Multicolor emission and thin film transistor properties of 1,8-diethynylcarbazole-based conjugated copolymers

1,8-Carbazole-based conjugated copolymers are synthesized by the Sonogashira polycondensation between the 1,8-diethynylcarbazole derivative and dibromo comonomers. The resulting polymers are fully characterized by GPC, and ¹H NMR and IR spectroscopies, and their high thermal stability with the 5% decomposition temperature exceeding 350 °C by thermogravimetric analyses. The optical properties of the carbazole polymers reveal that the comonomer structures significantly affect the absorption and emission spectra. For example, a bathochromic shift of the spectra is achieved when electron-accepting comonomers are selected, finally leading to the production of additive primaries. The mixtures of three carbazole polymers with red, green, and blue emission colors provide a white light emission both in solutions and in thin solid films. In addition, the thin film transistor properties of the carbazole polymers are investigated. The 1,8-carbazole-based polymers display an intermediate mobility between the 2,7-carbazole and 3,6-carbazole-based counter polymers. All these results suggest the potential application possibilities of the 1,8-carbazole-based conjugated polymers in optoelectronic devices.     

Thermally resistant carbazole‐modified phenol–formaldehyde resins

Phenol–formaldehyde resins were modified with carbazole in order to improve their thermal resistance. Attempts to incorporate carbazole rings into novolac and resol resins were made using three methods: (1) the addition of N‐(hydroxymethyl)carbazole (HMC) into a phenol–formaldehyde mixture, (2) the addition of carbazole into a phenol–hydroxymethyl derivative of acetone mixture, where the hydroxymethyl derivative of acetone was used as formaldehyde donor, and (3) by prolonging the time of high‐temperature reaction between phenol, carbazole and formaldehyde. The temperature and time of reaction were critical for incorporation of carbazole, which successfully led to highly temperature‐resistant carbazole‐modified novolacs for the latter procedure. When carbazole was incorporated into novolac structure at a level of 8 mol%, the thermal resistance increased by 118 °C measured as 5% mass loss temperature. Other procedures led to solids containing carbazole or HMC as physical admixtures. The obtained composites revealed variable thermal resistance effects; the carbazole‐modified resol containing 9 mol% of carbazole showed 47 °C increase of thermal resistance in comparison with non‐modified resol, measured as 5% mass loss temperature. © 2015 Society of Chemical Industry     

Synthesis of oxadiazole‐based polymers containing a carbazole–vinylene or fluorene–vinylene group and their hole‐injection/transport behavior in light‐emitting diodes

A series of conjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenyl)‐1,3,4‐oxadiazole]}) and nonconjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) and poly{9,9‐dihexyl‐2,7‐fluorene–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) polymers containing oxadiazole and carbazole or fluorene moieties in the polymer backbone were synthesized with a multiple‐step procedure. The properties of the polymers, including the photophysical and electrochemical characteristics, could be fine‐tuned by adjustment of the components or structures in the polymer chains. The polymers were used to examine the hole‐injection/transport behavior as hole‐injection/hole‐transport layers in double‐layer indium tin oxide (ITO)/polymer/aluminum tris(8‐hydroxyquinoline)/LiF/Al devices by the determination of their energy levels. The effects of the polymers in these devices on the charge‐transport behavior were compared with a control device fabricated with poly(ethylenedioxythiophene) (PEDOT)–poly(styrene sulfonate) (PSS). Devices containing the synthesized polymers showed comparable adhesion to the ITO anode and good hole‐injection/transport performance. In addition, they exhibited higher electroluminescence over an identical range of current densities than the control device. This was attributed to the prevention of radiative exciton quenching caused by the PEDOT–PSS interfaces and the improvement of electron/exciton blocking due to the higher electron affinity of the synthesized polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Organometallic synthesis of n‐type π‐conjugated polymers with dopant cation trapping sites and stability of n‐doping state against air

