K. P. Nagle

Surface Characterization of Polythiophene:Fullerene Blends on Different Electrodes Using Near Edge X-Ray Absorption Fine Structure

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.

A short working distance multiple crystal x-ray spectrometer

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.

Momentum-resolved Resonant and Nonresonant Inelastic X-ray Scattering at the Advanced Photon Source

The study of electronic excitations by inelastic X-ray scattering (IXS) has a rich history. Very early IXS work, for example, provided seminal demonstrations of the validity of relativistic kinematics and the quantum hypothesis [1] and of Fermi-Dirac statistics [2]. While there have been many important results in the interim [3], it has been the development of the third generation light sources together with continuing innovations in the manufacture and implementation [4–6] of dispersive X-ray optics that has led to the rapid growth of IXS studies of electronic excitations.

Deconvolving instrumental and intrinsic broadening in core-shell x-ray spectroscopies

Intrinsic and experimental mechanisms frequently lead to broadening of spectral features in core-shell 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 full width at half maximum 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 in 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.

The local electronic structure of α-Li3N

New theoretical and experimental investigations of the occupied and unoccupied local electronic densities of states (DOS) are reported for alpha-Li(3)N. Band-structure and density-functional theory calculations confirm the absence of covalent bonding character. However, real-space full-multiple-scattering (RSFMS) calculations of the occupied local DOS find less extreme nominal valences than have previously been proposed. Nonresonant inelastic x-ray scattering, RSFMS calculations, and calculations based on the Bethe-Salpeter equation are used to characterize the unoccupied electronic final states local to both the Li and N sites. There is a good agreement between experiment and theory. Throughout the Li 1s near-edge region, both experiment and theory find strong similarities in the s-and p-type components of the unoccupied local final DOS projected onto an orbital angular momentum basis (l-DOS). An unexpected, significant correspondence exists between the near-edge spectra for the Li 1s and N 1s initial states. We argue that both spectra are sampling essentially the same final DOS due to the combination of long core-hole lifetimes, long photoelectron lifetimes, and the fact that orbital angular momentum is the same for all relevant initial states. Such considerations may be generally applicable for low atomic number compounds.

Reducing radiation damage in macromolecular crystals at synchrotron sources

A new strategy is presented to reduce primary X-ray damage in macromolecular crystallography. The strategy is based on separating the diffracting and damaged regions as much as feasible. The source of the radiation damage to macromolecular crystals is from two primary mechanisms: the direct excitations of electrons by absorption, and inelastic scattering of the X-rays. The first produces photoelectrons with their accompanying Auger electrons from relaxation of the core hole and the second creates Compton electrons. The properties of these two mechanisms and calculations of primary X-ray damage quantify how to modify the spatial distribution of X-rays to reduce the deleterious effects of radiation damage. By focusing the incident X-rays into vertical stripes, it is estimated that the survival (the time during which quality diffraction data can be obtained with a given X-ray flux) of large crystals can be increased by at least a factor of 1.6, while for very small platelet crystals the survival can be increased by up to a factor of 14.

Effect of Pore Morphology on the Electrochemical Properties of Electric Double Layer Carbon Cryogel Supercapacitors

In this study a group of resorcinol-formaldehyde carbon cryogels (CC) have been processed chemically, via catalysis and activation, to obtain varied nanostructures and pore size distributions. To understand the relation between structure and electrochemical properties the capacitor can be studied as a dielectric system composed of a porous electrode and the electrolyte (Tetraethylammonium tetrafluoroborate in propylene carbonate). Using Electrochemical impedance spectroscopy (EIS) the complex capacitance and power are used to study the behavior of the system below the relaxation frequency f o (φ = −45°). Therefore, the relaxation of the capacitor system at the low frequency range, f f o , may be used as a measure of pore/electrolyte interaction. The approach here proposed also allows for a direct experimental characterization of the capacitance and power at low frequencies where small pores are likely to affect the diffusion dynamics of the electrolyte molecules. The results suggest a correlation between the occurrence of small micropores and that of high power losses that are related to the resistive element produced at the low frequency range. Moreover, the impact of the micropore structure upon the supercapacitors performance is apparent in its capacitance and energy as well. In addition to the complex power and capacitance other measurements including BET Nitrogen sorption, cyclic voltammetry, galvanic cycling and X-Ray Raman Scattering were used to characterize the samples and support these results.