Anionic triphenylamine‐ and fluorene‐based conjugated polyelectrolyte as a hole‐transporting material for polymer light‐emitting diodes

BACKGROUND: Hole‐transport layers (HTLs) play a crucial role in multilayer polymeric light‐emitting diodes (PLEDs) for the achievement of satisfactory device performance. During the fabrication of multilayer PLEDs via solution processing, the fabricated HTLs encounter the risk of erosion during the film‐forming process of subsequent emitting layers (EMLs). In contrast to the widely investigated crosslinkable HTLs, much less attention has been paid to the preparation of polar‐solvent‐soluble HTLs, which is a straightforward solution to overcome the interfacial mixing between HTLs and EMLs during solution processing. RESULTS: Alternating triphenylamine‐ and fluorene‐based anionic copolymer poly[9,9‐bis(4′‐sulfonatobutyl)fluorene‐alt‐N‐(p‐trifluoromethyl)phenyl‐4,4′‐diphenylamine]sodium salt (PFT‐CF3) was synthesized via a palladium‐catalyzed Suzuki coupling reaction. This polyelectrolyte is soluble only in polar solvents such as methanol, dimethylformamide and dimethylsulfoxide rather than in non‐polar solvents such as toluene, chloroform and xylene. The relatively high HOMO (?5.22 eV) and LUMO (?2.26 eV) levels of this polymer endow it simultaneously with good hole‐transporting and electron‐blocking capabilities. The performance of red‐, green‐ and blue‐emitting devices utilizing this polyelectrolyte as HTL was investigated. CONCLUSION: The anionic conjugated polyelectrolyte based on triphenylamine and fluorene, PFT‐CF₃, can serve as a promising hole‐transporting/electron‐blocking layer in multilayer PLEDs. Copyright © 2009 Society of Chemical Industry     

Synthesis,structures, and density functional theory computational study of thiophene‐containing and fluorodecorated imine‐linked polymers

A new series of extended–conjugated and thermally stable thiophene‐containing imine‐linked polymers were synthesized via a Schiff‐base condensation reaction between aryl aldehydes and 2,6‐diaminopyridine building blocks. The backbones of the polymers were functionalized with phenyl, fluorosubstituted phenyl, thienyl, and pyridyl aromatic rings. The successful synthesis was confirmed with spectrochemical characterization techniques, including IR, ¹H‐NMR, ¹³C‐NMR, and elemental analyses. The electronic properties of the polymers were investigated with ultraviolet–visible (UV–vis) absorption spectroscopy; the properties were collected experimentally and calculated with density functional theory (DFT) in the gas phase. The maximum absorption calculated from DFT was higher than the experimental values by about 60 nm; this was attributed to the absence of the solvent effect in the DFT case. The frontier molecular orbital ((HOMO) highest occupied molecular orbital and (LUMO) lowest unoccupied molecular orbital), optical band gap (E_g), and total energy (E_T) values of the optimized structures were calculated. Apparently, there was a significant relation between the number of thiophene rings and the resulting E_g and E_T values. As the number of thiophene rings in the polymer chain increased, E_g and E_T decreased, and the thermal stability of the polymers increased. E_g and the absorption band edges were determined experimentally from the UV–vis and transmittance spectra, respectively. Poly(terthienyl–azomethine–pyridine–azomethine), with the highest thiophene content, had the lowest experimental and calculated E_g values (2.10 and 2.63 eV, respectively). In contrast, upon fluorination, poly[(2,5‐dithienyl–1,4‐difluorobenzene)–azomethine–pyridine–azomethine] exhibited the highest E_g (2.81 eV) and absorption band edges (2.94 eV), whereas the thermal stability decreased to 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44331.     

