Naphthalene-Diimide-Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Self-doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3-dibromopropane ( NDI-NI ) or trans-1,4-dibromo-2-butene ( NDI-CI ) via quaternization polymerization. These NDI-based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene-based, non-fullerene-based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI-NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI-CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air-stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.     

Naphthalene‐Diimide‐Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Self‐doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3‐dibromopropane ( NDI‐NI ) or trans‐1,4‐dibromo‐2‐butene ( NDI‐CI ) via quaternization polymerization. These NDI‐based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene‐based, non‐fullerene‐based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI‐NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI‐CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air‐stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.     

Direct arylation polymerization toward efficient synthesis of benzo[1,2-c:4,5-c'] dithiophene-4,8-dione based donor-acceptor alternating copolymers for organic optoelectronic applications

Wide-bandgap π-conjugated donor-acceptor (D-A) alternating copolymers consisting of benzo[1,2-c:4,5-c']dithiophene-4,8-dione (BDTD) as the electron-accepting building block have demonstrated outstanding performances in organic bulk heterojunction (BHJ) solar cell devices. But the synthesis of these polymers has been largely limited to conventional polymerization techniques, particularly Stille-coupling based polycondensations, which often involve tedious preactivation of C-H bonds using highly flammable reagents such as butyl lithium and highly toxic reagents such as trialkyl tin chlorides. Herein, we report a “greener” synthetic route of direct arylation polymerization to a series of wide bandgap D-A copolymers with a common acceptor building block of BDTD. The structure–property relationship in these polymers is characterized. We also present the device performances of these polymers in both thin-film field-effect transistors and organic BHJ solar cells involving the BDTD-based polymers as the electron donors and fullerene derivatives as the electron acceptors. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2554–2564     

New Sn(IV) and Ti(IV) bis(trimethylsilyl)amides in d,l-lactide polymerization, SEM characterization of polymers

Ring-opening polymerization of d,l-lactide initiated with new chlorotris(bis(trimethylsilyl) amido) tin(IV), tetrakis(bis(trimethylsilyl)amido) tin(IV) and titanium(IV) was investigated. New complexes reveal practically quantitative conversion degrees and produced polymers with higher molecular weight with respect to reference alkoxo-species.The X-ray crystal structure of chlorotris(bis(trimethylsilyl)amido) tin (IV) was investigated. Axial enantiomerism of [SnCl{N(SiMe₃)₂}₃] molecules in solution was studied by high-field dynamic NMR, the value of Gibbs activation energy ΔG^‡ = 59.5 kJ/mol.Field emission SEM investigation of bulk polymer samples and thin films on conductive Al foil revealed a stratified fibrous textures in the bulk polymers, as well as nanoscaled topographical features due to coils and entanglements of individual macromolecules in thin films.     

Pyromellitic diimide‐based copolymers for ambipolar field‐effect transistors: Synthesis,characterization, and device applications

A pyromellitic diimide building block, 2,6‐bis(2‐decyltetradecyl)?4,8‐di(thiophen‐2‐yl)pyrrolo[3,4‐f]isoindole‐1,3,5,7(2H,6H)‐tetraone ( 4 ), is synthesized. Based on this building block and other electron‐rich units such as 2,2′‐bithiophene, thieno[3,2‐b]thiophene and 4,8‐bis(dodecyloxy)benzo[1,2‐b:4,5‐b′]dithiophene, three conjugated polymers P1 , P2 , and P3 are prepared in good yield via Stille coupling polymerization. These new copolymers have good solubility in common organic solvents and exhibit good thermal stability. The optical, electrochemical, and thermal properties of these polymers P1–P3 are carefully investigated, and their applications in solution‐processed organic field‐effect transistors are also studied. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2454–2464     

Naphtho[2,1‐b:3,4‐b′]dithiophene‐based Bulk Heterojunction Solar Cells: How Molecular Structure Influences Nanoscale Morphology and Photovoltaic Properties

