Alkyl-chain branched effect on the aggregation and photophysical behavior of polydiarylfluorenes toward stable deep-blue electroluminescence and efficient amplified spontaneous emission

The control of the condensed superstructure of light-emitting conjugated polymers(LCPs) is a crucial factor to obtain high performance and stable organic optoelectronic devices.Side-chain engineering strategy is an effective platform to tune inter chain aggregation and photophysical behaviour of LCPs.Herein,we systematically investigated the alkyl-chain branched effecton the conformational transition and photophysical behaviour of polydiarylfluorenes toward efficient blue optoelectronic devices.The branched side chain will improve materials solubility to inhibit interchain aggregation in solution according to DLS and optical analysis,which is useful to obtain high quality film.Therefore,our branched PEODPF,POYDPF pristine film present high luminance efficiency of 36.1% and 39.6%,enhanced about 20%relative to that of PODPF.Compared to the liner-type sides' chain,these branched chains also suppress chain planarization and improve film morphological stability effectively.Interestingly,the branched polymer also had excellent stable amplified spontaneous emission(ASE) behaviour with low threshold(4.72 μJ/cm~2) and a center peak of 465 nm,even thermal annealing at 220 C in the air atmosphere.Therefore,side-chain branched strategy for LCPs is an effective means to control interchain aggregation,film morphology and photophysical property of LCPs.     

Alkyl-chain branched effect on the aggregation and photophysical behavior of polydiarylfluorenes toward stable deep-blue electroluminescence and efficient amplified spontaneous emission

Robust branched polydiarylfluorenes are constructed forstable deep-blue electroluminescence and efficient amplified spontaneous emission.     

Insights into the β-phase of polyfluorene: characterization,regulation, and mechanism

Due to the unique blue-light properties, wide excited emission interval and so on, polyfluorenes (PFs) are among the most promising blue-light polymers that are widely used in organic lasers and organic light-emitting diodes. Usually, PFs exhibit two different phases: α-phase and β-phase, and the β-phase has higher photoluminescence efficiency and carrier mobility than the one of α-phase. Hence, improving the content of β-phase is very important to enhance the device performance. In this paper, we introduce the methods for characterizing the β-phase in PFs and summarize the recent research progress in regulating the β-phase content. Firstly, the differences between the α-phase and the β-phase of PFs in terms of structure, aggregation behavior, and optoelectronic properties are summarized. Then, the characterization for the β-phase, including ultraviolet–visible absorption spectrum (UV–vis), photoluminescence spectrum (PL), and Raman spectrum, transmission electron microscope (TEM), and X-ray diffraction (XRD) are introduced, and the calculating rules for the content of β-phase is also introduced. Furthermore, the methods to increase the content of β-phase are reviewed. Finally, a brief outlook on the challenges and future development prospects of β-phase in PFs are discussed.     

Control of Intrachain Morphology in the Formation of Polyfluorene Aggregates on the Single-Molecule Level

Controlling the morphology of π-conjugated polymers for organic optoelectronic devices has long been a goal in the field of materials science. Since the morphology of a polymer chain is closely intertwined with its photophysical properties, it is desirable to be able to change the arrangement of the polymers at will. We investigate the π-conjugated polymer poly(9,9-dioctylfluorene) (PFO), which can exist in three distinctly different structural phases: the α-, β-, and γ-phase. Every phase has a different chain structure and a unique photoluminescence (PL) spectrum. Due to its unique properties and the pronounced spectral structure-property relations, PFO can be used as a model system to study the morphology of π-conjugated polymers. To avoid ensemble averaging, we examine the PL spectrum of single PFO chains embedded in a non-fluorescent matrix. With single-molecule spectroscopy the structural phase of every single chain can be determined, and changes can be monitored very easily. To manipulate the morphology, solvent vapor annealing (SVA) was applied, which leads to a diffusion of the polymer chains in the matrix. The β- and γ-phases appear during the self-assembly of single α-phase PFO chains into mesoscopic aggregates. The extent of β- and γ-phase formation is directed by the solvent-swelling protocol used for aggregation. Aggregation unequivocally promotes formation of the more planar β- and γ-phases. Once these lower-energy more ordered structural phases are formed, SVA cannot return the polymer chain to the less ordered phase by aggregate swelling.     

