Side chain engineering of naphthalene diimide–bithiophene‐based polymer acceptors in all‐polymer solar cells

Two novel polymeric acceptors based on naphthalene diimide (NDI) and 2.2′‐bithiophene, named as P(NDI2THD‐T2) and P(NDI2TOD‐T2), were designed and synthesized for all polymer solar cells application. The structural and electronic properties of the two acceptors were modulated through side‐chain engineering of the NDI units. The optoelectronic properties of the polymers and the morphologies of the blend films composed of the polymer acceptors and a donor polymer PTB7‐Th were systemically investigated. With thiophene groups introduced into the side chains of the NDI units, both polymers showed wider absorption from 350 nm to 900 nm, compared with the reference polymer acceptor of N2200. No redshift of absorption spectra from solutions to films indicated reduced aggregation of the polymers due to the steric hindrance effect of thiophene rings in the side chains. The photovoltaic performance were characterized for devices in a configuration of ITO/PEDOT:PSS/PTB7‐Th:acceptors/2,9‐bis(3‐(dimethylamino)propyl)anthra[2,1,9‐def:6,5,10‐def]diisoquinoline‐1,3,8,10(2H,9H)‐tetraone (PDIN)/Al. With the addition of diphenyl ether as an additive, the power conversion efficiencies (PCEs) of 2.73% and 4.75% for P(NDI2THD‐T2) and P(NDI2TOD‐T2) based devices were achieved, respectively. The latter showed improved J_sc, Fill Factor (FF), and PCE compared with N2200 based devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3679–3689     

本征导电聚合物涂层及界面

本文结合我们实验研究结果及国外最近的研究进展，对在绝缘基质的表面本征导电聚合物涂层的形成、结构和性能作了扼要的分析，指出了化学反应法中通过单体向整体聚合物表层扩散聚合形成的导电膜、界面的偶联作用和电荷转移作用等几种新近证实的原理，在加速导电聚合物涂层的应用中，具有重要意义。     

Sulfur-Containing Bent N-Heteroacenes

A series of novel sulfur-containing bent N-heteroacenes were constructed and characterized by NMR and UV/Vis spectroscopy, cyclic voltammetry, and single-crystal X-ray diffraction. By introducing sulfur-containing groups (thio, sulfinyl, and sulfonyl) into bent azaacenes, their electronic delocalization was improved and frontier energy levels were modulated. The target products displayed tunable optical and electronic properties through altering the valence of sulfur and fused length of the azaacenes. For the first time, typical products were utilized as organic field effect transistor materials, affording promising results.     

Imide-Functionalized Polymer Semiconductors

Imide-functionalized π-conjugated polymer semiconductors have received a great deal of interest owing to their unique physicochemical properties and optoelectronic characteristics, including excellent solubility, highly planar backbones, widely tunable band gaps and energy levels of frontier molecular orbitals, and good film morphology. The organic electronics community has witnessed rapid expansion of the materials library and remarkable improvement in device performance recently. This review summarizes the development of imide-functionalized polymer semiconductors as well as their device performance in organic thin-film transistors and polymer solar cells, mainly achieved in the past three years. The materials mainly cover naphthalene diimide, perylene diimide, and bithiophene imide, and other imide-based polymer semiconductors are also discussed. The perspective offers our insights for developing new imide-functionalized building blocks and polymer semiconductors with optimized optoelectronic properties. We hope that this review will generate more research interest in the community to realize further improved device performance by developing new imide-functionalized polymer semiconductors.     

Synthesis and Optoelectronic Applications of dπ–pπ Conjugated Polymers with a Di-metallaaromatic Acceptor

The development of conjugated polymers especially n-type polymer semiconductors is powered by the design and synthesis of electron-deficient building blocks. Herein, a strong acceptor building block with di-metallaaromatic structure was designed and synthesized by connecting two electron-deficient metallaaromatic units through a π-conjugated bridge. Then, a double-monomer polymerization methodology was developed for inserting it into conjugated polymer scaffolds to yield metallopolymers. The isolated well-defined model oligomers indicated polymer structures. Kinetic studies based on nuclear magnetic resonance and ultraviolet–visible spectroscopies shed light on the polymerization process. Interestingly, the resulted metallopolymers with d_π–p_π conjugations are very promising electron transport layer materials which can boost photovoltaic performance of an organic solar cell, with power conversion efficiency up to 18.28 % based on the PM6 : EH-HD-4F non-fullerene system. This work not only provides a facile route to construct metallaaromatic conjugated polymers with various functional groups, but also discovers their potential applications for the first time.     

爆轰波与激波对撞爆轰状态演化机理研究

对当量比氢氧混合气体中爆轰波与激波的正面对撞过程进行了二维数值研究. 采用了二阶精度NND差分格式与改进的两阶段化学反应模型,并以数值x-t纹影图以及烟迹图记录了对撞过程. 数值研究表明,透射爆轰波受到膨胀影响首先会衰减,甚至产生局部解耦现象;然后由于三波点的碰撞又能再次重新耦合. 在爆轰波对撞过程中,由于燃烧不均匀性而产生的弱横波对爆轰胞格的形成起着重要作用.      

