Synthesis and photoelectric properties of new Pr-bonded polymers by coordination of isopropyloxide and bipyridine unit

A series of novel praseodymium(Pr)-bonded polymers were successfully synthesized via the coordination reaction and palladium-catalyzed Suzuki coupling reaction of 2,7-dibromo-9,9'-dioctylfluorene and different amounts of 5,5'-dibromo-2,2'-bipyridine. The resulting polymers were characterized by ~1H-NMR and GPC. The photoluminescence(PL) and electroluminescence(EL) properties of the resulting polymers were studied to explore the effects of the Pr triisopropyloxide. The results showed that the incorporation of Pr into the polymers caused better coplanarity and effective intermolecular or intramolecular interaction, leading to the higher emission intensity at long-wavelength. Further, it was also found that the emission light color could be tuned from blue to green by introduction of a small amount of Pr into the polymer main chain. A single-layer green emitting EL device based on PF(Bipy Pr)6 with 6 mol% Pr content was fabricated. The device had a low turn-on voltage of 6 V, a brightness of 705.3 cd·m~(-2), the maximum luminous efficiency of 1.53 cd·A~(-1) and the maximum power efficiency of 0.69 lm·W~(-1).     

CARRIER PHOTOGENERATION IN POLY（N-VINYL-CARBAZOLE）-BASED PHOTOCONDUCTIVE THIN-FILM DEVICES

In this paper, photoexcitation processes in the bilayer devices based on inorganic materials and poly（N-vinylcarbazole） （PVK） were investigated. In order to clarify the roles of inorganic materials in photoconductive properties of bilayer devices, TiO2 and ZnS were chosen to combine with PVK. A model for generation of photocurrent （Iph） in single layer device of PVK was obtained. It is deduced that the recombination rate constant （Pcomb） and the ionization rate constant （y） ofexcitons should be considered as the most important factors for Iph. For inorganic materials （TiO2 or ZnS）/PVK bilayer devices, in reverse bias of-4 V, the photocurrent of 115 mA/cm^2 in the TiO2/PVK device was observed, but the photocurrent in the ZnS/PVK device was only 10 mA/cma under the illumination light of 340 nm and the light intensity of 14.2 mW/cm^2. The weaker photocurrent is attributed to the absorption of ZnS within UV region and the energy offset at the interface between PVK and ZnS, which impedes the transport of charge carriers.     

Synthesis and Luminescence Property of 4,4＇-Bis（2,2-di（4-fluorophenyl）vinyl）biphenyl for Organic Blue-Light-Emitting Diodes

The novel fluorinated distyrylarylene, 4,4＇-bis（2,2-di（4-fluorophenyl）vinyl）biphenyl （DFPVBi）, was synthesized and fully characterized. The structure was confirmed with IR, 1↑H NMR, 13↑C NMR, 19↑F NMR and MS analyses. Its electronic and photoluminescence properties were investigated by UV-Vis absorption, cyclic voltammetry and fluorescence spectroscopy. The energy levels of the highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO） are --5.77 and --2.75 eV, respectively. The electroluminescence proper- ties of the organic light-emitting diode fabricated by DFPVBi were also studied. The device exhibits a pure blue emission peaked at 454 nm, which indicates a maximum luminance of 5872 cd/m ^2 at 14.2 V and a maximum current efficiency of 2.82 cd/A at 10V, respectively.     

CHARACTERIZATION AND LUMINESCENCE PROPERTIES OF THE DYE-DOPED POLYMER LANGMUIR-BLODGETT FILMS*

1,1,4,4-Tetraphenyl-1,3-butadiene (TPB) was successfully introduced into the polymer multilayerfilms by means of Langmuir-Blodgett (LB) technique. Results of UV-VIS spectra and X-ray diffractionshowed that the uniform films had a layer structure similar to the superlattice of organic multiple quantumwells. The electroluminescence (EL) devices fabricated from the doped polymer LB films emitted blue light.Compared with the casting films, the photoluminescence (PL) and EL spectra showed that the exciton energyshifts to higher and the half-width of the emission peak becomes narrower due to exciton confinement effect.     

A novel terbium complex using oxadiazole derivative as a neutral ligand： Synthesis and properties

A novel terbium complex using 1,3,4-oxadiazole derivative as a neutral ligand was synthesized and characterized. Its thermal stability and photoluminescent properties were studied. The strong emission peaked at 546 nm with a full width at half maximum of 5 nm was observed in the pure terbium complex film under excitation of 328 nm light, which is attributed to the characteristic emission of terbium ion. The good thermal stability and intense sharp emission of this terbium complex display its potential application in electroluminescence devices.     

