Suppressed phase segregation for triple-junction perovskite solar cells.

The tunable bandgaps and facile fabrication of perovskites make them attractive for multi-junction photovoltaics1,2. However, light-induced phase segregation limits their efficiency and stability3-5: this occurs in wide-bandgap (>1.65 electron volts) iodide/bromide mixed perovskite absorbers, and becomes even more acute in the top cells of triple-junction solar photovoltaics that require a fully 2.0-electron-volt bandgap absorber2,6. Here we report that lattice distortion in iodide/bromide mixed perovskites is correlated with the suppression of phase segregation, generating an increased ion-migration energy barrier arising from the decreased average interatomic distance between the A-site cation and iodide. Using an approximately 2.0-electron-volt rubidium/caesium mixed-cation inorganic perovskite with large lattice distortion in the top subcell, we fabricated all-perovskite triple-junction solar cells and achieved an efficiency of 24.3 per cent (23.3 per cent certified quasi-steady-state efficiency) with an open-circuit voltage of 3.21 volts. This is, to our knowledge, the first reported certified efficiency for perovskite-based triple-junction solar cells. The triple-junction devices retain 80 per cent of their initial efficiency following 420 hours of operation at the maximum power point.

Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene.

Converting CO2 to synthetic hydrocarbon fuels is of increasing interest. In light of progress in electrified CO2 to ethylene, we explored routes to dimerize to 1-butene, an olefin that can serve as a building block to ethylene longer-chain alkanes. With goal of selective and active dimerization, we investigate a series of metal-organic frameworks having bimetallic catalytic sites. We find that the tunable pore structure enables optimization of selectivity and that periodic pore channels enhance activity. In a tandem system for the conversion of CO2 to 1-C4H8, wherein the outlet cathodic gas from a CO2-to-C2H4 electrolyzer is fed directly (via a dehumidification stage) into the C2H4 dimerizer, we study the highest-performing MOF found herein: M' = Ru and M″ = Ni in the bimetallic two-dimensional M'2(OAc)4M″(CN)4 MOF. We report a 1-C4H8 production rate of 1.3 mol gcat-1 h-1 and a C2H4 conversion of 97%. From these experimental data, we project an estimated cradle-to-gate carbon intensity of -2.1 kg-CO2e/kg-1-C4H8 when CO2 is supplied from direct air capture and when the required energy is supplied by electricity having the carbon intensity of wind.

Organic Polar Crystals, Second Harmonic Generation, and Piezoelectric Effects from Heteroadamantanes in the Space Group R3m.

Polar crystalline materials, a subset of the non-centrosymmetric materials, are highly sought after. Their symmetry properties make them pyroelectric and also piezoelectric and capable of second-harmonic generation (SHG). For SHG and piezoelectric applications, metal oxides are commonly used. The advantages of oxides are durability and hardness - downsides are the need for high-temperature synthesis/processing and often the need to include toxic metals. Organic polar crystals, on the other hand, can avoid toxic metals and can be amenable to solution-state processing. While the vast majority of polar organic molecules crystallize in non-polar space groups, we found that both 7-chloro-1,3,5-triazaadamantane, for short Cl-TAA, and also the related Br-TAA (but not I-TAA) form polar crystals in the space group R3m, easily obtained from dichloromethane solution. Measurements confirm piezoelectric and SHG properties for Cl-TAA and Br-TAA. When the two species are crystallized together, solid solutions form, suggesting that properties of future materials can be tuned continuously.

Regioselectivity Switch of α-Amino Acid-Derived Esters and MBH Carbonates for the Synthesis of Allyl-Substituted Azlactones.

Allylic azlactones are greatly significant in terms of potential bioactivities and synthetic applications. Owing to the burgeoning interest of the pharmaceutical industry in α-amino acid derivatives, discovering strategies for the synthesis of allylic azlactones is important. Herein, we establish a transition-metal-free regioselectivity switch of α-amino acid-derived esters and MBH carbonates, which exhibits broad reaction scope and good reaction yields. Control reactions indicate that both base and solvent are important for regioselectivity.