Organic bulk heterojunction photovoltaic devices based on a series of three naphtho[2,1‐b:3,4‐b′]dithiophene (NDT) derivatives blended with phenyl‐C₇₁‐butyric acid methyl ester were studied. These three derivatives, which have NDT units with various thiophene‐chain lengths, were employed as the donor polymers. The influence of their molecular structures on the correlation between their solar‐cell performances and their degree of crystallization was assessed. The grazing‐incidence angle X‐ray diffraction and atomic force microscopy results showed that the three derivatives exhibit three distinct nanoscale morphologies. We correlated these morphologies with the device physics by determining the J–V characteristics and the hole and electron mobilities of the devices. On the basis of our results, we propose new rules for the design of future generations of NDT‐based polymers for use in bulk heterojunction solar cells.     

A Dual‐Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity

Single‐ligand‐based electronically conductive porous coordination polymers/metal–organic frameworks (EC‐PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π‐conjugated EC‐MOF containing copper units with mixed trigonal ligands was developed: Cu₃(HHTP)(THQ) (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene, THQ=tetrahydroxy‐1,4‐quinone). The modulated conductivity (σ≈2.53×10^?5 S cm^?1 with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m² g^?1) of the Cu₃(HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor.     

An Alternative Anionic Polyelectrolyte for Aqueous PEDOT Dispersions: Toward Printable Transparent Electrodes

Organic conducting polymers are promising electrode materials for printable organic electronics. One of the most studied conducting polymers is PEDOT:PSS, which is sufficiently conductive and transparent, but which shows some drawbacks, such as hygroscopicity and acidity. A new approach to stabilize PEDOT in aqueous dispersions involves the replacement of PSS with a basic polyanion based on a polystyrene backbone with (trifluoromethylsulfonyl)imide (TSFI) side groups. The PEDOT:PSTFSIK dispersions were obtained by oxidative polymerization of EDOT in an aqueous PSTFSIK solution and were characterized with regard to their composition, morphology, doping, rheological behavior, and optoelectronic performance. The PEDOT:PSTFSIK dispersions showed excellent printability and good optoelectronic performance (238 Ohm sq^?1 at 91 % transmittance, σ>260 S cm^?1) and were successfully integrated as flexible electrodes in OLED and OPV devices.     

Boron subphthalocyanine polymers: Avoiding the small molecule side product and exploring their use in organic light‐emitting diodes

In this study, we set out the steps to efficiently synthesize boron subphthalocyanine (BsubPc)‐containing polymers while circumventing the formation of a known side product. The synthesis was achieved using the post‐polymerization coupling reaction of a carboxylic acid functional prepolymer with bromo‐BsubPc. We have earlier shown that when copolymerizing styrene and acrylic acid (AA) a significant amount of an undesired side product is formed. In this study, we have determined that this side product persisted when styrene was copolymerized with AA or n‐butyl acrylate but could be avoided when styrene was copolymerized with methacrylic acid (MAA), methyl methacrylate, or acrylonitrile. Therefore, MAA/styrene copolymer, synthesized by nitroxide‐mediated polymerization was chosen to be coupled to BsubPc. The resulting BsubPc polymer was found to have similar electrochemical properties, solution state absorption and photoluminescence characteristics when compared against a small molecule model compound although the solid‐state PL emission of the polymer was found to be excitation wavelength dependent. Finally, preliminary organic light‐emitting diodes (OLEDs) were fabricated to assess the potential role(s) of the BsubPc polymer in organic electronic devices. These OLEDs represent the first‐solution processed organic electronic devices containing BsubPc polymers as a functional material. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1996–2006     

Surface Assisted Nucleation and Growth of Polymer Latexes on Organically-Modified Inorganic Particles

Summary: Polymer latex particles were synthesized in the presence of inorganic particles, which had been organically-modified to promote favorable interactions with growing macromolecules. The organic modification was performed using three different routes: (1) surface covalent grafting of vinyl trialkoxysilanes, (2) surface adsorption of polyethylene glycol-based macromonomers, and (3) bulk modification through ion exchange with cationic monomers or cationic initiators. Two types of mineral particles were studied: commercial and self-prepared silica particles (with diameters from 80 nm to 1 µm), and commercial laponite clay particles with a cation exchange capacity of 0.75 meq · g⁻¹. Emulsion polymerization was performed in the presence of styrene or butyl acrylate monomers. The morphologies of the nanocomposite particles were observed by (cryogenic) transmission electron microscopy and correlated to the organic modification procedure.     

