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The reversible device performance of organic solar cells is caused by light-induced long-persistent radicals, and can be released with activation energy provided by thermal annealing.
Solid–gas reactions and in situ powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF 3 ) 3 Pz]Ag} 3 and {[4-Br-3,5-(CF 3 ) 2 Pz]Ag} 3 supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver–ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF 3 ) 2 Pz]Ag} 3 under ethylene pressure and low-temperature conditions stops at an unusual silver–ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer–dimer reorganizations described above. Complete structural data of three novel silver–ethylene complexes are presented together with a thorough computational analysis of the mechanism.
A unique prospect of using halides as charge carriers is the possibility of the halides undergoing anodic redox behaviors when serving as charge carriers for the charge-neutrality compensation of electrodes. However, the anodic conversion of halides to neutral halogen species has often been irreversible at room temperature due to the emergence of diatomic halogen gaseous products. Here, we report that chloride ions can be reversibly converted to near-neutral atomic chlorine species in the Mn 3 O 4 electrode at room temperature in a highly concentrated chloride-based aqueous electrolyte. Notably, the Zn 2+ cations inserted in the first discharge and trapped in the Mn 3 O 4 structure create an environment to stabilize the converted chlorine atoms within the structure. Characterization results suggest that the Cl/Cl - redox is responsible for the observed large capacity, as the oxidation state of Mn barely changes upon charging. Computation results corroborate that the converted chlorine species exist as polychloride monoanions, e.g., [Cl 3 ] - and [Cl 5 ] - , inside the Zn 2+ -trapped Mn 3 O 4 , and the presence of polychloride species is confirmed experimentally. Our results point to the halogen plating inside electrode lattices as a new charge-storage mechanism.
An in-depth study of “Li 4 Mn 2 O 5 ”, a nanocomposite of Li 2 O and Li 4-x Mn 2 O 5 with a disordered rock salt structure (LMO), was conducted to determine the origins of the observed anomalously high charge and discharge capacity in lithium cells, which can exceed 350 mA h g -1 . Using soft and hard X-ray absorption spectroscopy (XAS), mapping of resonant inelastic X-ray scattering (mRIXS), and X-ray Raman spectroscopy (XRS), it was determined that electrochemical decomposition of Li 2 O upon charge and reduction of Mn to below 3+ during discharge is responsible for the capacities that are observed, with no evidence of contributions from reversible oxygen redox. Here, the over-reduction is exacerbated when charging limits of 4.5–4.8 V are used due to side reactions between electrolytic solution and the highly oxidized active material. These side reactions result in dissolution of Mn at room temperature and release of oxygen and other gases during initial cycles, which, in turn, cause rapid capacity fading. This is accompanied by evolution of the voltage profile upon cycling towards one that resembles that of manganese oxide spinels. The cycling behavior can be improved somewhat by reducing the upper voltage limit, although this results in a diminishment of the discharge capacities below 200 mA h g -1 . By adding various amounts of spinel LiMn 2 O 4 during synthesis, it was possible to produce LMOs with rock salt structures having significantly improved cycling behavior but still having capacities in excess of 250 mA h g -1 . An optimized modified material also exhibits better rate capability and much less gas evolution during initial cycles than the unmodified LMO. Interestingly, as-made modified materials generally exhibited lower than expected average Mn oxidation states attributable to oxygen loss during the synthesis process, as well as higher capacities than expected based on their manganese contents. The oxygen loss during processing may reduce the activity of the remaining oxygen and account for the lower reactivity of the spinel-modified material.
The reversible formation of adducts between a carbodiimide and a pyridine allows the slow release of fuels for transient anhydride bond formation.
Unconventional photoacid reversibly protonates strong bases under visible light.
Hyperpolarization derived from signal amplification by reversible exchange (SABRE) is a catalytic approach to enhance NMR detection. Here, we introduce light-triggered ejection of heterocyclic ligands to initiate the SABRE process.
The formate dehydrogenase subcomplex FdsBG from Cupriavidus necator has been electrochemically activated to reversibly interconvert NAD + /NADH and provide unique insight to its kinetics and reactivity.
A vertical heterojunction barrier Schottky diode was fabricated by combining a p-type SnO film array with a β-Ga 2 O 3 substrate, yielding a lower reverse leakage current and an improved breakdown voltage than its Schottky barrier diode counterpart.
In this Letter, we report the effect of replacing Mn{sup 2+} ions with Ni{sup 2+} on the ferroelectricity of multiferroic MnWO{sub 4} single crystals. When the amount of substitution was close to 16%, the sign of ferroelectric polarization spontaneously became negative with respect to initial dc poling field at a few degrees below T{sub C}. Neutron diffraction intensities revealed a sudden change in the underlying spiral spin ordering that occurred coincidentally with the observed sign reversal. This unusual behavior in zero magnetic fields suggests that strong competitions between the two different magnetic ions may provide an efficient route to manipulation of existing multiferroics.
Thin hydrogenated amorphous silicon (a-Si:H) films deposited on crystalline silicon (c-Si) surfaces are sensitive probes for the bulk electronic properties of a-Si:H. Here, we use such samples during repeated low-temperature annealing and visible-light soaking to investigate the long-term stability of a-Si:H films. We observe that during annealing the electronic improvement of the interfaces follows stretched exponentials as long as hydrogen evolution in the films can be detected. Once such evolution is no longer observed, the electronic improvement occurs much faster. Based on these findings, we discuss how the reversibility of light-induced defects depends on (the lack of observable) hydrogen evolution.
