Synergistic Effect of Excited State Property and Aggregation Characteristic of Organic Semiconductor on Efficient Hole-Transportation in Perovskite Device

Intrinsic characteristics of organic semiconductor-based hole transport materials (HTMs) such as facile synthesizability, energy level tunability, and charge transport capability have been highlighted as crucial factors determining the performances of perovskite photovoltaic (PV) cells. However, their properties in the excited state have not been actively studied, although PVs are operated under solar illumination. Here, the characteristics of organic HTMs in their excited state such as transition dipole moment can be a decisive factor that can improve built-in potential of PVs, consequently enhancing their charge extraction property as well as reducing carrier recombination. Moreover, the aggregation property of organic semiconductors, which has been an essential factor for high-performance organic HTMs to improve their carrier transport property, can induce a synergistic effect with their excited state property for the high-efficiency perovskite PVs. Additionally, it is also confirmed that their optical bandgaps, manipulated to have their absorption in the UV region, are beneficial to block UV light that degrades the quality of perovskite, consequently improving the stability of perovskite PV in p–i–n configuration. As a proof-of-concept, a model system, composed of triarylamine and imidazole-based organic HTMs, is designed, and it is believed that this strategy paves a way toward high-performance and stable perovskite PV devices.     

Rayleigh mixture model for plaque characterization in intravascular ultrasound

Vulnerable plaques are the major cause of carotid and coronary vascular problems, such as heart attack or stroke. A correct modeling of plaque echomorphology and composition can help the identification of such lesions. The Rayleigh distribution is widely used to describe (nearly) homogeneous areas in ultrasound images. Since plaques may contain tissues with heterogeneous regions, more complex distributions depending on multiple parameters are usually needed, such as Rice, K or Nakagami distributions. In such cases, the problem formulation becomes more complex, and the optimization procedure to estimate the plaque echomorphology is more difficult. Here, we propose to model the tissue echomorphology by means of a mixture of Rayleigh distributions, known as the Rayleigh mixture model (RMM). The problem formulation is still simple, but its ability to describe complex textural patterns is very powerful. In this paper, we present a method for the automatic estimation of the RMM mixture parameters by means of the expectation maximization algorithm, which aims at characterizing tissue echomorphology in ultrasound (US). The performance of the proposed model is evaluated with a database of in vitro intravascular US cases. We show that the mixture coefficients and Rayleigh parameters explicitly derived from the mixture model are able to accurately describe different plaque types and to significantly improve the characterization performance of an already existing methodology.     

Spirobifluorene Dimers: Understanding How The Molecular Assemblies Drive The Electronic Properties

Spirobifluorene (SBF) is one of the most important scaffolds used in the design of organic semi-conductors (OSCs) for electronics. In recent years, among all the structures developed for these applications, SBF dimers have been highlighted due to their great potential in thermally activated delayed fluorescence and in phosphorescent organic light-emitting diodes. Attaching two SBF units generate 10 dimers, each possessing its own structural specificity, which in turn drives its electronic properties. These ten SBF dimers are gathered herein. Understanding how the molecular assembly determines the electronic properties has been one of the pillars of organic electronics. This is the goal of this article. As positional isomerism is a key tool to design OSCs, defining the design guidelines for the SBF scaffold appears of interest for the future of this building block. Herein, the importance of the two main parameters involved in the electrochemical and photophysical properties, namely the nature of the phenyl linkages and the steric congestion between the two SBF units is discussed. The combination of these two parameters drives the electronic properties but their respective weight is different as a function of the regioisomer involved or of the property considered (frontier orbitals energy level, absorption, fluorescence, phosphorescence).     

Organic Single Crystal Patterning Method for Micrometric Photosensors

Light detection technologies are of interest due to their applications in energy conversion and optical communications. Single-crystal organic semiconductors, such as rubrene, present high detectivities and charge carrier mobility, making them attractive for light-sensing applications. Growth of high crystallinity organic crystals is achieved using vapor processes, forming crystals of arbitrary shapes and orientations and requiring posterior patterning processes. However, patterning the organic semiconductors using industry-standard microfabrication techniques is not straightforward, as these often cause irreversible damage to the crystals. Here the fabrication of patterned micrometric rubrene photosensors is demonstrated through a combination of photolithography and Reactive Ion Etching steps. Protective layers during microfabrication minimize degradation of optoelectronic properties of the organic single crystals during fabrication. Crystals undergoing the patterning process presented a survival rate of 39%. Photoresponse values of up to 41 mA W⁻¹ are obtained under illumination at 500 nm. This opens a route for the industrial-scale fabrication process of high-performance optoelectronic devices based on organic crystals semiconductors.     