Dependence of optical properties on the preparation methods of poly[(9,9′‐dialkylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)]

A blue‐light‐emissive fluorene‐based polyoxadiazole, an n‐type polyfluorene derivative, was synthesized by both one‐step and two‐step methods. Directly polymerized poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)] (PFOx‐DP) exhibited a higher molecular weight and a more efficient photoluminescence quantum yield than poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)] (PFOx) prepared via a polyhydrazide precursor, poly[9,9′‐didodecylfluorene‐2,7‐(2,5‐dihydrazide‐ 1,3,4‐oxadiazole). Both polymers, differently prepared, showed similar photoluminescent properties in 1,2‐dichloroethane. However, in a film state, the influence of the interchain interactions on the photoluminescence of PFOx with the lower molecular weight was larger than on the photoluminescence of PFOx‐DP. The electron‐deficient property of an oxadiazole group in the polymer backbone resulted in low‐lying highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of ?6.29 and ?3.26eV, respectively, of the polymer suitable for electron‐transport/hole‐blocking layers and emissive layers in multilayer electroluminescence devices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3112–3118, 2004     

Synthesis and properties of novel deep red‐emitting copolymers based on a poly(p‐phenylenevinylene) derivative

A series of novel copolymers based on a poly(p‐phenylenevinylene) (PPV) derivative with different content of narrow band‐gap unit 2,1,3‐benzoselenadiazolevinylene (BSeV) was prepared via Stille coupling reaction. The copolymers emit light from deep red to near‐infrared (NIR) depending on BSeV content in the copolymers. The electroluminescence (EL) emission peaked at 752 nm for the copolymer with the content of 30 mol % BSeV is among the longest reported so far for the PPV polymers. The best device performance is observed for the copolymer with 1 mol % BSeV content with external quantum efficiency (QE_ext) of 0.26% and CIE coordinate 0.65, 0.34 (x,y). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4321–4327, 2006     

Synthesis and characterization of greenish‐blue emitting vinyl copolymer containing pyrene and triarylamine moieties

Two fluorescent monomers N‐phenyl‐N‐(4‐vinylphenyl)pyren‐1‐amine (vinyl‐PyPA) and 1‐vinyl pyrene (VPy) were synthesized in good yields. A series of soluble conductive vinyl copolymers P(PyPA‐co‐VPy) containing vinyl‐PyPA and VPy moieties in different composition ratios were prepared by free radical solution polymerization. These copolymers showed high T_g (190?201 °C) and good thermal stability. The photoluminescence emission maxima of the copolymers were all in the range 474.5?478.5 nm, which was similar to the poly(N‐phenyl‐N‐(4‐vinylphenyl)pyren‐1‐amine) (P(PyPA)) (475 nm) but blue shifted compared with poly(1‐vinyl pyrene) (PVPy) (490.5 nm). The lifetime of the copolymers increased from 10.2 to 29.7 ns with an increase in pyrene content. The copolymers had higher quantum yields (0.51) than those of the homopolymers of P(PyPA) (0.48) and PVPy (0.13). The highest occupied molecular orbital of the copolymers remained relatively unchanged from P(PyPA), while the lowest unoccupied molecular orbital varied from ?2.41 eV to ?2.51 eV with an increase in pyrene ratio in the copolymers. The energy bandgaps of the copolymers (from 2.70 eV to 2.81 eV) were smaller than those of P(PyPA) (2.82 eV) and PVPy (3.47 eV). Two polymer light‐emitting diode (PLED) series were attempted including indium tin oxide (ITO) (fluorocarbon (CFx) treated)/P(PyPA‐co‐VPy)/LiF/Al and ITO(CFx treated)/P(PyPA‐co‐VPy)/1,3,5‐Tri(1‐phenyl‐1H‐benzo[d]imidazol‐2‐yl)phenyl (TPBi)/LiF/Al. The results suggested that the PyPA moiety is hole conducting and the PLEDs can achieve high luminance from 650 to 1150 cd m^?2 (at 100 mA cm^?2) only when an electron injecting layer TPBi is employed. © 2013 Society of Chemical Industry     

Investigation of liquid crystalline and photocrosslinkable poly[4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamate]s