n-Type D-A Conjugated Polymers: Relationship Between Microstructure and Electrical/Mechanical Performance

Conjugated polymers are widely applied in optoelectronic devices due to their excellent optoelectronic properties, solution processibility, and intrinsic flexibility. High-performance films could be achieved with joint efforts from both molecular structure and film solid microstructure. Herein, research progress of the relationship between microstructure and electrical/mechanical performance of poly{[N,N'-bis(2-octyldodecyl)-representative of n-type donor-acceptor conjugated polymers, is reviewed. Its strong aggregation in solution is underlined and the methods to tune the degree of aggregation, such as solvent quality, molecular weight, and regioregularity, are compared. A liquid-crystalline behavior is evidenced in highly concentrated solutions during film drying, which favors the formation of highly anisotropic structures. Moreover, alignment techniques and thermal annealing are used to regulate molecular orientation and polymorphism in films. These structure characteristics offer great potential for researchers to handle film performances. Up to now, more attention has been paid to optimize the electrical performance of the devices. Achieving high-performance n-type conjugated polymer films with both superior mechanical and electrical properties is a newly emerging focus.     

Spectroscopic study of α- and β-phase isotactic polypropylene and of atactic polypropylene in solution

Raman spectroscopy is used to investigate the conformation and packing of isotactic crystalline α-phase polypropylene compared with lower-order β-phase isotactic polypropylene and to study the solution behavior of atactic polypropylene. The high-frequency region of the spectrum is analyzed in light of a normal-mode calculation that takes into account the methyl-group vibrations. This region is sensitive to both chain conformation and packing, and because of the high intensity of the methyl and methylene high-frequency stretching modes, it can be used to probe small changes in intermolecular or intramolecular order. Differences in the thermal behavior between the two solid isotactic polypropylene samples are explained interms of packing defects which exist in the β-phase form. In the solution study, we demonstrate that, for molecules in which bands sensitive to intermolecular interactions exist, as is the case of the methyl and methylene vibrations of polypropylene, spectroscopic techniques can be used to estimate the minimum overlap concentration.     

Ultrathin-film growth of para-sexiphenyl (I): submonolayer thin-film growth as a function of the substrate temperature

The para-sexiphenyl (p-6P) monolayer film induces weak epitaxy growth (WEG) of disk-like organic semiconductors, and their charge mobilities are increased dramatically to the level of the corresponding single crystals [Wang et al., Adv. Mater. 2007, 19, 2168]. The growth behavior and morphology of p-6P monolayer film play decisive roles on WEG. Here, we investigated the growth behavior of p-6P submonolayer film as a function of the substrate temperature. Its growth exhibited two different mechanisms at high and low substrate temperature. At high substrate temperature (>60 degrees C), the mechanism of diffusion-limited aggregation controlled the growth of submonolayer thin film with fractal islands, whereas at low substrate temperature (< or =60 degrees C), the submonolayer thin film was composed of the compact islands. Its growth exhibited another growth mechanism in which the stable compact islands were formed by dissociation and reorganization of the metastable disordered film. The substrate temperature of about 180 degrees C may be optimal to fabricate high-quality p-6P monolayer film with large-size domains and low saturated island density of about 0.018 microm(-2).     

