3-methyl-4-metroxy-4'-nitrostilbene (MMONS) Crystal Growth and Studies of It

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Glass-forming liquids,anomalous liquids,and polyamorphism in liquids and biopolymers

Summary Glass formation in nature and materials science is reviewed and the recent recognition of polymorphism within the glassy state, polyamorphism, is discussed. The process by which the glassy state originates during the continuous cooling or viscous slowdown process, is examined and the three canonical characteristics of relaxing liquids are correlated through the fragility. The conversion of strong liquids to fragile liquids by pressure-induced coordination number increases is discussed, and then it is shown that for the same type of system it is possible to have the same conversion accomplished via a first-order transition within the liquid state. The systems in which this can happen are of the same type which exhibit polyamorphism, and the whole phenomenology can be accounted for by a recent simple modification of the van der Waals model for tetrahedrally bonded liquids. The concept of complex amorphous systems which can lose a significant number of degrees of freedom through weak first-order transitions is then used to discuss the relation between native and denatured hydrated proteins, since the latter have much in common with plasticized chain polymer systems. Finally, we close the circle by taking a short-time-scale phenomenon given much attention by protein physicists,viz., the onset of an anomaly in the Debye-Waller factor with increasing temperature, and showing that for a wide variety of liquids, including computer-simulated strong and fragile ionic liquids, this phenomenon is closely correlated with the experimental glass transition temperature. This implies that the latter owes its origin to the onset of strong anharmonicity in certain components of the vibrational density of states (evidently related to the boson peak) which then permits the system to gain access to its configurational degrees of freedom. The more anharmonic these vibrational components, the closer to the Kauzmann temperature will commence the exploration of configuration space and, for a given configurational microstate degeneracy, the more fragile the liquid will be. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

In Situ Deformation Topology of COFs with Shortened Channels and High Redox Properties for Li–S Batteries

Covalent organic frameworks (COFs) with various topologies are typically synthesized by selecting and designing connecting units with rich shapes. However, this process is time-consuming and labour-intensive. Besides, the tight stacking of COFs layers greatly restrict their structural advantages. It is crucial to effectively exploit the high porosity and active sites of COFs by topological design. Herein, for the first time, inducing in situ topological changes in sub-chemometric COFs by adding graphene oxide (GO) without replacing the monomer, is proposed. Surprisingly, GO can slow down the intermolecular stacking and induce rearrangement of COFs nanosheets. The channels of D- [4+3] COFs are significantly altered while the stacking of periodically expanded framework is weakened. This not only maximizes the exposure of pore area and polar groups, but also shortens the channels and increases the redox activity, which enables high loading while enhancing host-guest interactions. This topological transformation to exhibit the structural features of COFs for efficient application is an innovative molecular design strategy.     

One-Component Artificial Gustatory System Based on Hydrogen-Bond Organic Framework for Discrimination of Versatile Analytes

Hydrogen-bond organic frameworks (HOFs) with excellent structural and luminescent properties have emerged as a promising material for the construction of fluorescence sensors. However, designing a facile, universal and high throughput sensor with multiplex detection capacity still remains challenging. Herein, a one-component sensor array is constructed that mimics natural gustatory system for accurate and high-throughput discrimination and identification of versatile analytes. HOF as a single sensing element greatly simplifies the probe preparation in sensor array and detection procedure. Metal ions, proteins and bacteria as the model targets are rapid and accurately discriminated, presenting the universality of the system. Particularly, the system is successfully used for the classification of antibiotic mechanisms. The study expands the application scope of HOFs and provides a facile and universal system for sensing applications.     

Microporous,Crystalline, and Water-Processable Framework Materials of Organic Amphiphile Salts

Porous framework materials are of major importance for a wide range of technologies. Nevertheless, many of these materials lack processibility as they are typically synthesized under rather harsh conditions and obtained as microcrystalline powders that cannot easily be coated or deposited from solution. Herein, a new approach to water-processable metal–organic framework materials is presented. The materials are based on amphiphilic organic building blocks consisting of polar carboxylate groups and non-polar alkyl chains connected to a rigid aromatic core. The amphiphilic building blocks assemble to porous framework structures via bonding to kinetically labile sodium ions from concentrated aqueous solution. The obtained crystalline materials, termed amphiphile salt frameworks , are thermally and mechanically stable (some derivatives up to 365 °C and up to at least 4000 bar hydrostatic pressure), exhibit persistent microporous channels accessible to several gases (N₂, CO₂, propane, propylene, n-butane), and can be reversibly assembled/disassembled by crystallization from or dissolution in water. Systematic variation of the hydrophobic side chains of the amphiphile building blocks allows extracting structure-property relationships and first design rules for this new class of water-processable microporous framework materials.     

