnetic circular dichroism. Measurements were done on sub-millimeter sized pillars, with partial fluorescence yield detection. Fe L2,3 absorption spectra revealed that partial oxidation of Fe occurred during the microfabrication. The oxidation state could be reversibly controlled by an electric field, which also induced variations of the dichroic signal. These results show that electrochemical phenomena may influence the magnetism at a ferromagnet/insulator interface.

Electron yield soft X-ray photoabsorption spectroscopy under normal ambient-pressure conditions.

Ambient-pressure soft X-ray photoabsorption spectroscopy (XAS) was demonstrated to be applicable to the chemical analysis of hydrated transition-metal compounds. For this purpose, even under ambient-pressure conditions, electron yield detection XAS (EY-XAS), based on a simple drain-current set-up, was used to overcome a weakness in fluorescence yield detection XAS (FY-XAS), which does not give a pure soft XAS. The feasibility of EY-XAS was investigated and it was clarified that the EY-XAS under ambient-pressure conditions corresponds to the mixed data of the total EY and conversion EY spectra. Normal ambient-pressure EY-XAS analysis was applied to anhydrous (CoCl2) and to hydrated (CoCl2·6H2O) cobalt chloride at the Co L23-edge. The present measurements demonstrated the ability to unambiguously distinguish the different chemical states of cobalt ions, relying upon spectral differences that indicate octahedral/quasi-octahedral structural changes as a result of hydration/dehydration reactions.

Intrinsic deviations in fluorescence yield detected x-ray absorption spectroscopy: the case of the transition metal L2,3 edges

Fluorescence yield (FY) detected x-ray absorption spectra (XAS) of 3d transition metal ions are calculated from the integrated 2p3d resonant x-ray emission spectra. The resulting FY-XAS spectra are compared with the normal XAS spectra corresponding to the absorption cross section and significant deviations between the two spectra are found. This implies that the assumption that the FY-XAS spectrum identifies with the XAS spectrum is disproved. Especially for the early transition metal systems the differences between the FY-XAS and XAS are large, due to the opening of inelastic decay channels from selected x-ray absorption final states. The theoretical calculations show that the difference between FY detection and XAS is largest for the detection in depolarized geometry. The calculations are compared with experimental spectra for oxides and coordination compounds for Fe2+, Co2+ and Ni2+ systems. The implications for the sum rules in XAS and magnetic circular dichroism experiments are discussed.

Investigation of the structural changes in Li1−xFePO4 upon charging by synchrotron radiation techniques

A systematic study on a LiFePO4 sample with 600 nm particle size was carried out to investigate the electronic and crystal structure changes during charge and their relationships with the charging curve. In situX-ray diffraction data collected at 0.1C rate during first charge shows that the crystal FePO4 is observed at x = 0.3 in Li1−xFePO4, with significant delay than the beginning of the charge plateau. On the other hand, in situ X-ray absorption spectra for the Fe K-edge collected at 0.1C during first charge show that the average oxidation of Fe2+ to Fe3+ almost synchronized with the charging curve. In addition, the ex-situ soft X-ray absorption data for the Fe LII–III edges using surface sensitive partial electron yield detection mode show that the lithium content changes at the surface of the sample particles synchronized or ahead to the charge curve, while the data collected at the same time using bulk sensitive fluorescence yield detection mode show that the lithium content changes in the bulk of the particles lag behind the charging curve. The contents of FePO4 and LiFePO4 calculated from in situXRD in relating to the charge curve are quite different than those calculated from in situXAS and ex-situ soft X-ray absorption data. This tells us that cautious need to be taken when using XRD data alone to track the state of charge of LiFePO4 samples, significant delay in observing the new crystal phase formation could occur, especially at relatively high charging rate.

Temperature-induced obliteration of sub-oxide interfaces in amorphous GeO

Abstract The temperature-induced phase separation of native amorphous germanium monoxide, a-GeO, into Ge and GeO2 was studied by measurements of the Ge K-edge employing partial fluorescence yield detection. In the native a-GeO samples a significant amount of sub-oxides was found. This sub-oxide content decreases with increasing annealing temperature. At elevated temperatures the formation of nanocrystals was observed. The results indicate a structure of a-GeO which consists of nanoscaled Ge and GeO2 clusters separated by sub-oxide interfaces.

Investigation of the amorphous to crystalline phase transition of chemical solution deposited Pb(Zr0.3Ti0.7)O3 thin films by soft X-ray absorption and soft X-ray emission spectroscopy

Chemical solution deposited (CSD) complex oxide thin films attract considerable interest in various emerging fields as for example, fuel cells, ferroelectric random access memories or coated conductors. In the present paper the results of soft-X-ray spectroscopy between 280 and 560 eV on the amorphous to crystalline phase transition of ferroelectric Pb(Zr0.3Ti0.7)O3 (PZT) thin films are presented. Five CSD samples derived from the same wafer coated with a PZT film pyrolyzed at 350 °C were heat treated at different temperatures between 400 and 700 °C. At first the samples were morphologically and electrically characterized. Subsequently the soft-X-ray absorption and emission experiments were performed at the undulator beamline 8.0 of the Advanced Light Source of the Lawrence Berkeley National Laboratory. Soft-X-ray absorption spectra were acquired for the Ti L 2,3-, O K-, and C K-edge thresholds by using simultaneously the total electron yield (TEY) and total fluorescence yield (TFY) detection methods. For two samples, annealed at 400 and 700 °C, respectively, the resonant inelastic soft-X-ray spectroscopy (RIXS) was applied for various excitation energies near the Ti L-, O K-edges. We observed clear evidence of a rutile phase at untypically low temperatures. This rutile phase transforms into the perovskite phase upon increasing annealing temperature. These results are discussed in the framework of current microscopic models of the PZT (111) texture selection.

