Minimizing Interfacial Energy Loss and Volatilization of Formamidinium via Polymer-Assisted D-A supramolecular Self-Assembly Interface for Inverted Perovskite Solar Cells with 25.78% Efficiency.

2D perovskite passivation strategies effectively reduce defect-assisted carrier nonradiative recombination losses on the perovskite surface. Nonetheless, severe energy losses are causing by carrier thermalization, interfacial nonradiative recombination, and conduction band offset still persist at heterojunction perovskite/PCBM interfaces, which limits further performance enhancement of inverted heterojunction PSCs. Here, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (5FTPP) is introduced between 3D/2D perovskite heterojunction and PCBM. Compared to tetraphenylporphyrin without electron-withdrawing fluoro-substituents, 5FTPP can self-assemble with PCBM at interface into donor-acceptor (D-A) complex with stronger supramolecular interaction and lower energy transfer losses. This rapid energy transfer from donor (5FTPP) to acceptor (PCBM) within femtosecond scale is demonstrated to enlarge hot carrier extraction rates and ranges, reducing thermalization losses. Furthermore, the incorporation of polystyrene derivative (PD) reinforces D-A interaction by inhibiting self-π-π stacking of 5FTPP, while fine-tuning conduction band offset and suppressing interfacial nonradiative recombination via Schottky barrier, dipole, and n-doping. Notably, the multidentate anchoring of PD-5FTPP with FA+, Pb2+, and I- mitigates the adverse effects of FA+ volatilization during thermal stress. Ultimately, devices with PD-5FTPP achieve a power conversion efficiency of 25.78% (certified: 25.36%), maintaining over 90% of initial efficiency after 1000 h of continuous illumination at the maximum power point (65 °C) under ISOS-L-2 protocol.

Myocardial Bridging Increases the Risk of Adverse Cardiovascular Events in Patients without Coronary Atherosclerosis.

Background: Myocardial bridging (MB) is a congenital coronary anomaly and an important cause of chest pain. The long-term effects of MB on cardiovascular events remain elusive. Methods: We used the National Health Insurance Research Database of Taiwan to conduct an analysis. All patients who had undergone coronary angiography were considered for inclusion. The primary endpoint was a composite of nonfatal myocardial infarction, nonfatal ischemic stroke, and cardiovascular death. Results: We identified 10,749 patients from 2008 to 2018 and matched them with an equal number of controls by propensity-score matching. The mean follow-up period was 5.78 years. In patients without coronary artery disease, MB increased the risk of the composite endpoint (hazard ratio [HR]: 1.57, 95% confidence interval [CI]: 1.44-1.72, p < 0.001), which was driven by increased risks of nonfatal myocardial infarction and cardiovascular death. In patients with significant coronary artery disease, MB did not increase the risk of major adverse cardiovascular events. MB was identical to insignificant coronary artery disease from the viewpoint of clinical outcomes. Conclusions: The presence of MB significantly increases cardiovascular risks in patients with normal coronary vessels. Atherosclerotic coronary artery disease mitigates the effect of MB on cardiovascular outcomes. MB can be considered an insignificant coronary artery disease equivalent.

Sex differences in clinical characteristics and long-term clinical outcomes in Asian hospitalized heart failure patients.