Revealing and Eliminating the Light-Soaking Issue in Metal Oxide-Based Inverted Organic Solar Cells

Inverted organic solar cells (i-OSCs) provide an exciting opportunity for commercialization owing to their excellent device air stability. However, light soaking (LS) issue generally occurs in metal oxide based i-OSCs, causing drastically decreased performance. The underlying root of LS effect is not clearly clarified until now. Herein, it is demonstrated that the surface oxygen defects on metal oxide nanoparticles, such as chemisorbed superoxide (O²⁻) and hydroxide (OH) dangling bonds, are the main reasons for LS issue in i-OSCs. The O²⁻ layer induces band bending at the cathode interface and increases the work function (WF) of metal oxide, thus leading to inefficient charge transport. The dangling bonds serve as interfacial trap states and cause non-radiative recombination, thus leading to the reduced open circuit voltage (V_oc). With ultraviolet (UV) illumination, the surface oxygen defects are interacted with photogenerated carriers, thereby improving the photovoltaic performance. Additionally, UV pretreatment of metal oxide films is employed to eliminate the LS issue and the resulting device yields significantly improved fill factors from 50.20% to 73.50% in the pristine SnO₂ based i-OSCs. This study reveals the origin of LS effect in i-OSCs and proposes a suggested model for LS mechanism.     

Large-area,high-quality self-assembly electron transport layer for organic optoelectronic devices

We propose a self-assembly method for forming large-area high-quality solution-processed titanium oxide (TiO₂) films as efficient electron transport layer for organic solar cells. The self-assembled solution-processed TiO₂ layers are highly ordered and significantly improved in surface morphology over commonly-used spin-coating process resulting in better charge collection and significant material saving. When incorporated into polymer solar cells, the TiO₂ device shows enhanced performance. Furthermore, we demonstrate the TiO₂ can form large-area films, and achieve very uniform and improved device performances. Consequently, the self-assembled TiO₂ films can be efficient and low-cost electron transport layer potentially for large-area organic optoelectronics.     

Highly Crystalline Soluble Acene Crystal Arrays for Organic Transistors: Mechanism of Crystal Growth During Dip‐Coating

The preparation of uniform large‐area highly crystalline organic semiconductor thin films that show outstanding carrier mobilities remains a challenge in the field of organic electronics, including organic field‐effect transistors. Quantitative control over the drying speed during dip‐coating permits optimization of the organic semiconductor film formation, although the kinetics of crystallization at the air–solution–substrate contact line are still not well understood. Here, we report the facile one‐step growth of self‐aligning, highly crystalline soluble acene crystal arrays that exhibit excellent field‐effect mobilities (up to 1.5 cm V^?1 s^?1) via an optimized dip‐coating process. We discover that optimized acene crystals grew at a particular substrate lifting‐rate in the presence of low boiling point solvents, such as dichloromethane (b.p. of 40.0 °C) or chloroform (b.p. of 60.4 °C). Variable‐temperature dip‐coating experiments using various solvents and lift rates are performed to elucidate the crystallization behavior. This bottom‐up study of soluble acene crystal growth during dip‐coating provides conditions under which one may obtain uniform organic semiconductor crystal arrays with high crystallinity and mobilities over large substrate areas, regardless of the substrate geometry (wafer substrates or cylinder‐shaped substrates).     

Enhanced light trapping in solar cells using snow globe coating

A novel method, snow globe coating, is found to show significant enhancement of the short circuit current J_SC (35%) when applied as a scattering back reflector for polycrystalline silicon thin‐film solar cells. The coating is formed from high refractive index titania particles without containing binder and gives close to 100% reflectance for wavelengths above 400 nm. Snow globe coating is a physicochemical coating method executable in pH neutral media. The mild conditions of this process make this method applicable to many different types of solar cells. Copyright © 2012 John Wiley & Sons, Ltd.     

A universal roll‐to‐roll slot‐die coating approach towards high‐efficiency organic photovoltaics

This work develops a combinational use of solvent additive and in‐line drying oven on the flexible organic photovoltaics to improve large‐area roll‐to‐roll (R2R) slot‐die coating process. Herein, addition of 1,8‐diiodooctane (DIO) in the photoactive layer is conducted to yield a performance of 3.05% based on the blending of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PC₆₁BM), and a very promising device performance of 7.32% based on the blending of poly[[4,8‐bis[(2‐ethylhexyl)oxy] benzo[1,2‐b:4,5‐b’] dithiophene‐2,6‐diyl] [3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]] (PTB7) and [6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM). Based on this R2R slot‐die coating approach for various polymers, we demonstrate the high‐performance result with respect to the up‐scaling from small high‐PCE cell to large‐area module. This present study provides a route for fabricating a low‐cost, large‐area, and environmental‐friendly flexible organic photovoltaics.