New tetraphenylethylene-containing conjugated polymers: Facile synthesis,aggregation-induced emission enhanced characteristics and application as explosive chemsensors and PLEDs

In this paper, tetraphenylethylene (TPE) units, one of the typical aggregation-induced emission (AIE) moieties, are utilized to construct a new functional polyfluorene (PF) P1, which exhibited the exciting property of the aggregation-induced emission enhancement (AIEE), instead of the aggregation-caused quenching (ACQ) of normal PFs, and could probe the explosive with high sensitivity both in the nanoparticles and solid state. Three other TPE-containing polymers, P2–P4, were also successfully prepared, and demonstrated good performance as explosive chemosensors and light-emitting materials. P3, bearing carbazole as hole-transporting units showed the best performance with a maximum luminance efficiency of 1.17 cd/A and a maximum brightness of 3609 cd/m² at 12.9 V in its light-emitting diode device.     

Syntheses and properties of electroluminescent polyfluorene-based conjugated polymers, containing oxadiazole and carbazole units as pendants, for LEDs

New polyfluorenes (PF)-based conjugated copolymers, containing oxadiazole and carbazole units as pendants, were prepared as the electroluminescent (EL) layer in light-emitting diodes (LEDs) to show that most of them have higher maximum brightness and EL efficiency as compared to poly(2,7-(9,9-bis(2-ethylhexyl)fluorene)) (PF2/6). The prepared polymers, poly[(9-(6-(N-carbazolyl)-hexyl)-9-hexyl)-fluorene-2,7-diyl]-co-[(9-hexyl-9-(6-(4-(5-phenyl-1,3,4-oxadiazolyl)-phenoxy)-hexyl)-fluorene-2,7-diyl)] (Oxd-PF-co-Cz-PF), were soluble in common organic solvents and used as the EL layer in double layer light-emitting diodes (LEDs) (ITO/PEDOT/polymer/Al). All polymers show photoluminescence around λ_max=430 nm (exciting wavelength, 370 nm) and blue EL around λ_max=426 nm. The current–voltage–luminance (I–V–L) characteristics of the polymers show turn-on voltages of 3.5–5.5 V which are lower than that of PF2/6. The maximum brightness and EL efficiency of the device with the configuration of ITO/PEDOT/polymer/Al were 3000 cd/m² at 10 V and 2.13 cd/A at 10.6 mA/cm², respectively, which are all higher than those of PF2/6.     

Largely enhanced LED efficiency of carbazole-fluorene-silole copolymers by using TPBI hole blocking layer

A new series of soluble 3,6-carbazole-fluorene-silole copolymers (PCz-F-S) with M_w up to 52.1 kDa were synthesized by Suzuki coupling reactions. Chemical structures and optoelectronic properties of the copolymers were characterized by elemental analysis, NMR, UV absorption, cyclic voltammetry, photoluminescence (PL), and electroluminescence (EL) spectra. The main absorption peaks of solutions and films of the copolymers are at 354 nm and 347 nm, respectively, showing the combined contribution from the 3,6-carbazole and fluorene blocks. The silole absorption is at wavelength range between 400 nm and 500 nm. Compared with the solution absorption, largely decreased relative absorption of the silole to the 3,6-carbazole and fluorene blocks can be found for the films of the copolymers. The copolymers possess HOMO levels of around −5.36 eV, mainly from the contribution of 3,6-carbazole. Under excitation, the films of the copolymers show silole-dominated green emissions because of PL excitation energy transfer, with high absolute PL quantum yields up to 86%. EL devices with a configuration of ITO/PEDOT/PCz-F-S/Ba/Al only display a maximum external quantum efficiency of 0.48% whereas a device configuration of ITO/PEDOT/PCz-F-S/TPBI/Ba/Al with TPBI hole blocking layer greatly boosts the efficiency to 3.03% for a practical brightness of 236 cd/m². The improved EL efficiency suggests that more balanced charge injection and transport can be realized by inserting the TPBI hole blocking layer.     