n‐Type π‐conjugated polymers comprising a 1,2,4‐triazole ring substituted by a benzo‐15‐crown 5‐ether (benzo15C5) subunit at the 4‐position of the 1,2,4‐triazole ring and n‐type aromatic rings such as pyridine‐2,5‐diyl and 2,1,3‐benzothiadiazole‐4,7‐diyl rings were synthesized by organometallic polycondensation. The UV‐visible spectra of the polymers exhibited absorption maxima (λ_max values) at a longer wavelength than that exhibited by 3,5‐bis(2‐bromopyridyl)‐4‐benzo15C5‐1,2,4‐triazole, revealing that their π‐conjugation system was expanded along the polymer chain. The polymers with the benzo15C5 subunit underwent an electrochemical reduction (n‐doping), and the corresponding oxidation (n‐dedoping) occurred at an unusually high potential in an acetonitrile solution of NaClO₄; the factor responsible for the unusually high oxidation potential was the stabilized n‐doping state that was attributed to the inclusion of Na⁺ in the 15C5 ring. The polymers with the benzo15C5 subunit exhibited a considerably higher stability of the n‐doping state in air than did those without this subunit. Copyright © 2012 Society of Chemical Industry     

Peripheral carbazole or cyano substitutents in poly (aryl ether) based bipolar polymeric hosts: Increase the hole or electron injection properties for blue phosphorescent polymer light emitting diodes

A series of poly (aryl ether) based bipolar polymer hosts, PCzOPOC8, PCzOPOCz, and PCzOPOCN with a peripheral carbazole or cyano unit which joins the main chain by a nonconjugated linker of a hexyl group, were synthesized and characterized. They depicted high triplet level (E_T) (>2.80 eV), which was probably attributed to oxygen-interrupted nonconjugated main chains of polymers as well as carbazole and phosphine oxide groups with high E_T. While doped with a 10 wt% typical blue phosphor {iridium(III)[bis(4,6-difluoro phenyl)pyridinato-N, C2]picolinate, FIrpic)}, compared with those of nonsubstituted PCzOPOC8 and peripheral cyano-substituted PCzOPOCN, PCzOPOCz with carbazole moiety gave better performances due to balance of carrier flux from carbazole moiety with good hole transport ability.     

Carbazoles on same main chain for polymer solar cells

Planar conjugated 2,7‐linked carbazole blocks: Q1(2,7‐dibromo‐9‐octyl‐9H‐carbazole); Q2(7,7′‐dibromo‐9,9′‐dioctyl‐9H,9′H‐2,2′‐bicarbazole); Q3 (7‐bromo‐7′‐(7‐bromo‐9‐octyl‐9H‐carbazol‐2‐yl)‐9,9′‐dioctyl‐9H,9′H‐2,2′‐bicarbazole) were coupled with same acceptor (4,7‐di[2,5‐thiophene]‐5,6‐dioctyloxy‐2,1,3‐Benzothiadiazole) to prepare polymers HXS‐1, 2, 3 (Scheme 1 ). Bulk‐heterojunction polymer solar cells (BHJ PSCs) with these polymers were made. Power conversion efficiency of HXS‐1 was proved to be over 5.4%. It declined dramatically to 0.43% and 0.23% for HXS‐2 and 3 respectively. Their absorption and X‐ray diffraction pattern show the torsion angle in main chain increased when more carbazole units were added. More carbazoles will make polycondensation reaction more difficult to get high molecular weight polymers. The torsion angle was calculated using a semiempirical molecular orbital method. All the results pointed out that the coplanarity in the conjugated backbone was destroyed. Electron delocalization was disturbed because p‐orbital overlapping only occurs effectively in the parallel orbit so charge cannot move a longer distance. This study offers a useful and important insight to designing polymers for high performance PSCs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Optical properties of block copolymers containing pendant carbazole groups and in situ synthesized CdS nanoclusters