EMISSION CHARACTERISTICS OF ORGANIC LIGHT-EMITTING DIODES WITH A HETEROSTRUCTURE OF DYE DOPED POLY(N-VINYLCARBAZOLE)/TRIS(8-HYDROXYQUINOLINE) ALUMINUM*

Organic electroluminescent diodes with a heterostructure of 9,10-bis(phenylethnyl) anthracene(BPEA) doped poly(N-vinylcarbazole) (PVK)/tris(8-hydroxyquinoline)aluminum (Alq_3) have beenfabricated. The electroluminescence (EL) both from BPEA and Alq_3 were observed when the Alq_3 layer isthin enough. With increasing thickness of the Alq_3 layer, the relative emission intensity of BPEA is graduallydecreased. For the thin Alq_3 layer structure, the light emission of Alq_3 becomes more dominant as the appliedvoltage increases. It is proposed that the electron-hole recombination takes place in both PVK and Alq_3 films.The field-induced quenching theory has also been applied to explain the change of the EL spectra withapplied voltage.     

Green-emitting Polyfluorenes Containing Hexylthiophen-dibenzothiophene-<Emphasis Type="Italic">S</Emphasis>,<Emphasis Type="Italic">S</Emphasis>-dioxide Unit with Large Two-photon Absorption Cross Section

Green light-emitting polyfluorenes containing 3,7-bis(4-hexylthiophen-2-yl)dibenzo[b,d]thiophene 5,5-dioxide (DHTSO) unit were synthesized.All the resulted polymers show high thermal stability with the decomposition temperatures (Td) over 420 ℃ and the glass transition temperatures (Tg) over 75 ℃.The polymers exhibit the enhanced highest occupied molecular orbital (HOMO) energy levels and the depressed lowest unoccupied molecular orbital (LUMO) energy levels with the increase of DHTSO unit in polymers.The photoluminescence (PL) spectra of the polymers show positive solvatochromism in solution with the variation of solution polarities,indicating remarkable intramolecular charge transfer (ICT) effect in the polymers containing DHTSO moiety.The fluorescence quantum yields (ΦPL) are in the range of 34％-67％ for PF-DHTSOs in film.All polymers possess two photon absorption (TPA) properties,and the TPA cross sections (δ2) are enhanced with increasing DHTSO unit in polymers.The highest δ2 is 2392 GM for PF-DHTSO 15 in chloroform solution upon 740 nm excitation.The device of PF-DHTSO15 shows green emission with the Commission Intemationale de L'.Eclairage (CIE) coordinates of (0.26,0.59),and the maximum luminous efficiency (LEmax) of 10.8 cd·A-1 with the configuration of ITO/PEDOT:PSS/EL/CsF/Al.These results indicate that introducing DHTSO unit into polyfluorene backbone could be a promising molecular design strategy for TPA and effective green-light emission.     

Electroluminescence from Exciplex on the Interface Between TPD and La（PMIP）3（Bipy）

The bilayer organic light-emitting diode(OLED) with a blue fluorescent lanthanum complex, tris(1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone)-(2,2′-dipyridyl) lanthanum [La(PMIP)3(Bipy)], as a light emitting material and N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine(TPD) as a hole transporting material emits bright green light instead of blue light. The data of the absorption, the photoluminescence(PL) and the photoluminescence excitation(PLE) spectra of TPD, La(PMIP)3(Bipy) and the mixture of TPD and La(PMIP)3(Bipy)(molar ratio 1∶1) prove that the electroluminescent emission originates from the exciplex on the interface between TPD and La(PMIP)3(Bipy). By improving device configuration with tris(8-hydroxyquinoline) aluminum(ALQ) as an electron transporting material, a maximum luminance of 800 cd/m2 was obtained.     

PROBE FOR THE FORMATION RATIO BETWEEN EXCITED TRIPLETS AND SINGLETS AS GENERATED IN POLYMER LIGHT-EMITTING DIODES*

The electroluminescence (EL) produced by a highly luminescent phosphorescent dye Cu_4(C≡CPh)_4L_2 (L = 1.8-bis(di-phenylphosphino)-3, 6-dioxaoctane, Cu_4) doped polymer as emitting layer is reported. The effects o f the chargeinjection balance on the polymers, in particular, poly(N-vinylcarbazole) (PVK) have been studied by usingphotoluminescence and elecholuminescence spectroscopy. Changes in the emission spectra demonstrate the influence of thecharge injection balance on the formation ratio of triplet and singlet excitons. (This provides a new technical approach torealize the color patterning in polymer LEDs.     