Chirality and Solvent Coassist the Structural Evolution of Hybrid Manganese Chlorides with Second-Harmonic-Generation Response.

Chiral hybrid metal halides have shown great potential in optoelectronics, including for spin splitting, circularly polarized luminescence, and nonlinear-optical properties. However, despite their inherent inversion symmetry breaking, studies on second harmonic generation (SHG) of chiral hybrid manganese(II) halides remain relatively rare. Here, we report a series of structurally diverse hybrid manganese(II) chlorides: (Rac-MBA)2[MnCl4(H2O)2] (1), (S-MBA)2[MnCl4(H2O)2] (2), (S-MBA)2[Mn2Cl6(H2O)4] (3), and (S-MBA)[MnCl3(MeOH)] (4), where MBA = α-methylbenzylammonium, providing tunability of the coordination environment and structural dimensionality via fine control of the MBA cation chiral state and crystal preparation process, thereby enabling modulation of the SHG effects. Specifically, as the amount of methanol increases during the crystal preparation process, the structures of the chiral compounds vary from a 0D structure consisting of isolated octahedra to a 0D structure composed of octahedra dimers and to 1D chains of edge-sharing Mn-centered octahedra. In contrast, the structure of the racemic compound remains unchanged, independent of the crystal preparation pathway. The structural details, including the coordination environment, H-bonding, dimensionality, and lattice distortion, are described. The SHG response of the racemic compound derives only from the inorganic lattice, while the responses of the chiral compounds are attributed to the synergetic effect of the chiral cations and inorganic moieties.

The impact of perceived life stress and online social support on university students' mental health during the post-COVID era in Northwestern China: gender-specific analysis.

BACKGROUND: Before the pandemic, research had already established the potential impact of perceived life stress and social support on the mental health status of Chinese students. However, in the Post-COVID Era, the specific mechanisms linking these variables and the distinct role of online social support remain relatively unexplored. METHODS: After the cessation of China's dynamic zeroing policy, a total of 1180 university students from Northwestern China participated in this study by completing a demographic questionnaire, as well as self-report measures assessing mental health, perceived life stress, and online social support. RESULTS: Approximately 25% of students exhibited psychological symptoms. When examining different categories of perceived life stress, males reported experiencing a significantly greater impact in terms of punishment and interpersonal relationships compared to females. Females experienced significantly higher levels of learning pressure compared to males. Specific types of perceived life stress were found to be significant predictors of students' mental health status. Moreover, online social support was identified as a significant moderator in the relationship between all types of perceived life stress and mental health, irrespective of gender. CONCLUSION: Our study findings unveiled two significant aspects: Firstly, the impact of perceived life stress on the mental health of students was identified as a risk factor. Secondly, the role of online social support emerged as a protective factor, particularly in the post-pandemic context. Additionally, gender-specific patterns were observed in these relationships.

Rosemary: Unrevealing an old aromatic crop as a new source of promising functional food additive-A review.

Rosemary (Rosmarinus officinalis L.) is one of the most famous spice plants belonging to the Lamiaceae family as a remarkably beautiful horticultural plant and economically agricultural crop. The essential oil of rosemary has been enthusiastically welcome in the whole world for hundreds of years. Now, it is wildly prevailing as a promising functional food additive for human health. More importantly, due to its significant aroma, food, and nutritional value, rosemary also plays an essential role in the food/feed additive and food packaging industries. Modern industrial development and fundamental scientific research have extensively revealed its unique phytochemical constituents with biologically meaningful activities, which closely related to diverse human health functions. In this review, we provide a comprehensively systematic perspective on rosemary by summarizing the structures of various pharmacological and nutritional components, biologically functional activities and their molecular regulatory networks required in food developments, and the recent advances in their applications in the food industry. Finally, the temporary limitations and future research trends regarding the development of rosemary components are also discussed and prospected. Hence, the review covering the fundamental research advances and developing prospects of rosemary is a desirable demand to facilitate their better understanding, and it will also serve as a reference to provide many insights for the future promotion of the research and development of functional foods related to rosemary.