Ultraviolet–visible absorption spectra and photoluminescence spectra were used to demonstrate efficient charge‐carrier migration in a novel bulk heterogeneous block copolymer system. One moiety of the block copolymer was functionalized with charge‐transporting carbazole groups, whereas the other block formed domains suitable for the in situ synthesis of CdS nanoclusters. The excitation of the cluster‐free copolymers with 350‐nm‐wavelength radiation led to a strong emission peak at 450 nm that was associated with the carbazole groups. When CdS clusters were present in nearby but spatially distinct domains, the carbazole emission was completely quenched and replaced by a very broad emission in the visible range (near 560 nm). The implications of these observations are discussed in the context of the energy‐transfer mechanism and possible device applications. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 177–182, 2003     

Synthesis and characterization of electrically conducting copolymer of aniline and o‐bromoaniline using methane sulfonic acid as dopant

Polyaniline (PAN), poly(o‐bromoaniline) (POBA), and poly(aniline‐co‐o‐bromoaniline) (PABA) were synthesized by oxidative coupling. These polymers are protonated by 10–20% methane sulfonic acid (MSA) and 1M HCl. The new polymer bases have greater solubility than that of PAN in common polar organic solvents; PAN–MSA was observed to be the most thermally stable of these polymers. POBA is associated with residual quinoid diimine units as illustrated in the IR and UV‐vis spectra, after reduction with hydrazine dihydrochloride. Both the doping agents cause a downward shift of the quinoid absorption in the IR spectra. MSA‐ and HCl‐doped PAN and PABA polymers exhibit a coil‐like conformation in DMSO, whereas only MSA‐doped PAN and PABA show an “expanded coil‐like” conformation in m‐cresol with a “free carrier tail” above 800 nm in their electronic spectra. XPS spectra indicated the presence of covalent bromine in the POBA and PABA polymers. Bromine retention was greater in the homopolymer as evidenced by the IR studies after aging at 350°C. Compared to HCl, MSA is found to be a more effective dopant, enhancing the conductivity of the copolymers by 10²–10³ times in magnitude. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2662–2669, 2002     

XPS and ESR studies of electrochemically synthesized polycarbazole post‐doped with iodine

Polycarbazole powders obtained by electrochemical oxidation of carbazole thin films or of carbazole in solution in the electrolyte have been post‐doped with iodine and characterized by room temperature electrical conductivity, X‐ray photoelectron spectroscopy (XPS), and electron spin resonance (ESR). Similar results are obtained with polymers saturated with iodine at room temperature after 6 weeks and with polymers doped at 383 K for 24 h. The polymers obtained from carbazole thin films have a higher electrical conductivity (ς ∼ 10⁻⁴ Ω⁻¹ cm⁻¹) and a higher spin density (9.9 10²¹ spins mol⁻¹ g⁻¹), which corresponds to 71 atom % of ionic iodine. The polymer radicals are located on the nitrogen, and the percentage of N⁺ is 40 atom %. The electrical conductivity of the polymers obtained from carbazole in solution in the electrolyte is two order of magnitude smaller. The percentage of N⁺ is only 25 atom % with an ionic iodine percentage of 13 atom %. So, the most important parameter is not the iodine percentage introduced after doping into the polymers but the percentage of ionic iodine present in the polymers. The differences that are put in evidence can be explained by a better polymerization efficiency of the carbazole when it is deposited on thin film form by vacuum evaporation before electrochemical oxydation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 115–124, 1999     

含咔唑基聚合物的合成、发光性能及应用

采用封管聚合法合成了3种含咔唑基聚合物——聚乙烯基咔唑(PVK)、聚2-(9-咔唑基)乙基甲基丙烯酸酯(PCEM)和聚N-〔3-(9-乙基咔唑基)〕甲基丙烯酰胺(PECMA),考察了其紫外光谱和荧光光谱,探讨了取代基对咔唑基团发光性能的影响。结果表明,单体CEM和ECMA表现出明显的结构自猝灭效应(SSQE),而相应的聚合物未见SSQE。单体乙烯基咔唑(NVK)、CEM的荧光最大发射波长分别为440、435 nm,相对于咔唑(418nm)有明显的红移,ECMA则蓝移(410 nm),而相应的聚合物红移或蓝移都不明显。将聚合物作为空穴传输材料,通过共聚引入8-羟基喹啉铝高分子后,8-羟基喹啉铝高分子发光材料的电致发光起亮电压由14 V下降至9V,发光效率提高了3~4倍。     

