Ultranarrow Bandwidth Organic Photodiodes by Exchange Narrowing in Merocyanine H‐ and J‐Aggregate Excitonic Systems

Ultranarrowband organic photodiodes (OPDs) are demonstrated for thin film solid state materials composed of tightly packed dipolar merocyanine dyes. For these dyes the packing arrangement can be controlled by the bulkiness of the donor substituent, leading to either strong H‐ or strong J‐type exciton coupling in the interesting blue (H‐aggregate) and NIR (J‐aggregate) spectral ranges. Both bands are shown to arise from one single exciton band according to fluorescence measurements and are not just a mere consequence of different polymorphs within the same thin film. By fabrication of organic thin‐film transistors, these dyes are demonstrated to exhibit hole transport behavior in spin‐coated thin films. Moreover, when used as organic photodiodes in planar heterojunctions with C₆₀ fullerene, they show wavelength‐selective photocurrents in the solid state with maximum external quantum efficiencies of up to 11% and ultranarrow bandwidths down to 30 nm. Thereby, narrowing the linewidths of optoelectronic functional materials by exciton coupling provides a powerful approach to produce ultranarrowband organic photodiodes.     

Vanadium Doping Enhanced Electrochemical Performance of Molybdenum Oxide in Lithium‐Ion Batteries

Molybdenum trioxide (MoO₃) suffers from poor conductivity, a low rate capability, and unsatisfactory cycling stability in lithium‐ion batteries. The aliovalent ion doping may present an effective way to improve the electrochemical performances of MoO₃. Here, it is shown, by first‐principle calculations, that doping MoO₃ with V by 12.5% can modulate significantly electronic structure and provide a small diffusion barrier for enhancing the electrochemical performance of MoO₃. The ultralong Mo_0.88V_0.12O_2.94 nanostructures, which retain the h‐MoO₃ structure and present an exceptionally high conductivity and fast ionic diffusion due to the substitution of V, facilitating lithiation/delithiation behavior, and induce a fine nanosized structure with a reduced volume change are prepared. As a result, the stress and strain are alleviated during the Li‐ion intercalation/deintercalation processes, improving the cycling stability and rate capability. Such a large improvement in the electrochemical properties can be ascribed to the stabilizing effect of V, the small migration energy barrier, and short diffusion path, which arise from the introduction of V into MoO₃. The unique engineering strategy and facile synthesis route open up a new avenue in modifying and developing other species of electrode materials.     

Long‐Term Electrical and Mechanical Function Monitoring of a Human‐on‐a‐Chip System

The goal of human‐on‐a‐chip systems is to capture multiorgan complexity and predict the human response to compounds within physiologically relevant platforms. The generation and characterization of such systems is currently a focal point of research given the long‐standing inadequacies of conventional techniques for predicting human outcome. Functional systems can measure and quantify key cellular mechanisms that correlate with the physiological status of a tissue, and can be used to evaluate therapeutic challenges utilizing many of the same endpoints used in animal experiments or clinical trials. Culturing multiple organ compartments in a platform creates a more physiologic environment (organ–organ communication). Here is reported a human 4‐organ system composed of heart, liver, skeletal muscle, and nervous system modules that maintains cellular viability and function over 28 days in serum‐free conditions using a pumpless system. The integration of noninvasive electrical evaluation of neurons and cardiac cells and mechanical determination of cardiac and skeletal muscle contraction allows the monitoring of cellular function, especially for chronic toxicity studies in vitro. The 28‐day period is the minimum timeframe for animal studies to evaluate repeat dose toxicity. This technology can be a relevant alternative to animal testing by monitoring multiorgan function upon long‐term chemical exposure.     

Square and Hexagonal Columnar Liquid Crystals Confined in Square and Triangular Pores

Columnar liquid crystals confined in cylindrical pores are known to orient perpendicular to the pore axis, although for potential nanoelectronic applications they would need to be aligned axially. The X‐ray diffraction study reveals that while in all three compounds examined, the columns arrange in concentric circles in circular pores, axial alignment is indeed achieved for the hexagonal phase of a discotic hexa‐peri‐hexabenzocoronene in “triangular pores,” and for the square phase of a T‐shaped amphiphile in “square pores.” For the third compound, a carbazole dendron with very soft hexagonal columns, a new three‐circle configuration is observed by atomic force microscopy (AFM) in triangular pores. The complex structure of domain walls in columnar liquid crystals is thus seen for the first time on the level of individual columns. A simple estimation of free energies confirms that it is the distortion of polygonal columnar lattice that prevents axial orientation in circular pores. The model also explains the appearance of the three‐circle arrangement of soft columns.     