Three series of liquid‐crystalline‐cum‐photocrosslinkable polymers were synthesized from 4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamates (x = ? H, ? OCH₃ and ? CN; m = 6, 8 and 10) by free radical solution polymerization using azobisisobutyronitrile as an initiator in tetrahydrofuran at 60 °C. All the monomers and polymers were characterized using intrinsic viscosity, and FTIR, ¹H NMR and ¹³C NMR spectroscopy. The liquid crystalline behavior of these polymers was examined using a hot stage optical polarizing microscope. All the polymers exhibited liquid crystalline behavior. The hexamethylene spacer‐containing polymers exhibited grainy textures; in contrast, the octamethylene and decamethylene spacer‐containing polymers showed nematic textures. Differential scanning calorimetry data confirmed the liquid crystalline property of the polymers. Thermogravimetric analysis revealed that all the polymers were stable between 236 and 344 °C in nitrogen atmosphere and underwent degradation thereafter. As the methylene chain length increases in the polymer side‐chain, the thermal stability and char yield of the polymers decrease. The photocrosslinking property of the polymers was investigated using the technique of exposing the polymer solution to UV light and using UV spectroscopy. The crosslinking reaction proceeds via 2π–2π cycloaddition reactions of the ? CH?CH? of the pendant cinnamate ester. The polymers containing electron‐releasing substituents (? OCH₃) showed faster crosslinking than the unsubstituted polymers and those containing electron‐withdrawing substituents (? CN). Copyright © 2007 Society of Chemical Industry     

Ionic polymers with expanded π‐conjugation systems derived from through‐space interaction in piperazinium and homopiperazinium rings

Reactions of N‐(2,4‐dinitrophenyl)‐4‐arylpyridinium chlorides (aryl (Ar) = phenyl and 4‐biphenyl) with piperazine or homopiperazine caused opening of the pyridinium ring and yielded polymers that consisted of 5‐piperazinium‐3‐arylpenta‐2,4‐dienylideneammonium chloride (? N(CH₂CH₂)₂N⁺ (Cl^?)?CH? CH?C(Ar)? CH?CH? ) or 5‐homopiperazinium‐3‐arylpenta‐2,4‐dienylideneammonium chloride (? N(CH₂CH₂CH₂)(CH₂CH₂)N⁺ (Cl^?)?CH? CH?C(Ar)? CH?CH? ) units. ¹H NMR spectral analysis suggested that the π‐electrons of the penta‐2,4‐dienylideneammonium group of the polymers were delocalized. UV‐visible spectral measurements revealed that the π‐conjugation system expanded along the polymer chains because of the orbital interaction between electrons of the two nitrogen atoms of the piperazinium and homopiperazinium rings. However, the π‐conjugation length depended on the distance between the two nitrogen atoms; that is, the polymers containing the piperazinium ring had a longer π‐conjugation length than those containing the homopiperazinium ring. Conversion of the piperazinium and homopiperazinium rings from the boat to the chair form led to a decrease in the π‐conjugation length. The surface of pellets that were molded from the polymers exhibited metallic luster, and these polymers underwent electrochemical oxidation in solution. Copyright © 2010 Society of Chemical Industry     

Electroluminescent Performances of Iridium Complexes with Dibenzo-18-crown-6

Three novel iridium complexes with dibenzo-18-crown-6 substituted 2-penylpyridine (ppy) ligand have been synthesized and characterized. In order to investigate the electroluminescent properties of the resulting iridium complexes, polymer light-emitting diodes (PLEDs) with device structure of ITO/PEDOT:PSS/Emissive Layer/LiF/Al are fabricated using soluble poly(N-vinylcarbazole) (PVK) as the host and the resultant iridium complexes as dopant. Consequently, the PLEDs with G1 as dopant exhibited the highest luminous efficiencies of 13.3 cd A^?1 and the maximal brightness of 13523 cd m^?2 at the doping concentration of 8 wt%. Moreover, the iridium complexes G1, G2 and G3 exhibited nearly identical Commission Internationale de L’Eclairage (CIE) coordinates of (0.34?±?0.1, 0.62?±?0.1), which are very close to the CIE coordinates of (0.33, 0.61) for Ir(ppy)₃. This indicates that the CIE coordinates of the iridium complexes would not be influenced as the dibenzo-18-crown-6 groups pended on the meta-position of benzene ring of ppy.     

