I07-Surface & interface diffraction
|
Abstract: The nanoscale morphology within the photoactive layer of organic solar cells is critical in determining the power conversion efficiency (PCE). Here, we draw attention to the roles of molecular arrangement, and domain size in improving performance, which can be tuned by subjecting the photovoltaic materials to solvent vapor annealing (SVA). In our PTB7-Th:ITIC devices, the PCE can be improved by exposing the device to solvent vapor for 60 s after solution casting. The solvent vapor prolongs reorganizational time and increases molecular ordering and domain size/phase separation, which are sub-optimal in pristine PTB7-Th:ITIC blend films. This improved morphology results in better charge mobility, reduced recombination, and ultimately an improved PCE from 7.1% to 7.9% when using CS2 as the annealing solvent. This simple SVA technique can be applied to a range of OPV systems where the molecular ordering is inferior within the as-cast photoactive layer.
|
Oct 2019
|
|
I15-Extreme Conditions
|
Hangboce
Yin
,
Yongjiang
Huang
,
Dominik
Daisenberger
,
Peng
Xue
,
Songshan
Jiang
,
Weinan
Ru
,
Sida
Jiang
,
Ying
Bao
,
Xilei
Bian
,
Xing
Tong
,
Hongxian
Shen
,
Jianfei
Sun
Diamond Proposal Number(s):
[17412]
Abstract: The atomic structure evolution of Gd36Tb20Co20Al24 high entropy metallic glass microwire from room to cryogenic temperature has been studied by in-situ high energy synchrotron X-ray diffraction. During the cooling process, the atomic volume decreases. For short-range order, the coordination numbers of all atomic pairs increase. As the temperature decreases, bond lengths of large atom-small atom and small atom-small atom pairs keep decreasing whereas that of large atom-large atom pairs unexpectedly increases continuously. The mechanism of atomic structure evolution is proposed, which might be helpful for better understanding the low temperature magnetocaloric effect of high entropy metallic glasses.
|
Apr 2019
|
|
I04-Macromolecular Crystallography
|
Samuel T.
Cahill
,
Jonathan M.
Tyrrell
,
Iva
Hopkins Navratilova
,
Karina
Calvopina
,
Sean W.
Robinson
,
Christopher T.
Lohans
,
Michael A.
Mcdonough
,
Ricky
Cain
,
Colin W. G.
Fishwick
,
Matthew B.
Avison
,
Timothy R.
Walsh
,
Christopher J.
Schofield
,
Jurgen
Brem
Abstract: Background: The β-lactam antibiotics represent the most successful drug class for treatment of bacterial infections. Resistance to them, importantly via production of β-lactamases, which collectively are able to hydrolyse all classes of β-lactams, threatens their continued widespread use. Bicyclic boronates show potential as broad spectrum inhibitors of the mechanistically distinct serine- (SBL) and metallo- (MBL) β-lactamase families. Methods: Using biophysical methods, including crystallographic analysis, we have investigated the binding mode of bicyclic boronates to clinically important β-lactamases. Induction experiments and agar-based MIC screening against MDR-Enterobacteriaceae (n = 132) were used to evaluate induction properties and the in vitro efficacy of a bicyclic boronate in combination with meropenem. Results: Crystallographic analysis of a bicyclic boronate in complex with AmpC from Pseudomonas aeruginosa reveals it binds to form a tetrahedral boronate species. Microbiological studies on the clinical coverage (in combination with meropenem) and induction of β-lactamases by bicyclic boronates further support the promise of such compounds as broad spectrum β-lactamase inhibitors. Conclusions: Together with reported studies on the structural basis of their inhibition of class A, B and D β-lactamases, biophysical studies, including crystallographic analysis, support the proposal that bicyclic boronates mimic tetrahedral intermediates common to SBL and MBL catalysis. General significance: Bicyclic boronates are a new generation of broad spectrum inhibitors of both SBLs and MBLs.
