Fluorene‐based copolymers with donor–acceptor units on the side chain and main chain: Synthesis and application in polymer solar cells

Two narrow band gap fluorene‐based copolymers with donor–acceptor (D–A) structure on the polymer side chain and/or main chain are synthesized by Pd‐catalyzed Stille coupling reactions. The two copolymers have excellent thermal stability. The effects of D–A structure on the main and side chains on the absorption and electrochemical properties are studied. The copolymer PF‐BTh‐DBT with D–A structure both on the main and side chains has broader and stronger absorption and narrower band gap than the copolymer PF‐BTh with only a pendent D–A structure. The power conversion efficiency of the assembled solar cell using PF‐BTh‐DBT as donor and PC₇₁BM as acceptor is 1.6% with open‐circuit voltage (V_oc) 0.84 V under simulated AM 1.5 G solar irradiation (100 mW/cm²). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3276–3281, 2013     

Synthesis and characterization of a novel fluorene‐alt‐carbazole polymer to host green,blue, and red phosphorescence

A novel fluorene‐alt‐carbazole polymer host Poly(9,9‐dioctyl‐9H‐fluorene‐2,7‐diyl‐alt‐N‐tetrahydropyran‐3,6‐carbazole) (PFCz), composed of N‐tetrahydropyran‐3,6‐carbazole and 9,9‐dioctyl‐2,7‐fluorene in the polymer backbone, was synthesized by Suzuki coupling. The PFCz possesses good thermal stability and proper lowest unoccupied molecular orbital (LUMO)/highest occupied molecular orbital (HOMO) energy levels to facilitate the injection and transport of electrons and holes. Upon doping with blue, green, and red phosphors, red ‐ green ‐ blue (R‐G‐B) phosphorescent devices hosted by PFCz have been fabricated and investigated. In contrast to those of blue and green devices, the red devices give better performances with a maximum luminous efficiency of 4.88 cd/A and a maximum power efficiency of 1.85% at 149.84 cd/m², due to favorable triplet energy level (E_T) of PFCz for red phosphor, bis(2‐methyldibenzo[f,h]quinoxaline)(acetylacetonate)iridium(III) [Ir(MDQ)₂(acac)]. Additionally, with different doped concentrations of Ir(MDQ)₂(acac), the PFCz‐related red devices emit nearly pure red light with Commission Internationale de L'Eclairage (CIE) coordinates of (0.57, 0.38), (0.60, 0.38), (0.61, 0.38), and (0.62, 0.38), which were very close to the standard red (0.66, 0.34) by the National Television System Committee. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43234.     

Synthesis and solar cells applications of EO‐PF‐DTBT polymer

Poly{[2,7‐(9,9‐bis‐(1‐(2‐(2‐methoxyethoxy)ethoxy)ethyl)‐fluorene)]‐alt‐[5,5‐(4,7‐di‐2′‐thienyl‐2,1,3‐benzothiadiazole)]} (EO‐PF‐DTBT) was synthesized by Suzuki coupling reaction. The polymer is soluble in common organic solvent, such as toluene, THF, and chloroform, and it also shows solubility in polar solvent, such as cyclopentanone. Solar cells based on EO‐PF‐DTBT and PC₆₁BM show maximum power conversion efficiency of 2.65% with an open circuit voltage (V_OC) of 0.86 V, a short circuit current density (J_SC) of 6.10 mA/cm², and a fill factor of 51% under AM 1.5G illumination at 100 mW/cm², which is the best results for fluorene and 4,7‐di‐2‐thienyl‐2,1,3‐benzothiadiazole copolymers and PC₆₁BM blend. The 1,8‐diiodooctane can work well to reduce the over‐aggregated phase structure in polymer solar cells. Our results suggest that the introducing high hydrophilic side chain into conjugated polymer donor materials can tune the aggregation structure and improve the solar cells performances. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40478.     

Synthesis and characterization of poly(2,5‐didecyl‐1,4‐phenylene vinylene), poly(2,5‐didecyloxy‐1,4‐phenylene vinylene), and their alternating copolymer

The preparation of dialkyl‐substituted poly(2,5‐didecyl‐1,4‐phenylene vinylene) ( PDDPV ) by the Horner‐Emmons polycondensation is described. Its performance in an organic light‐emitting diode (OLED) device architecture is compared with devices prepared from the analogous dialkoxy‐substituted poly(2,5‐didecyloxy‐1,4‐phenylene vinylene) ( PDOPV ) and the corresponding alkyl‐alkoxy‐substituted alternating copolymer. Additionally, the structure, stability, electrochemical, and optical properties of the PPVs were characterized by gel permeation chromatography, thermogravimetric analysis, NMR spectroscopy, cyclic voltammetry, UV‐Visible spectroscopy, and fluorescence spectroscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41162.     