Properties of polymer light‐emitting diodes coated on surface‐treated ITO/glass substrates

We fabricated blue polymer light‐emitting diodes (PLEDs) with indium tin oxide (ITO)/PEDOT : PSS/PVK/PFO‐poss/LiF/Al structures. All of the organic film layers were prepared by the spin‐coating method on plasma and heat‐treated ITO/glass substrates. The dependences of the optical and electrical properties of the PLEDs on the plasma and heat treatment of the ITO film and the introduction of poly(N‐vinylcarbazole) (PVK) layer were investigated. The AFM measurements indicated that the surface roughness of the ITO transparent film was improved by the plasma and heat treatment. In the emission spectra, the intensity of the excimer peaks of the PFO‐poss [polyhedral oligomeric silsesquioxane‐terminated poly(9,9‐dioctylfluorene)] emission layer were decreased for the PLED device with the PVK film layer compared with the one without the PVK layer. The maximum current density, luminance and current efficiency of the PLEDs were found to be about 470 mA/cm², 486 cd/m² at an input voltage of 12 V and 0.55 cd/A at 100 cd/m² in luminance, respectively. The color coordinates (CIE chart) of the blue PLEDs were in the range of x = 0.17 ～ 0.20, y = 0.13 ～ 0.16, and the peak emission spectrum was about 430 nm, showing a good blue color. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Blue fluorescent conductive poly(9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene) homopolymer and its highly soluble copolymers with styrene or 9‐vinylcarbazole

A new blue fluorescent monomer, 9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene, was designed and synthesized in good yield. Its homopolymer poly(9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene) (P(ADN)) and soluble conductive vinyl copolymers poly[(9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene)‐co‐styrene] (P(ADN‐co‐S)) and poly[(9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene)‐co‐(9‐vinylcarbazole)] (P(ADN‐co‐VK)) were synthesized using free radical solution polymerization. All the polymers showed high glass transition mid‐point temperatures (203 to 237 °C) and good thermal stabilities. The photoluminescence emission of the copolymers was similar to that of P(ADN) (with two maxima at 423 and 442 nm). The lifetimes of P(ADN‐co‐S) (6.82 to 7.91 ns) were all slightly less than that of P(ADN) (8.40 ns). The lifetime of P(ADN‐co‐VK) increased from 7.8 to 8.8 ns with an increase in VK content. The fluorescence quantum yields of P(ADN‐co‐S) showed an overall increasing tendency from 0.42 to 0.58. The quantum efficiencies of P(ADN‐co‐VK) decreased from 0.36 to 0.19 with an increase of VK fraction. With increasing S/VK content, the highest occupied molecular orbital of P(ADN‐co‐S)/P(ADN‐co‐VK) ranged from ?5.58 to ?5.73 eV, which was similar to that of P(ADN) (?5.71 eV). The band gaps of P(ADN‐co‐S) and P(ADN‐co‐VK) were about 2.97 eV, which were equal to that of P(ADN), and smaller than that of 2‐methyl‐9,10‐di(1‐naphthalenyl)anthracene (MADN) (3.04 eV) and poly(9‐vinylcarbazole) (3.54 eV). Preliminary electroluminescence results were obtained for a homojunction device with the configuration ITO/MoO₃ (20 nm)/P(ADN)/LiF (1 nm)/Al (100 nm), which achieved only 30–50 cd m^?2, due to P(ADN) having a low mobility of 4.7 × 10^?8 cm² V^?1 s^?1 compared to that of its model compound MADN of 6.5 × 10^?4 cm² V^?1 s^?1. © 2013 Society of Chemical Industry     