|
Apr 2019
|
|
I15-Extreme Conditions
|
Diamond Proposal Number(s):
[10617, 11896, 15288, 17994]
Abstract: We report on laser-heated diamond anvil cell (LHDAC) experiments in the FeO–MgO–SiO2–CO2 (FMSC) and CaO–MgO–SiO2–CO2 (CMSC) systems at lower mantle pressures designed to test for decarbonation and diamond forming reactions. Sub-solidus phase relations based on synthesis experiments are reported in the pressure range of ∼35 to 90 GPa at temperatures of ∼1600 to 2200 K. Ternary bulk compositions comprised of mixtures of carbonate and silica are constructed such that decarbonation reactions produce non-ternary phases (e.g. bridgmanite, Ca-perovskite, diamond, CO2–V), and synchrotron X-ray diffraction and micro-Raman spectroscopy are used to identify the appearance of reaction products. We find that carbonate phases in these two systems react with silica to form bridgmanite ±Ca-perovskite + CO2 at pressures in the range of ∼40 to 70 GPa and 1600 to 1900 K in decarbonation reactions with negative Clapeyron slopes. Our results show that decarbonation reactions form an impenetrable barrier to subduction of carbonate in oceanic crust to depths in the mantle greater than ∼1500 km. We also identify carbonate and CO2–V dissociation reactions that form diamond plus oxygen. On the basis of the observed decarbonation reactions we predict that the ultimate fate of carbonate in oceanic crust subducted into the deep lower mantle is in the form of refractory diamond in the deepest lower mantle along a slab geotherm and throughout the lower mantle along a mantle geotherm. Diamond produced in oceanic crust by subsolidus decarbonation is refractory and immobile and can be stored at the base of the mantle over long timescales, potentially returning to the surface in OIB magmas associated with deep mantle plumes.
|
Apr 2019
|
|
B18-Core EXAFS
|
Diamond Proposal Number(s):
[7943]
Abstract: Using Ce LIII edge X-ray absorption near edge spectroscopy (XANES), it is shown that acceptor dopants introduced to cerium members of the rare earth ortho-niobate series, Ce1-xSrxNbO4±δ and Ce1-xCaxNbO4±δ, are charge compensated by the formation of holes on the cerium sublattice. These spectroscopic studies are complemented by structural studies, using X-ray and neutron powder diffraction, determining that the solubility limit of the strontium and calcium dopants within the CeNbO4+δ structure is ~10% and ~30% respectively. Under oxidising conditions, the Ce3+/Ce4+ redox couple facilitates reversible redox processes, and it is observed that the Ce1-xSrxNbO4±δ and Ce1-xCaxNbO4±δ materials form commensurate and incommensurately modulated oxygen hyperstoichiometric phases as a function of temperature. Under reducing atmospheres, this redox activity is suppressed, and charge-compensating Ce4+ holes are annihilated.
|
Mar 2019
|
|
|
Open Access
Abstract: Smooth CrSb(0001) films have been grown by molecular beam epitaxy on MnSb(0001) – GaAs(111) substrates. CrSb(0001) shows (2 × 2), triple domain (1 × 4) and (√3×√3)R30° reconstructed surfaces as well as a (1 × 1) phase. The dependence of reconstruction on substrate temperature and incident fluxes is very similar to MnSb(0001).
|
Mar 2019
|
|
I19-Small Molecule Single Crystal Diffraction
|
Diamond Proposal Number(s):
[18735]
Abstract: The compound Cp(IPr)Ru(H)2SiH(Ph)Cl (IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene) (1) was subject to low temperature (30 K), high resolution X-ray structural analysis to obtain a high quality electron density map. This map was subject to a Bader analysis to ascertain the possibility of a Ru–H⋯Si interaction. For comparison, DFT calculations employing the well known B3LYP functional in conjunction with a triple zeta basis set was employed. Thus, we not only report the results of a possible Ru–H⋯Si interaction but also benchmark the use of the employed level of theory against experimental results.
|
Mar 2019
|
|
I18-Microfocus Spectroscopy
|
Open Access
Abstract: We have determined the chemical speciation of dissolved sulfur and the sulfur concentration at fixed oxygen and sulfur fugacities for a wide range of silicate melt compositions (from Fe-rich basalt to dacite). Each melt was equilibrated at 1300 °C and 1-atmosphere pressure at oxygen fugacities (fO2) between −1.67 and +1.6 log units relative to the Fayalite–Magnetite–Quartz (FMQ) buffer and absolute sulfur fugacities between −5.1 and −1.2 log units. The fO2 and fS2 of the experiments were controlled by using gas mixtures of CO–CO2–SO2. The speciation of sulfur in the quenched glasses was determined using both X-ray Absorption Near-Edge Spectroscopy (XANES), and from the dependence of equilibrium sulfur concentration on the fS2/fO2 ratio measured by secondary-ion mass spectrometry (SIMS) and electron microprobe.
The speciation of dissolved sulfur in each melt undergoes an abrupt transformation from S2− to S6+ with increasing fO2, and this transition is shifted ∼0.5 log units higher in fO2 as melt FeO concentration increases from ∼5 wt% to ∼18 wt%. Since sulfide concentrations at constant fO2 and fS2 are consistently greater for more FeO-rich melts, the compositional effect on speciation may be explained by the well-known sensitivity of the sulfide capacity (
CS2−
) of the melt to FeO concentration.