Radical annihilation of γ‐ray‐irradiated contact lens blanks made of a 2‐hydroxyethyl methacrylate copolymer at elevated temperatures

The annihilation of the radicals in irradiated 2‐hydroxyethyl methacrylate copolymer was analyzed by the use of electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra were deconvoluted into three radicals: a quartet (Ra), a triplet (Rb), and a broad singlet (Rc). Radical Ra was attributed to coupling with a methyl radical and/or a doublet or triplet with about the same hyperfine coupling due to a methylene radical. Radical Rb was due to a methylene radical produced by main‐chain scission. Radical Rc was attributed to various free radicals without coupling to protons. By comparing the EPR spectra of radicals Ra, Rb, and Rc with the spectrum of a 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) standard with a known spin number, we calculated the spin numbers of the radicals, which decreased with time in the temperature range 25–45°C, regardless of the irradiation dose. The annealing of Ra and Rb and the annealing of Rc at longer times followed second‐order kinetics; these were different from the kinetics for the color formation and defect‐controlled hardening of polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of soluble poly(arylene ether ketone)s with high glass transition temperature based on 3,6‐bi(4‐fluorobenzoyl)‐N‐alkylcarbazole

3,6‐bi(4‐fluorobenzoyl)‐N‐methylcarbazole and 3,6‐bi(4‐fluorobenzoyl)‐N‐ethylcarbazole were synthesized and used to prepare poly(arylene ether ketone)s (PAEKs) with high glass transition temperatures (T_g) and good solubility. High molecular weight amorphous PAEKs were prepared from these two difluoroketones with hydroquinone, phenolphthalein, 9,9‐bis(4‐hydroxyphenyl)fluorene and 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, respectively. All these polymers presented high thermal stability with glass transition temperatures being in the range 239–303 °C and a 5% thermal weight loss temperature above 460 °C. Compared with the T_g of phenolphthalein‐based PAEK (PEK‐C), fluorene‐based PAEK (BFEK) and phthalazinone‐based PAEK (DPEK) not containing a carbazole unit, these polymers presented a 30–50 °C increase in T_g. Meanwhile, PAEKs prepared from N‐ethylcarbazole difluoroketone showed good solubility in ordinary organic solvents, and all polymers exhibited excellent resistance to hydrochloric acid (36.5 wt%) and sodium hydroxide (50 wt%) solutions. In particular, phthalazinone‐based PAEK bearing N‐ethylcarbazole afforded simultaneously a T_g of 301 °C with good solubility. Tensile tests of films showed that these polymers have desirable mechanical properties. The carbazole‐based difluoroketones play an important role in preparing soluble PAEKs with high T_g by coordinating the relationship between chain rigidity resulting from the carbazole unit and chain distance from the side alkyl. © 2014 Society of Chemical Industry     

Studies on the synthesis and optical properties of novel blue light‐emitting polymers containing phosphorus and oxadiazole structures

Novel phosphorus‐containing polymers with high‐electron‐affinity oxadiazole were synthesized and characterized by thermal analysis and spectroscopy (infrared, ultraviolet‐visible, photoluminescence, cyclic voltammetry) measurements. These new polymers can be used as blue electroluminescent materials and as electron‐transport layers in polymer light‐emitting diodes. In this study, aromatic polyethers containing electron‐transporting chromophores and emission chromophores were synthesized from 2,5‐bis‐(4‐fluoroaryl)‐1,3,4‐oxadiazole and 2‐(6‐oxido‐6H‐dibenz<c,e><1,2> oxaphosphorin‐6‐yl)‐1,4‐naphthalenediol (DOPO‐NBQ). The effects of reaction temperature and time on the formation of polyethers were investigated to obtain optimum conditions for polyether manufacturing. All the resulting polymers were thermally stable at <460 °C. The absorption peaks of these polymers were at 350–365 nm, whereas the photoluminescent peaks were at 460–481 nm. But, the intensity of polymer absorption decreased and a blue shift was observed in the photoluminescent spectra as the temperature increased. In addition, these polymers containing the electron‐transporting oxadiazole indeed showed extra reduction potentials in cyclic voltammetry measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2367–2376, 2002     