Synthesis,electroluminescence, and photovoltaic cells of new vinylene‐copolymers with 4‐(anthracene‐10‐yl)‐2,6‐diphenylpyridine segments

Three new soluble vinylene‐copolymers F , C, and P that contain 4‐(anthracene‐10‐yl)‐2,6‐diphenylpyridine as common segment and fluorene, carbazole, or phenylene, respectively, as alternating segment were prepared by Heck coupling. The glass transition temperature was high for F and C (110 and 117°C), whereas was lower than 25°C for P . The polymers were stable up to ～ 300°C. They emitted blue–green light with maximum located at wavelength of 456–550 nm, which was of the order F < C < P . The photoluminescence quantum efficiency in THF solution was ～ 30% for F and P and only 5% for C . All three copolymers were used as active layers for polymer light emitting diodes (PLEDs) and organic photovoltaic cells. The double PLEDs with configuration of indium‐tin oxide (ITO)/poly(ethylenedioxythiophene (PEDOT) : poly(styrenesulfonate)(PSS)/Copolymer F , C , or P /TPBI(1,3,5‐tris(2‐N‐phenylbenzimidazolyl)benzene)/Ca/Al were fabricated. Copolymer P emitted green light with maximum brightness of 28 cd/m² and a current yield of 0.85 cd/A. Organic photovoltaics with the configuration of ITO/PEDOT : PSS/Copolymer and [6,6]‐phenyl‐C61‐butyric acid methyl ester blend (1 : 1) /Ca/Al were also fabricated. Copolymer P showed the highest power conversion efficiency of 0.034%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Metallo-homopolymer and metallo-copolymers containing light-emitting poly(fluorene/ethynylene/(terpyridyl)zinc(II)) backbones and 1,3,4-oxadiazole (OXD) pendants

A series of novel metallo-polymers containing light-emitting poly(fluorene/ethynylene/(terpyridyl)zinc(II)) backbones and electron-transporting 1,3,4-oxadiazole (OXD) pendants (attached to the C-9 position of fluorene by long alkyl spacers) were synthesized by self-assembled reactions. The integrated ratios of ¹H NMR spectra reveal a facile result to distinguish the well-defined main-chain metallo-polymeric structures which were constructed by different monomer ligand systems (i.e. single, double, and triple monomer ligands with various pendants). Furthermore, UV-vis and photoluminescence (PL) spectral titration experiments were carried out to verify the metallo-polymeric structures by varying the molar ratios of zinc(II) ions to monomers. As a result, the enhancement of thermal stability (T_d) and quantum yields were introduced by the metallo-polymerization, and their physical properties were mainly affected by the nature of the pendants. The photophysical properties of these metallo-polymers exhibited blue PL emissions (around 418 nm) with quantum yields of 34-53% (in DMF). In contrast to metallo-polymers containing alkyl pendants, the quantum yields were greatly enhanced by introducing 1,3,4-OXD pendants but reduced by carbazole (CAZ) pendants. Moreover, electroluminescent (EL) devices with these light-emitting metallo-polymers as emitters showed green EL emissions (around 550 nm) with turn-on voltages of 6.0-6.5 V, maximum efficiencies of 1.05-1.35 cd A⁻¹ (at 100 mA/cm⁻²), and maximum luminances of 2313-3550 cd/m² (around 15 V), respectively.     

Phosphorescent,green-emitting Ir(III) complexes with carbazolyl-substituted 2-phenylpyridine ligands: Effect of binding mode of the carbazole group on photoluminescence and electrophosphorescence

The ligands, 9-((6-phenylpyridin-3-yl)methyl)-9H-carbazole and 9-(4-(pyridin-2-yl)benzyl)-9H-carbazole were synthesized by attaching a carbazolyl group to the pyridine and phenyl rings of 2-phenylpyridine, respectively. Ir(III) complexes were prepared by a simple procedure and the solubility of the novel complexes was significantly better than that of the conventional, green-emitting conventional fac-tris(2-phenylpyridinato-C²,N)iridium(III). The Ir(III) complexes were used to prepare electrophosphorescent polymer light-emitting devices. The device comprising 10% of fac-tris(2-(4′-((9H-carbazol-9-yl)methyl)phenyl)pyridinato-C²,N)iridium(III) exhibited an external quantum efficiency of 7.88%, luminous efficiency of 23.01 cd/A, and maximum brightness of 32,640 cd/m². The color of the emissions of fac-tris(2-(4′-((9H-carbazol-9-yl)methyl)phenyl)pyridinato-C²,N)iridium(III) was similar to that of conventional fac-tris(2-phenylpyridinato-C²,N)iridium(III). This work shows that integration of a rigid hole-transporting carbazole and phosphorescent complex in one molecule provides a new route to highly efficient, solution-processable complexes for electrophosphorescent applications.     