Sn掺杂ZnO纳米针的结构及其生长机制(英文)

利用包括磁控溅射和热氧化的两步法在Si(111)衬底上制备了Sn掺杂ZnO纳米针.首先用磁控溅射法在Si(111)衬底上制备Sn:Zn薄膜,然后在650℃的Ar气氛中对薄膜进行热氧化,制备出Sn掺杂ZnO纳米针.样品的结构、成分和光学性质采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高分辨透射电子显微镜(HRTEM)、能量散射X射线(EDX)谱和光致发光(PL)光谱等技术手段进行分析.结果表明,制备的样品为具有六方纤锌矿结构的单晶Sn掺杂ZnO纳米针,Sn掺杂量为2.5%(x,原子比),底部和头部直径分别为200-500 nm和40 nm,长度为1-3μm,结晶质量较高.室温光致发光光谱显示紫外发光峰比纯ZnO的发光峰稍有蓝移,这可归因于能谱分析中探测到的Sn的影响.基于本实验的实际条件,简单探讨了Sn掺杂ZnO纳米针的生长机制.     

Topochemical Polymerization of 1,3‐Diene Monomers and Features of Polymer Crystals as Organic Intercalation Materials

From the viewpoint of controlled polymer synthesis, topochemical polymerization based on crystal engineering is very useful for controlling not only the primary chain structures but also the higher‐order structures of the crystalline polymers. We found a new type of topochemical polymerization of muconic and sorbic acid derivatives to give stereoregular and high‐molecular weight polymers under photo‐, X‐ray, and γ‐ray irradiation of the monomer crystals. In this article, we describe detailed features and the mechanism of the topochemical polymerization of diethyl‐(Z,Z)‐muconate as well as of various alkylammonium derivatives of muconic and sorbic acids, which are 1,3‐diene mono‐ and dicarboxylic acid derivatives, to control the stereochemical structures of the polymers. The polymerization reactivity of these monomers in the crystalline state and the stereochemical structure of the polymers produced are discussed based on the concept of crystal engineering, which is a useful method to design and control the reactivity, structure, and properties of organic solids. The reactivity of the topochemical polymerization is determined by the monomer crystal structure, i.e. the monomer molecular arrangement in the crystals. Polymer crystals derived from topochemical polymerization have a high potential as new organic crystalline materials for various applications. Organic intercalation using the polymer crystals prepared from alkylammonium muconates and sorbates is also described.     

Vapor phase oxidative synthesis of conjugated polymers and applications

Since their discovery, electrically conductive polymers have gained immense interest both in the fields of basic and applied research. Despite their vast potential in the fabrication of efficient, flexible, and low‐cost electronic and optoelectronic devices, they are often difficult to process by wet‐chemical methods due to their very low to poor solubility in organic solvents. The use of vapor‐based synthetic routes, in which conductive polymers can be synthesized and deposited as a thin film directly on a substrate from the vapor phase, provides many unique advantages. This article discusses oxidative vapor deposition processes, primarily vapor phase polymerization and oxidative chemical vapor deposition, of conjugated polymers and their applications. The mild operating conditions (near room temperature processing) allow conformal and functional coatings of conjugated polymers on delicate substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Cyclopentadithiophene based branched polymer electrets synthesized by friedel–crafts polymerization

