Graded doped structure fabricated by vacuum spray method to improve the luminance of polymer light-emitting diodes

An increase in luminance of a polymer light-emitting diode(PLED) was obtained by fabricating a graded doping structure using a vacuum spray method. The small electron transport molecule, Tris(8-hydroxyquinolinato) aluminum(III)(Alq3), was graded dispersed along the film in the direction of growth in the hole transport polymer poly(3-hexylthiophene-2,5-diyl)(P3HT, regiorandom) layer of the PLED, despite being dissolved in the same organic solvent as the polymer. The PLED reported here, which is composed of a graded structure, emitted brighter light than PLEDs composed of pure polymer or of a blend of active layers prepared by spin coating and/or vacuum spray methods.

Solution Processable Material Derived from Aromatic Triazole, Azomethine and Tris: Preparation and Hole-Buffering Application in Polymer Light-Emitting Diodes

This work presents the synthesis of a new hole-buffering material TAZS and its successful application in polymer light-emitting diodes to enhance device performance. The TAZS is composed of aromatic 1,2,4-triazolylcore linked with three trihydroxy tert-butyl terminals via azomethine linkages. The TAZS forms ashomogeneous film deposited by spin-coating process. The HOMO and LUMO levels of TAZS are -5.23 eV and -2.40 eV, respectively, as estimated from cyclic voltammogram. The current density results of hole-only and electron-only devices confirm strong hole-buffering capability of TAZS layer. Multilayer PLEDs with different thickness of TAZS (ITO/PEDOT: PSS/TAZS (x nm)/SY/ETL/LiF/Al) have been successfully fabricated, using spin-coating process to deposit hole-injecting PEDOT: PSS, TAZS, and emissive SY layers. The PLED with 16 nm TAZS reveals the optimal device performance, with maximum luminance and maximum current efficiency of 19,046 cd/m2 and 4.08 cd/A, respectively, surpassing those without TAZS as HBL (8484 cd/m2, 2.13 cd/A). The hole-buffering characteristic of TAZS contributes greatly to improved charges’ recombination ratio and enhanced emission efficiency.

Hole-Buffer Material Derived from Pyrene, Schiff Base and Tris to Enhance Emission Efficiency of Polymer Light-Emitting Diodes

Inserting a hole-buffer layer is an effective way to enhance emission efficiency of electroluminescence devices. We have successfully synthesized a new hole-buffer material PSB composed of pyrene, Schiff base and trihydroxy tert-butyl groups by the Suzuki-coupling reaction. The HOMO and LUMO lev-els were -6.33 eV and -2.55 eV, respectively, as estimated from cyclic volt-ammograms. In addition, homogeneous films (rms roughness ~2 nm) were readily obtained by spin-coating process. Multilayer polymer light-emitting diodes, ITO/PEDOT:PSS/PSB/SY/LiF/Al, have been fabricated using PSB as hole-buffer layer (HBL). Inserting PSB as HBL significantly enhances the per-formance (maximum luminance: 26,439 cd/m2, maximum current efficiency: 7.03 cd/A), compared with the one without PSB (9802 cd/m2, 2.43 cd/A). It is also superior to the device with conventional BCP as hole-blocking layer (ITO/PEDOT:PSS/SY/BCP/LiF/Al: 15,496 cd/m2, 5.56 cd/A). Current results strongly indicate that the PSB is a potential hole-buffer material for electrolu-minescent devices.

FLUORENE-BASED LIGHT-EMITTING POLYMERS

Several series of fluorene-based light-emitting polymers with the emphasis on achieving efficient and stable bluelight emission are reported. Spiro-functionalization may narrow the emission spectra (with smaller tail at Ionger wavelengths)of fluorene homopolymers to provide purer blue emission. The thermal spectral stability of the polymers could also beimproved because of the elevation of the glass transition temperature caused by the spiro-functionalization. However, theexcimer emission in fluorene homopolymers is not suppressed by the spiro-functionalization. Alternate copolymers of 9,9-dihexylfluorene and substituted phenylenes may emit efficient blue ligh both in solution and in film. The optical propertiesare dependent on the substituion on the phenylene ring. The alkoxy-substituted polymers displayed efficient PL and EL andgood thermal spectral stability. The HOMO and LUMO energy levels of the polymers based on the backbone structure couldbe tuned in a wide range by attaching different functional groups on the phenylene ring. By attaching europium(III) complexat the ends of the side chains in the alternate copolymers, we have demonstrated a new approach to achieving red emissionwith a very narrow spectrum. The copolymers of 9,9-dihexylfluorene and thiophene and bithiophene with differentsubstitutions were also synthesized to study the effect of substitution and regioregularity on the optical and other physicalproperties of the polymers.

