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Emergent phases at the interfaces in strongly correlated oxide heterostructures display novel properties not akin to those of constituting materials. The interfacial ferromagnetism in (LaMnO3)m/(SrMnO3)n (LMO)m/(SMO)n superlattices (SLs) with antiferromagnetic bulk LMO and SMO layers is believed to be a result of the interfacial charge transfer (CT). By using in situ optical ellipsometry, it is demonstrated directly that CT and emergent magnetism in (LMO)m/(SMO)n SLs are controlled by the LMO/SMO thickness ratio, chosen as m/n = 1 and 2. The enhanced CT in SLs with m/n = 2 favors the high‐TC emergent ferromagnetism with TC = 350–360 K, whereas the reduced CT in m/n = 1 SLs suppresses it yielding TC = 300 K. A complex dependence of the saturation magnetization as a function of interface density Λ = (m + n)−1 with minima at Λ = 0.11 (m/n = 2) and Λ = 0.25 (m/n = 1) was observed and rationalized by the competition of ferromagnetic and antiferromagnetic contributions, originating from the volume of LMO and SMO layers as well as from the LMO/SMO interfaces. The role of epitaxy stress and MnO6 octahedral tilts in the emergent magnetic behavior is discussed. [ABSTRACT FROM AUTHOR]

In this study, transmission electron microscopy atomic force microscopy, and surface enhanced Raman spectroscopy are combined through a direct imaging approach, to gather structural and chemical information of complex molecular systems such as ion channels in their original plasma membrane. Customized microfabricated sample holder allows to characterize Nav channels embedded in the original plasma membrane extracted from neuronal cells that are derived from healthy human induced pluripotent stem cells. The identification of the channels is accomplished by using two different approaches, one of them widely used in cryo‐EM (the particle analysis method) and the other based on a novel Zernike Polynomial expansion of the images bitmap. This approach allows to carry out a whole series of investigations, one complementary to the other, on the same sample, preserving its state as close as possible to the original membrane configuration. [ABSTRACT FROM AUTHOR]

Owing to its capacity for reversible hydrogen storage, formic acid (FA) holds great promise as an alternative energy carrier to conventional fossil fuel systems. Whereas the decomposition of FA to hydrogen (H2) and carbon dioxide (CO2) through homogeneous catalysis is well established, the selective and efficient dehydrogenation of FA by a robust heterogeneous catalyst remains a challenge. A new heterogeneous ruthenium pincer framework with single-atomic sites was prepared in one step by the direct knitting of a phosphorus–nitrogen PN3Ppincer ruthenium complex in a porous organic polymer. The heterogeneous ruthenium complex efficiently dehydrogenates formic acid in both organic and aqueous media with remarkably enhanced stability. Notably, no detectable CO was generated and a turnover number (TON) of 145 300 was attained in a continuous experiment with no significant decline in catalytic activity (in sharp contrast, a total TON of only 5600 was obtained with the homogeneous analog under the same conditions). The single-atomic sites in the porous framework combined the desirable attributes of high reactivity and selectivity of a homogeneous catalyst with the significantly enhanced catalyst stability and reusability benefits of heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Abstract: This work reports the synthesis, characterization, photophysical, and photovoltaic properties of five new thieno[3,2‐b][1]benzothiophene isoindigo (TBTI)‐containing low bandgap donor–acceptor conjugated polymers with a series of comonomers and different side chains. When TBTI is combined with different electron‐rich moieties, even small structural variations can have significant impact on thin film morphology of the polymer:phenyl C70 butyric acid methyl ester (PCBM) blends. More importantly, high‐resolution electron energy loss spectroscopy is used to investigate the phase‐separated bulk heterojunction domains, which can be accurately and precisely resolved, enabling an enhanced correlation between polymer chemical structure, photovoltaic device performance, and morphology. [ABSTRACT FROM AUTHOR]