Effect of chlorination and fluorination of benzothiadiazole on the performance of polymer solar cells

In order to explore the effects of chlorine and fluorine on photophysical properties and the differences, in this work, we synthesized five new polymers, P1 – P5 , in which benzo[1,2-b:4,5-b]dithiophene as the electron donating and benzothiadiazole as electron withdrawing. Analysis of these five polymers showed that the introduction of Cl and F atoms can deeper the highest occupied molecular orbital of these polymers and enhance the absorption of light by the species, thereby improving V_oc and J_sc. Chlorination has a stronger ability to reduce energy levels and broaden the absorption spectrum compared to fluorination. Among them, P2 showed an efficiency of 4.08% with J_sc of 11.28 mA/cm², V_oc of 0.79 V, and fill factor (FF) of 0.45. Since chlorination is easier than fluorination in terms of synthesis, it is advantageous for practical applications. Therefore, we think that chlorination should not be ignored when designing high efficiency photovoltaic materials, especially when their fluorinated counterparts have proven to have good properties.     

Electroluminescent fluorene‐based alternating polymers bearing triarylamine or carbazole moieties in the main chain: Synthesis and properties

Two soluble conjugated polyfluorenes, poly{9,9‐dioctylfluorene‐2,7‐diyl‐co‐4,4′‐bis[2‐(4‐phenyl)‐2‐cyanovinyl]triphenylamine}(PF‐BCT) and poly{9,9‐dioctylfluorene‐2,7‐diyl‐co‐3,6‐bis[2‐(4‐phenyl)‐2‐cyanovinyl]‐9‐octyl carbazole}(PF‐BCC), have been synthesized from 2,7‐dibromo‐9,9‐dioctylfluorene and 4,4′‐bis[2‐(4‐bromophenyl)‐ 2‐cyanovinyl]triphenylamine or 3,6‐bis[2‐(4‐bromophenyl)‐2‐cyanovinyl]‐9‐octyl carbazole comonomers through a Suzuki polymerization reaction. The copolymers are characterized by gel permeation chromatography, elemental analysis, thermogravimetric analysis. The polymers have good thermal stability with 5 wt % loss temperatures of more than 380°C. Cyclic voltammetry measurements show that the polymers present good electron and hole‐injection abilities. PF‐BCC possesses higher oxidization potential than that of PF‐BCT, which indicates that PF‐BCT has better hole injection ability. The photophysical properties of the polymers are investigated in both solutions and spinning‐coated films. Compared to that of PF‐BCC, the absorption and emission peaks of PF‐BCT bathochromic shift in the solid film or solution states. Single layer light‐emitting devices have been fabricated in the ITO/PEDOT: PSS/polymer/Ca/Al configuration. The electroluminescence (EL) device based on PF‐BCT shows yellow emission with the current efficiency of 0.21 cd/A, while PF‐BCC shows greenish yellow emission with the current efficiency of 0.08 cd/A. In addition, to improve the electroluminescence of PF‐BCC, a PVK layer is introduced, the brightness and efficiency get improved to 700 cd/m² and 0.12 cd/A, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and photocurrent generation of an electrostatically self‐assembled film of hemicyanine and poly(4‐styrenesulfonic acid‐co‐maleic acid)

In this article, we report on electrostatically self‐assembled thin films prepared by the alternative immersion of quartz‐coated and indium tin oxide coated glass substrates in aqueous solutions of a copolymer of poly(4‐styrenesulfonic acid‐co‐maleic acid) (PSSMA) and a hemicyanine of (E)?1,1′‐(propane‐1,3‐diyl)bis{4‐[4‐(dimethylamino)styryl]pyridinium} bromide (H³Br₂). The films were studied by means of ultraviolet–visible absorption and X‐ray photoelectron spectroscopies, scanning electron microscopy, and photoelectrochemical measurements. When irradiated with white light, the PSSMA/H³ monolayer film gave a stable cathodic photocurrent. The effects of the applied bias voltages, layer numbers of the (PSSMA/H³)_n films (where n stands for the number of bilayer films on both sides of the substrates), light intensities, pH value, and electron acceptor on the photocurrent generation of the (PSSMA/H³)_n film were examined. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39871.     