A novel electrochemically and thermally stable polythiophene for photovoltaic application

Conjugated polymers having good electrochemical and thermal stability are highly desired in optoelectronics. We report a new polythiophene consisting of alternating 4,4′‐didodecyl‐2,2′‐bithiophene and terthiophene units (HPL1) synthesized via Stille coupling reaction. The optical band gap of HPL1 (1.92 eV) is similar to that of regioregular poly(3‐hexylthiophene) (rr‐P3HT, 1.89 eV). In comparison to rr‐P3HT, the HPL1 when subjected to the cyclic voltammetry as thin film shows much superior electrochemical stability and a lower highest occupied molecular orbital energy level (?4.87 eV for rr‐P3HT and ?4.95 eV for HPL1). The transient photoluminescence study of HPL1 and rr‐P3HT shows that both materials have two exciton decay processes, and the excitons of rr‐P3HT are quenched more quickly. The onset decomposition, T_d for rr‐P3HT (465°C) is 4°C lower than HPL1 (469°C). Preliminary photovoltaic study disclosed that the polymer solar cell based on HPL1:[6,6]‐phenyl‐C₆₁‐butyric acid methyl ester blend showed a power conversion efficiency of 0.63%, with a V_oc of 0.6 V, and a short circuit current (J_sc) of 2.79 mA cm^?2 under AM 1.5 illumination (100 mW cm^?2). The whole study provided an important example to design new electrochemically and thermally stable polymers with longer exciton life time for application in bulk heterojunction polymer solar cells. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Halogenation effect promoted low bandgap polymers based on asymmetric isoindigo unit with low energy loss

To optimize the energy levels of the structural framework of isoindigo polymers, a series of asymmetric isoindigo based low bandgap polymers with chlorine, fluorine and thiazole substituents was constructed and their optical, electrochemical and photovoltaic properties were comparatively evaluated for the impact of different substitutions. In comparison with the polymer based on 2,2'‐bithiophene and isoindigo unit (PTi) with non‐substituted bithiophene as the donor moiety, the highest occupied molecular orbital energy level for the newly synthesized polymers is significantly decreased, and in turn an improvement of the open‐circuit voltage (V_OC) is noted in the corresponding photovoltaic devices. More importantly, combined with a low bandgap of 1.32 eV, the energy losses (E_loss) could be reduced to 0.61 eV for polymer based on chlorinated 2,2'‐bithiophene and isoindigo unit (PCl). In addition, the halogen moieties are observed to be superior in device fabrication and give better values than the thiazole substituent. Both fluorinated and chlorinated polymer donors exhibited improved performance compared with the original polymer PTi. Consequently, this work not only presents the influence of different electron withdrawing substituents on the physicochemical and photovoltaic performance, but also backs the concept of how to reduce the energy loss via the heteroatom effect. © 2020 Society of Chemical Industry     

Enhancing the electroluminescence properties of novel blue light emitting polymer and MEH‐PPV based white light emitting polymer devices by processing condition optimization

A series of triarylaminooxadiazole‐containing tetraphenylsilane light emitting polymer (PTOA) and poly(2‐methoxy, 5‐(2′‐ethyl‐hexyloxy)‐p‐phenylene‐vinylene) (MEH‐PPV) based white light emitting polymer devices (PLEDs) were fabricated to study blue and orange–red emitter composition and light emitting layer processing effects on white emission electroluminescence properties. Color purity, current turn‐on voltage, brightness, and current efficiency were strongly determined by MEH‐PPV content and the thin film processing condition. The intensity of PTOA blue emission was equal to that of MEH‐PPV orange–red emission when the device was fabricated by a polymer composite film containing 10 wt % of MEH‐PPV. Color purity [Commission Internationale de L'Eclairage (CIE_x,y) coordinates (0.26,0.33)] was nearly white emission under applied 8 V. The brightness and current efficiency of PTOA‐MEH‐PPV composite film based devices increased as MEH‐PPV content increased. Furthermore, white emission blue shifted with increasing spin‐rate of thin film coating and applied voltage. Low turn‐on voltage, high current density, and high brightness were obtained for the device fabricating with light emitting layer coating with high spin‐rate. Moreover, low current efficiency was obtained for the PLED with a thinner light‐emitting layer. A white emission CIE (0.28,0.34) was obtained for PTOA‐MEH‐PPV based white PLED. White PLED brightness and efficiency can be as high as 700 cd/m² and 0.78 cd/A, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of poly(fluorene vinylene) copolymers containing thienylene–vinylene units