Nanoscale Insight Into Lead‐Free BNT‐BT‐xKNN

Piezoresponse force microscopy (PFM) is used to afford insight into the nanoscale electromechanical behavior of lead‐free piezoceramics. Materials based on Bi_1/2Na_1/2TiO₃ exhibit high strains mediated by a field‐induced phase transition. Using the band excitation technique the initial domain morphology, the poling behavior, the switching behavior, and the time‐dependent phase stability in the pseudo‐ternary system (1–x)(0.94Bi_1/2Na_1/2TiO₃‐0.06BaTiO₃)‐xK_0.5Na_0.5NbO₃ (0 <= x <= 18 mol%) are revealed. In the base material (x = 0 mol%), macroscopic domains and ferroelectric switching can be induced from the initial relaxor state with sufficiently high electric field, yielding large macroscopic remanent strain and polarization. The addition of KNN increases the threshold field required to induce long range order and decreases the stability thereof. For x = 3 mol% the field‐induced domains relax completely, which is also reflected in zero macroscopic remanence. Eventually, no long range order can be induced for x >= 3 mol%. This PFM study provides a novel perspective on the interplay between macroscopic and nanoscopic material properties in bulk lead‐free piezoceramics.     

Sodium‐Ion Batteries: Building Effective Layered Cathode Materials with Long‐Term Cycling by Modifying the Surface via Sodium Phosphate

Surface stabilization of cathode materials is urgent for guaranteeing long‐term cyclability, and is important in Na cells where a corrosive Na‐based electrolyte is used. The surface of P2‐type layered Na_2/3[Ni_1/3Mn_2/3]O₂ is modified with ionic, conducting sodium phosphate (NaPO₃) nanolayers, ≈10 nm in thickness, via melt‐impregnation at 300 °C; the nanolayers are autogenously formed from the reaction of NH₄H₂PO₄ with surface sodium residues. Although the material suffers from a large anisotropic change in the c‐axis due to transformation from the P2 to O2 phase above 4 V versus Na⁺/Na, the NaPO₃‐coated Na_2/3[Ni_1/3Mn_2/3]O₂/hard carbon full cell exhibits excellent capacity retention for 300 cycles, with 73% retention. The surface NaPO₃ nanolayers positively impact the cell performance by scavenging HF and H₂O in the electrolyte, leading to less formation of byproducts on the surface of the cathodes, which lowers the cell resistance, as evidenced by X‐ray photoelectron spectroscopy and time‐of‐flight secondary‐ion mass spectroscopy. Time‐resolved in situ high‐temperature X‐ray diffraction study reveals that the NaPO₃ coating layer is delayed for decomposition to Mn₃O₄, thereby suppressing oxygen release in the highly desodiated state, enabling delay of exothermic decomposition. The findings presented herein are applicable to the development of high‐voltage cathode materials for sodium batteries.     

High‐Performance Sodium‐Ion Hybrid Supercapacitor Based on Nb2O5@Carbon Core–Shell Nanoparticles and Reduced Graphene Oxide Nanocomposites

Sodium‐ion hybrid supercapacitors (Na‐HSCs) have potential for mid‐ to large‐scale energy storage applications because of their high energy/power densities, long cycle life, and the low cost of sodium. However, one of the obstacles to developing Na‐HSCs is the imbalance of kinetics from different charge storage mechanisms between the sluggish faradaic anode and the rapid non‐faradaic capacitive cathode. Thus, to develop high‐power Na‐HSC anode materials, this paper presents the facile synthesis of nanocomposites comprising Nb₂O₅@Carbon core–shell nanoparticles (Nb₂O₅@C NPs) and reduced graphene oxide (rGO), and an analysis of their electrochemical performance with respect to various weight ratios of Nb₂O₅@C NPs to rGO (e.g., Nb₂O₅@C, Nb₂O₅@C/rGO‐70, ‐50, and ‐30). In a Na half‐cell configuration, the Nb₂O₅@C/rGO‐50 shows highly reversible capacity of ≈285 mA h g^?1 at 0.025 A g^?1 in the potential range of 0.01–3.0 V (vs Na/Na⁺). In addition, the Na‐HSC using the Nb₂O₅@C/rGO‐50 anode and activated carbon (MSP‐20) cathode delivers high energy/power densities (≈76 W h kg^?1 and ≈20 800 W kg^?1) with a stable cycle life in the potential range of 1.0–4.3 V. The energy and power densities of the Na‐HSC developed in this study are higher than those of similar Li‐ and Na‐HSCs previously reported.