Robust phase determination in complex solid solutions using diffuse multiple scattering.

A novel methodology is presented for identifying and distinguishing between structural phases in multi-phasic systems, such as piezoelectric materials like PMN-PT [Pb(Mg1/3Nb2/3)O3-PbTiO3], PIN-PMN-PT [Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3] and PZT [Pb(Zr,Ti)O3], using diffuse multiple scattering and Kossel line diffraction techniques. The method exploits the splitting of triple line intersections from special coplanar reflections combined with logical constraints to generate a splitting fingerprint for robust crystallographic phase determination and discrimination.

Rational redesign of the ferredoxin-NADP+-oxido-reductase/ferredoxin-interaction for photosynthesis-dependent H2-production.

Utilization of electrons from the photosynthetic water splitting reaction for the generation of biofuels, commodities as well as application in biotransformations requires a partial rerouting of the photosynthetic electron transport chain. Due to its rather negative redox potential and its bifurcational function, ferredoxin at the acceptor side of Photosystem 1 is one of the focal points for such an engineering. With hydrogen production as model system, we show here the impact and potential of redox partner design involving ferredoxin (Fd), ferredoxin-oxido-reductase (FNR) and [FeFe]­hydrogenase HydA1 on electron transport in a future cyanobacterial design cell of Synechocystis PCC 6803. X-ray-structure-based rational design and the allocation of specific interaction residues by NMR-analysis led to the construction of Fd- and FNR-mutants, which in appropriate combination enabled an about 18-fold enhanced electron flow from Fd to HydA1 (in competition with equimolar amounts of FNR) in in vitro assays. The negative impact of these mutations on the Fd-FNR electron transport which indirectly facilitates H2 production (with a contribution of ≤42% by FNR variants and ≤23% by Fd-variants) and the direct positive impact on the Fd-HydA1 electron transport (≤23% by Fd-mutants) provide an excellent basis for the construction of a hydrogen-producing design cell and the study of photosynthetic efficiency-optimization with cyanobacteria.

The interfacial nature of proximity-induced magnetism and the Dzyaloshinskii-Moriya interaction at the Pt/Co interface.

The Dzyaloshinskii-Moriya interaction has been shown to stabilise Nèel domain walls in magnetic thin films, allowing high domain wall velocities driven by spin current effects. The interfacial Dzyaloshinskii-Moriya interaction (IDMI) occurs at the interface between ferromagnetic and heavy metal layers with strong spin-orbit coupling, but details of the interaction remain to be understood and the role of proximity induced magnetism (PIM) in the heavy metal is unknown. Here IDMI and PIM are reported in Pt determined as a function of Au and Ir spacer layers in Pt/Co/Au,Ir/Pt. Both interactions are found to be sensitive to sub-nanometre changes in the spacer thickness, correlating over sub-monolayer spacer thicknesses, but not for thicker spacers where IDMI continues to change even after PIM is lost.

Si1-x Ge x /Si Interface Profiles Measured to Sub-Nanometer Precision Using uleSIMS Energy Sequencing.

The utility of energy sequencing for extracting an accurate matrix level interface profile using ultra-low energy SIMS (uleSIMS) is reported. Normally incident O2 (+) over an energy range of 0.25-2.5 keV were used to probe the interface between Si0.73Ge0.27/Si, which was also studied using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). All the SIMS profiles were linearized by taking the well understood matrix effects on ion yield and erosion rate into account. A method based on simultaneous fitting of the SIMS profiles measured at different energies is presented, which allows the intrinsic sample profile to be determined to sub-nanometer precision. Excellent agreement was found between the directly imaged HAADF-STEM interface and that derived from SIMS. Graphical Abstract ᅟ.

Long-range magnetic interactions and proximity effects in an amorphous exchange-spring magnet.

Low-dimensional magnetic heterostructures are a key element of spintronics, where magnetic interactions between different materials often define the functionality of devices. Although some interlayer exchange coupling mechanisms are by now well established, the possibility of direct exchange coupling via proximity-induced magnetization through non-magnetic layers is typically ignored due to the presumed short range of such proximity effects. Here we show that magnetic order can be induced throughout a 40-nm-thick amorphous paramagnetic layer through proximity to ferromagnets, mediating both exchange-spring magnet behaviour and exchange bias. Furthermore, Monte Carlo simulations show that nearest-neighbour magnetic interactions fall short in describing the observed effects and long-range magnetic interactions are needed to capture the extent of the induced magnetization. The results highlight the importance of considering the range of interactions in low-dimensional heterostructures and how magnetic proximity effects can be used to obtain new functionality.