Effects of hydrosilyl monomers on the performance of polysiloxane encapsulant/phosphor blend based hybrid white‐light‐emitting diodes

Polysiloxane‐based encapsulants were prepared by a hydrosilylation reaction of methacryl polyhedral oligomeric silsesquioxane and different hydrosilyl monomers. With the wavelength conversion method, white‐light‐emitting diodes (WLEDs) were produced by the application of a thermally cured polysiloxane encapsulant/phosphor composite as a wavelength converter on blue‐light‐emitting InGaN diodes. The color rendering index, the Commission Internationale de l'Éclairage coordinates, correlated the color temperature, and the luminous efficacy of the WLEDs with different encapsulants were evaluated. The effects of the chemical structures of hydrosilyl monomers on the optical, mechanical, and thermal resistance properties of the encapsulants, together with the performance of the WLEDs, were investigated. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44524.     

Optical and electrochemical properties of polyfluorenes with pyridine–triphenylamine bipolar unit

Two new polyfluorenes were synthesized by Suzuki coupling polymerization, and their photophysical and electrochemical properties were studied. Both polymers contained the bipolar unit 4‐(2,6‐diphenylpyridin‐4‐yl)phenyl‐diphenylamine consisting of pyridine (Py) and triphenylamine (TPA) subunits. The bipolar unit was linked to the polymer chain via TPA or Py subunit, which affected the properties of the polymers. The polymers showed a weak intramolecular charge transfer character. They showed emission at 466 nm in solution and at 512‐538 nm in thin film. Their emission could be tuned by protonation and N‐alkylation of Py. Cyclic voltammetry experiments showed a quasi‐reversible oxidation process for both polymers. Their highest occupied molecular orbital levels were estimated at ? 5.13 and ? 5.21 eV. © 2012 Society of Chemical Industry     

Matched‐dual‐polymer electrochromic lenses,using new cathodically coloring conducting polymers,with exceptional performance and incorporated into automated sunglasses

Reported are syntheses of several new monomer precursors of cathodically coloring conducting polymers (CPs), based on a propylene dioxythiophene skeleton. These are shown to yield CPs—both as homopolymers and as copolymers—that are nearly “perfectly” matched electrochemically and electrochromically with a set of anodically coloring poly(aromatic amines), for use in dual‐polymer electrochromic lenses. Resulting dual‐polymer electrochromic lenses display very high light/dark contrast (typically up to 70/7% or 50/0.5% Transmission (integrated over visible spectrum, vs. air reference), Haze < 2%, very high cyclability (> 10 K cycles), multiyear shelf life, appealing transparent to dark‐blue‐black transition, and excellent optical memory. Dramatic lowering of switching time, from 8 to < 1 s, is demonstrated using unique applied‐potential algorithm resident on inexpensive Microcontroller chip. Working, practical dual‐polymer electrochromic spectacles are demonstrated with electrochromic lenses retrofitted to spectacles meeting ANSI Z87.1, GL‐PD 10–12 (U.S. military) specifications. These incorporate photosensor, rechargeable Li battery, Microcontroller, allow for automated operation. Ab‐initio‐design spectacles, also conforming to above specifications, are also demonstrated, with components seamlessly hidden within frame. To the best of our knowledge, the electrochromic lenses and sunglasses reported herein represent the best visible‐region electrochromic performance for dual‐polymer CP electrochromic systems to date and the first practical implementation in working sunglasses. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41043.     

环糊精改性超支化聚合物的合成与性能评价

以丙烯酰胺(AM)、丙烯酸(AA)、环糊精改性超支化功能单体(MAH-β-CD-HPEA)、甜菜碱(DEPS)为原料合成了四元共聚物PADAH。考察了引发剂质量分数、AM与AA质量比、DEPS与MAH-β-CD-HPEA质量比对聚合物溶液黏度的影响。得到的最佳合成条件为:AM与AA的质量比为2∶1(共占单体总质量的85%),DEPS与MAH-β-CD-HPEA的质量比为14.5∶0.5(共占单体总质量的15%),引发剂质量分数为0.3%。性能研究表明,该共聚物的质量浓度为2000 mg/L时,溶液黏度可达643 mPa·s,3500 r/min剪切20 s后黏度保留率高于80%;90℃时,PADAH的黏度为237m Pa·s,黏度保留率为37.5%,均优于未加MAH-β-CD-HPEA的甜菜碱型聚合物(PADA)和普通部分水解聚丙烯酰胺(HPAM)。     

Enhanced performance of polymer light‐emitting device via optimization of processing conditions and device configuration