Optimal extent of fluorination enabling strong temperature-dependent aggregation,favorable blend morphology and high-efficiency polymer solar cells

Temperature-dependent aggregation is a key property for some donor polymers to realize favorable bulk-heterojunction(BHJ)morphologies and high-efficiency(10%) polymer solar cells.Previous studies find that an important structural feature that enables such temperature-dependent aggregation property is the 2nd position branched alkyl chains sitting between two thiophene units.In this report,we demonstrate that an optimal extent of fluorination on the polymer backbone is a second essential structural feature that enables the strong temperature-dependent aggregation property.We compare the properties of three structurally similar polymers with 0,2 or 4 fluorine substitutions in each repeating unit through an in-depth morphological study.We show that the non-fluorinated polymer does not aggregate in solution(0.02 mg mL~(-1) in chlorobenzene) at room temperature,which results in poor polymer crystallinity and extremely large polymer domains.On the other hand,the polymer with four fluorine atoms in each repeating unit exhibits an excessively strong tendency to aggregate,which makes it difficult to process and causes a large domain.Only the polymer with two fluorine atoms in each repeating unit exhibits a suitable extent of temperature-dependent aggregation property.As a result,its blend film achieves a favorable morphology and high power conversion efficiency.This provides another key design rationale for developing donor polymers with suitable temperature-dependent aggregation properties and thus high performance.     

Microfluidic fabrication of β-phase enriched poly(vinylidene fluoride) microfibers toward flexible piezoelectric sensor

β-phase enriched piezoelectric poly(vinylidene fluoride) (PVDF) films/fibers are often prepared by high-energy costing methods, including mechanical stretching, high-electric field or electrospinning. In this study, PVDF piezoelectric microfibers, for the first time, were prepared by microfluidic spinning technology. The β-phase enriched PVDF microfibers with various diameters could be easily obtained inside the microfluidic channel due to the mass transfer induced phase inversion of the inner PVDF solution. The influence of diameter of the fibers, PVDF concentration of the inner phase and water content of the outer phase on the β-phase content and crystallinity degree of the obtained fibers was studied in detail. The obtained β-phase enriched fiber was weaved into meshes. Flexible piezoelectric fabrics were then developed based on these meshes, and further used as in-situ and real time human motion monitoring. This simple and effective strategy provides a promising microfluidic spinning technique toward the development of functional microfibers and wearable piezoelectric sensors, which may also give some implies for the industrial wet-spinning of piezoelectric PVDF fibers in the future.     

Tunable disintegration of layer-by-layer assembly multilayer films based on hydrolytical-polybetaine at wide-range time

Many efforts have been performed on the poly(vinylidene fluoride), PVDF, due to its piezoelectric, pyroelectric and ferroelectric potentials. In this regard, how to fabricate the PVDF with high content of β-phase, which is also the direct contribution to PVDF's prominent property, becomes a critical issue. In this study, starting with the α-phase dominated sample, the PVDF with extremely high content of β-crystalline phase was obtained by the incorporation of multiwalled carbon nanotubes (MWCNTs) modified by hyperbranched copolymers (HBCs). We proved that, via XRD, DSC as well as the structural characterizations from the polarized optical microscopy and transmission electron microscopy (TEM), the success of this strategy was ascribed to the enhanced dispersibility and stability of MWCNTs endowed by the HBCs, which significantly favors the formation of the β-crystalline phase of PVDF.     

Phase transformation to β-poly(vinylidene fluoride) by milling

Cryogenic mechanical milling successfully converted α-phase poly(vinylidene fluoride) (PVDF) powder into β-phase PVDF, as measured by wide-angle X-ray diffraction. The presence of β-phase PVDF became more pronounced with increased milling times over the limited time range evaluated. This was the first recorded instance of β-phase powders forming from the α phase through milling. These β-phase powders maintained their crystal structure during compression molding at 70 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 91–97, 2004     

Synthesis of aromatic polyamides having pyridine moiety and their lyotropic properties in solution

Fully aromatic polyamide containing pyridine moieties (PPy) were successfully synthesized either by interfacial or solution polycondensation to prepare polyamide with inherent viscosity as high as 4. Solution properties of PPy in sulfuric acid were investigated in terms of solution viscosity and lyotropic behavior. The polyamide had a better solubility in sulfuric acid than in poly(p-phenylene terephthalamide) (PT) and the PPy solution in sulfuric acid exhibited an optically anisotropic property in a wider range of concentrations at relatively low temperatures in comparison with the PT solution. Viscosities of the PPy solution and the film cast from the PPy solution indicated a phenomenon characteristic of a highly oriented rigid polymer molecule caused by a lyotropic behavior.     

