Angular-dependent magnetoresistance modulated by interfacial magnetic state in Pt/LSMO heterostructures.

The interfaces between heavy metals and antiferromagnetic materials have garnered significant attention due to their interesting physical properties. La0.35Sr0.65MnO3 (LSMO), as a typical manganite, exhibits an antiferromagnetic ground state that can be controlled through epitaxial strain and interfacial spin-orbit coupling. In this work, we reported the diverse magnetoresistance, influenced by the interfacial magnetic state, in Pt (3 nm)/LSMO (6-20 nm) heterostructures. The strong spin-orbit coupling of Pt and Dzyaloshinskii-Moriya interaction alter the spin structure and enhance the electron scattering at the Pt/LSMO interface, resulting in positive magnetoresistance. The interfacial angular-dependent magnetoresistance modulated by the interfacial magnetic states was also observed in the Pt/LSMO (20 nm) heterostructures. Our findings contribute to a broader understanding of interfacial properties between heavy metals and antiferromagnetic manganites.

Uranium Oxide Hydrate Frameworks with Dy(III) or Lu(III) Ions: Insights Into the Framework Structures With Lanthanide Ions.

Two uranium oxide hydrate frameworks (UOHFs) with either Dy3+ or Lu3+ ions, Dy1.36(H2O)6[(UO2)10UO13(OH)4] (UOHF-Dy) or Lu2(H2O)8[(UO2)10UO14(OH)3] (UOHF-Lu), were synthesized hydrothermally and characterized with a range of structural and spectroscopic techniques. Although SEM-EDS analysis confirmed the same atomic ratio of ~5.5 for U : Dy and U : Lu, they displayed different crystal morphologies, needles for UOHF-Dy in the orthorhombic C2221 space group and plates for UOHF-Lu in the triclinic P-1 space group. Both frameworks are composed of ß-U3O8 type layers linked by pentagonal bipyramidal uranium polyhedra, with the Dy3+/Lu3+ ions inside the channels. However, the arrangements of Dy3+/Lu3+ ions are different, with disordered Dy3+ ions well aligned at the centers of the channels and single Lu3+ ions well-separated in a zigzag pattern in the channels. While the characteristic vibrational modes were revealed by Raman spectroscopy, the presence of a pentavalent uranium center in UOHF-Lu was confirmed with diffuse reflectance spectroscopy. The formation of two types of UOHFs with lanthanide ions, high or low symmetry, and the structure trend were discussed regards to synthesis conditions and lanthanide ionic radius. This work highlights the complex chemistry driving the formation of UOHFs with lanthanide ions and has implications to the spent nuclear fuel under geological disposal.

Kinetic Process with Anti-Frenkel Disorder in a CsPbI3 Perovskite.

Halide perovskites are rich in ionic diffusion phenomena due to their low activation energy. The soft lead iodide lattice can, in theory, endow the system with more complex defect collaborative motions. In this work, we systematically investigated the hopping mechanics of iodide interstitials with respect to various defect behaviors, such as anti-Frenkel disorder creation and annihilation. We found that the existence of iodide vacancies and interstitials can effectively lower the creation barrier of additional anti-Frenkel disorder in the halide perovskite. The free energy barriers for generating additional Frenkel defect pairs vary from 0.25 to 0.43 eV, in the proximity of those of the original iodide defects at 300 K. This finding suggests that the spontaneous creation of a specific level of anti-Frenkel disorder facilitates long-range annihilation and defect hopping processes.

A trinity strategy enabled by iodine-loaded nitrogen-boron-doped carbon protective layer for dendrite-free zinc-ion batteries.

Although aqueous zinc ion batteries (AZIBs) have the merits of environmental friendliness, high safety and theoretical capacity, the slow kinetics associated with zinc deposition and unavoidable interfacial corrosion have seriously affected the commercialization of aqueous zinc ion batteries. In this work, an ingenious "trinity" design is proposed by applying a porous hydrophilic carbon-loaded iodine coating to the zinc metal surface (INBC@Zn), which simultaneously acts as an artificial protective layer, electrolyte additive and anode curvature regulator, so as to reduce the nucleation overpotential of Zn and promote the preferential deposition of (002) planes to some extent. With this synergistic effect, INBC@Zn exhibits high reversibility and strong side reaction inhibition. As a result, INBC@Zn shows high symmetric cycling stability up to 4500 h at 1 mA cm-2. An ultra-long cycle stability of 1500 cycles with high Coulombic efficiency (99.8 %) is achieved in the asymmetric cell. In addition, the INBC@Zn//NVO full cells exhibit impressive capacity retention (96 % after 1000 cycles at 3 A/g). Importantly, the designed pouch cell demonstrates stable performance and shows certain prospects for application. This work provides a facile and instructive approach toward the development of high-performance AZIBs.