Surface characterization ofMnxGe1−xandCryMnxGe1−x−ydilute magnetic semiconductors

We have used x-ray photoemission electron microscopy (XPEEM) and x-ray absorption spectroscopy (XAS) to characterize MnxGe1-x and CryMnxGe1-x-y films grown by molecular beam epitaxy. The surface layers of the as-grown films probed by XPEEM present segregation of Mn-rich phases. XAS using both total electron yield and fluorescence yield detection shows that the films are heavily oxidized after exposure to air. Etching in HF and HCl can be used to reduce oxidation, but inhomogeneities in the surface composition might not be completely eliminated depending on the Mn concentration. X-ray magnetic circular dichroism (XMCD) measurements reveal that neither the etched nor the as-grown films present remanent ferromagnetic behavior down to a temperature of 5 K within the probing depth of the fluorescence yield (similar to 20 nm). Mn is paramagnetic in both the oxidized and etched samples, with an increased tendency to order magnetically toward the interior of the films. Cr in CryMnxGe1-x-y possesses a paramagnetic moment only in the oxidized form. A comparison of the XAS line shapes obtained in the present study with those of Mn impurities deposited on Ge and GaAs surfaces demonstrates that the interpretation of XAS spectra of Mn-doped dilute magnetic semiconductors in the literature is often affected by residual oxidation.

Magnetic and chemical properties of Co2MnSi thin films compared to the Co2MnSi∕Al-O interface

The Heusler alloy Co2MnSi with theoretically predicted 100% spin polarization has been successfully implemented in Co2MnSi∕AlOx∕Co7Fe3 magnetic tunnel junctions recently. Here we investigated 100 nm thick Co2MnSi films grown on a vanadium buffer and capped by a thin alumina film. This stack is similar to the lower electrode including the tunneling barrier of magnetic tunnel junctions. By soft x-ray absorption spectroscopy and magnetic circular dichroism in fluorescence and total electron yield detection we determined differences between the chemical and magnetic properties of the Co2MnSi thin films and the Co2MnSi∕AlOx interface. Whereas MnO was formed directly at the interface during plasma oxidation of the Al layer, the interfacial Co was not oxidized and its x-ray absorption line shape at the L2,3 edge was similar to the line shape of bulk Co2MnSi. The atomically ordered bulk Co2MnSi showed characteristic differences in the x-ray absorption spectra in comparison with the disordered samples: in the ordered state of the bulk both, Co and Mn, showed additional shoulders about 4 eV above the L2,3 resonances, a large circular dichroism, and a pronounced x-ray absorption near edge fine structure. The same was found for interfacial Co, whereas for interfacial Mn these features were masked by the characteristic absorption multiplet structure of MnO right at the interface which also resulted in a strong reduction of the interfacial Mn moment in annealed samples.

Study of oxygen-C 60 compound formation by NEXAFS and RIXS

The interaction of oxygen with C60 molecules was studied on a C60 film which had been exposed simultaneously to oxygen and UV-light for 190 hours, producing an approximately C60O1 stoichiometry in the bulk of the sample. C K-edge and O K-edge NEXAFS (using total fluorescence yield detection) and resonant X-ray inelastic scattering (RIXS) spectra from the sample film were measured and the C K-edge data were compared to the spectra from pristine C60 as reference. The C K-edge absorption and emission spectral profiles of the oxygen-doped sample are similar to those of the C60 reference, suggesting that cage breaking of C60 under these conditions, if any, is negligible. However, the redistribution of intensities in the spectra indicates changes in the occupancies of different molecular orbitals, possibly due to changes in electron density upon reaction. Similarities of the O K-edge soft X-ray emission (SXES) spectra to several small oxygen-containing molecules is being discussed in terms of bonding models.

First-shell bond lengths inSixGe1−xcrystalline alloys

Si and Ge K-edge x-ray absorption fine structure (XAFS) spectra of strained and relaxed ${\mathrm{Si}}_{x}{\mathrm{Ge}}_{1\ensuremath{-}x}$ crystalline alloys grown by molecular beam epitaxy on Si(001) substrates are reported. For alloys with less than 30% Si, fluorescence yield detection is shown to be essential to avoid distortions of the Si K-edge XAFS signal caused by the underlying Ge L-edge XAFS signal from the majority Ge species. The average first shell structure has been deduced using simultaneous fitting of all data for relaxed alloys, while imposing physically reasonable constraints. The Ge-Ge, Ge-Si, and Si-Si first-shell distances are found to vary with composition. The results are compared with other experimental results and theoretical predictions in the literature. Our results are generally consistent with other experimental studies but they differ from recent theoretical predictions based on macroscopic elastic properties in that we observe a different compositional dependence [i.e., slope of $R(x)$ lines] for the Ge-Ge and Si-Si bond lengths. The slope for the Ge-Si bond length composition line was found to be intermediate between that of Si-Si and Ge-Ge.

Local structure of pre-alloyed Al/Y/SiCN nanopowders studied by XAS at the Al K-edge using fluorescence yield detection.

Local structure of pre-alloyed Al/Y/SiCN nanopowders studied by XAS at the Al K-edge using fluorescence yield detection.