In this report, the BF₃·Et₂O catalyzed Friedel–Crafts polymerization of cyclopentadithiophene monomers for branched conjugation‐interrupted polymer electrets with the potential application in OFET memories were demonstrated. Branched polycyclopentadithiophenes with controlled molecular weights (M_n) of approximately 8800 g/mol and narrow polydispersity index (PDI = 1.08–1.49) were obtained through the optimized polymerization temperature and time, and monomer addition strategy. OFET memories by using the synthesized polymers as the electret layers were fabricated and exhibited multilevel flash memory behaviors, wide memory windows, high on/off ratios, and long retention lifetime. Impressively, due to the strong hydrophobic, extended pi‐conjugation and electron‐donating properties, the branched polycyclopentadithiophene based OFET memory exhibited much lower programming voltage than other branched polymer electrets based devices. It is expected that the branched polycyclopentadithiophenes probably have potential application in other organic electronic devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3140–3150     

Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework

Metal–organic frameworks can be used as porous templates to exert control over polymerization reactions. Shown here are the possibilities offered by these crystalline, porous nanoreactors to capture highly‐reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework the polymerization of pyrrole is restricted, capturing the formation of terpyrrole cationic intermediates. Single‐crystal X‐ray diffraction is used to provide definite information on the supramolecular interactions that induce the formation and stabilization of a conductive array of cationic complexes.     

Self‐Assembled Monolayers of Alkoxy‐Substituted Octadehydrodibenzo[12]annulenes on a Graphite Surface: Attempts at peri‐Benzopolyacene Formation by On‐Surface Polymerization

Self‐assembled monolayers of a series of tetraalkoxy‐substituted octadehydrodibenzo[12]annulene (DBA) derivatives 1 c – g possessing butadiyne linkages were studied at the 1,2,4‐trichlorobenzene (TCB) or 1‐phenyloctane/graphite interface by scanning tunneling microscopy (STM). The purpose of this research is not only to investigate the structural variation of two‐dimensional (2D) monolayers, but also to assess a possibility for peri‐benzopolyacene formation by two‐dimensionally controlled polymerization on a surface. As a result, the formation of three structures, porous, linear, and lamella structures, were observed by changing the alkyl chain length and the solute concentration. The formation of multilayers of the lamella structure was often observed for all compounds. The selection of molecular networks is basically ascribed to intermolecular and molecule–substrate interactions per unit area and network density. The selective appearance of the linear structure of 1 d is attributed to favorable epitaxial registry matching between the substrate lattice and the overlayer lattice. Even though the closest interatomic distance between the diacetylenic units of the DBAs in the lamella structure (≈0.6 nm) is slightly larger compared to the typical distances necessary for topochemical polymerization, the reactivity toward external stimuli (electronic‐pulse irradiation from an STM tip and UV irradiation) was investigated. Unfortunately, no evidence for polymerization of the DBAs on the surface was observed. The present results indicate the necessity for further designing a suitable system for the on‐surface construction of structurally novel conjugated polymers, which are otherwise difficult to prepare.     

Biotin functionalized poly(sulfonic acid)s for bioconjugation: In situ binding monitoring by QCM‐D

We describe the synthesis of biotin end functionalized poly(sulfonic acid)s via living radical polymerization (LRP) for conjugation to Avidin. Quartz crystal microbalance (QCM‐D) and competitive binding studies were used to confirm this conjugation. A biotin initiator for copper‐mediated LRP was used to provide acrylamide and methacrylate based polymers with the functional end group. This investigation revealed that 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid was not a suitable monomer in its acid form but was successfully used in its sodium salt form. A second monomer, 3‐sulfopropylmethacrylate as the potassium salt was also studied and both monomers produced polymers with polydispersities <1.3 and 1.4, respectively. Evolution of molecular weight with respect to time indicated that the polymerization of the acrylamide polymer is controlled. Quartz crystal microbalance with dissipation monitoring was used to confirm that the biotinylated polymers were able to bind to Avidin in situ. The gold surface of a quartz crystal was chemically modified resulting in a stable monolayer of Avidin; the biotinylated polymers were passed over the functionalized surface and their grafting ability was examined. A competitive binding evaluation was undertaken with 2‐(4‐hydroxyphenylazo)benzoic acid (HABA) dye to provide visual verification of conjugation. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Multi-Spectroscopic Interrogation of the Spatial Linker Distribution in Defect-Engineered Metal–Organic Framework Crystals: The [Cu3(btc)2−x(cydc)x] Showcase