Hierarchical Metamaterials for Multispectral Camouflage of Infrared and Microwaves

Camouflage is an emerging application of metamaterials owing to their exotic electromagnetic radiative properties. Based on the use of a selective emitter and an absorber as the metamaterials, most reported articles have suggested the use of single‐band camouflage, however, multispectral camouflage is a challenging issue owing to a difference of several orders of magnitude in the unit cell structure. Herein, hierarchical metamaterials (HMMs) for multispectral signal control when dissipating the absorbed energy of microwaves through the selective emission of infrared (IR) waves from the unit cell structure of the HMM are demonstrated. Integrating an IR selective emitter (IRE) with a microwave selective absorber, multispectral signal control with the large‐sized unit cell structures of up to 10 cm are realized. With an IRE, the emissive power from the HMM toward 5–8 µm is 1570% higher than the Au surface, which is preventing the occurrence of thermal instability. Furthermore, we determine that the signature levels of targeted IR waves (8–12 µm) and microwaves (2.5–3.8 cm) are reduced by up to 95% and 99%, respectively, when applying the HMM.     

Impact of the Solvation State of Lead Iodide on Its Two‐Step Conversion to MAPbI3: An In Situ Investigation

Producing high efficiency solar cells without high‐temperature processing or use of additives still remains a challenge with the two‐step process. Here, the solution processing of MAPbI₃ from PbI₂ films in N,N‐dimethylformamide (DMF) is investigated. In‐situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) measurements reveal a sol–gel process involving three PbI₂‐DMF solvate complexes—disordered (P₀) and ordered (P₁, P₂)—prior to PbI₂ formation. When the appropriate solvated state of PbI₂ is exposed to MAI (methylammonium Iodide), it can lead to rapid and complete room temperature conversion into MAPbI₃ with higher quality films and improved solar cell performance. Complementary in‐situ optical reflectance, absorbance, and quartz crystal microbalance with dissipation (QCM‐D) measurements show that dry PbI₂ can take up only one third of the MAI taken up by the solvated‐crystalline P₂ phase of PbI₂, requiring additional annealing and yet still underperforming. The perovskite solar cells fabricated from the ordered P₂ precursor show higher power conversion efficiency (PCE) and reproducibility than devices fabricated from other cases. The average PCE of the solar cells is greatly improved from 13.2(±0.53)% (from annealed PbI₂) to 15.7(±0.35)% (from P₂) reaching up to 16.2%. This work demonstrates the importance of controlling the solvation of PbI₂ as an effective strategy for the growth of high‐quality perovskite films and their application in high efficiency and reproducible solar cells.     

Studies of Functional Defects for Fast Na‐Ion Conduction in Na3−yPS4−xClx with a Combined Experimental and Computational Approach

All‐solid‐state rechargeable sodium (Na)‐ion batteries are promising for inexpensive and high‐energy‐density large‐scale energy storage. In this contribution, new Na solid electrolytes, Na_3?yPS_4?xCl_x, are synthesized with a strategic approach, which allows maximum substitution of Cl for S (x = 0.2) without significant compromise of structural integrity or Na deficiency. A maximum conductivity of 1.96 mS cm^?1 at 25 °C is achieved for Na_3.0PS_3.8Cl_0.2, which is two orders of magnitude higher compared with that of tetragonal Na₃PS₄ (t‐Na₃PS₄). The activation energy (E_a) is determined to be 0.19 eV. Ab initio molecular dynamics simulations shed light on the merit of maximizing Cl‐doping while maintaining low Na deficiency in enhanced Na‐ion conduction. Solid‐state nuclear magnetic resonance (NMR) characterizations confirm the successful substitution of Cl for S and the resulting change of P oxidation state from 5+ to 4+, which is also verified by spin moment analysis. Ion transport pathways are determined with a tracer‐exchange NMR method. The functional detects that promote Na ‐ion transport are maximized for further improvement in ionic conductivity. Full‐cell performance is demonstrated using Na/Na_3.0PS_3.8Cl_0.2/Na₃V₂(PO₄)₃ with a reversible capacity of ≈100 mAh g^‐1 at room temperature.     