Simultaneous dynamic electrical and structural measurements of functional materials.

A new materials characterization system developed at the XMaS beamline, located at the European Synchrotron Radiation Facility in France, is presented. We show that this new capability allows to measure the atomic structural evolution (crystallography) of piezoelectric materials whilst simultaneously measuring the overall strain characteristics and electrical response to dynamically (ac) applied external stimuli.

Focused-ion-beam induced interfacial intermixing of magnetic bilayers for nanoscale control of magnetic properties.

Modification of the magnetic properties in a thin-film ferromagnetic/non-magnetic bilayer system by low-dose focused ion-beam (FIB) induced intermixing is demonstrated. The highly localized capability of FIB may be used to locally control magnetic behaviour at the nanoscale. The magnetic, electronic and structural properties of NiFe/Au bilayers were investigated as a function of the interfacial structure that was actively modified using focused Ga(+) ion irradiation. Experimental work used MOKE, SQUID, XMCD as well as magnetoresistance measurements to determine the magnetic behavior and grazing incidence x-ray reflectivity to elucidate the interfacial structure. Interfacial intermixing, induced by low-dose irradiation, is shown to lead to complex changes in the magnetic behavior that are associated with monotonic structural evolution of the interface. This behavior may be explained by changes in the local atomic environment within the interface region resulting in a combination of processes including the loss of moment on Ni and Fe, an induced moment on Au and modifications to the spin-orbit coupling between Au and NiFe.

Depth-dependent magnetism in epitaxial MnSb thin films: effects of surface passivation and cleaning.

Depth-dependent magnetism in MnSb(0001) epitaxial films has been studied by combining experimental methods with different surface specificities: polarized neutron reflectivity, x-ray magnetic circular dichroism (XMCD), x-ray resonant magnetic scattering and spin-polarized low energy electron microscopy (SPLEEM). A native oxide ∼4.5 nm thick covers air-exposed samples which increases the film's coercivity. HCl etching efficiently removes this oxide and in situ surface treatment of etched samples enables surface magnetic contrast to be observed in SPLEEM. A thin Sb capping layer prevents oxidation and preserves ferromagnetism throughout the MnSb film. The interpretation of Mn L(3,2) edge XMCD data is discussed.

Strain dependent selection of spin-slip phases in sputter deposited thin-film epitaxial holmium.

We report the structural and magnetic characterization of sputter deposited epitaxial Ho. We present room temperature characterization by atomic force microscopy and x-ray diffraction and temperature dependent characterization by x-ray diffraction and neutron diffraction. The data show the onset and change of the magnetic state as a function of temperature. Films of different thickness, exhibiting signs of differing epitaxially induced strain, tend towards specific spin-slip phases in the low temperature regime. The more highly strained thinnest films tend towards values with a longer magnetic wavelength.

Identification of N-terminal regions of wheat leaf ferredoxin NADP+ oxidoreductase important for interactions with ferredoxin.

Wheat leaves contain two isoproteins of the photosynthetic ferredoxin:NADP(+) reductase (pFNRI and pFNRII). Truncated forms of both enzymes have been detected in vivo, but only pFNRII displays N-terminal length-dependent changes in activity. To investigate the impact of N-terminal truncation on interaction with ferredoxin (Fd), recombinant pFNRII proteins, differing by deletions of up to 25 amino acids, were generated. During purification of the isoproteins found in vivo, the longer forms of pFNRII bound more strongly to a Fd affinity column than did the shorter forms, pFNRII(ISKK) and pFNRII[N-2](KKQD). Further truncation of the N-termini resulted in a pFNRII protein which failed to bind to a Fd column. Similar k(cat) values (104-140 s(-1)) for cytochrome c reduction were measured for all but the most truncated pFNRII[N-5](DEGV), which had a k(cat) of 38 s(-1). Stopped-flow kinetic studies, examining the impact of truncation on electron flow between mutant pFNRII proteins and Fd, showed there was a variation in k(obs) from 76 to 265 s(-1) dependent on the pFNRII partner. To analyze the sites which contribute to Fd binding at the pFNRII N-terminal, three mutants were generated, in which a single or double lysine residue was changed to glutamine within the in vivo N-terminal truncation region. The mutations affected binding of pFNRII to the Fd column. Based on activity measurements, the double lysine residue change resulted in a pFNRII enzyme with decreased Fd affinity. The results highlight the importance of this flexible N-terminal region of the pFNRII protein in binding the Fd partner.