A direct evidence for Time Reversal Violation (TRV) means an experiment that, considered by itself, clearly shows TRV independent of, and unconnected to, the results for CP Violation. No existing result before the recent BABAR experiment with entangled neutral B mesons had demonstrated TRV in this sense. There is a unique solution for the test of TRV with unstable particles thanks to the Einstein-Podolsky-Rosen (EPR) Entanglement between the two neutral mesons in B, and φ, Factories. The two quantum effects of the decays as filtering measurements of the meson states and the transfer of information of the first decay to the still living partner allow performing a genuine TRV asymmetry with the exchange of “in” and “out” states. With four independent TRV asymmetries, BABAR observes a large deviation of T-invariance with a statistical significance of 14 standard deviations, far more than needed to declare the result as a discovery. This is the first direct observation of TRV in the time evolution of any system. The perspectives for future additional studies of TRV are discussed.
Nanoporous graphene (NPG) shows tremendous promise as an ultra-permeable membrane for water desalination thanks to its atomic thickness and precise sieving properties. However, a significant gap exists in the literature between the ideal conditions assumed for NPG desalination and the physical environment inherent to reverse osmosis (RO) systems. In particular, the water permeability of NPG has been calculated previously based on very high pressures (1000–2000 bars). Does NPG maintain its ultrahigh water permeability under real-world RO pressures (<100 bars)? Here, we answer this question by drawing results from molecular dynamics simulations. Our results indicate that NPG maintains its ultrahigh permeability even at low pressures, allowing a permeate water flux of 6.0 l/h-bar per pore, or equivalently 1041 ± 20 l/m{sup 2}-h-bar assuming a nanopore density of 1.7 × 10{sup 13} cm{sup −2}.
Magnetoelectric (ME) coupling in materials offer tremendous advantages in device functionality enabling technologies including advanced electronic memory, combining electronic speed, and efficiency with magnetic robustness. However, low cost polycrystalline ME materials are excluded from most commercial applications, operating only at cryogenic temperatures, impractically large electric/magnetic fields, or with low ME coefficients (1-100 mV/cm Oe). Despite this, the technological potential of single compound ME coupling has continued to drive research into multiferroics over the last two decades. Here we show that by manipulating the large induced atomic strain within the polycrystalline, room temperature multiferroic compound 0.7BiFeO{sub 3}–0.3PbTiO{sub 3}, we can induce a reversible, piezoelectric strain controlled ME effect. Employing an in situ neutron diffraction experiment, we have demonstrated that this piezomagnetoelectric effect manifests with an applied electric field >8 kV/mm at the onset of piezoelectric strain, engineered in to the compound by crystallographic phase mixing. This produces a remarkable intrinsic ME coefficient of 1276 mV/cm Oe, due to a strain driven modification to the oxygen sub-lattice, inducing an increase in magnetic moment per Fe{sup 3+} ion of +0.142 μ{sub B}. This work provides a framework for investigations into strain engineered nanostructures to realize low-cost ME devices designed from the atoms up, as well as contributing to the deeper understanding of single phase ME coupling mechanisms.
The A1-L1{sub 0} phase transformation has been investigated in (001) FeCuPt thin films prepared by atomic-scale multilayer sputtering and rapid thermal annealing (RTA). Traditional x-ray diffraction is not always applicable in generating a true order parameter, due to non-ideal crystallinity of the A1 phase. Using the first-order reversal curve (FORC) method, the A1 and L1{sub 0} phases are deconvoluted into two distinct features in the FORC distribution, whose relative intensities change with the RTA temperature. The L1{sub 0} ordering takes place via a nucleation-and-growth mode. A magnetization-based phase fraction is extracted, providing a quantitative measure of the L1{sub 0} phase homogeneity.
Magnetization reversal of a magnetic free layer under spin transfer torque (STT) effect from a magnetic hard layer with a fixed magnetization direction and an oscillating layer is investigated. By including STT from the oscillating layer with in-plane anisotropy and orthogonal polarizer, magnetization-time dependence of free layer is determined. The results show that the frequency and amplitude of oscillations can be varied by adjusting the current density and magnetic properties. For an optimal oscillation frequency (f{sub opt}), a reduction of the switching time (t{sub 0}) of the free layer is observed. Both f{sub opt} and t{sub 0} increase with the anisotropy field of the free layer.
An opposite interfacial exciton dissociation behavior at the metal (Al)/organic cathode interface in regular and inverted organic solar cells (OSCs) was analyzed using transient photocurrent measurements. It is found that Al/organic contact in regular OSCs, made with the blend layer of poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl] -[3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl]] (PTB7):3′H-Cyclopropa [8,25][5,6] fullerene-C70-D5h(6)-3′-butanoicacid,3′-phenyl-,methyl ester (PC{sub 70}BM), always hampers the electron collection. However, this is not observed in their reverse geometry OSCs fabricated using the same PTB7:PC{sub 70}BM blend system. The detrimental interfacial exciton dissociation in regular OSCs originates the compensation of field drifted photo-generated electrons at Al/organic interface. The unfavorable interfacial exciton dissociation can be eliminated, e.g., by interposing a ZnO-based interlayer between Al and organic layer, attaining an efficient electron collection, thereby power conversion efficiency.
An enhanced mid-infrared absorption in Ag nanoparticles-decorated TiO{sub 2} microflowers was reported. It was found that the mid-infrared absorption of the Ag/TiO{sub 2} complex depends strongly on the content and size of Ag nanoparticles, the higher the Ag nanoparticles content, the stronger the infrared absorption. The average reflectivity in the entire mid-infrared region of the microflowers drops from 57.6% to 10.5% after Ag nanoparticles decoration. Reversible modulated mid-infrared absorption properties were found in the Ag/TiO{sub 2} complexes upon alternative illumination of visible and UV light due to the photoinduced interfacial electron transfer between TiO{sub 2} semiconductor and Ag nanoparticles.