Synthesis and blue light-emitting properties of 4,4＇-bis（diphenylamino）-quinque（p-phenyl）s

An excellent organic blue light-emitting diode based on 4,4＇-bis（diphenylamino）-quinque（p-phenylene）s （OPP（5）-NPh） with a maximum luminance of up to 5000 cd/m^2 and a luminanous efficiency of 1.3 cd/A was reported. This diode was made by using a wide band-gap hole-blocking layer, F-TBB instead of PBD in the OLED devices. We attribute the good performance to the one trade-off involved in the use of F-TBB to obtain higher luminance is the increased turn-on voltages and slightly decreased device efficiencies.     

Heat revolution on photophysical properties and electroluminescent performance of Ir(ppy)3-doped bipolar host of oxadiazole derivatives attaching with inert group of tert-butyl moiety

Two bipolar materials,2,5-bis(2-(9H-carbazole-9-yl)phenyl)-1,3,4-oxadiazole(o-CzOXD)and 2,5-bis(2-(3',6'-di-tert-butyl-9H-carbazole-9-yl)phenyl)-1,3,4-oxadiazole(tBu-o-CzOXD),were synthesized according to reported methods.In parallel study,it was demonstrated that introduction of inert tert-butyl group improved material thermal stability,even though this modification only had a slight influence to the photophysical and electrochemical properties of these materials.A comparative study focusing on effects of heat treatment was carried out on the quartz glass substrates with vacuum deposited films containing one of the bipolar host doped with 6 wt%fac-tris(2-phenylpyridinato-N,C2’)iridium(Ir(ppy)3).Results show that when the two samples were heated,the absorption,emission,and photo images of the host:dopant system changed,with the o-CzOXD suffering more severe degradation under high temperature,which is consistent with their thermal stability.In addition,it was proved that the high temperature-annealed host:dopant system can enhance the emission of the dopant.This finding was used as a guideline to improve our device performance.We fabricated two types of phosphorescent organic light-emitting devices(PhOLEDs),one was based on o-CzOXD,the other was based on tBu-o-CzOXD.They had analogous structure.We investigated the effect of heat on device performance by selectively annealing.Although these two freshly prepared devices exhibited similar performance,when annealed at 90°C for 10 min,the OLEDs based on tBu-o-CzOXD showed significant performance enhancement,which can be attributed to the observation that annealing Ir(ppy)3 doped host can change film morphology and enhance the dopant emission.The maximum efficiencies of the freshly prepared tBu-o-CzOXD device were 25.8 cd A-1,23.1lm W-1,and 9.3%;whereas those for annealed device were 47.0 cd A-1,42.2 lm W-1,and 13.4%.     

High-efficiency saturated red emission from binuclear cyclo-metalated platinum complex containing 5-(4-octyloxyphenyl)-1,3,4-oxadiazole-2-thiol ancillary ligand in PLED

A novel red-emitting binuclear platinum complex (dfppy)2Pt2(C8OXT)2 was synthesized and characterized,in which dfppy represents 2-(4’,6’-difluorophenyl)pyridinato unit and C8OXT is abbreviated for 5-(4-octyloxyphenyl)-1,3,4-oxadiazole-2-thiol as a bridging ancillary ligand.Its photophysical,electrochemical and electroluminescent characteristics were primarily studied.The made single-emissive-layer (SEL) polymer light-emitting devices using (dfppy)2Pt2(C8OXT)2 as emitter exhibited a saturated red emission peaked at 620nm.The best device performances were obtained in the device at 8wt% dopant concentration,with a maximum external quantum efficiency of 8.4%,a current efficiency of 4.2cd/A and brightness of 3228cd/m2.This work provides an effective approach to obtain high-efficiency red emission through construction of new binuclear platinum complex and its doped SEL devices.     