In the past few years, defect-engineered metal–organic frameworks (DEMOFs) have been studied due to the plethora of textural, catalytic, or magnetic properties that can be enhanced by carefully introducing defect sites into the crystal lattices of MOFs. In this work, the spatial distribution of two different non-defective and defective linkers, namely 1,3,5-benzenetricarboxylate (BTC) and 5-cyano-1,3-benzenedicarboxylate (CYDC), respectively, has been studied in different DEMOF crystals of the HKUST-1 topology. Raman micro-spectroscopy revealed a nonhomogeneous distribution of defect sites within the [Cu₃(btc)_2−x(cydc)_x] crystals, with the CYDC linker incorporated into defect-rich or defect-free areas of selected crystals. Additionally, advanced bulk techniques have shed light on the nature of the copper species, which is highly dynamic and directly affects the reactivity of the copper sites, as shown by probe molecule FTIR spectroscopy. Furthermore, electron microscopy revealed the effect of co-crystallizing CYDC and BTC on the crystal size and the formation of mesopores, further corroborated by X-ray scattering analysis. In this way we have demonstrated the necessity of utilizing micro-spectroscopy along with a whole array of bulk spectroscopic techniques to fully describe multicomponent metal–organic frameworks.     

Preparation and characterization of solution processable phthalocyanine‐containing polymers via a combination of RAFT polymerization and post‐polymerization modification techniques

In this work, a benzenedinitrile functionalized monomer, 2‐methyl‐acrylic acid 6‐(3,4‐dicyano‐phenoxy)‐hexyl ester, was successfully polymerized via the reversible addition‐fragmentation chain transfer method. The polymerization behavior conveyed the characteristics of “living”/controlled radical polymerization: the first‐order kinetics, linear increase of number‐average molecular weight with monomer conversion, narrow molecular weight distribution, and successful chain‐extension experiment. The soluble Zn(II) phthalocyanine (Pc)‐containing (ZnPc) polymers were achieved by post‐polymerization modification of the obtained polymers. The Zn(II) phthalocyanine‐functionalized polymer was characterized by FTIR, UV–vis, fluorescence, atomic absorption spectroscopy, and thermogravimetric analysis. The potential application of above ZnPc‐functionalized polymer as electron donor material in bulk heterojunction organic solar cell was studied. The device with ITO/PEDOT:PSS/ZnPc‐Polymer/PC₆₁BM/LiF/Al structure provided a power conversion efficiency of 0.014%, fill factor of 0.24, open circuit voltage (V_oc) of 0.21 V, and short‐circuit current (J_sc) of 0.28 mA/cm². © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 691–698     

Exploring the effects of solvents on an organic explosive: Insights from the electron structure,electrostatic potential,and conformational transformations of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane

In order to attain comprehensive insights into the crystallization of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) from solutions, the geometric and electronic structures and conformational transformations of its β-, γ-, ε-, ζ- and η- forms in six organic solvents (ethanol, ethyl acetate, methanol, acetone, acetonitrile, and 2-propanol) were evaluated using quantum chemistry calculations. Results showed that solvents have little effect on the geometric structures of molecules but greatly impact the energy and electronic structure of CL-20. The electron density, atomic charges, and electrostatic potential of CL-20 exhibit polarization due to the solvent effect, especially in alcohols. The polarity of CL-20 increased because of the change in electron density. The transformations of the five conformers of CL-20 were studied thoroughly, and the energy barriers were evaluated using the Gibbs energies. Importantly, the reason η-CL-20 is only found in CL-20-based cocrystals was suggested. These results indicate that solvents play a critical role in crystal growth.