The improved performance of polyalkylfluorene light‐emitting device has been achieved through the optimization of processing conditions and device configuration. The current density, brightness, power efficiency, and operation lifetime of polymer light‐emitting device (PLED) were strongly dependent on the surface treatment of anode, the film thickness of light‐emitting polymer (LEP), and the cathode configuration. The anode surface treated with O₂ plasma exhibited a higher current density and brightness than the CF₄ plasma treated device. However, better operation stability was obtained for the CF₄ plasma treated device than for the O₂ plasma treated device. The maximum of brightness and power efficiency has been achieved for the PLED with an LEP thickness of 80 nm. The PLED with LiF/Ca/Al cathode possesses a better power efficiency and operation stability than does the Ca/Al or LiF/Al based PLED. The influences of device fabrication conditions and device configuration on the performance of a polyalkylfluorene‐based PLED are discussed in detail. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 133–141, 2006     

Sensing and surface morphological properties of a poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐bithiophene] liquid‐crystalline polymer for optoelectronic applications

The sensing properties of a poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐bithiophene] (F8T2) polymer were investigated at different concentrations and volume percentages. The effects of the concentrations and volume percentages on the sensing parameters were investigated. The sensitivities of F8T2 were found to be 3.190, 1.434, and 0.362 dB/vol % at 290, 580, and 940 nm, respectively. The response of the F8T2 increased with increasing concentration. F8T2 exhibited good sensitivity and response behaviors. Then, the optical parameters based on the refractive indices of the F8T2 at different molarities were calculated. The dispersion energy, moment of the dielectric constant optical spectrum (M_?1, M_?3), oscillator strength, and contrast of the F8T2 increased with increasing molarity, whereas the average excitation energy or single‐oscillator energy decreased with increasing molarity. The surface morphological properties of the F8T2 polymer film were investigated, and the roughness parameters were obtained. The F8T2 polymer could be used in the fabrication of various sensors because of the good solubility, sensitivity, and response behaviors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41659.     

Synthesis and properties of a new crosslinkable polymer containing benzoxazine moiety in the main chain

Using difunctional phenolic and amine compounds, a new polymer with benzoxazine groups in the main chain has been synthesized through the Mannich reaction of a phenol, formaldehyde, and an amine. ¹H and ¹³C nuclear magnetic resonance spectroscopies, Fourier transform infrared spectroscopy, size exclusion chromatography, and elemental analysis are used to characterize the resulting polymer. Polymer with molecular weight of approximately 10,000 Da is obtained. The resultant polymer has a moderately broad polydispersity index. The thermal properties of the polymer have also been studied by differential scanning calorimetry and thermogravimetric analysis.     

Elemental sulfur‐based polymeric materials: Synthesis and characterization

New elemental sulfur‐based polymeric materials called poly(sulfur‐random‐divinylbenzene) [poly(S‐r‐DVB)] were synthesized by ring opening polymerization via inverse vulcanization technique in the presence of a mixture of o‐, m‐, and p‐diviniylbenzene (DVB) as a cross‐linker. A clear yellow/orange colored liquid was obtained from the elemental sulfur melted at 160 °C and then by adding various amounts of DVB to this liquid directly via a syringe at 200 °C viscous reddish brown polymeric materials were obtained. The copolymers are soluble in common solvents like tetrahydrofuran, dichloromethane, and chloroform, and they can be coated on any surface as a thin film by a spray coating technique. The characterization of the materials was performed by using nuclear magnetic resonance, fourier transform infrared, and Raman spectroscopies. The morphological properties were monitored via scanning electron microscope technique. Thermal analysis showed that an increase in the amount of DVB in the copolymers resulted in an increase in the thermal decomposition temperature. On the other hand, poly(S‐r‐DVB) copolymers exhibited good percent transmittance as 50% T between 1500 and 13,000 nm in electromagnetic radiation spectrum, which makes them good candidates to be amenable use in military and surveillance cameras. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43655.     

Synthesis of two D‐π‐A polymers π‐bridged by different blocks and investigation of their photovoltaic property

The synthesis, characterization, photophysical and photovoltaic properties of two 5,6‐bis(octyloxy)benzo[c][1,2,5]thiadiazole‐containing wide‐band‐gap donor and acceptor D‐π‐A alternating conjugated polymers (HSD‐a and HSD‐b) have been reported. These two polymers absorb in the range of 300–700 nm with a band gap of about 1.88 and 1.97 eV. The HOMO energy levels were ?5.44 eV for HSD‐a and ?5.63 eV for HSD‐b. Polymer solar cells with HSD‐b :PC₇₁BM as the active layer demonstrated a power conversion efficiency (PCE) of 2.59% with a high V_oc of 0.93 V, a J_sc of 7.3 mA/cm², and a comparable fill factor (FF) of 0.38 under simulated solar illumination of AM 1.5G (100 mW/cm²) without annealing. In addition, HSD‐a :PC₇₁BM blend‐based solar cells exhibit a PCE of 2.15% with a comparable V_oc of 0.64 V, J_sc of 8.75 mA/cm^?2, and FF of 0.40. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41587.     