Narrow‐band‐gap 2,5‐thienylene‐divinylene (ThV) units were incorporated into the poly(fluorene vinylene) backbone via a Gilch reaction as an energy trap with various feed ratios; this yielded pronounced changes in the electrochemical and optical properties of the material. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the polymers {poly(9,9‐di‐iso‐octylfluorene vinylene) [poly(fluorene vinylene‐co‐thiophene vinylene (FV))], C1, and C2 } were estimated to be ?5.53 to ?5.10 eV and ?2.98 to ?2.84 eV, respectively, by cyclic voltammetry measurements. In comparison with poly(FV), the HOMO energy levels of polymers poly(fluorene vinylene‐co‐thiophene vinylene (FV) (90 : 10) ( C1 ) and poly(fluorene vinylene‐co‐thiophene vinylene (FV) (80 : 20) ( C2 ) were significantly increased, but their LUMO energy levels were slightly decreased. The optical properties were investigated by absorption and emission spectra of the polymers. The good spectral overlap between the emission of poly(FV) and the absorption of polymers C1 and C2 revealed a sufficient energy transfer from the majority of 9,9‐di‐iso‐octylfluorene vinylene units to the minority of ThV units. The reduction of self‐absorption losses of polymers C1 and C2 due to spectral separation caused by the incorporation of ThV units could be indirectly confirmed by nonlinear optical (NLO) properties. The result of the NLO properties of the polymers showed that the third‐order NLO coefficients of poly(FV), C1, and C2 were 8.1 × 10^?10, 1.35 × 10^?9, and 1.51 × 10^?9 esu, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of molecular weight on spherulitic growth rate of poly(ϵ‐caprolactone) and poly(ϵ‐caprolactone)‐b‐poly(ethylene glycol)

The spherulitic growth rates of a series poly (?‐caprolactone) homopolymers and poly(?‐caprolactone)‐b‐ poly(ethylene glycol) (PCL‐b‐PEG) block copolymers with different molecular weights but narrow polydispersity were studied. The results show that for both PCL homopolymers and PCL‐b‐PEG block copolymers, the spherulitic growth rate first increases with molecular weight and reaches a maximum, then decreases as molecular weight increases. Crystallization temperature has greater influence on the spherulitic growth rate of polymers with higher molecular weight. Hoffman–Lauritzen theory was used to analyze spherulitic growth kinetics and the free energy of the folding surface (σ_e) was derived. It is found that the values of σ_e decrease with molecular weight at low molecular weight level and become constant for high molecular weight polymers. The chemically linked PEG block does not change the values of σ_e significantly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Blue‐light‐emitting poly(arylene ethynylenes) containing alternating sequences of biphenylene or fluorenediyl and p‐phenylene moieties linked through triple bonds