AIMS: Sex differences in long-term post-discharge clinical outcomes in Asian patients hospitalized for acute decompensated heart failure (HF) persist despite the world-wide implementation of guideline-directed medical therapy for decades. The present study aims to elucidate the puzzling dilemma and to depict the directions of solution. METHODS AND RESULTS: Between 2011 and 2020, a total of 12 428 patients (6518 men and 5910 women, mean age 73.50 ± 14.85) hospitalized for acute decompensated HF were retrospectively enrolled from a university HF cohort. Compared with men, women hospitalized for acute decompensated HF were older in age (76.40 ± 13.43 vs. 71.20 ± 15.67 years old, P < 0.0001) with more coexisting hypertension, diabetes, hyperlipidaemia and moderate to severe chronic kidney disease, but less with ischaemic heart disease, cerebrovascular disease and chronic obstructive pulmonary disease (P < 0.0001). In echocardiography measurement parameters, women had smaller left ventricular and left atrial dimensions, higher left ventricular mass index, higher left ventricular ejection fraction (LVEF) and more in HF with preserved ejection fraction (EF) category (LVEF > 50%) than men (P < 0.0001). In HF therapy, women compared with men received more guideline-directed medical HF therapies including angiotensin-converting enzyme inhibitors, angiotensin receptor blockers, angiotensin receptor-neprilysin inhibitors and sodium-glucose cotransporter-2 inhibitors, but similar beta-blockers and mineralocorticoid receptor antagonists (P < 0.0001). Post-discharge long-term clinical outcomes after multivariate-adjusted analysis revealed that women compared with men had lower all-cause mortality [adjusted hazard ratio (aHR): 0.89, 95% confidence interval (CI): 0.84-0.93], lower cardiovascular mortality (aHR: 0.89, 95% CI: 0.80-0.99) and lower 1 year mortality (aHR: 0.91, 95% CI: 0.84-0.99) but similar HF rehospitalization rate (aHR: 1.02, 95% CI: 0.95-1.09) over 8 years of follow-up. The superiority of women over men in all-cause mortality was shown in HF with preserved EF (>50%) and HF with mildly reduced EF (40%-50%), but not in HF with reduced EF (<40%) category. Subgroup forest plot analysis showed body mass index, coexisting hypertension and chronic obstructive pulmonary disease as significant interacting factors. CONCLUSIONS: With more coronary risk factors and medical comorbidities, less cardiac remodelling and better adherence to guideline-directed HF therapy, women hospitalized for acute decompensated HF demonstrated superiority over men in long-term post-discharge clinical outcomes, including all-cause mortality, cardiovascular mortality and 1 year mortality, and mainly in HF with preserved and mid-range EF categories, in the Asian HF cohort.

Enhancing the Efficiency and Stability of Inverted Formamidinium-Cesium Lead-Triiodide Perovskite Solar Cells through Lewis Base Pretreatment of Buried Interfaces.

Mixed components of formamidinium(FA) and cesium (Cs)-based perovskite solar cells are the most hopeful for commercialization owing to their excellent operational and phase stabilities, especially for devices with inverted structure. The nonradiative recombination of carriers can be effectively suppressed through interface optimization, therefore, the performance of devices can be improved. Notably, the buried interface emerges as critical aspects such as charge transport, charge recombination kinetics, and morphology of perovskite films. This study focuses on a straightforward yet effective approach to overcome buried interface challenges between organic polymers (poly(-triarylamine) (PTAA) and FACs-based perovskite films. The PTAA substrate is pretreated with a Lewis base known as 2-butynoic acid (BA) with a C═O functional group. First, it can be an interfacial buffering layer, harmonizing stress mismatch between the perovskite and PTAA layers, consequently optimizing crystallization and improving perovskite film quality. Second, Pb2+ defect can be passivated at the buried interface of the perovskite film through binding with the C═O group of the BA molecule. This dual-function strategy leads to a substantial enhancement in both photoelectric conversion efficiency (PCE) and stability of devices. Finally, the PCE of the device-modified buried interface with BA reaches an impressive 23.33%. Furthermore, unencapsulated devices with BA treatment maintain approximately 94% of their initial efficiency after aging at maximum power point tracking for 1000 h.

Efficient Charge Transport in Inverted Perovskite Solar Cells via 2D/3D Ferroelectric Heterojunction.

While the 2D/3D heterojunction is an effective method to improve the power conversion efficiency (PCE) of perovskite solar cells (PSCs), carriers are often confined in the quantum wells (QWs) due to the unique structure of 2D perovskite, which makes the charge transport along the out-of-plane direction difficult. Here, a 2D/3D ferroelectric heterojunction formed by 4,4-difluoropiperidine hydrochloride (2FPD) in inverted PSCs is reported. The enriched 2D perovskite (2FPD)2PbI4 layer with n = 1 on the perovskite surface exhibits ferroelectric response and has oriented dipoles along the out-of-plane direction. The ferroelectricity of the oriented dipole layer facilitates the enhancement of the built-in electric field (1.06 V) and the delay of the cooling process of hot carriers, reflected in the high carrier temperature (above 1400 K) and the prolonged photobleach recovery time (139.85 fs, measured at bandgap), improving the out-of-plane conductivity. In addition, the alignment of energy levels is optimized and exciton binding energy (32.8 meV) is reduced by changing the dielectric environment of the surface. Finally, the 2FPD-treated PSCs achieve a PCE of 24.82% (certified: 24.38%) with the synergistic effect of ferroelectricity and defect passivation, while maintaining over 90% of their initial efficiency after 1000 h of maximum power point tracking.