Optically active tyrosine‐containing poly(N‐propargylamides): Synthesis,helical conformation,and infrared emissivity study

Novel optically active and racemic poly(N‐propargylamides) bearing tyrosine pendants (LPT, DPT, and RPT) were synthesized and characterized. The polymers possessed moderate molecular weights and were thoroughly soluble in common organic solvents. The secondary structure of these three polymers in chloroform was studied and the results indicated that LPT and DPT could adopt helical structures with predominantly one‐handed screw sense according to their intense Cotton effect and large specific rotation values, while RPT adopted random coiled polymer chain. The amide groups could form amide‐amide hydrogen bonds to engender the twist of dihedral angle and the strong steric repulsion of phenol groups might have the opposite effect on the helix. The helical structure of the optically active polymers were conclusively constructed and stabilized by the optimization of intra‐ and intermolecular hydrogen bonding and steric repulsion of the side chains. Moreover, the infrared emissivity values of LPT and DPT at 30 °C were 0.682 and 0.671, which were much lower than RPT. LPT and DPT also showed superior heat resistance due to their unique helical conformation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44824.     

Photoluminescence emission of a stable and well‐dispersed unsaturated polyester‐co‐rare‐earth complex

A series of unsaturated polyester (UPR)‐co‐rare‐earth complex (REX) photoluminescence materials with red and green luminescence were fabricated. REXs with double bonds, including complex of europium (Eu³⁺) (methacrylic acid)₃ and 1,10‐phenanthroline (Phen) [Eu(MAA)₃Phen], and complex of terbium (Tb³⁺)(methacrylic acid)₃ and Phen [Tb(MAA)₃Phen], and UPR acted as functional monomers and the polymer matrix, respectively. Fourier transform infrared and UV absorption spectroscopy confirmed the chemical structure of the resulting UPR‐co‐REX according to the free‐radical polymerization mechanism. The study of fluorescence distribution by means of laser scanning confocal microscopy indicated that the REX materials were uniformly dispersed in the UPR matrix. The effects of the type and dosage of REX on the fluorescence intensity and stability were examined via fluorescence spectrometry. We found that the optical/physical properties of the REX were improved by UPR molecular skeleton structures. The fluorescence intensity increased with increasing use of the REX and reached a maximum value when the REX content was 12 wt %. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45253.     

Optical nonlinearity and photoinduced anisotropy of an azobenzene‐containing ionic liquid crystalline polymer

The nonlinear optical properties of an azobenzene‐containing ionic liquid crystalline polymer were investigated using single‐beam Z‐scan and optical Kerr effect (OKE). The polymer film exhibited large nonlinear absorption (～10^?6 cm W^?1) and nonlinear refraction (～10^?11 cm² W^?1) under 532 nm ps excitation. The femtosecond time‐resolved OKE results suggested that the nonlinear optical response time in off‐resonant region was as fast as 300 fs. Moreover, stable molecular reorientation and a large photoinduced birefringence ( ) were achieved in the polymer film with a 405 nm continous wave (CW) laser as pump light. The large optical nonlinearity, ultrafast response, and effective photoinduced molecular reorientation of the polymer films indicated their potential applications in nonlinear photonic devices and optical storage. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of multi‐hollow opaque polymer pigments

A new generation multihollow opaque polymer pigment was synthesized by suspension polymerization of “water‐in‐oil‐in‐water” emulsion method, where methyl methacrylate and ethylene glycol dimethacrylate monomer mixture was used as oil phase. The effects of surfactant and cosurfactant composition in terms of “hydrophilic/lipophilic balance” on the stability of the “water‐in‐oil” emulsion and the size of water droplets were studied. Low droplet sizes and the optimum stability were obtained with “Span 80&Tween 80” surfactant mixture at an HLB value of 8. The desired size distribution was obtained at “monomer/surfactant/water” ratio of 75.5/9.4/15.1 at an ultrasonic mixing power of 80 W lasting for 30 s. The surface morphology and hollow structure of polymer pigments were analyzed by scanning and transmission electron microscopy techniques. L*a*b color and gloss properties of polymer pigments were examined. The opacity values were assessed by contrast ratio measurements, and the pigments provided up to 97.3% opacity with 50% v/v solid content in resin. In addition, the pigments exhibited low gloss values and yielded matte films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43696.