Disorder models from reciprocal space analysis in single crystal diffuse scattering

The thesis presented here deals with complex diffuse diffraction patterns. The analysis of disorder diffuse scattering in molecular materials is approached by the derivation of analytical expressions for displacement and/or substitutional disorder. Complex diffraction patterns of atomistic systems with diffuse maxima at general positions in reciprocal space, sharp satellites on top of diffuse scattering, or highly structured plane or curved diffuse features, are treated with a novel modulation wave approach.Die vorliegende Dissertation mit dem Titel „Fehlordnungsmodelle durch Analyse des reziproken Raums in diffuser Einkristallstreuung“ beschäftigt sich mit der Analyse komplex verteilter diffuser Streuung im reziproken Raum. Diffuse Streuung aufgrund von Fehlordnung in molekularen Materialien wird über die Herleitung analytischer Ausdrücke für Besetzungs- und Verschiebungsfehlordung behandelt. Die komplexen Beugungsdiagramme von atomaren Systemen, welche diffuse Maxima auf allgemeinen Positionen im reziproken Raum zeigen, scharfe Satelliten auf breiter, diffuser Streuung oder stark strukturierte planare oder gebogene diffuse Verteilungen, werden über einen neuartigen Modulationswellen-Ansatz interpretiert

Quantitative three-dimensional local order analysis of nanomaterials through electron diffraction

Structure-property relationships in ordered materials have long been a core principle in materials design. However, the introduction of disorder into materials provides structural flexibility and thus access to material properties that are not attainable in conventional, ordered materials. To understand disorder-property relationships, the disorder – i.e., the local ordering principles – must be quantified. Local order can be probed experimentally by diffuse scattering. The analysis is notoriously difficult, especially if only powder samples are available. Here, we combine the advantages of three-dimensional electron diffraction – a method that allows single crystal diffraction measurements on sub-micron sized crystals – and three-dimensional difference pair distribution function analysis (3D-ΔPDF) to address this problem. In this work, we compare the 3D-ΔPDF from electron diffraction data with those obtained from neutron and x-ray experiments of yttria-stabilized zirconia (Zr0.82Y0.18O1.91) and demonstrate the reliability of the proposed approach

Direct interpretation of the X-ray and neutron three-dimensional difference pair distribution functions (3D-ΔPDFs) of yttria-stabilized zirconia

Three-dimensional difference pair distribution functions (3D-ΔPDFs) from X-ray and neutron diffraction experiments are reported for yttria-stabilized zirconia (Zr0.82Y0.18O1.91). A quantitative analysis of the signatures in the three-dimensional difference pair distribution functions is used to establish that oxygen ions neighbouring a vacancy shift by 0.525 (5) Å along ⟨1, 0, 0⟩ towards the vacancy while metal ions neighbouring a vacancy shift by 0.465 (2) Å along ⟨1, 1, 1⟩ away from the vacancy. The neutron 3D-ΔPDF shows a tendency for vacancies to cluster along ⟨½, ½, ½⟩, which results in sixfold coordinated metal ions

Interplay of thermal diffuse scattering and correlated compositional disorder in KCl1−xBrx

Single-crystal X-ray diffuse scattering measurements are reported of the compositional series KCl1–xBrx, a model system for the broader family of disordered rocksalts. Using a combination of Monte Carlo simulations and attice dynamical calculations, we show that the observed diffuse scattering is well described in terms of (i) non-statistical anion distributions, (ii) local lattice relaxations accompanying Cl/Br substitution, and (iii) the contribution from low-energy phonons. It is found that a tendency for compositional domain formation broadens the thermal diffuse scattering by splitting and softening the acoustic phonon branches. This effect, which is strongest for intermediate compositions, is seen in both experiment and calculation alike. These results establish a link between local compositional order and unconventional lattice dynamics in this system, and reinforce emerging design principles of exploiting compositional fluctuations to tailor physical properties, such as thermal conductivity, that depend on phonon broadening

Crystal-structure of active layers of small molecule organic photovoltaics before and after solvent vapor annealing

It is demonstrated by a detailed structural analysis that the crystallinity and the efficiency of small molecule based organic photovoltaics can be tuned by solvent vapor annealing (SVA). Blends made of the small molecule donor 2,2′-[(3,3′″,3″″,4′-tetraoctyl[2,2′:5′,2″:5″,2′″:5′″,2″″-quinquethiophene]-5,5″″-diyl)bis[(Z)-methylidyne(3-ethyl-4-oxo-5,2-thiazolidinediylidene)]]bis-propanedinitrile (DRCN5T) and the acceptor [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) were annealed using solvent vapors with either a high solubility for the donor (tetrahydrofuran), the acceptor (carbon disulfide) or both (chloroform). The samples were analyzed by grazing-incidence wide-angle X-ray scattering (GIWAXS), electron diffraction, X-ray pole figures, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). A phase separation of DRCN5T and PC71BM is induced by SVA leading to a crystallization of DRCN5T and the formation of a DRCN5T enriched layer. The DRCN5T crystallites possess the two dimensional oblique crystal system with the lattice parameters a = 19.2 Å, c = 27.1 Å, and β = 111.1° for the chloroform case. No major differences in the crystal structure for the other solvent vapors were observed. However, the solvent choice strongly influences the size of the DRCN5T enriched layer. Missing periodicity in the [010]-direction leads to the extinction of all Bragg reflections with k ≠ 0. The annealed samples are randomly orientated with respect to the normal of the substrate (fiber texture)