2D Hybrid Perovskites Employing an Organic Cation Paired with a Neutral Molecule.

Two-dimensional (2D) hybrid perovskites harness the chemical and structural versatility of organic compounds. Here, we explore 2D perovskites that incorporate both a first organic component, a primary ammonium cation, and a second neutral organic module. Through the experimental examination of 42 organic pairs with a range of functional groups and organic backbones, we identify five crystallization scenarios that occur upon mixing. Only one leads to the cointercalation of the organic modules with distinct and extended interlayer spacing, which is observed with the aid of X-ray diffraction (XRD) pattern analysis combined with cross-sectional transmission electron microscopy (TEM) and elemental analysis. We present a picture in which complementary pairs, capable of forming intermolecular bonds, cocrystallize with multiple structural arrangements. These arrangements are a function of the ratio of organic content, annealing temperature, and substrate surface characteristics. We highlight how noncovalent bonds, particularly hydrogen and halogen bonding, enable the influence over the organic sublattice in hybrid halide perovskites.

Control of Halogen Atom in Inorganic Metal-Halide Perovskites Enables Large Piezoelectricity for Electromechanical Energy Generation.

Regulating the strain of inorganic perovskites has emerged as a critical approach to control their electronic and optical properties. Here, an alternative strategy to further control the piezoelectric properties by substituting the halogen atom (I/Br) in the CsPbX3 perovskite (X = Cl, Br) structure is adopted. A series of piezoelectric materials with excellent piezoelectric coefficients (d33 ) are unveiled. Iodine-incorporated CsPbBr2 I demonstrates the record intrinsic piezoelectric response (d33 ≈47 pC N-1 ) among all inorganic metal halide perovskites. This leads to an excellent electrical output power of ≈ 0.375 mW (24.8 µW cm-2 N-1 ) in the piezoelectric energy generator (PEG) which is higher than those of the pristine/mixed perovskite references with CsPbX3 (X = I, Br, Cl). With its structural phase remaining unchanged, the strained CsPbBr2 I retains its superior piezoelectricity in both thin film and nanocrystal powder forms, further demonstrating its repeatability and versatility of applications. The origin of high piezoelectricity is found to be due to halogen-induced anisotropic lattice strain in the unit-cell along the c-axis, and octahedral distortion. This study reveals an avenue to design new piezoelectric materials by modifying their halide constituents and paves the way to design efficient PEGs for improved electromechanical energy conversion.

Rigid Conjugated Diamine Templates for Stable Dion-Jacobson-Type Two-Dimensional Perovskites.

Hybrid organic-inorganic perovskites (HOIPs) have garnered widespread interest, yet stability remains a critical issue that limits their further application. Compared to their three-dimensional (3D) counterparts, two-dimensional (2D)-HOIPs exhibit improved stability. 2D-HOIPs are also appealing because their structural and optical properties can be tuned according to the choice of organic ligand, with monovalent or divalent ligands forming Ruddlesden-Popper (RP) or Dion-Jacobson (DJ)-type 2D perovskites, respectively. Unlike RP-type 2D perovskites, DJ-type 2D perovskites do not contain a van der Waals gap between the 2D layers, leading to improved stability. However, bifunctional organic ligands currently used to develop DJ-type 2D perovskites are limited to commercially available aliphatic and single-ring aromatic ammonium cations. Large conjugated organic ligands are in demand for their semiconducting properties and their potential to improve materials stability further. In this manuscript, we report the design and synthesis of a new set of larger conjugated diamine ligands and their incorporation into DJ-type 2D perovskites. Compared with analogous RP-type 2D perovskites, DJ 2D perovskites reported here show blue-shifted, narrower emissions and significantly improved stability. By changing the structure of rings (benzene vs thiophene) and substituents, we develop structure-property relationships, finding that fluorine substitution enhances crystallinity. Single-crystal structure analysis and density functional theory calculations indicate that these changes are due to strong electrostatic interactions between the organic templates and inorganic layers as well as the rigid backbone and strong π-π interaction between the organic ligands themselves. These results illustrate that targeted engineering of the diamine ligands can enhance the stability of DJ-type 2D perovskites.