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 photovoltaic properties of D-π-A copolymers based on thieno[3,2-b]thiophene bridge unit

Three D-π-A copolymers containing thieno[3,2-b]thiophene (TT) bridge and BDT, carbazole, fluorene as D units and benzothiadiazole as A unit were synthesized and characterized. These copolymers of PBDT-tt-BT, PC-tt-BT and PF-tt-BT exhibited enough high thermal stabilites and good solubilites in chloroform and dichlorobenzene. Among the copolymers, with the increase of the electron-donating abilities of the D units from fluorene to carbazole further to BDT, the absorption spectra of PF-tt-BT shows blue shift and that of PBDT-tt-BT shows red shift comparing to that of PC-tt-BT in their solutions and films. Meanwhile, by electrochemical cyclic voltammetry measurements we found the HOMO levels vary in the same trench according to their electron-donating abilities. Under the illumination of AM 1.5G, 100 mW/cm², power conversion efficiency (PCE) of the PSCs based on these copolymers as donors and PC₇₀BM as acceptor were measured and PBDT-tt-BT shows a higher efficiency of 4.91% than PC-tt-BT and PF-tt-BT based devices mostly due to its higher hole mobility and broader absorption range. These results indicate that PBDT-tt-BT is a promising photovoltaic polymer donor material for efficient PSCs.     

Deep blue light-emitting polymers with fluorinated backbone for enhanced color purity and efficiency

Two fluorene-based copolymers (PF-33F and PF-50F) with p-difluorophenylene units in the backbone were synthesized. In comparison with the reference poly(9,9-dioctylfluorene) (PFO), the introduction of p-difluorophenylene units not only increased the fluorescent quantum yields, but also improved the spectra purity and stability of these deep blue emitting copolymers. The famous green emission band at 520 nm from fluorenone defects was never detected for these copolymers even after they were thermal annealed in air at 150 °C. Organic light-emitting diodes were fabricated using them as emitting layer and pure blue electroluminescence was obtained. It was observed that PF-33F based device exhibited much higher current density and brightness than PF-50F and PFO devices. A maximum external quantum efficiency of 1.14% (1.14 cd A^?1) and the CIE (0.16, 0.13) were achieved for PF-33F device, which are among the best performance for polyfluorenes reported so far.     

D-A-based polyfluorene derivatives end-capped with cyclometalated iridium complexes by unconjugated linkage: Structure-property relationships

A series of donor(D)-acceptor(A)-based polyfluorene derivatives, which contain carrier-transporting units of carbazole and oxadiazole as the substitutes of the C-9 position of ?uorene and are end-capped with the red-emitting iridium bi(phenylisoquilonato)(picolinato) unit by unconjugated linkage, were synthesized and characterized. The molar ratios between the donor of carbazole and the acceptor of oxadiazole moieties were found to significantly influence photoluminescent efficiency, electrochemical and electroluminescent properties of these D-A-based polyfluorene derivatives. While the ratio increased to 3:7, the PFCz3OXD7Ir showed the best device performance in the polymer light-emitting device with a configuration of ITO/PEDOT/polymers/LiF/Al. A turn-on voltage of 6.0 V, a maximum current efficiency of 0.59 cd/A and the highest luminance of 917 cd/m² were presented.     

Synthesis and light emitting properties of sulfide-containing polyfluorenes and their nanocomposites with CdSe nanocrystals: A simple process to suppress keto-defect

A new series of sulfide-containing polyfluorene homopolymers and copolymers (PFS, PF1, PF3 and PF4) comprising 9,9-di[11-(decylsulfanyl)undecyl] fluorene, 9,9-dihexylfluorene, triphenylamine or benzothiadiazole moieties were synthesized by Ni(0)-mediated Yamamoto-coupling and palladium-catalyzed Suzuki polymerizations. Three other polyfluorenes (PF2, PF5 and PFC6) without sulfur atom in the alkyl side chains were also synthesized by a similar method for comparison purpose. These fluorene-based polymers were characterized using FT-IR spectroscopy, elemental analysis, DSC, TGA, photoluminescence (PL) and electroluminescence (EL) spectroscopies. The synthesized polymers PFS and PF1–PF3 emit blue light at around 440–468 nm, while copolymers PF4 and PF5 emit green light at around 540 nm. In annealing experiments, these polymer films show better stability against thermal oxidation than polymer PFC6. Sulfide-containing polymers show not only good electroluminescent color stability, but their EL spectra also remain unchanged at high driving voltage. A multi-layer electroluminescent device with the configuration of ITO/PEDOT/PF1/CsF/Al exhibited a stable sky-blue emission with color coordinates (0.21, 0.23) at 10 V, which showed a maximum brightness of 2991 cd/m² at 8 V (75 mA/cm²) and a maximum efficiency of 1.36 cd/A. Finally, by ligand exchange process, the sulfur element could form coordination bonding with quantum dots, and PLED devices using these new QDs-containing organic/inorganic hybrid materials as light-emitting layers exhibit superior or comparable EL performance compared to those without quantum dots.     