聚丙烯的结晶形态调控与高性能化

聚丙烯作为目前最重要的通用塑料之一,对其进行高质化改性具有重大的现实意义.基于聚丙烯的同质多晶态行为,加入成核剂进行β结晶改性是改善聚丙烯韧性和热稳定性的有效方式.过去的研究主要关注结晶度、β晶含量等对性能的影响.而近年来我们提出通过调控聚丙烯的β结晶形态来实现其高性能化的新思路,并开展了卓有成效的研究工作:(1)利用小分子成核剂的溶解性及自组装影响聚丙烯的结晶行为,获得了如球晶、横晶、花瓣状晶等形态,实现了对β结晶形态的有效调控;(2)特定的结晶形态能够使聚丙烯的韧性显著增加,并且热变形温度进一步提高,证实结晶形态会对宏观性能发挥重要作用;(3)β结晶形态调控有利于获得更佳的成孔均匀性与高的孔隙率,对制备高品质锂电池隔膜有明显的指导意义.结晶形态调控可望成为实现结晶性聚合物高性能化与功能化通行的、高效的策略.     

Boron(III)‐Containing Donor–Acceptor Compound with Goldlike Reflective Behavior for Organic Resistive Memory Devices

A small‐molecule‐based boron(III)‐containing donor–acceptor compound has been designed and synthesized. Interesting goldlike reflective behavior was observed in the neat thin‐film sample from simple spin‐coating preparation, which can serve as a potential organic thin‐film optical reflector. The small thickness in nanometer range and the relatively smooth surface morphology, together with simple preparation and easy solution processability, are attractive features for opening up new avenues for the fabrication of reflective coatings. Moreover, this donor–acceptor compound has been employed in the fabrication of organic resistive memory device, which exhibited good performance with low turn‐on voltage, small operating bias, large ON/OFF ratio, and long retention time.     

离子液体/聚偏氟乙烯纳米纤维的防结冰性能

通过静电纺丝方法制备了掺杂离子液体([BMIM][PF₆])的聚偏氟乙烯(PVDF)纳米纤维. 研究结果表明, [BMIM][PF₆]与PVDF具有相互作用, 并可促进PVDF形成β相晶体. 在溶剂挥发后, 离子液体存在于PVDF纳米纤维的表面. 纳米纤维中的离子液体含量对复合纳米纤维的表面形态和润湿性具有显著影响. 通过离子液体的引入, 可有效推迟水滴在纳米纤维表面的结冰时间, 降低水滴的结晶温度, 并且降低冰黏附强度. 研究结果显示含有10%[BMIM][PF₆]的PVDF纳米纤维疏水性最高, 并具有优异的防结冰性质.     

Unusual Salt‐Induced Color Modulation through Aggregation‐Induced Emission Switching of a Bis‐cationic Phenylenedivinylene‐Based π Hydrogelator

The synthesis, hydrogelation, and aggregation‐induced emission switching of the phenylenedivinylene bis‐N‐octyl pyridinium salt is described. Hydrogelation occurs as a consequence of π‐stacking, van der Waals, and electrostatic interactions that lead to a high gel melting temperature and significant mechanical properties at a very low weight percentage of the gelator. A morphology transition from fiber‐to‐coil‐to‐tube was observed depending on the concentration of the gelator. Variation in the added salt type, salt concentrations, or temperature profoundly influenced the order of aggregation of the gelator molecules in aqueous solution. Formation of a novel chromophore assembly in this way leads to an aggregation‐induced switch of the emission colors. The emission color switches from sky blue to white to orange depending upon the extent of aggregation through mere addition of external inorganic salts. Remarkably, the salt effect on the assembly of such cationic phenylenedivinylenes in water follow the behavior predicted from the well‐known Hofmeister effects. Mechanistic insights for these aggregation processes were obtained through the counterion exchange studies. The aggregation‐induced emission switching that leads to a room‐temperature white‐light emission from a single chromophore in a single solvent (water) is highly promising for optoelectronic applications.     