S6+/S2− ratios for the glasses exhibit a linear relationship with Fe3+/Fe2+, indicating that the redox couples for iron and sulfur can be directly related to one another. We used thermodynamic data to model the interrelationship between Fe and S oxidation states in terms of the equilibrium
FeS+8FeO1.5=8FeO+FeSO4
Fitting the data to our experiments at 1300 °C we obtained the following expression for the temperature-dependence of speciation:
log(S6+S2−)=8log(Fe3+Fe2+)+8.7436×106T2−27703T+20.273
This equation fits the data for all our compositions and is also consistent with earlier results at 1050 °C and 950 °C. We used the interdependence of S and Fe oxidation states to infer electron transfer between Fe2+ and S6+ during quenching of glasses from Mauna Kea, Hawaii. The effect is sufficient to cause significant overestimation of equilibrium Fe3+/ΣFe in natural glasses and corresponding overestimate of fO2 by about 0.8 log units.
Glasses equilibrated under the most oxidizing conditions (containing S6+ only) have equilibrium S concentrations that are negatively correlated with their mole fractions of tetrahedral (Si + Ti) cations.
|
Feb 2019
|
|
I02-Macromolecular Crystallography
|
Diamond Proposal Number(s):
[5745, 8028]
Abstract: Many myodocopid ostracods are unusual in that they have well-developed compound eyes yet must view their environment through a shell. The cypridinid Macrocypridina castanea is relatively large among ostracods (about 5–10 mm) and is a pelagic predator. This species possess highly pigmented shells with a transparent region lying just above the eye. Here we examine the ultrastructure and transparency of this window using electron microscopy, serial-block face scanning electron microscopy and X-ray diffraction analysis and optical modelling. An internal, laminar stack was identified within the window region of the shell that formed a more regular half-wave reflector than in non-window regions, and where the distance between molecules in the chitin–protein fibrils decreases as compared to the non-window area. This results in excellent transmission properties—at around 99% transmission—for wavelengths between 350 and 630 nm due to its half-wave reflector organization. Therefore, blue light, common in the mid and deep sea, where this species inhabits, would be near-optimally transmitted as a consequence of the sub-micrometre structuring of the shell, thus optimizing the ostracod's vision. Further, pore canals were identified in the shell that may secrete substances to prevent microbial growth, and subsequently maintain transparency, on the shell surface.
|
Feb 2019
|
|
I10-Beamline for Advanced Dichroism
|
Wenjing
Li
,
Iuliia
Bykova
,
Shilei
Zhang
,
Guoqiang
Yu
,
Riccardo
Tomasello
,
Mario
Carpentieri
,
Yizhou
Liu
,
Yao
Guang
,
Joachim
Gräfe
,
Markus
Weigand
,
David M.
Burn
,
Gerrit
Van Der Laan
,
Thorsten
Hesjedal
,
Zhengren
Yan
,
Jiafeng
Feng
,
Caihua
Wan
,
Jinwu
Wei
,
Xiao
Wang
,
Xiaomin
Zhang
,
Hongjun
Xu
,
Chenyang
Guo
,
Hongxiang
Wei
,
Giovanni
Finocchio
,
Xiufeng
Han
,
Gisela
Schütz
Diamond Proposal Number(s):
[18898]
Abstract: Room temperature magnetic skyrmions in magnetic multilayers are considered as information carriers for future spintronic applications. Currently, a detailed understanding of the skyrmion stabilization mechanisms is still lacking in these systems. To gain more insight, it is first and foremost essential to determine the full real-space spin configuration. Here, two advanced X-ray techniques are applied, based on magnetic circular dichroism, to investigate the spin textures of skyrmions in [Ta/CoFeB/MgO]n multilayers. First, by using ptychography, a high-resolution diffraction imaging technique, the 2D out-of-plane spin profile of skyrmions with a spatial resolution of 10 nm is determined. Second, by performing circular dichroism in resonant elastic X-ray scattering, it is demonstrated that the chirality of the magnetic structure undergoes a depthdependent evolution. This suggests that the skyrmion structure is a complex 3D structure rather than an identical planar texture throughout the layer stack. The analyses of the spin textures confirm the theoretical predictions that the dipole–dipole interactions together with the external magnetic field play an important role in stabilizing sub-100 nm diameter skyrmions and the hybrid structure of the skyrmion domain wall. Our combined X-ray-based approach opens the door for in-depth studies of magnetic skyrmion systems, which allows for precise engineering of optimized skyrmion heterostructures.
|
Feb 2019
|
|