Toward stabilization of formamidinium lead iodide perovskites by defect control and composition engineering.

Phase instability poses a serious challenge to the commercialization of formamidinium lead iodide (FAPbI3)-based solar cells and optoelectronic devices. Here, we combine density functional theory and machine learning molecular dynamics simulations, to investigate the mechanism driving the undesired α-δ phase transition of FAPbI3. Prevalent iodine vacancies and interstitials can significantly expedite the structural transition kinetics by inducing robust covalency during transition states. Extrinsically, the detrimental roles of atmospheric moisture and oxygen in degrading the FAPbI3 perovskite phase are also rationalized. Significantly, we discover the compositional design principles by categorizing that A-site engineering primarily governs thermodynamics, whereas B-site doping can effectively manipulate the kinetics of the phase transition in FAPbI3, highlighting lanthanide ions as promising B-site substitutes. A-B mixed doping emerges as an efficient strategy to synergistically stabilize α-FAPbI3, as experimentally demonstrated by substantially higher initial optoelectronic characteristics and significantly enhanced phase stability in Cs-Eu doped FAPbI3 as compared to its Cs-doped counterpart. This study provides scientific guidance for the design and optimization of long-term stable FAPbI3-based solar cells and other optoelectronic devices through defect control and synergetic composition engineering.

Serratia marcescens induces apoptosis in Diaphorina citri gut cells via reactive oxygen species-mediated oxidative stress.

BACKGROUND: Asian citrus psyllid, Diaphorina citri, is a notorious pest in the citrus industry because it transmits Candidatus Liberibacter asiaticus, which causes an uncurable, devastating disease in citrus worldwide. Serratia marcescens is widely distributed in various environments that exhibits toxic effects to many insects. To develop strategies for enhancing the efficiency of pathogen-induced host mortality, a better understanding of the toxicity mechanism of Serratia marcescens on Diaphorina citri is critical. RESULTS: Serratia marcescens KH-001 successfully colonized Diaphorina citri gut by feeding artificial diets, resulting in the damage of cells including nucleus, mitochondria, vesicles, and microvilli. Oral ingestion of Serratia marcescens KH-001 strongly induced apoptosis in gut cells by enhancing levels of Cyt c, p53 and caspase-1 and decreasing levels of inhibitors of apoptosis (IAP) and Bax inhibitor-1 (BI-1). The expression of dual oxidase (Duox) and nitric oxide synthase (Nos) was up-regulated by Serratia marcescens KH-001, which increased hydrogen peroxide (H2 O2 ) levels in the gut. Injection of abdomen of Diaphorina citri with H2 O2 accelerated the death of the adults and induced apoptosis in the gut cells by activating Cyt c, p53 and caspase-1 and suppressing IAP and BI-1. Pretreatment of infected Diaphorina citri with vitamin c (Vc) increased the adult survival and diminished the apoptosis-inducing effect. CONCLUSIONS: The colonization of Serratia marcescens KH-001 in the guts of Diaphorina citri increased H2 O2 accumulation, leading to severe changes and apoptosis in intestinal cells, which enhanced a higher mortality level of D. citr. This study identifies the underlying virulence mechanism of Serratia marcescens KH-001 on Diaphorina citri that contributes to a widespread application in the integrated management of citrus psyllid. © 2023 Society of Chemical Industry.

Filling the gaps of uranium oxide hydrates with magnesium(II) ions: unique layered structures and the role of additional sodium(I) ions.