Synthesis and Characterization of Poly(1-methoxy-4-octyloxy)-Para-Phenylene Vinylen for Light-Emitting Diodes Application

In this study, the conjugated polymer, poly(1-methoxy-4-octyloxy)-para-phenylene vinylene (MO-p-PPV) was synthesized and characterized. MO-p-PPV was synthesized according to Gilch polymerization mechanism by using 4-methoxyphenol as starting material in the presence of potassium tert-butoxide (1M in THF). The product was further purified by multiple precipitations in different solvents such as methanol, tetrahydrofuran, isopropyl alcohol and hexane. The final product was dried to afford MO-p-PPV as a red solid. The resulting polymer was completely soluble in common organic solvents. The structure of monomer and optical properties of polymer were characterized by proton nuclear magnetic resonance (1H-NMR) spectroscopy, UV-vis spectroscopy, and fluorescence spectroscopy. The UV-vis spectrum showed absorption maxima for MO-p-PPV at 491 nm. Similarly, fluorescence spectrum showed λmax emission at 540 nm.

Realizing External Quantum Efficiency over 25% with Low Efficiency Roll-Off in Polymer-Based Light-Emitting Diodes Synergistically Utilizing Intramolecular Sensitization and Bipolar Thermally Activated Delayed Fluorescence Monomer

Since polymer-based light-emitting diodes(PLEDs)arewellsuited building blocks for large-area and low-cost flexible display equipment,state-of-the-art thermally activated delayed fluorescence(TADF)PLEDs are in high demand.To respond to this demand,light-emitting TADF units have initially been modified with electron-transporting units to balance the carrier transport of regiorandom TADF polymers,and simultaneously,an intramolecular sensitizing strategy has also been employed by covalently incorporating TADF sensitizers with light-emitting TADF units and hosts in conjugated polymers to accelerate the spin-flip of triplet excitons.Superior photophysical properties have been achieved by a rational regulation of the proportions of each component,achieving a photoluminescence quantumyield of 90%,an extremely high rate of reverse intersystem crossing of 3×106 s−1,and a relatively low nonradiative decay rate of around 105 s−1.As a result,the solutionprocessed PLEDs can attain an external quantum efficiency(EQE)value of 25.4%with emission peaks of around 550 nm,representing record-high performance for PLEDs.The efficiency roll-off can also be significantly suppressed,maintaining an EQE value of 24.2%at 1000 cd/m2 with ideal efficiency roll-off of lower than 5%.Encouragingly,this work provides a valid strategy to tackle the imperative need for PLEDs with high EQE and low efficiency roll-off.

Fluorene pendant-functionalization of poly(N-vinylcarbazole)as deep-blue fluorescent and host materials for polymer light-emitting diodes

π-Electron coupling of pendant conjugated segment inπ-stacked semiconducting polymers always causes the formation of defect trapped sites and further quenched high-band excitons,which is harmful to the performance and stability of deep-blue polymer light-emitting diodes(PLEDs).Herein,considerate of“defect”carbazole(Cz)electromers in poly(N-vinylcarbazole)(PVK),a series of fluorene units are introduced into pendant segments(PVCz-DMeF,PVCz-FMeNPh and PVCz-DFMeNPh)to suppress the strongπ-electron coupling of pendant Cz units and enhance radiative transition toward fabricating sable PLEDs.Compared to PVCz-FMeNPh and PVCz-DFMeNPh,PVCz-DMeF spin-coated films show a relatively efficient deep-blue emission,completely similar to its single pendant chromophore,confirmed an extremely weak charge-transfer and electron coupling between adjacent pendant segments.Therefore,PLEDs based on PVCz-DMeF present stable and deep-blue emission with a high color purity(0.17,0.08),associated with extremely weak defect emission at 600∼700nm(induced by carbazole electromers).Finally,PLEDs based on PVCz-DMeF/F8BT blended films(1:1)also present the high maximum luminance(Lmax)of 6261 cd/m2 and current efficiency(CE_(max))of 2.03 cd/A,confirmed slightly trapped sites formation.Therefore,precisely control the arrangement and packing model of pendant units inπ-stacked polymer is an essential prerequisite for building efficient and stable emitter for optoelectronic devices.