Abstract: Reaching device efficiencies that can rival those of polymer‐fullerene Bulk Heterojunction (BHJ) solar cells (>10%) remains challenging with the “All‐Small‐Molecule” (All‐SM) approach, in part because of (i) the morphological limitations that prevail in the absence of polymer and (ii) the difficulty to raise and balance out carrier mobilities across the active layer. In this report, the authors show that blends of the SM donor DR3TBDTT (DR3) and the nonfullerene SM acceptor O‐IDTBR are conducive to “All‐SM” BHJ solar cells with high open‐circuit voltages (VOC) >1.1 V and PCEs as high as 6.4% (avg. 6.1%) when the active layers are subjected to a post‐processing solvent vapor‐annealing (SVA) step with dimethyl disulfide (DMDS). Combining electron energy loss spectroscopy (EELS) analyses and systematic carrier recombination examinations, the authors show that SVA treatments with DMDS play a determining role in improving charge transport and reducing non‐geminate recombination for the DR3:O‐IDTBR system. Correlating the experimental results and device simulations, it is found that substantially higher BHJ solar cell efficiencies of >12% can be achieved if the IQE and carrier mobilities of the active layer are increased to >85% and >10−4 cm2 V−1 s−1, respectively, while suppressing the recombination rate constant k to <10−12 cm3 s−1. [ABSTRACT FROM AUTHOR]

A specific allotrope of titanium dioxide (anatase) was synthesized both with a standard thermodynamic morphology ({101}-anatase) and with a highly anisotropic morphology ({001}-anatase) dominated by the {001} facet (81%). The surface chemistry of both samples after dehydroxylation was studied by 1H NMR and FT-IR. The influence of surface fluorides on the surface chemistry was also studied by 1H NMR, FT-IR and DFT. Full attribution of the IR spectra of anatase with dominant {001} facets could be provided based on experimental data and further confirmed by DFT. Our results showed that chemisorbed H2O molecules are still present on anatase after dehydroxylation at 350 °C, and that the type of surface hydroxyls present on the {001} facet is dependent on the presence of fluorides. They also provided general insight into the nature of the surface species on both fluorinated and fluorine-free anatase. The use of vanadium oxychloride (VOCl3) allowed the determination of the accessibility of the various OH groups spectroscopically observed. [ABSTRACT FROM AUTHOR]

We report on a set of two analogous, F-substituted oligothiophene derivatives (D5T6F-M and D7T8F-M), in which systematic fluorination at the thienyl moieties is shown to induce a sufficient increase in electron affinity (EA; i.e. suppressed LUMO level) and in ionization potential (IP; i.e. deeper HOMO) to (i) impart the molecules with electron-accepting and -transporting characteristics, and (ii) yield high open-circuit voltages ＞1 V in BHJ solar cells when combined with a low-bandgap polymer donor (PCE10) commonly used with fullerenes. The nonfullerene BHJ devices with the SM acceptor D5T6F-M achieve power conversion efficiencies (PCEs) of up to ca. 4.5% (vs. ca. 2% for D7T8F-M-based devices). Our study shows that –F substitutions in SM systems – otherwise used as donors – is an effective approach in the design of nonfullerene acceptors for efficient BHJ solar cells with polymer donors. [ABSTRACT FROM AUTHOR]

Abstract: Persistent photoconductivity (PPC) is an intriguing physical phenomenon, where electric conduction is retained after the termination of electromagnetic radiation, which makes it appealing for applications in a wide range of optoelectronic devices. So far, PPC has been observed in bulk materials and thin‐film structures, where the current flows in the plane, limiting the magnitude of the effect. Here using epitaxial Nb:SrTiO3/Sm0.1Bi0.9FeO3/Pt junctions with a current‐perpendicular‐to‐plane geometry, a colossal X‐ray‐induced PPC (XPPC) is achieved with a magnitude of six orders. This PPC persists for days with negligible decay. Furthermore, the pristine insulating state could be fully recovered by thermal annealing for a few minutes. Based on the electric transport and microstructure analysis, this colossal XPPC effect is attributed to the X‐ray‐induced formation and ionization of oxygen vacancies, which drives nonvolatile modification of atomic configurations and results in the reduction of interfacial Schottky barriers. This mechanism differs from the conventional mechanism of photon‐enhanced carrier density/mobility in the current‐in‐plane structures. With their persistent nature, such ferroelectric/semiconductor heterojunctions open a new route toward X‐ray sensing and imaging applications. [ABSTRACT FROM AUTHOR]