Alkaline earth metal ions play an important role in the formation of secondary uranium minerals due to their abundance in the Earth's crust. Although uranium oxide hydrate (UOH) minerals and synthetic phases with calcium, strontium and barium ions have been investigated, their counterparts with magnesium ions are much less studied. In this work, synthetic UOH materials with magnesium ions have been investigated with three new compounds being synthesised and characterised. Compound Mg2(H3O)2(H2O)6[(UO2)3O4(OH)]2 (U-Mg1 with a U : Mg ratio of 3 : 1) crystallises in the monoclinic P21/c space group having a layered crystal structure, constructed by ß-U3O8 layers with 6-fold coordinated Mg2+ ions as interlayer cations. Compound Na2Mg(H2O)4[(UO2)3O3(OH)2]2 (U-Mg2p with U : Mg : Na ratios of 6 : 1 : 2) crystallises in the triclinic P1̄ space group having a layered structure, constructed by a unique type of uranium oxide hydroxide layer containing both α-U3O8 and ß-U3O8 features, with alternating layers of 6-fold coordinated Mg2+ and 6-/8-fold coordinated Na+ interlayer cations. Compound Na2Mg(H2O)4[(UO2)4O3(OH)4]2 (U-Mg2n with U : Mg : Na ratios of 8 : 1 : 2) crystallises in the triclinic P1̄ space group having a corrugated layer structure, constructed by a unique type of uranium oxide hydroxide layer with mixed 6-fold coordinated Mg2+ and 7-fold coordinated Na+ interlayer cations. The structural diversity in the UOH-Mg system was achieved by adjusting the solution pH using NaOH, highlighting the importance of solution pH control and the additional Na+ ions in the formation of UOH phases. The extra structural flexibility offered by the Na+ ions emphasizes the opportunity for synthesising UOHs with dual-cations to further improve our understanding of the alteration products of spent nuclear fuel under geological disposal.

Highly Stable and Efficient Formamidinium-Based 2D Ruddlesden-Popper Perovskite Solar Cells via Lattice Manipulation.

Formamidinium (FA)-based 2D perovskites have emerged as highly promising candidates in solar cells. However, the insertion of 2D spacer cations into the perovskite lattice concomitantly introduces microstrain and unfavorable orientations that hinder efficiency and stability. In this study, by finely tuning the FA-based 2D perovskite lattice through spacer cation engineering, a stable lattice structure with balanced distortion, microstrain relaxation, and reduced carrier-lattice interactions is achieved. These advancements effectively stabilize the inherently soft lattice against light and thermal-aging stress. To reduce the photocurrent loss induced by undesired crystal texture, a polarity-matched molecular-type selenourea (SENA) additive is further employed to modulate the crystallization kinetics. The introduction of the SENA significantly inhibits the disordered crystallization induced by spacer cations and drives the templated growth of the quantum well structure with a vertical orientation. This controlled crystallization process effectively reduces crystal defects and enhances charge separation. Ultimately, the optimized FA-based perovskite photovoltaic devices achieve a remarkable power conversion efficiency (PCE) of 20.03% (certified steady-state efficiency of 19.30%), setting a new record for low-n 2D perovskite solar cells. Furthermore, the devices exhibit less than 1% efficiency degradation after operating at maximum power point for 1000 h and maintain excellent stability after thermal aging and cycles of cold-warm shock, respectively.

Realization of High Magnetization in Artificially Designed Ni/NiO Layers through Exchange Coupling.

High-magnetization materials play crucial roles in various applications. However, the past few decades have witnessed a stagnation in the discovery of new materials with high magnetization. In this work, Ni/NiO nanocomposites are fabricated by depositing Ni and NiO thin layers alternately, followed by annealing at specific temperatures. Both the as-deposited samples and those annealed at 373 K exhibit low magnetization. However, the samples annealed at 473 K exhibit a significantly enhanced saturation magnetization exceeding 607 emu cm-3 at room temperature, surpassing that of pure Ni (480 emu cm-3 ). Material characterizations indicate that the composite comprises NiO nanoclusters of size 1-2 nm embedded in the Ni matrix. This nanoclustered NiO is primarily responsible for the high magnetization, as confirmed by density functional theory calculations. The calculations also indicate that the NiO clusters are ferromagnetically coupled with Ni, resulting in enhanced magnetization. This work demonstrates a new route toward developing artificial high-magnetization materials using the high magnetic moments of nanoclustered antiferromagnetic materials.

Origin of Enhanced Nonradiative Carrier Recombination Induced by Oxygen in Hybrid Sn Perovskite.