White organic light-emitting diodes using a quantum dot as a color changing material

White organic light-emitting diodes (WOLEDs) were fabricated by using a blue emitting layer combined with quantum dot (QD) based color converting materials. Orange emitting QD was used as a color converting material and effective color conversion was realized. A white color coordinate of (0.32, 0.41) was obtained with a current efficiency of 8.3 cd/A at 1000 cd/m².     

Functional derivatives of (bi)phenyl-substituted carbazoles as building blocks for electro-active polymers

(Bi)phenyl-substituted carbazoles containing reactive functional groups were synthesized by the multi-step synthetic rout. The monomers were examined by various techniques including thermogravimetry, differential scanning calorimetry, UV and fluorescence spectrometry as well as electron photoemission technique. These derivatives were also tested as hole transporting materials in bilayer OLEDs with Alq₃ as the emitter. The devices exhibited promising overall performance with a turn-on voltage of ～3 V, a maximal photometric efficiency of 5.1 cd/A and maximum brightness of 12,200–15,600 cd/m².     

Novel yellow phosphorescent iridium complexes containing a carbazole–oxadiazole unit used in polymeric light-emitting diodes

Yellow iridium complexes Ir(PPOHC)₃ and (PPOHC)₂Ir(acac) (PPOHC: 3-(5-(4-(pyridin-2-yl)phenyl)-1,3,4-oxadiazol-2-yl)-9-hexyl-9H-carbazole) were synthesized and characterized. The Ir(PPOHC)₃ complex has good thermal stability with 5% weight-reduction occurring at 370 °C and a glass-transition temperature of 201 °C. A polymeric light-emitting diode using the Ir(PPOHC)₃ complex as a phosphorescent dopant showed a luminance efficiency of 16.4 cd/A and the maximum external quantum efficiency of 6.6% with CIE coordinates of (0.50, 0.49). A white polymeric light-emitting diode was fabricated using Ir(PPOHC)₃ which showed a luminance efficiency of 15.3 cd/A, with CIE coordinates of (0.39, 0.44). These results indicate that the iridium complexes containing a linked carbazole–oxadiazole unit are promising candidates in high-efficiency electroluminescent devices.     

Color stability and suppressed efficiency roll-off in white organic light-emitting diodes through management of interlayer and host properties

Color stability and efficiency roll-off of white light-emitting diodes (WOLEDs) with blue fluorescent and red phosphorescent emitting materials were manipulated by controlling the charge transport properties of interlayer and triplet host materials. A pure white emission was observed in WOLEDs with a bipolar interlayer and a hole transport type triplet host material. A white color coordinate of (0.31, 0.35) and a current efficiency of 14.4 cd/A were obtained. In addition, color index of WOLEDs could be kept stable up to a high luminance of 10,000 cd/m² and an efficiency roll-off was also suppressed.     

Alternating-current white a-C:H thin-film light-emitting diodes with composition-graded carrier injection layers

The optoelectronic characteristics of hydrogenated intrinsic amorphous carbon (i-a-C:H) alternating-current white thin-film light-emitting diodes (ACW-TFLEDs) with composition-graded (CG) hydrogenated intrinsic amorphous silicon carbide (i-a-SiC:H, CG C) layers had been obviously improved with additionally incorporated CG hydrogenated intrinsic amorphous silicon germanium (i-a-SiGe:H, CG Ge) carrier injection layers. For an ACW-TFLED with CG Ge carrier injection layers, the electroluminescence (EL) threshold voltage and brightness were improved from 9 V 344 cd/m² of a CG C one to 7.5 V, 1000 cd/m² under direct-current forward bias, and from 9 V, 200 cd/m² of a CG C one to 7.8 V, 560 cd/m² under direct-current reverse bias, respectively, at an injection current density of 300 mA/cm² for brightness measurement. The enhancement of EL performance with CG Ge carrier injection layers was due to the increased carrier injection efficiency and reduced contact resistance resulting from the lower barrier and partially formed polycrystalline Ge layer between the Al (electrode)/Ge interface. Moreover, the EL intensity of an obtained ACW-TFLED increased with the frequency up to 20 kHz and then decreased rapidly and became very weak as the frequency was increased to about 100 kHz. This frequency-dependent EL behavior would be qualitatively explained with the mobility of charge carriers.     