Acquiring High-TC Layered Metal Halide Ferroelectrics via Cage-Confined Ethylamine Rotators.

Two-dimensional (2D) organic-inorganic hybrid perovskite (OIHP) ferroelectrics have attracted widespread interest in the field of optoelectronics due to the combination of excellent semiconducting and ferroelectric properties. The Curie temperature (TC ), below which ferroelectricity exists, is a crucial parameter for ferroelectrics. However, the lack of research on TC tuning of 2D OIHP ferroelectrics hinders their further progress. Here, through incorporating ethylammonium (EA) as cage-confined rotators, we obtained two 2D OIHP ferroelectrics, (IBA)2 (EA)Pb2 Br7 (2L; IBA=isobutylammonium), and (IBA)2 (EA)2 Pb3 Br10 (3L). Intriguingly, TC is successfully tuned from 326 K (2L) to 370 K (3L) with increasing layer thickness. Structural and computational analyses suggest that the improvement of TC is due to the higher phase-transition energy barrier triggered by the cage-confined EA rotators with increased layer thickness. This work suggests that EA is an effective "cage-confined rotator" to rationally design high-TC 2D OIHP ferroelectrics.

Trilayered Lead Chloride Perovskite Ferroelectric Affording Self-Powered Visible-Blind Ultraviolet Photodetection with Large Zero-Bias Photocurrent.

Perovskite ferroelectrics, in which the spontaneous polarization (Ps) is conducive to the separation of photoexcited charge carriers, have shown great potential for self-powered photodetection. Nevertheless, such self-powered ferroelectric photodetectors are mostly dominated by traditional inorganic oxides and exhibit relatively small zero-bias photocurrent, which limit their further application. Herein, we present a wide-bandgap 2D trilayered lead chloride hybrid perovskite ferroelectric, EA4Pb3Cl10 (1, EA = ethylammonium), which shows a notable Ps of ∼4.5 µC/cm2 and a high Curie temperature (415 K) beyond that of BaTiO3 (393 K). Significantly, benefiting from the wide bandgap of 3.39 eV, a self-powered visible-blind ultraviolet (UV) photodetector has been successfully realized, with a zero-bias photocurrent as high as 18.6 µA/cm2, which is nearly 2 orders of magnitude larger than those of mostly conventional inorganic ferroelectrics. As a pioneering study, this work offers an efficient approach for exploring wide-bandgap perovskite ferroelectrics and will excavate their application in the field of self-powered visible-blind UV photodetection.

A Potential Sn-Based Hybrid Perovskite Ferroelectric Semiconductor.

Ferroelectric semiconductors, combining semiconduction, spontaneous polarization, and photoinduced excitation, show great promise to enhance the performance of solar cells, pressure sensors, and photodetectors. Particularly, organic-inorganic lead halide perovskite ferroelectrics have been explored for their prominent carrier transport properties and structural tunability. However, a high concentration of toxic Pb is a stumbling block for their further application. Here, we present a lead-free hybrid perovskite semiconductor, (C4H9NH3)2(NH3CH3)2Sn3Br10 (1), which exhibits a large spontaneous polarization of 11.76 µC cm-2 at room temperature. Significantly, 1 presents a spontaneous polar ordering transition, similar to the better-known perovskite ferroelectrics, and exhibits ferroelectric phase transition behaviors. To our best knowledge, 1 is the first example of a Sn-based hybrid perovskite semiconductor featuring ferroelectric performance. Mechanistic studies reveal that such ferroelectricity can be attributable to the synergistic effects of ordering of organic cations and stereochemically active lone-pair electrons inducing distortion of inorganic octahedra. This work provides an effective way to explore "green" ferroelectric semiconductors with potentially enhanced energy conversion efficiency.

