Dopant-additive synergism enhances perovskite solar modules.

Perovskite solar cells (PSCs) are among the most promising photovoltaic technologies owing to their exceptional optoelectronic properties1,2. However, the lower efficiency, poor stability and reproducibility issues of large-area PSCs compared with laboratory-scale PSCs are notable drawbacks that hinder their commercialization3. Here we report a synergistic dopant-additive combination strategy using methylammonium chloride (MACl) as the dopant and a Lewis-basic ionic-liquid additive, 1,3-bis(cyanomethyl)imidazolium chloride ([Bcmim]Cl). This strategy effectively inhibits the degradation of the perovskite precursor solution (PPS), suppresses the aggregation of MACl and results in phase-homogeneous and stable perovskite films with high crystallinity and fewer defects. This approach enabled the fabrication of perovskite solar modules (PSMs) that achieved a certified efficiency of 23.30% and ultimately stabilized at 22.97% over a 27.22-cm2 aperture area, marking the highest certified PSM performance. Furthermore, the PSMs showed long-term operational stability, maintaining 94.66% of the initial efficiency after 1,000 h under continuous one-sun illumination at room temperature. The interaction between [Bcmim]Cl and MACl was extensively studied to unravel the mechanism leading to an enhancement of device properties. Our approach holds substantial promise for bridging the benchtop-to-rooftop gap and advancing the production and commercialization of large-area perovskite photovoltaics.

Electric Polarization Switching on an Atomically Thin Metallic Oxide.

Materials with reduced dimensions have been shown to host a wide variety of exotic properties and novel quantum states that often defy textbook wisdom. Polarization switching and metallic screening are well-known examples of mutually exclusive properties that cannot coexist in bulk solids. Here we report the fabrication of (SrRuO3)1/(BaTiO3)10 superlattices that exhibits reversible polarization switching in an atomically thin metallic layer. A multipronged investigation combining structural analyses, electrical measurements, and first-principles electronic structure calculations unravels the coexistence of two-dimensional (2D) metallicity in the SrRuO3 layer accompanied by the breaking of inversion symmetry, supporting electric polarization along the out-of-plane direction. Such a 2D ferroelectric-like metal paves a novel way to engineer a quantum multistate with unusual coexisting properties, such as ferroelectrics and metals, manipulated by external fields.

Molecular Dynamics of Hexamethylbenzene at Low Temperatures: Evidence of Unconventional Magnetism Based on Rotational Motion of Protons.

The types of magnetism known to date are all mainly based on contributions from electron motion. We show how rotational motion of protons (H+ ) within the methyl groups in hexamethylbenzene (C6 (CH3 )6 ) also contribute significantly to the magnetic susceptibility. Starting from below 118 K, as the rotational motion of the methyl groups set in, an associated magnetic moment positive in nature due to charge of the protons renders the susceptibility to become anomalously dependent on temperature. Starting from 20 K, the susceptibility diverges with decreasing temperature indicative of spin-spin interactions between methyl groups aligned in a previously unclassified type of anti-ferromagnetic configuration. Complementary dielectric constant measurements also show the existence of magneto-dielectric coupling. Our findings allow for the study of strongly correlated systems that are based on a species that possesses much slower dynamics.

Bifunctional Square-Planar NiO4 Coordination of Topotactic LaNiO2.0 Films for Efficient Oxygen Evolution Reaction.

The high-efficient and low-cost oxygen evolution reaction (OER) is decisive for applications of oxide catalysts in metal-air batteries, electrolytic cells, and energy-storage technologies. Delicate regulations of active surface and catalytic reaction pathway of oxide materials principally determine thermodynamic energy barrier and kinetic rate during catalytic reactions, and thus have crucial impacts on OER performance. Herein, a synergistic modulation of catalytically active surface and reaction pathway through facile topotactic transformations switching from perovskite (PV) LaNiO3.0 film to infinite-layer (IL) LaNiO2.0 film is demonstrated, which absolutely contributes to improving OER performance. The square-planar NiO4 coordination of IL-LaNiO2.0 brings about more electrochemically active metal (Ni+ ) sites on the film surface. Meanwhile, the oxygen-deficient driven PV- IL topotactic transformations lead to a reaction pathway converted from absorbate evolution mechanism to lattice-oxygen-mediated mechanism (LOM). The non-concerted proton-electron transfer of LOM pathway, evidenced by the pH-dependent OER kinetics, further boosts the OER activity of IL-LaNiO2.0 films. These findings will advance the in-depth understanding of catalytic mechanisms and open new possibilities for developing highly active perovskite-derived oxide catalysts.

Inducing Fe 3d Electron Delocalization and Spin-State Transition of FeN4 Species Boosts Oxygen Reduction Reaction for Wearable Zinc-Air Battery.

Transition metal-nitrogen-carbon materials (M-N-Cs), particularly Fe-N-Cs, have been found to be electroactive for accelerating oxygen reduction reaction (ORR) kinetics. Although substantial efforts have been devoted to design Fe-N-Cs with increased active species content, surface area, and electronic conductivity, their performance is still far from satisfactory. Hitherto, there is limited research about regulation on the electronic spin states of Fe centers for Fe-N-Cs electrocatalysts to improve their catalytic performance. Here, we introduce Ti3C2 MXene with sulfur terminals to regulate the electronic configuration of FeN4 species and dramatically enhance catalytic activity toward ORR. The MXene with sulfur terminals induce the spin-state transition of FeN4 species and Fe 3d electron delocalization with d band center upshift, enabling the Fe(II) ions to bind oxygen in the end-on adsorption mode favorable to initiate the reduction of oxygen and boosting oxygen-containing groups adsorption on FeN4 species and ORR kinetics. The resulting FeN4-Ti3C2Sx exhibits comparable catalytic performance to those of commercial Pt-C. The developed wearable ZABs using FeN4-Ti3C2Sx also exhibit fast kinetics and excellent stability. This study confirms that regulation of the electronic structure of active species via coupling with their support can be a major contributor to enhance their catalytic activity.