锆金属粉尘云的爆炸特性

采用20 L近球形爆炸实验系统对锆粉尘云的爆炸特性开展了实验研究,分别分析了初始点火能量、点火延迟时间、粉尘云浓度3种因素对锆粉尘云爆炸强度的影响,揭示了锆粉尘云在密闭容器中的爆炸特性。在本实验条件下,结果表明:初始点火能量对锆粉尘云最大爆炸压力有显著影响,锆粉尘云最大爆炸压力随初始点火能量的增大而增大;随点火延迟时间的增加,锆粉尘云最大爆炸压力先增大后减小,存在最佳点火延迟时间;随粉尘云浓度的增大,锆粉尘云最大爆炸压力先增大后减小,存在最佳锆粉尘云浓度,得到锆粉尘云的爆炸下限为18~20 g/m3。     

A Finite Element-based Heuristic Estimation of Local Preform Permeability for Resin Transfer Molding

Uniformity of fabrics significantly affects the resin flow behavior in the resin transfer molding (RTM) process. Due to fabric defects or improper fiber preform preparation/loading, non-uniformity in fabric structure frequently occurs in RTM processing and creates local permeability variations. Such variations often lead to unbalanced resin flow patterns and thus result in defects of finished composite parts. In RTM process modeling, an accurate estimation of the whole field permeability profile of the fiber preform is critical for predicting resin flow pattern correctly. In this article, a finite element-based heuristic computing method is introduced for estimating the in situ whole-field isotropic permeability profile of the preform using a steady flow of gas. Compared with conventional approaches, this method is effective in measuring local permeability variations and applicable to molds with complex 2-D geometries, as well as diverse injection strategies. Several case studies were presented with experimental designs and numerical computations to illustrate the effectiveness and efficiency of the method.     

Trident Nano-Indexing the Proteomics Table: Next-Version Clustering of Iron Carbide NPs and Protein Corona

Protein corona composition and precise physiological understanding of differentially expressed proteins are key for identifying disease biomarkers. In this report, we presented a distinctive quantitative proteomics table of molecular cell signaling differentially expressed proteins of corona that formed on iron carbide nanoparticles (NPs). High-performance liquid chromatography/electrospray ionization coupled with ion trap mass analyzer (HPLC/ESI-Orbitrap) and MASCOT helped quantify 142 differentially expressed proteins. Among these proteins, 104 proteins showed upregulated behavior and 38 proteins were downregulated with respect to the control, whereas 48, 32 and 24 proteins were upregulated and 8, 9 and 21 were downregulated CW (control with unmodified NPs), CY (control with modified NPs) and WY (modified and unmodified NPs), respectively. These proteins were further categorized on behalf of their regularity, locality, molecular functionality and molecular masses using gene ontology (GO). A STRING analysis was used to target the specific range of proteins involved in metabolic pathways and molecular processing in different kinds of binding functionalities, such as RNA, DNA, ATP, ADP, GTP, GDP and calcium ion bindings. Thus, this study will help develop efficient protocols for the identification of latent biomarkers in early disease detection using protein fingerprints.     

Bithiophene-imide-based polymeric semiconductors for field-effect transistors: synthesis, structure-property correlations, charge carrier polarity, and device stability

Developing new high-mobility polymeric semiconductors with good processability and excellent device environmental stability is essential for organic electronics. We report the synthesis, characterization, manipulation of charge carrier polarity, and device air stability of a new series of bithiophene-imide (BTI)-based polymers for organic field-effect transistors (OFETs). By increasing the conjugation length of the donor comonomer unit from monothiophene (P1) to bithiophene (P2) to tetrathiophene (P3), the electron transport capacity decreases while the hole transport capacity increases. Compared to the BTI homopolymer P(BTimR) having an electron mobility of 10(-2) cm(2) V(-1) s(-1), copolymer P1 is ambipolar with balanced hole and electron mobilities of ～10(-4) cm(2) V(-1) s(-1), while P2 and P3 exhibit hole mobilities of ～10(-3) and ～10(-2) cm(2) V(-1) s(-1), respectively. The influence of P(BTimR) homopolymer M(n) on film morphology and device performance was also investigated. The high M(n) batch P(BTimR)-H affords more crystalline film microstructures; hence, 3× increased electron mobility (0.038 cm(2) V(-1) s(-1)) over the low M(n) one P(BTimR)-L (0.011 cm(2) V(-1) s(-1)). In a top-gate/bottom-contact OFET architecture, P(BTimR)-H achieves a high electron mobility of 0.14 cm(2) V(-1) s(-1), only slightly lower than that of state-of-the-art n-type polymer semiconductors. However, the high-lying P(BTimR)-H LUMO results in minimal electron transport on exposure to ambient. Copolymer P3 exhibits a hole mobility approaching 0.1 cm(2) V(-1) s(-1) in top-gate OFETs, comparable to or slightly lower than current state-of-the-art p-type polymer semiconductors (0.1-0.6 cm(2) V(-1) s(-1)). Although BTI building block incorporation does not enable air-stable n-type OFET performance for P(BTimR) or P1, it significantly increases the OFET air stability for p-type P2 and P3. Bottom-gate/top-contact and top-gate/bottom-contact P2 and P3 OFETs exhibit excellent stability in the ambient. Thus, P2 and P3 OFET hole mobilities are almost unchanged after 200 days under ambient, which is attributed to their low-lying HOMOs (>0.2 eV lower than that of P3HT), induced by the strong BTI electron-withdrawing capacity. Complementary inverters were fabricated by inkjet patterning of P(BTimR)-H (n-type) and P3b (p-type).