Two new poly(arylene ethynylenes) were synthesized by the reaction of 1,4‐diethynyl‐2.5‐dioctylbenzene either with 4,4′‐diiodo‐3,3′‐dimethyl‐1,1′‐biphenyl or 2,7‐diiodo‐9,9‐dioctylfluorene via the Sonogashira reaction, and their photoluminescence (PL) and electroluminescence (EL) properties were studied. The new poly(arylene ethynylenes) were poly[(3,3′‐dimethyl‐1,1′‐biphenyl‐4,4′‐diyl)‐1,2‐ethynediyl‐(2,5‐dioctyl‐1,4‐phenylene)‐1,2‐ethynediyl] (PPEBE) and poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐1,2‐ethynediyl‐(2,5‐dioctyl‐1,4‐phenylene)‐1,2‐ethynediyl] (PPEFE), both of which were blue‐light emitters. PPEBE not only emitted better blue light than PPEFE, but it also performed better in EL than the latter when the light‐emitting diode devices were constructed with the configuration indium–tin oxide/poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonic acid) (50 nm)/polymer (80 nm)/Ca:Al. The device constructed with PPEBE exhibited an external quantum efficiency of 0.29 cd/A and a maximum brightness of about 560 cd/m², with its EL spectrum showing emitting light maxima at λ = 445 and 472 nm. The device with PPEFE exhibited an efficiency of 0.10 cd/A and a maximum brightness of about 270 cd/m², with its EL spectrum showing an emitting light maximum at λ = 473 nm. Hole mobility (μ_h) and electron mobility (μ_e) of the polymers were determined by the time‐of‐flight method. Both polymers showed faster μ_h values. PPEBE revealed a μ_h of 2.0 × 10^?4 cm²/V·s at an electric field of 1.9 × 10⁵ V/cm and a μ_e of 7.0 × 10^?5 cm²/V·s at an electric field of 1.9 × 10⁵ V/cm. In contrast, the mobilities of the both carriers were slower for PPEFE, and its μ_h (8.0 × 10^?6 cm²/V·s at an electric field of 1.7 × 10⁶ V/cm) was 120 times its μ_e (6.5 × 10^?8 cm²/V·s at an electric field of 8.6 × 10⁵ V/cm). The much better balance in the carriers' mobilities appeared to be the major reason for the better device performance of PPEBE than PPEFE. Their highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels were also a little different from each other. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 299–306, 2006     

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.     

Synthesis and characterizations of poly(4‐alkylthiazole vinylene)

Two poly(thiazole vinylene) derivatives, poly(4‐hexylthiazole vinylene) (P4HTzV) and poly(4‐nonylthiazole vinylene) (P4NTzV), were synthesized by Pd‐catalyzed Stille coupling method. The polymers are soluble in common organic solvents such as o‐dichlorobenzene and chloroform, and possess good thermal stability. P4HTzV and P4NTzV films exhibit broad absorption bands at 400–720 nm with an optical bandgap of 1.77 eV and 1.74 eV, respectively. The HOMO (the highest occupied molecular orbital) energy levels of P4HTzV and P4NTzV are ?5.11 and ?5.12 eV, respectively, measured by cyclic voltammetry. Preliminary results of the polymer solar cells based on P4HTzV : PC₆₁BM ([6,6]‐phenyl‐C‐61‐butyric acid methyl ester) (1 : 1, w/w) show a power conversion efficiency of 0.21% with an open‐circuit voltage of 0.55 V and a short circuit current density of 1.11 mA cm^?2, under the illumination of AM1.5G, 100 mW cm^?2. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Thermogelling of highly branched poly(N‐isopropylacrylamide)

Highly branched poly(N‐isopropylacrylamide) (PNIPAM) has been synthesized by a reversible addition‐fragmentation chain transfer (RAFT) copolymerization of NIPAM and a vinyl contained trithiocarbonate RAFT agent. ¹H‐NMR measurements revealed that the degrees of branch (DB) are in the range of 0.032–0.105. Laser light scattering (LLS) measurements gave the hydrodynamic radii (R_h) of the polymers to be 3.6–5.7 nm with molecular weight in the range of 1.3 × 10⁴ g/mol–2.3 × 10^?4 g/mol. Highly branched PNIPAM with terminal thiol groups were obtained by aminolysis the polymers, and the product can be oxidized by air to form disulfide bonds (? S? S? ) among chains and resulting in the formation of nanoparticle in aqueous solution. Interestingly, the nanoparticle in size of R_h ? 80 nm showed a thermogelling behavior to form bulk hydrogel when the temperature was increased up to 25°C due to the thermo‐induced association of the PNIPAM chains among the nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010