Synthesis and optical properties of π-conjugated polymers composed of diester-substituted bithiophene and dibenzothiophene or carbazole

Novel π-conjugated polymers composed of diester-subsituted bithiophene and dibenzothiophene (PDBT-DEBT) or N-alkyl carbazole (PCz-DEBT) were prepared via the Stille cross-coupling polymerization using Pd(0) catalyst. The structures of obtained polymers were confirmed by ¹H NMR and IR spectroscopies. Optical properties of the polymers were investigated by UV–vis and photoluminescence spectroscopies. The photoluminescence spectra of the polymers showed strong emission peaks in the green region.     

Synthesis of isoelectronic polyazomethine and poly(arylene vinylene) by a palladium‐catalyzed Suzuki coupling method

Two fully conjugated copolymers containing 2,7‐(9,9‐dioctyl) fluorene and 3,6‐(N‐hexyl‐9H‐carbazole) disubstituted rings and arylene vinylene or azomethine units in the main chain were synthesized through a palladium‐catalyzed Suzuki coupling method of 2,7‐bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)‐9,9‐dioctyl fluorene with 1,4‐bis(6‐bromo‐N‐hexyl‐9H‐carbazole‐3‐yl vinyl) benzene or N,N‐bis(6‐bromo‐N‐hexyl‐9H‐carbazole‐3‐yl methylidene) 1,4‐phenylenediamine. Bisbromine arylene vinylene and arylenazomethine monomers were synthesized by condensation of 3‐formyl‐N‐hexyl‐6‐bromo carbazole with tetraethyl‐p‐xylylene diphosphonate or 1,4‐phenylenediamine. Copolymers were characterized by FTIR, ¹H‐NMR, DSC, UV‐visible and photoluminescence methods. Copyright © 2005 Society of Chemical Industry     

Synthesis and properties of photoluminescent copolymer containing 1,3,4‐oxadiazole and carbazole rings

The luminescent copolymer 2‐phenyl‐5‐[3′‐(methacrylamido)phenyl]‐1,3,4‐oxadiazole and vinylcarbazole (PMAPO–VCZ), combining hole‐facilitating moiety, carbazole ring, and electron‐facilitating moiety, 1,3,4‐oxadiazole, as side groups, was synthesized by a radical polymerization of the olefinic monomer PMAPO and VCZ. For comparison, the homopolymer P‐PMAPO was also synthesized by similar procedures. The solubility, thermal, and optical properties of the copolymers were investigated. The synthesized copolymer was soluble in common organic solvents but the homopolymer of PMAPO was dissolved only by hot THF. Thermogravimetric analysis and differential scanning calorimetry measurements showed that the copolymer and homopolymer exhibit good thermal stability up to 360 and 340°C with glass‐transition temperatures higher than 105 and 65°C, respectively. The photoluminescence properties were investigated. The results showed that the copolymer emits blue and blue‐green light and the emission spectra of monomer and polymers exhibit obvious solvent effect. With the increase of polarity of solvents, the fluorescence spectra distinctly change, appearing with a red shift at room temperature. The concentration‐dependent emission spectra change significantly with the increase of concentration. In addition, when N,N‐dimethylaniline (DMA) was gradually added to the solution of copolymers, the emission intensity of fluorescence was dramatically increased. However, when the concentration of DMA was increased beyond a certain level, the emission intensity of fluorescence gradually decreased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2777–2783, 2004     

