Resonant Grazing-Incidence Small-Angle X-ray Scattering at the Sulfur K-Edge for Material-Specific Investigation of Thin-Film Nanostructures

Abstract

Scattering techniques are a powerful tool for probing thin-film nanomorphologies but often require additional characterization by other methods. We applied the well-established grazing-incidence small-angle X-ray scattering (GISAXS) technique for a selection of energies around the absorption edge of sulfur to exploit the resonance effect (grazing incidence resonant tender X-ray scattering, GIR-TeXS) of the sulfur atoms within a poly(3-hexylthiophene-2,5-diyl):phenyl-C61-butyric acid methyl ester (P3HT:PC61BM) sample to gain information about the composition of the film morphology. With this approach, it is possible not only to identify structures within the investigated thin film but also to link them to a particular material combination.

Photoacid-Modified Nafion Membrane Morphology Determined by Resonant X-ray Scattering and Spectroscopy

“…However, very limited studies have implemented RXS at energies near the sulfur K-edge to investigate polymeric materials in general. [33][34][35] In this study, we show that attachment of photoacid dyes to Nafion alters ionomer domain spacing and short-range order. RXS in the tender X-ray regime, which includes the sulfur K-edge (around 2.5 keV or 0.5 nm), has enhanced contrast due to the presence of sulfur-containing functional groups on both the Nafion side-chain (sulfonate) and the attached photoacid dye (sulfonamide), and this enables probing of internal morphology.…”

Resonant soft X‐ray scattering in polymer science

“…At the thin side, beam damage becomes a major concern as increased exposure times are necessary, while at the thick side the thin film approximations begin to break down, absorption reduces the signal and fluorescence becomes a larger component of a measured signal. There is promise of work in a reflection geometry, 56,77 which would allow for at least the surfaces of bulk samples to be measured. The thickness requirement for transmission measurements extends to the film substrate as well.…”

“…This higher energy is often called tender rather than Soft, but many of the sample requirements are still quite important, and all measurements take place in a vacuum environment with thin samples supported on a substrate in transmission geometry. 64,77,126 The use of sulfur edge for RSoXS measurements allow for analysis more akin to REXS, where utilizing the extra information of a unit cell can allow for much more concrete information content to be available. In cases of polymers containing these higher Z atoms, it is highly advantageous to collect measurements at each of those edges to determine the structure completely, although spanning many energies would likely require multiple beamlines and measurements.…”

Vacuum-compatible photon-counting hybrid pixel detector for wide-angle x-ray scattering, x-ray diffraction, and x-ray reflectometry in the tender x-ray range

“…An in-vacuum PILATUS 1M is part of the smallangle X-ray scattering (SAXS) setup at the four-crystal monochromator (FCM) beamline in the laboratory of the Physikalisch-Technische Bundesanstalt (PTB) and is described in detail by Wernecke et al 3 . It is successfully applied for SAXS 4,5 and grazing incidence SAXS (GISAXS) [6][7][8] . In contrast to commercially available hybrid pixel detectors which are operated in air, the invacuum PILATUS 1M can access lower photon energies in the tender X-ray regime covered by the FCM beamline 3 .…”