Aggregation-enhanced emission and efficient electroluminescence of conjugated polymers containing tetraphenylethene units

Tetraphenylethene (TPE) is a popular luminogen characterized by aggregation-induced emission and has been widely used to construct solid-state emissive materials. In this work, two thermally stable polymers (P1 and P2) consisting of TPE conjugated to the 2,7-positions of fluorene and carbazole, respectively, are synthesized and characterized. Both polymers are weakly fluorescent in solutions but show greatly enhanced emission as the aggregate formation, presenting an aggregation-enhanced emission feature. Two kinds of polymer light-emitting diodes are fabricated utilizing P1 and P2 as emitters (EML) (device I: ITO/PEDOT:PSS (45 nm)/PVK:EML (1:1 wt%, 55 nm)/TPBI (38 nm)/Ca:Ag; device II: ITO/PEDOT:PSS (45 nm)/ PVK:OXD-7:EML (3:1:3 wt%, 55 nm)/TPBI (38 nm)/Ca:Ag). The device II of P2 shows the best performances, affording a maximum luminance of 6500 cd/m 2 and a high peak efficiency of 2.11 cd/A.     

Electronic Properties of Two Series of Blue-Emitting Conjugated Oligomers and Polymers Based on Cyanostilbene： A Quantum Chemistry Study

One of the drawbacks of the electroluminescence （EL） polymers is that they are usually much better at accepting and transporting holes than electrons due to their inherent richness of π-electrons. One approach improving electron injection and transport in conjugated polymers is to incorporate moieties with high electron affinities. In this theoretical work, to gain an insight into the chemical structure-property relationships was aimed by controllable modification of the main chain structures. Two cyanovinylene derivatives with 2,7-fluorenylene and p-phenylene moieties in the main chains, namely, poly { （2,5-dimethoxy-p-phenylene- 1,4-ylene）-alt-[ 1,2-bis（p-phenylene）- 1- cyanovinylene]} （PPhCN） and poly{[9,9-dimethyl-2,7-fluorenylene]-alt-[1,2-bis（p-phenylene）-1-cyanovinylene]} （PFCN）, were studied employing density functional theory （DFT） and time dependent density functional theory （TD-DFT） with B3LYP functional. The electronic properties of the neutral molecules, extrapolated ionization potentials （IP） and electron affinities （EA）, and energy gaps were investigated in comparison with pristine poly（2,7- fluorenylene）. From comparison with poly（2,7-fluorenylene） （PF）, the 1,2-bis（p-phenylene）-1-cyanovi-nylene unit was found to be a good electron-withdrawing moiety for electronic materials and the incorporation of 1,2-bis（p- phenylene）-1-cyanovinylene resulted in a narrow band gap and a red shift of both the absorption and photoluminescence emission peaks. Most importantly, the LUMO energies of PFCN are around 1 eV lower than those of PF, which results in the decrement of EA about 0.9 eV, indicating that the 1,2-bis（p-phenylene）-1-cyanovinylene unit has significantly improved the electron-accepting properties of the copolymer PFCN. Substitution of 2,5-dimethoxy-p-phenylene for 9,9-dimethyl-2,7-fluorenylene induced larger band gaps and thus a blue-shift in absorption and emission peaks, which can be attributed to the better conjugated backbone in PFCN.     

Synthesis, Structure and Optical Properties of Cerium（Ⅲ） Triphosphate CeP3O9

The single crystal and crystallized powder of triphosphate CeP3O9 have been syn-thesized,and the space group of CeP3O9 has been determined to be C2221 with the cell parameters of a=8.6059,b=11.2437,c=7.3518 ,V=711.4(3) 3,Z=4,Dc=3.520 g/cm3,F(000)=700,R=0.0377 and wR=0.0930. The absorption and emission spectra have been measured,for which the strongest absorption and emission peaks are located at 280 and 320 nm,respectively. The density of state (DOS) and dielectric function have been calculated by the DFT method. The crystal is transparent provided the wavelength is larger than 341 nm,and the observed ultraviolet cut-off edge is at about 350 nm for a polycrystalline power sample. It is possible that the triphosphate CeP3O9 will become an ultraviolet emission material.     

Photophysical Study of Pyrene-labelled St/DVB Copolymers

The photophysical properties of a series of pyrene-labelled styrene/divinyl benzene (St/ DVB) copolymers have been studied for the first time by steady-state fluorescence spectra. The results indicate that when pyrenyl content (mol%) in the copolymer is lower than 0. 006% , the fluorescence spectra only show the pyrenyl monomer emission, while the 0-0 transition band is much suppressed and the vibronic structure is partially lost. However, in the fluorescence spectra of the copolymers with pyrenyl content higher than 0.3%, there appear some new emission bands at ca 420 nm, 440 nm and 475 nm. These results are explained in terms of the formation of ground-state and excited-state aggregates, which reveals the heterogeneity of the crosslinked networks.     