Degradation behavior of poly(lactide-co-glycolide)/β-TCP composites prepared using microwave energy

Biodegradable poly(lactide-co-glycolide) (PLGA)/β-tricalcium phosphate (β-TCP) composites were synthesized through polymerization using microwave energy. The degradation behavior of the PLGA/β-TCP composites was carried out at 37 °C in a SBF without changing the solution in order to examine the effect of β-TCP on the degradation behavior. The changes in the molecular weight, mass, and morphology of the composites were examined with respect to the soaking time. An incubation time of 2 weeks was needed to degrade the β-TCP of the composites, indicating that degradation of β-TCP could be started when β-TCP was detached from the PLGA matrix or exposed from composites surface, caused by PLGA matrix was degraded into the SBF solution. The mass loss of the composites with respect to the soaking time revealed that PLGA transformed from a polymer to an oligomer as the degradation process proceeded. The whisker-like morphological changes, caused by the transformation and degradation of the polymer were observed in the composites after week 2. The degradation behavior of the PLGA/β-TCP composites was influenced by the β-TCP content in the composite, and the degradation rate of the composite could be controlled by the initial molecular weight of PLGA.     

ASSOCIATION OF ETHYLENE—VINYL ACETATE COPOLYMER IN DILUTE SOLUTIONS Ⅲ. CRITICAL ASSOCIATION CONCENTRATION*

Association behavior of ethylene vinyl acetate (EVA) copolymer in foursolvents 1, 2-dichloroethane (DCE), cyclohexane (CYH), xylene (XYL) and chloroform(CF) has been investigated by dilute solution viscometry The critical association concen-tration (C_A) was determined at which the incipient decrease in slope of the η_(sp)/C～ Ccurve in solutions at the dilute regime. Our results showed that whether the CA couldexist depends on solvent property. The values of CA in DCE increase with increasing, oftemperature and vinyl acetate (VA) content in EVA and decreasing of molecular weight ofEVA.     

Tuning of the electronic properties of self-assembling and highly sensitive chromic polyalkylthiophenes

The solvatochromic behaviour of different functional group-bearing and self-interacting polyalkylthiophenes with strong chromic responses in solution and self-assembling capacity in the solid state is investigated here. The menagerie of species deriving from the conformational freedom of the conjugated chains in solution has been examined in different solvent mixtures as their physico-chemical nature sensibly affects final material morphology in the solid (film) state. Memory of solution curling shape and of the degree of aggregation is in fact retained through casting or spin-coating procedures and permanently endures in the polymeric film. The efficiency of the final device based on the ICP (inherent conducting polymer) film may therefore be improved by simply acting on its morphology, which is directly determined by polymer dissolution conditions.     

Thin Layer Multicycle Cathodic-Anodic Chronoamperometry of Atomic Hydrogen Injection–Extraction into Metals with Regard to the Stage of Phase Boundary Exchange

The method of potentiostatic anodic-cathodic chronoamperometry of atomic hydrogen injection into a metal film and its subsequent extraction is theoretically discussed. By combining the methods for studying the phase-structure state and surface morphology with multicycle cathodic-anodic chronoamperometry, the injection (and subsequent extraction) of atomic hydrogen into a 47Pd53Cu (at %) film synthesized by ion-plasma spraying is studied. It is found that the initial stage of hydrogenation proceeds under the mixed diffusion-phase-boundary control and passes to the purely diffusion control in 3–4 s. The main kinetic parameters of the stages of phase-boundary hydrogen penetration and its solid-phase diffusion are found. It is shown that the mass transfer in the film alloy proceeds mainly through the grain bodies rather than along intergrain boundaries. The increase in the β-phase content in the alloy leads to the noticeable increase in the diffusion coefficient of hydrogen, whereas the effective equilibrium constant of the phase-boundary process decreases.