[(N-AEPz)ZnCl4]Cl: A "Green" Metal Halide Showing Highly Efficient Bluish-White-Light Emission.

Benefiting from their structural flexibility and solution processability, organic-inorganic metal halide hybrids with efficient white-light emission present a great promise for solid-state lighting and display applications. However, most of these reported high-performance single-component white-light materials contain lead. Herein, we report a "green" organic zinc halide, [(N-AEPz)ZnCl4]Cl (1; N-AEPz = N-aminoethylpiperazine), exhibiting prominent bluish-white-light emission with a photoluminescence quantum efficiency as high as 11.52%. Such a value is among the highest in the reported metal halide white-light emitters. Mechanism studies disclose that the broad-band emission is ascribed to the synergistic work of organic salts and inorganic clusters. This work would incent research on single-component white-light materials for next-generation display and lighting technologies.

Exploiting the Bulk Photovoltaic Effect in a 2D Trilayered Hybrid Ferroelectric for Highly Sensitive Polarized Light Detection.

Polarized light detection is attracting increasing attention for its wide applications ranging from optical switches to high-resolution photodetectors. Two-dimensional (2D) hybrid perovskite-type ferroelectrics combining inherent light polarization dependence of bulk photovoltaic effect (BPVE) with excellent semiconducting performance present significant possibilities. Now, the BPVE-driven highly sensitive polarized light detection in a 2D trilayered hybrid perovskite ferroelectric, (allyammonium)2 (ethylammonium)2 Pb3 Br10 (1), is presented. It shows a superior BPVE with near-band gap photovoltage of ca. 2.5 V and high on/off switching ratio of current (ca. 104 ). Driven by the superior BPVE, 1 exhibits highly sensitive polarized light detection with a polarization ratio as high as ca. 15, which is far more beyond than those of structural anisotropy-based monocomponent devices. This is the first realization of BPVE-driven polarized light detection in hybrid perovskite ferroelectrics.

Discovery of an Above-Room-Temperature Antiferroelectric in Two-Dimensional Hybrid Perovskite.

Antiferroelectric materials have been regarded as a promising candidate for electronic energy storage devices, due to their natural double polarization versus electric field ( P- E) hysteresis loops. Currently, two-dimensional organic-inorganic hybrid perovskites with structural diversity and tunability, have received blooming interests, whereas above-room-temperature antiferroelectrics are still unreported in this perovskite system. Herein, for the first time, we successfully acquire a two-dimensional Ruddlesden-Popper hybrid perovskite antiferroelectric, ((CH3)2CHCH2NH3)2CsPb2Br7 (1), which shows an above-room-temperature Curie temperature at 353 K, trigging by the synergistic dynamic motion of inorganic Cs atoms and organic isobutylammonium cations. Intriguingly, the antiferroelectricity of 1 existing over a wide temperature range of 298-353 K are revealed by the distinct double P- E hysteresis loops. Besides, 1 possesses remarkable energy storage efficiency up to 69%, comparable to those of some reported inorganic antiferroelectric ceramics, promoting 1 potential application in energy storage devices. This work provides an avenue to construct novel antiferroelectric materials for high-performance electronic device applications.

An Unprecedented Biaxial Trilayered Hybrid Perovskite Ferroelectric with Directionally Tunable Photovoltaic Effects.

Multiaxial molecular ferroelectrics, in which multiple-directional switching of spontaneous polarization creates diverse properties, have shown many intriguing advantages, making them indispensable complements to conventional inorganic oxides. Despite recent blooming advances, multiaxial molecular ferroelectric with bulk photovoltaic effects still remains a huge blank. Herein, we report a biaxial lead halide ferroelectric, EA4Pb3Br10 (1, EA = ethylammonium), which adopts the unique trilayered perovskite motif with a high Curie temperature of ∼384 K. Particularly, for 1, the distinct symmetry breaking with 4/ mmmF mm2 species leads to the emergence of four equivalent polarization directions in the ferroelectric phase. Based on its biaxial nature, the bulk photovoltaic effect of 1 can be facilely tuned between such multiple directions through electric poling. As far as we know, this is the first report on biaxial hybrid perovskite ferroelectric showing directionally tunable photovoltaic activity. This work provides an avenue to control the bulk physical properties of multiaxial molecular ferroelectrics, and highlights their potential for further applications in the field of smart devices.