Microstrain and Crystal Orientation Variation within Naked Triple-Cation Mixed Halide Perovskites under Heat, UV, and Visible Light Exposure.

The instability of perovskite absorbers under various environmental stressors is the most significant obstacle to widespread commercialization of perovskite solar cells. Herein, we study the evolution of crystal structure and microstrain present in naked triple-cation mixed CsMAFA-based perovskite films under heat, UV, and visible light (1 Sun) conditions by grazing-incidence wide-angle X-ray scattering (GIWAXS). We find that the microstrain is gradient distributed along the surface normal of the films, decreasing from the upper surface to regions deeper within the film. Moreover, heat, UV, and visible light treatments do not interfere with the crystalline orientations within annealed polycrystalline films. However, when subjected to heat, the naked perovskite films exhibit a rapid component decomposition, induced by phase separation and ion migration. Conversely, under exposure to UV and 1 Sun light soaking, the naked perovskite films undergo a self-optimization structure evolution during degradation and develop into smoother films with reduced surface potential fluctuations.

Dynamic Transition between Monomer and Excimer Phosphorescence in Organic Near-Infrared Phosphorescent Crystals.

Achieving efficient near-infrared room-temperature phosphorescence of purely organic phosphors remains scarce and challenging due to strong nonradiative decay. Additionally, the investigation of triplet excimer phosphorescence is rarely reported, despite the fact that excimer, a special emitter commonly formed in crystals with strong π-π interactions, can efficiently change the fluorescent properties of compounds. Herein, a series of dithienopyrrole derivatives with low triplet energy levels and stable triplet states, exhibiting persistent near-infrared room-temperature phosphorescence, is developed. Via the modification of halogen atoms, the crystals display tunable emissions of monomers from 645 to 702 nm, with a maximum lifetime of 3.68 ms under ambient conditions. Notably, excimer phosphorescence can be switched on at low temperatures, enabled by noncovalent interactions rigidifying the matrix and stabilizing triplet excimer. Unprecedentedly, the dynamic transition process is captured between the monomer and excimer phosphorescence with temperature variations, revealing that the unstable triplet excimers in crystals with a tendency to dissociate can result in the effective quench of room-temperature phosphorescence. Excited state transitions across varying environments are elucidated, interpreting the structural dynamics of the triplet excimer and demonstrating strategies for devising novel near-infrared phosphors.

Infiltrated 2D/3D Heterojunction with Tunable Electric Field Landscape for Robust Inverted Perovskite Solar Cells with over 24% Efficiency.

In inverted perovskite solar cells, conventional planar 2D/3D perovskite heterojunctions typically exhibit a type-II band alignment, where the electric field tends to drive the electron motion in the opposite direction to the direction of electron transfer. Here, a 2D/3D gradient heterojunction is developed by allowing the 2D perovskite to infiltrate the 3D perovskite surface along the grain boundaries using the interaction between the organic cation of the 2D perovskite and the pseudohalogen thiocyanate ion (SCN-), which has the ability to diffuse downward. The infiltrated 2D perovskite not only fills the gaps of grain boundaries with improved structural stability, but it also reconstructs the original landscape of the electric field toward the n-doped surface to enable more rapid electron transfer and weaken the adverse type-II band alignment effect. Since 2D perovskite seals the GBs, the nonvolatile SCN- can accumulate at the top and bottom dual interfaces, releasing residual stress and significantly inhibiting nonradiative recombination. The device exhibits an excellent efficiency of 24.76% (certified 24.29%) and long-term stability that is >90% of the original PCE value after 800 h of heating at 85 °C or in high humidity (≈65%).