Oxygen ingression has been shown to substantially decrease the carrier lifetime of Sn-based perovskites, behind which the mechanism remains yet unknown. Our first-principles calculations reveal that in prototypical MASnI3 (MA = CH3NH3), oxygen by itself is not a recombination center. Instead, it tends to form substitutional OI through combining with native I vacancies (VI) and remarkably increases the original recombination rate of VI by 2-3 orders of magnitude. This rationalizes the experimentally observed sharp decline of carrier lifetime in perovskites exposed to air. The significantly enhanced carrier recombination is due to a smaller electron capture barrier of OI, resulting from lattice strengthening and the suppressed structural relaxation upon electron capture. These insights offer a route to further improve device performance via anion engineering in broad Sn-based perovskite optoelectronics operating in ambient air. Moreover, our results highlight the important role of lattice relaxation for nonradiative carrier capture in materials in general.

Fluoride-assisted detection of glutathione by surface Ce3+/Ce4+ engineered nanoceria.

Nanoceria has evolved as a promising nanomaterial due to its unique enzyme-like properties, including excellent oxidase mimetic activity, which significantly increases in the presence of fluoride ions. However, this significant increase in oxidase activity has never been utilised as a signal enhancer for the detection of biological analytes partly because of the lack of understanding of the mechanism involved in this process. In this study, we show that the surface oxidation state of cerium ions plays a very crucial role in different enzymatic activities, especially the oxidase mimetic activity by engineering nanoceria with three different surface Ce4+/Ce3+ compositions. Using DFT calculations combined with Bader charge analysis, it is demonstrated that stoichiometric ceria registers a higher oxidase mimetic activity than oxygen-deficient ceria with a low Ce4+/Ce3+ ratio due to a higher charge transfer from a substrate, 3,3',5,5' tetramethylbenzidine (TMB), to the ceria surface. We also show that the fluoride ions can significantly increase the charge transfer from the TMB surface to ceria irrespective of the surface Ce4+/Ce3+ ratio. Using this knowledge, we first compare the fluoride sensing properties of nanoceria with high Ce4+ and mixed Ce4+/Ce3+ oxidation states and further demonstrate that the linear detection range of fluoride ions can be extended to 1-10 ppm for nanoceria with mixed oxidation states. Then, we also demonstrate an assay for fluoride assisted detection of glutathione, an antioxidant with elevated levels during cancer, using nanoceria with a high surface Ce4+/Ce3+ ratio. The addition of fluoride ions in this assay allows the detection of glutathione in the linear range of 2.5-50 ppm with a limit of detection (LOD) of 3.8 ppm. These studies not only underpin the role of the surface Ce4+/Ce3+ ratio in tuning the fluoride assisted boost in the oxidase mimetic activity of nanoceria but also its strategic application in designing better colourimetric assays.

Transporting holes stably under iodide invasion in efficient perovskite solar cells.

Highly efficient halide perovskite solar cells generally rely on lithium-doped organic hole transporting layers that are thermally and chemically unstable, in part because of migration of iodide anions from the perovskite layer. We report a solution strategy to stabilize the hole transport in organic layers by ionic coupling positive polymer radicals and molecular anions through an ion-exchange process. The target layer exhibited a hole conductivity that was 80 times higher than that of the conventional lithium-doped layer. Moreover, after extreme iodide invasion caused by light-soaking at 85°C for 200 hours, the target layer maintained high hole conductivity and well-matched band alignment. This ion-exchange strategy enabled fabrication of perovskite solar cells with a certified power conversion efficiency of 23.9% that maintained 92% under standard illumination at 85°C after 1000 hours.

Localization of the Optical Phonon Modes in Boron Nitride Nanotubes: Mixing Effect of 10B Isotopes and Vacancies.

We explored the mixing effect of 10B isotopes and boron (B) or nitrogen (N) vacancies on the atomic vibrational properties of (10,0) single-wall boron nitride nanotubes (BNNTs). The forced oscillation technique was employed to evaluate the phonon modes for the entire range (0-100%) of 10B isotopes and atomic vacancy densities ranging from 0 to 30%. With increasing isotope densities, we noticed a blue shift of the Raman-active A1 phonon peak, whereas an increased density of mixed or independent B and N vacancies resulted in the emergence of a new low-frequency peak and the annihilation of the A1 peak in the phonon density of states. High-energy optical phonons were localized as a result of both 10B isotopes and the presence of mixing defects. We found an asymmetrical nature of the localization length with increasing 10B isotope content, which corresponds well to the isotope-inherited localization length of carbon nanotubes and monolayer graphene. The localization length falls abruptly with the increase in concentration of both atomic vacancies (B or N) and mixing defects (10B isotope and vacancies). These findings are critical for understanding heat conduction and nanoscopic vibrational investigations such as tip-enhanced Raman spectra in BNNTs, which can map local phonon energies.