Morphology and Mechanical Properties of Nylon 6/PBT Blends Compatibilized with Styrene/Maleic Anhydride Copolymer

The mechanical properties and dynamic mechanical properties of blends composed of Nylon 6 and poly(butylenes terephthalate)(PBT),with styrene/maleic anhydride(SMA)as compatibilizer,were studied.The observation on the morphologies of the etched surfaces of the cryogenically fractured specimens via scanning electron microscopy(SEM)demonstrated that in the compatibilized Nylon 6/PBT blends,there exists a finer and more uniform dispersion induced by the in-situ interfacial chemical reactions during the preparation than that in the corresponding uncompatibilized blends.On the other hand,the overall mechanical properties of the compatibilized blends could be remarkably improved compared with those of the uncompatibilized ones.Moreover,increasing the amount of the compatibilizer SMA leads to a more efficient dispersion of the PBT phase in Nylon 6/PBT blends.Furthermore,there exists an optimum level of SMA added to achieve the maximum mechanical properties.As far as the mechanism of this reactive compatibilization is concerned,the enhanced interfacial adhesion is necessary to obtain improved dispersion,stable phase morphology,and better mechanical properties.     

Effects of AlN Layer and Impurities on Optical Properties of GaN

The effects of the incorporated oxygen and the different buffer layers on the optical properties and surface morphology of GaN were studied. The results show that the decrease of the concentration of the incorporated oxygen has no effect on the surface morphology, but improves the optical properties. While the introduction of the AIN buffer layer makes not only the surface morphology but also the optical properties improve. Both the oxygen contamination from the nitrogen source and the resulted morphology are directly related to the line width of the low-temperature photoluminescence(PL) spectra.     

Crystalline Morphology and Crystallization Kinetics of Melt-miscible Crystalline/Crystalline Polymer Blends of Poly（vinylidene fluoride） and Poly（butylene succinate-co-24mol% hexamethylene succinate）

Poly（vinylidene fluoride） （PVDF） and poly（butylene succinate-co-24 mol% hexamethylene succinate） （PBHS）, both crystalline polymers, formed melt-miscible crystalline/crystalline polymer blends. Both the characteristic diffraction peaks and nonisothermal melt crystallization peak of each component were found in the blends, indicating that PVDF and PBHS crystallized separately. The crystalline morphology and crystallization kinetics of each component were studied under different crystallization conditions for the PVDF/PBHS blends. Both the spherulitic growth rates and overall isothermal melt crystallization rates of blended PVDF decreased with increasing the PBHS composition and were lower than those of neat PVDF, when the crystallization temperature was above the melting point of PBHS component. The crystallization mechanism of neat and blended PVDF remained unchanged, despite changes of blend composition and crystallization temperature. The crystallization kinetics and crystalline morphology of neat and blended PBHS were further studied, when the crystallization temperature was below the melting point of PBHS component. Relative to neat PBHS, the overall crystallization rates of the blended PBHS first increased and then decreased with increasing the PVDF content in the blends, indicating that the preexisting PVDF crystals may show different effects on the nucleation and crystal growth of PBHS component in the crystalline/crystalline polymer blends.     

Synthesis and electroluminescent properties of naphthalimide derivatives

Naphthalimide derivatives, N-ethyl-4-acetylamino-l ,8-naphthalimide (EAAN) and polymer with N-propyl-4-acetylamino-l,8-naphthalimide (PAAN) side-chain (P-PAAN) were successfully synthesized. Electroluminescent devices of ITO/PVK(120nm)/EAAN(50nm)/Al(150nm) (Ⅰ) and ITO/PVK P-PAAN( 10:1) (50nm)/Al(150nm) (Ⅱ) constructed with EAAN and P-PAAN as the emitting layer were investigated, whereas the single-layer devices of ITO/EAAN or P-PAAN(50nm)/Al(l50nm) (Ⅲ) were not observed to have any e-mission light. The emission results revealed that the exciton recombination formed by positive and negative charge carriers injected from electrodes of devices Ⅰ and Ⅱ was much more balanced than that of devices Ⅲ, which implied that naphthalimide derivatives are a new type of electron-transporting materials with high performance. The electron-transporting properties of naphthalimide derivatives were also elucidated by investigation of the electroluminescent behaviors from both devices of ITO/PPV (80nm)/Al and ITO/P