Tailored Synthesis of an Unprecedented Pb-Mn Heterometallic Halide Hybrid with Enhanced Emission.

Organic-inorganic lead halide hybrids have attracted extensive interest in solid-state lighting, due to their superior color tunability and low-cost solution processing. However, the relatively low photoluminescence quantum efficiency (PLQE) is a common issue for most bulk lead halide hybrids. Inspired by the intriguing luminescence properties of heterometallic complexes, we rationally developed an unprecedented two-dimensional (2D) Pb-Mn heterometallic halide hybrid, (C5H14N2)2Pb4MnCl14 (2), through a precisely tailored synthetic approach based on (C5H14N2)2Pb5Cl14 (1). Intriguingly, 2 features a unique 2D heterometallic halide layer configuration, in which the strong quantum confinement facilitates efficient energy transfer from bound excitons to d-states of Mn2+, resulting in highly sensitized Mn2+emission. The PLQE of 2 is up to 32%, considerably higher than that of pristine 1 (less than 1%). Moreover, 2 presents significant environmental and thermal stability, benefiting from its cluster feature. To our best knowledge, this is the first example of construction of a Pb-Mn heterometallic halide hybrid with bulk highly efficient red emission. This work provides a way to enhance the PLQE of lead halide hybrids via sensitization in rationally designed heterometallic halide hybrids.

Synergistic Intra- and Intermolecular Noncovalent Interactions for Ultralong Organic Phosphorescence.

Metal-free ultralong organic phosphorescence (UOP) materials have attracted significant attention owing to their anomalous photophysical properties and potential applications in various fields. Here, three pyrimidine-based organic luminogens, 9-(pyrimidin-2-yl)-9H-carbazole, 9-(4,6-dimethylpyrimidin-2-yl)-9H-carbazole, and 9-(5-bromopyrimidin-2-yl)-9H-carbazole are designed and synthesized, which show efficient yellow UOP with the longest lifetimes up to 1.37 s and the highest absolute phosphorescence quantum yields up to 23.6% under ambient conditions. Theoretical calculations, crystal structures, and photophysical properties of these compounds reveal that intramolecular hydrogen bonding, intermolecular π-π interactions, and intermolecular electronic coupling are responsible for forming dimers and generating highly efficient UOP. Their efficacy as solid materials for data encryption is demonstrated.

Polarization-Driven Self-Powered Photodetection in a Single-Phase Biaxial Hybrid Perovskite Ferroelectric.

Self-powered photodetection driven by ferroelectric polarization has shown great potential in next-generation optoelectronic devices. Hybrid perovskite ferroelectrics that combine polarization and semiconducting properties have a promising position within this portfolio. Herein, we demonstrate the realization of self-powered photodetection in a new developed biaxial ferroelectric, (EA)2 (MA)2 Pb3 Br10 (1, EA is ethylammonium and MA is methylammonium), which displays high Curie temperature (375 K), superior spontaneous polarization (3.7 µC cm-2 ), and unique semiconducting nature. Strikingly, without an external energy supply, 1 exhibits an direction-selectable photocurrent with fascinating attributes including high photocurrent density (≈4.1 µA cm-2 ), high on/off switching ratio (over 106 ), and ultrafast response time (96/123 µs); such merits are superior to those of the most active ferroelectric oxide BiFeO3 . Further studies reveal that strong inversion symmetry breaking in 1 provides a desirable driving force for carrier separation, accounting for such electrically tunable self-powered photoactive behaviors. This work sheds light on exploring new multifunctional hybrid perovskites and advancing the design of intelligent photoelectric devices.