Electric Control of Exchange Bias at Room Temperature by Resistive Switching via Electrochemical Metallization.

Electric field control of exchange bias (EB) plays an important role in spintronics due to its attractive merit of lower energy consumption. Here, we propose a novel method for electrically tunable EB at room temperature in a device with the stack of Si/SiO2/Ta/Pt/Ag/Mn-doped ZnO (MZO)/Pt/FeMn/Co/ITO by resistive switching (RS) via electrochemical metallization (ECM). The device shows enhanced and weakened EB when set at high-resistance state (HRS) and low-resistance state (LRS), respectively. For the device at LRS, the aberration-corrected scanning transmission electron microscopy (STEM) characterizations unambiguously reveal that the Ag filaments grow initially from the Ag anode and then elongate toward the ITO cathode. It is inferred that at LRS, a small portion of Ag filaments have passed through the MZO and the intervening thin Pt layer and extended into the FeMn layer. After applying reverse voltage, these Ag filaments are electrochemically dissolved and ruptured near the MZO/Pt interface. This is considered to be the main mechanism responsible for RS and switchable EB as well. This work presents a new strategy for designing low-power, nonvolatile magnetoelectric random access memory devices.

Ordered Mesoporous Boron Carbon Nitrides with Tunable Mesopore Nanoarchitectonics for Energy Storage and CO2 Adsorption Properties.

Porous boron carbon nitride (BCN) is one of the exciting systems with unique electrochemical and adsorption properties. However, the synthesis of low-cost and porous BCN with tunable porosity is challenging, limiting its full potential in a variety of applications. Herein, the preparation of well-defined mesoporous boron carbon nitride (MBCN) with high specific surface area, tunable pores, and nitrogen contents is demonstrated through a simple integration of chemical polymerization of readily available sucrose and borane ammonia complex (BAC) through the nano-hard-templating approach. The bimodal pores are introduced in MBCN by controlling the self-organization of BAC and sucrose molecules within the nanochannels of the template. It is found that the optimized sample shows a high specific capacitance (296 F g-1 at 0.5 A g-1 ), large specific capacity for sodium-ion battery (349 mAg h-1 at 50 mAh g-1 ), and excellent CO2 adsorption capacity (27.14 mmol g-1 at 30 bar). Density functional theory calculations demonstrate that different adsorption sites (BC, BN, CN, and CC) and the large specific surface area strongly support the high adsorption capacity. This finding offers an innovative breakthrough in the design and development of MBCN nanostructures for energy storage and carbon capture applications.

Minimizing and Controlling Hydrogen for Highly Efficient Formamidinium Lead Triiodide Solar Cells.

Formamidinium lead triiodide (FAPbI3) currently holds the record conversion efficiency in the single-junction perovskite solar cell. Iodine management is known to be essential to suppress defect-induced nonradiative losses in FAPbI3 active layers. However, the origin of nonradiative losses and the underlying mechanism of suppressing such losses by iodine-concentration management remain unknown. Here, through first-principles simulation, we demonstrate that native point defects are not responsible for the nonradiative losses in FAPbI3. Instead, hydrogen ions, which can be abundant under both iodine-rich and iodine-poor conditions in FAPbI3, act as efficient nonradiative recombination centers and are proposed to be responsible for the suppressed power conversion efficiency. Moreover, iodine-moderate synthesis conditions can favor the formation of electrically inactive molecular hydrogen, which can dramatically suppress the detrimental hydrogen ions. This work identifies the dominant nonradiative recombination centers in the widely used FAPbI3 layers and rationalizes how the prevailing iodine management reduces the nonradiative losses. Minimizing the unintentional hydrogen incorporation in the perovskite is critical for achieving high device performance.

Synthetic uranium oxide hydrate materials: Current advances and future perspectives.