Perpendicular Manganite Magnetic Tunnel Junctions Induced by Interfacial Coupling.

The half-metallic manganite oxide La2/3Sr1/3MnO3 (LSMO) has a very high spin polarization of ∼100%, making it ideal for ferromagnetic electrodes to realize tunneling magnetoresistance (TMR). Because of the in-plane magnetic anisotropy of the ferromagnetic LSMO electrode, which leads to the density limit of memory, realizing perpendicular tunneling in manganite-based magnetic tunnel junctions (MTJ) is critical for future applications. Here, we design and fabricate manganite-based MTJs composed of alternately stacked cobaltite and manganite layers that demonstrate strong perpendicular magnetic anisotropy (PMA) induced by interfacial coupling. Moreover, spin-dependent tunneling behaviors with an out-of-plane magnetic field were observed in the perpendicular MTJs. We found that the direct tunneling effect plays a dominant role in the low bias region during the transport behavior of devices, which is associated with thermionic emission of electrons or oxygen vacancies in the high bias region. Our works of realizing perpendicular tunneling in manganite-based MTJs lead to new approaches for designing and developing all-oxide spintronic devices.

High-Conductive Protonated Layered Oxides from H2 O Vapor-Annealed Brownmillerites.

Protonated 3d transition-metal oxides often display low electronic conduction, which hampers their application in electric, magnetic, thermoelectric, and catalytic fields. Electronic conduction can be enhanced by co-inserting oxygen acceptors simultaneously. However, the currently used redox approaches hinder protons and oxygen ions co-insertion due to the selective switching issues. Here, a thermal hydration strategy for systematically exploring the synthesis of conductive protonated oxides from 3d transition-metal oxides is introduced. This strategy is illustrated by synthesizing a novel layered-oxide SrCoO3 H from the brownmillerite SrCoO2.5 . Compared to the insulating SrCoO2.5 , SrCoO3 H exhibits an unprecedented high electronic conductivity above room temperature, water uptake at 250 °C, and a thermoelectric power factor of up to 1.2 mW K-2 m-1 at 300 K. These findings open up opportunities for creating high-conductive protonated layered oxides by protons and oxygen ions co-doping.

Super-Flexible Freestanding BiMnO3 Membranes with Stable Ferroelectricity and Ferromagnetism.

Multiferroic materials with flexibility are expected to make great contributions to flexible electronic applications, such as sensors, memories, and wearable devices. In this work, super-flexible freestanding BiMnO3 membranes with simultaneous ferroelectricity and ferromagnetism are synthesized using water-soluble Sr3 Al2 O6 as the sacrificial buffer layer. The super-flexibility of BiMnO3 membranes is demonstrated by undergoing an ≈180° folding during an in situ bending test, which is consistent with the results of first-principles calculations. The piezoelectric signal under a bending radius of ≈500 µm confirms the stable existence of electric polarization in freestanding BiMnO3 membranes. Moreover, the stable ferromagnetism of freestanding BiMnO3 membranes is demonstrated after 100 times bending cycles with a bending radius of ≈2 mm. 5.1% uniaxial tensile strain is achieved in freestanding BiMnO3 membranes, and the piezoresponse force microscopy (PFM) phase retention behaviors confirm that the ferroelectricity of membranes can survive stably up to the strain of 1.7%. These super-flexible membranes with stable ferroelectricity and ferromagnetism pave ways to the realizations of multifunctional flexible electronics.

Ferroelectricity and Ferromagnetism Achieved via Adjusting Dimensionality in BiFeO3/BiMnO3 Superlattices.

Integrating characteristics of materials through constructing artificial superlattices (SLs) has raised extensive attention in multifunctional materials. Here, we report the synthesis of BiFeO3/BiMnO3 SLs with considerable ferroelectric polarizations and tunable magnetic moments. The polarization of BiFeO3/BiMnO3 SLs presents a decent value of 12 µC/cm2, even as the dimensionality of BiFeO3 layers per period is reduced to about five-unit cells when keeping the BiMnO3 layers same. Moreover, it is found that the tunable magnetic moments of SLs are linked intimately to the dimensionality of BiFeO3 layers. Our simulations demonstrate that the superexchange interaction of Fe-O-Mn tends to be antiferromagnetic (AFM) with a lower magnetic domain formation energy rather than ferromagnetic (FM). Therefore, as the dimensionality of BiFeO3 per period is reduced, the AFM superexchange interaction between BiFeO3 and BiMnO3 in the SLs becomes weak, promoting a robust magnetization. This interlayer modulation effect in SLs presents an alluring way to accurately control the multiple order parameters in a multiferroic oxide system.

Modulation of Abnormal Poisson's Ratios and Electronic Properties in Mixed-Valence Perovskite Manganite Films.

Epitaxy and misfit strain imposed by underlying substrates have been intensively used to tailor the microstructure and electronic properties of oxide films, but this approach is largely restricted by commercially limited substrates. In contrast to the conventional epitaxial misfit strains with a positive Poisson's constant, we show here a tunable Poisson's ratio with anomalous values from negative, zero, to positive. This permits effective control over the out-of-plane lattice parameters that strongly correlate the magnetic and transport properties in perovskite mixed-valence La1- xSr xMnO3 thin films. Our results provide an unconventional approach to better modulation and understanding of elastic-mediated microstructures and physical properties of oxide films by engineering the Poisson's ratios.