Benzooxadiazole-based donor/acceptor copolymers imparting bulk-heterojunction solar cells with high open-circuit voltages

In this study we used Suzuki cross-coupling to synthesize three new donor/acceptor copolymers—PFTBO, PAFTBO, and PCTBO—featuring soluble alkoxy-modified 2,1,3-benzooxadiazole (BO) moieties as acceptor units and electron-rich building blocks—dialkyl fluorene (F), alkylidene fluorene (AF), and carbazole (C), respectively—as donor units. These polymers, which we characterized using gel permeation chromatography, thermogravimetric analysis, NMR spectroscopy, UV–Vis absorption spectroscopy, and electrochemical cyclic voltammetry, exhibited good solubility, low-lying energy levels for their highest occupied molecular orbitals, excellent thermal stability, and air stability. Using these polymers, we fabricated bulk-heterojunction solar cell devices having the structure indium tin oxide/poly(3,4-ethylenedioxythiophene):polystyrenesulfonate/polymer:[6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM) (1:1, w/w)/Ca/Al. Under AM 1.5G illumination (100 mW cm^?2), the solar cell incorporating PFTBO exhibited a high value of V_oc of 1.04 V and that based on PCTBO provided a power conversion efficiency of 4.1% without the need for any post treatment.     

Hybrid Organic Light-Emitting Diodes with Low Color-Temperature and High Efficiency for Physiologically-Friendly Night Illumination

Low color-temperature (CT) light sources are preferred for physiologically-friendly illumination at night due to their low suppression of melatonin secretion. We fabricated low-CT hybrid organic light-emitting diodes (OLEDs) by constructing a double emissive-layer (EML) structure, with a blue-red fluorescent-phosphorescent hybrid EML and a green phosphorescent EML, separated by a bipolar interlayer. By doping a red phosphor in a blue fluorescent mixed-host with a decent concentration, blue and red emissions from the host and dopant, respectively, were obtained. The CT of the optimized device was tuned to less than 2500 K, with the brightness ranging from 100 to 10,000 cd m⁻². In addition, the low-CT OLED exhibited much higher efficacy than other low-CT light sources, such as incandescent bulbs and candles. The maximum power efficiency and external quantum efficiency of the hybrid OLED reached 54.6 lm W⁻¹ and 24.3 %, respectively, which only rolled off to 44.2 lm W⁻¹ and 23.6 % at 1000 cd m⁻², with a CT of 1910 K. Low-CT OLEDs with high efficacy provide a promising alternative for night lighting that will safeguard human health.     

White Electroluminescence from a Single-Polymer System with Simultaneous Three-color Emission

A series of polymers were synthesized by incorporating low contents of fluorenone (FO) and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (DBT) into the main chain of poly(9,9-dioctylfluorene). White-light emission was obtained from a single polymer by adjusting the FO and DBT contents. All polymers showed good thermal stability with 5% weight loss up to 410 °C and good solubility in common organic solvents. Electroluminescence devices with indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)/emission layer/Ca/Al structure were found to emit white light with Commission Internationale de l’Eclairage coordinate of (0.37, 0.34). These devices exhibited a maxium brightness of 3414 cd/m² and a maximum current efficiency of 2.79 cd/A.     

Improved electroluminescence efficiency of polyfluorenes by simultaneously incorporating dibenzothiophene-S,S-dioxide unit in main chain and oxadiazole moiety in side chain

A series of efficient and spectrally stable blue light-emitting polyfluorene derivatives containing 3,7-dibenzothiophene-S,S-dioxide (SO) unit in main chain and oxadiazole (OXD) moiety in the side chain were synthesized via Suzuki copolymerization. It was realized that the glass transition temperatures of the resulted copolymers PFSO-OXD increased gradually with the content of OXD, while the UV-vis absorption, photoluminescence spectra, as well as electrochemical properties were not significantly influenced by the molar ratio of OXD unit. Apparent solvatochromism of copolymers PFSO-OXD can be realized by varying polarity of solvents from toluene to dichloromethane. Light-emitting devices based on PFSO-OXD exhibited superior performances to those of PFSO and PF-OXD20 due to the more balanced charge carrier mobility of the devices. The electroluminescence spectra of all copolymers are independent with the current densities and thermal annealing. The best device performance was achieved based on PFSO-OXD20 with a maximal luminous efficiency of 4.9 cd A⁻¹ with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.16, 0.12). The results indicated that the strategy of concurrently incorporating SO and OXD unit into the main chain and side chain of polyfluorenes, respectively has great potential to achieve efficient blue light-emitting polymers.