Abstract: Achieving efficient bulk‐heterojunction (BHJ) solar cells from blends of solution‐processable small‐molecule (SM) donors and acceptors is proved particularly challenging due to the complexity in obtaining a favorable donor–acceptor morphology. In this report, the BHJ device performance pattern of a set of analogous, well‐defined SM donors—DR3TBDTT (DR3), SMPV1, and BTR—used in conjunction with the SM acceptor IDTTBM is examined. Examinations show that the nonfullerene “All‐SM” BHJ solar cells made with DR3 and IDTTBM can achieve power conversion efficiencies (PCEs) of up to ≈4.5% (avg. 4.0%) when the solution‐processing additive 1,8‐diiodooctane (DIO, 0.8% v/v) is used in the blend solutions. The figures of merit of optimized DR3:IDTTBM solar cells contrast with those of “as‐cast” BHJ devices from which only modest PCEs <1% can be achieved. Combining electron energy loss spectrum analyses in scanning transmission electron microscopy mode, carrier transport measurements via “metal‐insulator‐semiconductor carrier extraction” methods, and systematic recombination examinations by light‐dependence and transient photocurrent analyses, it is shown that DIO plays a determining role—establishing a favorable lengthscale for the phase‐separated SM donor–acceptor network and, in turn, improving the balance in hole/electron mobilities and the carrier collection efficiencies overall. [ABSTRACT FROM AUTHOR]

Poly(isoindigo- alt-3,4-difluorothiophene) (PIID[2F]T) analogues used as 'polymer acceptors' in bulk-heterojunction (BHJ) solar cells achieve >7 % efficiency when used in conjunction with the polymer donor PBFTAZ (model system; copolymer of benzo[1,2- b:4,5- b′]dithiophene and 5,6-difluorobenzotriazole). Considering that most efficient polymer-acceptor alternatives to fullerenes (e.g. PC61BM or its C71 derivative) are based on perylenediimide or naphthalenediimide motifs thus far, branched alkyl-substituted PIID[2F]T polymers are particularly promising non-fullerene candidates for 'all-polymer' BHJ solar cells. [ABSTRACT FROM AUTHOR]

Poly(isoindigo- alt-3,4-difluorothiophene) (PIID[2F]T) analogues used as 'polymer acceptors' in bulk-heterojunction (BHJ) solar cells achieve >7 % efficiency when used in conjunction with the polymer donor PBFTAZ (model system; copolymer of benzo[1,2- b:4,5- b′]dithiophene and 5,6-difluorobenzotriazole). Considering that most efficient polymer-acceptor alternatives to fullerenes (e.g. PC61BM or its C71 derivative) are based on perylenediimide or naphthalenediimide motifs thus far, branched alkyl-substituted PIID[2F]T polymers are particularly promising non-fullerene candidates for 'all-polymer' BHJ solar cells. [ABSTRACT FROM AUTHOR]

'Nonfullerene' acceptors are proving effective in bulk heterojunction (BHJ) solar cells when paired with selected polymer donors. However, the principles that guide the selection of adequate polymer donors for high-efficiency BHJ solar cells with nonfullerene acceptors remain a matter of some debate and, while polymer main-chain substitutions may have a direct influence on the donor-acceptor interplay, those effects should be examined and correlated with BHJ device performance patterns. This report examines a set of wide-bandgap polymer donor analogues composed of benzo[1,2- b:4,5- b′]dithiophene (BDT), and thienyl ([2H]T) or 3,4-difluorothiophene ([2F]T) motifs, and their BHJ device performance pattern with the nonfullerene acceptor 'ITIC'. Studies show that the fluorine- and ring-substituted derivative PBDT(T)[2F]T largely outperforms its other two polymer donor counterparts, reaching power conversion efficiencies as high as 9.8%. Combining several characterization techniques, the gradual device performance improvements observed on swapping PBDT[2H]T for PBDT[2F]T, and then for PBDT(T)[2F]T, are found to result from (i) notably improved charge generation and collection efficiencies (estimated as ≈60%, 80%, and 90%, respectively), and (ii) reduced geminate recombination (being suppressed from ≈30%, 25% to 10%) and bimolecular recombination (inferred from recombination rate constant comparisons). These examinations will have broader implications for further studies on the optimization of BHJ solar cell efficiencies with polymer donors and a wider range of nonfullerene acceptors. [ABSTRACT FROM AUTHOR]

Van der Waals materials exhibit intriguing structural, electronic, and photonic properties. Electron energy loss spectroscopy within scanning transmission electron microscopy allows for nanoscale mapping of such properties. However, its detection is typically limited to energy losses in the eV range—too large for probing low-energy excitations such as phonons or mid-infrared plasmons. Here, we adapt a conventional instrument to probe energy loss down to 100 meV, and map phononic states in hexagonal boron nitride, a representative van der Waals material. The boron nitride spectra depend on the flake thickness and on the distance of the electron beam to the flake edges. To explain these observations, we developed a classical response theory that describes the interaction of fast electrons with (anisotropic) van der Waals slabs, revealing that the electron energy loss is dominated by excitation of hyperbolic phonon polaritons, and not of bulk phonons as often reported. Thus, our work is of fundamental importance for interpreting future low-energy loss spectra of van der Waals materials. [ABSTRACT FROM AUTHOR]