Synthesis and characterization of nylon 6/polyalkylaniline conducting composites

Conducting composite films of polyalkylanilines with nylon 6 as the insulating matrix were electrochemically synthesized and characterized. The electrochemical properties of the alkylanilines and their composites were investigated with a cyclic voltammetry technique. The magnetic properties of the polymers and composites were analyzed, and their conducting mechanisms were found to be of bipolaron nature. With Fourier transform infrared spectra, it was clarified that polymerization occurred via the ? NH₂ group in a head‐to‐tail mechanism. Through thermogravimetric analyses, the thermal properties of the polymers and their composites were elucidated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1693–1701, 2003     

“Living”/controlled polymerization of methyl acrylate mediated by dithiocarbamates under γ‐ray irradiation

γ‐Ray initiated reversible addition–fragmentation chain transfer (RAFT) polymerizations of methyl acrylate (MA) were investigated in bulk using five different dithiocarbamate structures, 2‐phenyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1b ), 2‐methyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1c ), 2‐pheny‐indole‐1‐cardithioic acid benzyl ester ( 1d ), 2‐(carbazole‐9‐carbothioylsulfanyl)‐2‐methyl‐propionic acid ester ( 1e ), and carbazole‐9‐carbodithioic acid naphthalene‐1‐ylmethyl ester ( 1f ), as RAFT agents. The experiment results showed that MA polymerized in a controlled way under a low irradiation dose rate, i.e., first‐order kinetic plots, the experimental molecular weights increased linearly with monomer conversions. The polydispersity indices of polymers generally remained at a relatively low value (lower than 1.4). The effect of irradiation dose on the polymerization results was investigated. The obtained polymers were characterized with ¹H NMR and GPC. Chain‐extension reaction was also successfully carried out using the obtained polymer as the macro‐RAFT agent and styrene as the second monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1769–1775, 2007     

Synthesis and study of new polyamides with side oxadiazole rings

A series of six new aromatic polyamides with side oxadiazole rings has been synthesized by polycondensation reaction of aromatic diamines containing pendent substituted oxadiazole groups with a silicon‐containing diacid chloride [namely, bis(p‐chlorocarbonyl‐phenylene)diphenylsilane] or with a fluorine‐containing diacid chloride [namely, hexafluoroisopropylidene‐bis(p‐benzoyl chloride)]. All polymers were easily soluble in amidic solvents, such as N‐methylpyrrolidinone and dimethylformamide, and gave thin transparent films by casting such solutions. Very thin coatings were deposited onto silicon wafers and exhibited smooth, pinhole‐free surfaces in atomic force microscopy investigations. The polymers showed high thermal stability, with decomposition temperature >400°C. Some of them did exhibit a glass transition, in the range 152–276°C, with a reasonable interval between glass transition and decomposition. Four of these polymers showed blue photoluminescence, in the range 460–480 nm, which makes them promising candidates for future use as high‐performance materials in the construction of light‐emitting devices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 714–721, 2003     

Polycarbazole obtained by electrochemical polymerization of monomers either in solution or in thin film form

Polycarbazole has been synthesized by electrochemistry. The carbazole monomer source consists either in carbazole in solution in the electrolyte or in carbazole deposited in thin film form onto the working electrode. The two families of polymers have been studied by infrared absorption, X‐ray diffraction, thermal gravimetric analysis, scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy, electron spin resonance, and electrical conductivity measurements. It is shown that the polycarbazole films obtained with carbazole deposited in the thin film form exhibit a better polymerization efficiency and an electrical conductivity one order of magnitude higher. This result is in good accordance with a higher spin density and homogeneity. It is proposed that not only are some monomers activated during the evaporation but also that the physical contact between the working electrode and the continuous carbazole films induces the growth of homogenous highly polymerized polycarbazole films. In agreement with this suggestion, the SEM study shows that this type of polycarbazole thin films keep in memory the morphology of the SnO₂ under layer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1561–1568, 2000