Uranium oxide hydrate (UOH) materials, a group of minerals and synthetic phases, have attracted recent attention due to their high structural flexibility and diversity as well as their primary relationship with natural weathering of the mineral uraninite and the alteration of spent nuclear fuel (SNF) in geological disposal. Due to the limited structural and chemical understanding of UOH minerals, synthetic UOH phases provide a unique opportunity to fill existing knowledge gaps through the exploration of further structural diversity and distinctive properties, as well as potential applications. Some of the latest developments of synthetic UOH phases include the incorporation of 3d transition metal and lanthanide ions, the evolution of uranyl oxide hydroxide layers driven by interlayer charge, the structural diversity of uranyl oxide hydrate frameworks, and the intrinsic driving force for the formation of diversified structural types. The purpose of this review is to provide a comprehensive summary of the latest advancements of synthetic UOH phases with 3d transition and lanthanide metal ions, including their syntheses, structural diversities, microstructures, uranium valences, vibration modes, and structural and chemical complexities. It also highlights the subsequent implications of these advancements on uranium geochemistry and SNF alterations, amongst other potential applications. A further discussion on technical challenges and knowledge gaps is included to identify areas for future research.

Boosting Oxygen Reduction Activity of Manganese Oxide Through Strain Effect Caused By Ion Insertion.

Transition-metal oxides with a strain effect have attracted immense interest as cathode materials for fuel cells. However, owing to the introduction of heterostructures, substrates, or a large number of defects during the synthesis of strain-bearing catalysts, not only is the structure-activity relationship complicated but also their performance is mediocre. In this study, a mode of strain introduction is reported. Transition-metal ions with different electronegativities are intercalated into the cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2) structure with K ions as the template, resulting in the octahedral structural distortion of MnO6 and producing strains of different degrees. Experimental studies reveal that Ni-OMS-2 with a high compressive strain (4.12%) exhibits superior oxygen reduction performance with a half-wave potential (0.825 V vs RHE) greater than those of other reported manganese-based oxides. This result is related to the increase in the covalence of MnO6 octahedral configuration and shifting down of the eg band center caused by the higher compression strain. This research avoids the introduction of new chemical bonds in the main structure, weakens the effect of eg electron filling number, and emphasizes the pure strain effect. This concept can be extended to other transition-metal-oxide catalysts.

Atom probe specimen preparation methods for nanoparticles.

Revealing the position of materials with chemical selectivity at atomic scale within functional nanoparticles is essential to understand and control their performance and cutting-edge atom probe tomography is a powerful tool to undertake this task. In this paper, we demonstrate three effective methods to prepare the needle-shaped specimens required for atom probe tomography measurements from nanoparticles of different sizes and provide examples of how atom probe can be used to provide data that is critical to their functionality. Samples measured include lithium-ion batteries (LIBs) cathode nanoparticles (300 - 500 nm), nickel-doped silicon dioxide (Ni@SiO2) catalytic nanoparticles (100 - 200 nm) and tin-doped copper (Sn@Cu) catalytic nanoparticles (<100 nm). The methods presented can be used to address the ongoing challenge of specimen preparation from particle samples for atom probe measurement, and they provide high quality data. These methods will broaden the application of atom probe tomography and will provide alternative option for researchers to assess the performance/structure of their functional nanomaterials.

Hydrogen-Anion-Induced Carrier Recombination in MAPbI3 Perovskite Solar Cells.

Identification and passivation of defect-induced electron-hole recombination centers are currently crucial for improving the efficiency of hybrid perovskite solar cells. Besides general intrinsic defects, experimental reports have indicated that hydrogen interstitials are also abundant in hybrid perovskite layers; however, few reports have evaluated the effect of such defects on the charge carrier recombination and device efficiencies. Here, we reveal that under I-poor synthesis conditions, the negatively charged monatomic hydrogen interstitial, Hi-, will form in the prototypical CH3NH3PbI3 perovskite layer, acting as a detrimental deep-level defect, which leads to efficient electron-hole recombination and lowers the cell performance. We further rationalize that Br doping can mitigate the large atomic displacement caused by the presence of Hi- and hence suppress the formation of the deep localized state. The results advance the knowledge of the deep-level defects in hybrid perovskites and provide useful information for enhancing solar cell performance by defect engineering.