The development of a straightforward method is reported to form hybrid polymer/gold planet-satellite nanostructures (PlSNs) with functional polymer. Polyacrylate type polymer with benzyl chloride in its backbone as a macromolecular tracer is synthesized to study its localization within PlSNs by analyzing the elemental distribution of chlorine. The functionalized nanohybrid structures are analyzed by scanning transmission electron microscopy, electron energy loss spectroscopy, and spectrum imaging. The results show that the RAFT (reversible addition-fragmentation chain transfer) polymers' sulfur containing end groups are colocalized at the gold cores, both within nanohybrids of simple core-shell morphology and within higher order PlSNs, providing microscopic evidence for the affinity of the RAFT group toward gold surfaces. [ABSTRACT FROM AUTHOR]

Activation of Fe2O3-Al2O3 with CH4 (instead of H2) is a meaningful method to achieve catalytic methane decomposition (CMD). This reaction of CMD is more economic and simple against commercial methane steam reforming (MSR) as it produces CO x-free H2. In this study, for the first time, structure changes of the catalyst were screened during CH4 reduction with time on stream. The aim was to optimize the pretreatment conditions through understanding the activation mechanism. Based on results from various characterization techniques, reduction of Fe2O3 by CH4 proceeds in three steps: Fe2O3→Fe3O4→FeO→Fe0. Once Fe0 is formed, it decomposes CH4 with formation of Fe3C, which is the crucial initiation step in the CMD process to initiate formation of multiwall carbon nanotubes. [ABSTRACT FROM AUTHOR]

Hexagonal orthoferrites have recently attracted much attention as possible high-temperature ferromagnetic ferroelectrics. The ferroelectric domain structure of hexagonal RMnO3, their antiferromagnetic structural analogies, has recently shown an atypical and complicated behavior. Hexagonal RFeO3 are expected to exhibit similar domain structure that should coexist with weak ferromagnetic order and may represent a material with a unusual magnetoelectric interaction. In this report, we discuss microscopic ferroelectric domain structure of hexagonal orthoferrites in a thin-film state and demonstrate a distinct and unusual improper ferroelectric behavior of these oxide materials. [ABSTRACT FROM AUTHOR]

Impurities produced during the synthesis process of a material pose detrimental impacts upon the intrinsic properties and device performances of the as-obtained product. This effect is especially pronounced in graphene, where surface contamination has long been a critical, unresolved issue, given graphene's two-dimensionality. Here we report the origins of surface contamination of graphene, which is primarily rooted in chemical vapour deposition production at elevated temperatures, rather than during transfer and storage. In turn, we demonstrate a design of Cu substrate architecture towards the scalable production of super-clean graphene (>99% clean regions). The readily available, super-clean graphene sheets contribute to an enhancement in the optical transparency and thermal conductivity, an exceptionally lower-level of electrical contact resistance and intrinsically hydrophilic nature. This work not only opens up frontiers for graphene growth but also provides exciting opportunities for the utilization of as-obtained super-clean graphene films for advanced applications. The intrinsic properties of graphene and the resulting device performance are hindered by the impurities produced during the synthesis process. Here, the authors elucidate the origin of contaminations in CVD-grown graphene and devise a strategy towards the scalable production of ultra-clean graphene with >99% clean regions and low contact resistance. [ABSTRACT FROM AUTHOR]

The effect of direct or indirect binding of intercalant molecules on DNA structure is of fundamental importance in understanding the biological functioning of DNA. Here we report on self-suspended DNA nanobundles as ultrasensitive nanomechanical resonators for structural studies of DNA-ligand complexes. Such vibrating nanostructures represent the smallest mechanical resonator entirely composed of DNA. A correlative analysis between the mechanical and structural properties is exploited to study the intrinsic changes of double strand DNA, when interacting with different intercalant molecules (YOYO-1 and GelRed) and a chemotherapeutic drug (Cisplatin), at different concentrations. Possible implications of our findings are related to the study of interaction mechanism of a wide category of molecules with DNA, and to further applications in medicine, such as optimal titration of chemotherapeutic drugs and environmental studies for the detection of heavy metals in human serum. Intercalating molecules can significantly change the conformation of DNA. Here, the authors fabricated resonators fully composed of DNA forming bundles between microfabricated pillars to study the vibration property of the DNA bundles with/without intercalant molecules. [ABSTRACT FROM AUTHOR]