V2O5 xerogel films were fabricated by casting V2O5 sols onto fluorine-doped tin oxide (FTO) glass substrates and annealing at 300 °C for 3 h in different annealing atmospheres of air and nitrogen. Films prepared in different annealing conditions possess different grain sizes and crystallinity, while the vanadium ion oxidation state also varies, as identified by X-ray absorption spectroscopy. A nitrogen annealing atmosphere induces the presence of defects, such as V4+ ions, and associated oxygen vacancies. Thus, the presence of defects, whether on the film surface or in the bulk, can be controlled by using air and nitrogen annealing atmospheres in the proper order. Electrochemical impedance analyses reveal enhanced charge-transfer conductivity in films with more V4+ and oxygen vacancies on the film surface, that is, a film annealed, first, for 0.5 h in air and then for 2.5 h in nitrogen. Lithium-ion intercalation measurements show that, at a charge/discharge current density of 600 mA g−1, this film possesses a noticeably better lithium-ion storage capability than films without surface defects. This sample starts with an initial discharge capacity of 139 mA h g−1, and the capacity increases slowly to a maximum value of 156 mA h g−1 in the 15th cycle, followed by a mild capacity degradation in later cycles. After 50 cycles, the discharge capacity is still as high as 136 mA h g−1. A much improved lithium-ion intercalation capacity and cyclic stability are attributed to V4+ surface defects and associated oxygen vacancies introduced by N2 annealing.

We study the top surface composition of blends of the conjugated polymer regioregular poly-3-hexylthiophene (P3HT) with the fullerene (6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM), an important model system for organic photovoltaics (OPVs), using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). We compare the ratio of P3HT to PCBM near the air/film interface that results from preparing blend films on two sets of substrates: (1) poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) coated indium tin oxide (ITO) as is commonly used in conventional OPV structures and (2) ZnO substrates that are either unmodified or modified with a C(60)-like self-assembled monolayer, similar to those that have been recently reported in inverted OPV structures. We find that the top surface (the film/air interface) is enriched in P3HT compared to the bulk, regardless of substrate or annealing conditions, indicating that changes in device performance due to substrate modification treatments should be attributed to the buried substrate/film interface and the bulk of the film rather than the exposed film/air interface.

Intrinsic and experimental mechanisms frequently lead to broadening of spectral features in excited-state spectroscopies. For example, intrinsic broadening occurs in x-ray absorption spectroscopy (XAS) measurements of heavy elements where the core-hole lifetime is very short. On the other hand, nonresonant x-ray Raman scattering (XRS) and other energy loss measurements are more limited by instrumental resolution. Here, we demonstrate that the Richardson-Lucy (RL) iterative algorithm provides a robust method for deconvolving instrumental and intrinsic resolutions from typical XAS and XRS data.For the K-edge XAS of Ag, we find nearly complete removal of ~9.3 eV FWHM broadening from the combined effects of the short core-hole lifetime and instrumental resolution. We are also able to remove nearly all instrumental broadening in an XRS measurement of diamond, with the resulting improved spectrum comparing favorably with prior soft x-ray XAS measurements. We present a practical methodology for implementing the RL algorithm to these problems, emphasizing the importance of testing for stability of the deconvolution process against noise amplification, perturbations in the initial spectra, and uncertainties in the core-hole lifetime.

Bound-state, valence electronic excitation spectra of N2 are probed by nonresonant inelastic x-ray and electron scattering. Within usual theoretical treatments, dynamical structure factors derived from the two probes should be identical. However, we find strong disagreements outside the dipole scattering limit, even at high probe energies. This suggests an unexpectedly important contribution from intramolecular multiple scattering of the probe electron from core electrons or the nucleus. These effects should grow progressively stronger as the atomic number of the target species increases.

For x-ray spot sizes of a few tens of microns or smaller, a millimeter-sized flat analyzer crystal placed approximately 1 cm from the sample will exhibit high energy resolution while subtending a collection solid angle comparable to that of a typical spherically bent crystal analyzer (SBCA) at much larger working distances. Based on this observation and a nonfocusing geometry for the analyzer optic, we have constructed and tested a short working distance (SWD) multicrystal x-ray spectrometer. This prototype instrument has a maximum effective collection solid angle of 0.14 sr, comparable to that of 17 SBCA at 1 m working distance. We find good agreement with prior work for measurements of the Mn Kbeta x-ray emission and resonant inelastic x-ray scattering for MnO, and also for measurements of the x-ray absorption near-edge structure for Dy metal using Lalpha(2) partial-fluorescence yield detection. We discuss future applications at third- and fourth-generation light sources. For concentrated samples, the extremely large collection angle of SWD spectrometers will permit collection of high-resolution x-ray emission spectra with a single pulse of the Linac Coherent Light Source. The range of applications of SWD spectrometers and traditional multi-SBCA instruments has some overlap, but also is significantly complementary.