Flexible and Transparent Electrochromic Displays with Simultaneously Implementable Subpixelated Ion Gel‐Based Viologens by Multiple Patterning

Electrochromic materials reversibly change colors by redox reactions depending on the oxidation states. To utilize electrochromic materials for active‐matrix display applications, an electrochromic display (ECD) requires simultaneous implementation of various colors and a fine‐pixelation process. Herein, flexible and transparent ECDs with simultaneously implementable subpixelated EC gels by sequential multiple patterning are successfully demonstrated. Ionic liquid‐based EC gels of monoheptyl‐viologen, diheptyl‐viologen (DHV), and diphenyl‐viologen (DPV) are used to create the colors of ECDs: magenta, blue, and green, respectively. Especially, to realize an improved green color, DHV–DPV composite gels are synthesized. Three EC gels exhibit stable properties without degradation during repetitive operation. Moreover, a transmittance greater than 90% is maintained in a bleached state, which is sufficient for application as a transparent display. The subpixelation process for multicolored‐flexible ECDs is designed to facilitate both easy fabrication and rapid operation with various patterns at low cost. The subpixelated EC gels using a film mask can be implemented to a minimum size of 200 µm. Furthermore, the subpixelated flexible ECDs exhibit high durability even after 1000 cycles of mechanical bending tests at a bending radius of 10 mm. Therefore, these EC materials can be used directly for flexible and transparent active‐matrix displays.     

Anti‐Oxygen Leaking LiCoO2

LiCoO₂ is a prime example of widely used cathodes that suffer from the structural/thermal instability issues that lead to the release of their lattice oxygen under nonequilibrium conditions and safety concerns in Li‐ion batteries. Here, it is shown that an atomically thin layer of reduced graphene oxide can suppress oxygen release from Li_xCoO₂ particles and improve their structural stability. Electrochemical cycling, differential electrochemical mass spectroscopy, differential scanning calorimetry, and in situ heating transmission electron microscopy are performed to characterize the effectiveness of the graphene‐coating on the abusive tolerance of Li_xCoO₂. Electrochemical cycling mass spectroscopy results suggest that oxygen release is hindered at high cutoff voltage cycling when the cathode is coated with reduced graphene oxide. Thermal analysis, in situ heating transmission electron microscopy, and electron energy loss spectroscopy results show that the reduction of Co species from the graphene‐coated samples is delayed when compared with bare cathodes. Finally, density functional theory and ab initio molecular dynamics calculations show that the rGO layers could suppress O₂ formation more effectively due to the strong C? O_cathode bond formation at the interface of rGO/LCO where low coordination oxygens exist. This investigation uncovers a reliable approach for hindering the oxygen release reaction and improving the thermal stability of battery cathodes.     

Precise Molecular Engineering of Photosensitizers with Aggregation‐Induced Emission over 800 nm for Photodynamic Therapy

Owing to efficient singlet oxygen (¹O₂) generation in aggregate state, photosensitizers (PSs) with aggregation‐induced emission (AIE) have attracted much research interests in photodynamic therapy (PDT). In addition to high ¹O₂ generation efficiency, strong molar absorption in long‐wavelength range and near‐infrared (NIR) emission are also highly desirable, but difficult to achieve for AIE PSs since the twisted structures in AIE moieties usually lead to absorption and emission in short‐wavelength range. In this contribution, through acceptor engineering, a new AIE PS of TBT is designed to show aggregation‐induced NIR emission centered at 810 nm, broad absorption in the range between 300 and 700 nm with a large molar absorption coefficient and a high ¹O₂ generation efficiency under white light irradiation. Further, donor engineering by attaching two branched flexible chains to TBT yielded TBTC8 , which circumvented the strong intermolecular interactions of TBT in nanoparticles (NPs), yielding TBTC8 NPs with optimized overall performance in ¹O₂ generation, absorption, and emission. Subsequent PDT results in both in vitro and in vivo studies indicate that TBTC8 NPs are promising candidates in practical application.