Synthesis and optical properties of an alternating copolymer composed of MEHPV and 1,3,4-oxadiazole

A poly （ p-phenylenevinylene ） （ PPV ） alternating copolymer, poly [ （ 2, 5-diphenylene-1, 3, 4-oxadiazole ）-4-4＇ - vinylene-alt-2-methoxy-5-（ 2-ethylhexyloxy ）-1, 4-phenylenevinylene] （oxa-MEHPV）, is synthesized by Heck coupling reaction and characterized with UV-vis, Fourier transform infrared （ FT-IR ）, ^1H-NMR and photoluminescence （ PL ） spectroscopy, oxa-MEHPV possesses an outstanding thermal stability and shows excellent solubility in common organic solvents such as dichloromethane, chloroform, toluene, and tetrahydrofuran（THF）. The introduction of the electron-deficient 1, 3, 4-oxadiazole units into the MEH-PPV backbone also increases the electron affinities of the conjugated segment, which leads to the blue-shift of the maximum absorption wavelength and makes the polymer have a high optical band-gap energy, good electron-transporting stability and high PL quantum yield.

A novel crosslinkable electron injection/transporting material for solution processed polymer light-emitting diodes

A novel crosslinkable water/alcohol soluble conjugated polymer PFN-C containing oxetane groups and aminoalkyl groups in the side chains has been developed and used as highly efficient electron injection and transporting material for polymer light-emitting diodes (PLEDs). The unique solubility in polar solvents and crosslinkable ability of PFN-C render it a good can- didate for solution processed multilayer PLEDs. It was found that PFN-C can greatly enhance the electron injection from high work-function metal cathode, due to its pendant amino groups. As a result, PLEDs with PFN-C/Al cathode exhibited compara- ble device performance to the devices with Ba/Al cathode. The resulting green light-emitting device showed promising perfor- mance with a maximum luminance efficiency of 13.53 cd A-1.

Through-space charge transfer blue polymers containing acridan donor and oxygen-bridged triphenylboron acceptor for highly efficient solution-processed organic light-emitting diodes

Three kinds of through-space charge transfer(TSCT)blue polymers containing non-conjugated polystyrene backbone together with spatially-separated acridan donor and oxygen-bridged triphenylboron acceptors having different substituents of tert-butyl,hydrogen and fluorine are designed and synthesized.The designed TSCT blue polymers possess photoluminescence quantum yields up to 70%in solid-state film,single-triplet energy splitting below 0.1 eV,and typical thermally activated delayed fluorescence(TADF)effect.Meanwhile,the resulting polymers exhibit aggregation-induced emission(AIE)effect with emission intensity increased by up to^27 folds from solution to aggregation state.By changing the substituent of acceptors to tune the charge transfer strength,blue emission with peaks from 444 to 480 nm can be realized for the resulting polymers.Solution-processed organic light-emitting diodes based on the polymers exhibit excellent device performance with Commission Internationale de L’Eclairage(CIE)coordinates of(0.16,0.27),together with the maximum luminous efficiency of 30.7 cd A-1 and maximum external quantum efficiency of 15.0%,which is the best device efficiency for blue TADF polymers.

Through-space charge transfer polymers for solution-processed organic light-emitting diodes

Through-space charge transfer(TSCT)polymers are an attractive class of luminescent polymers with spatial donor/acceptor architecture and thermally activated delayed fluorescence effect,different from conventional luminescent polymers with conjugated donor-acceptor structure and through-bond charge transfer emission.Their emission comes from the intramolecular charge transfer by through-space pathway because the donor and acceptor segments are spatially proximate to each other in each repeating unit but are physically separated by nonconjugated polymer backbone.In this review,recent advances in TSCT polymers with linear,bottlebrush,and dendritic architectures are presented,with the focus on their molecular design,photophysical behavior,and device performance.We hope that this review shall provide a useful insight of new luminescent polymers with TSCT effect for use in solution-processed organic light-emitting diodes.

Synthesis of Polyfluorene-Polytriarylamine Block Copolymer with Emitting Part at Junction Point for Light Emitting Applications

A block copolymer consisting of polyfluorene (PF) and polytriarylamine (PTAA) functionalized with green emitting phenoxazine moiety at the junction point of two blocks was designed and prepared for electroluminescent application. PF homopolymer was synthesized by Suzuki coupling polymerization, and was reacted with brominated phenoxazine. In the presence of the resulting PF functionalized with phenoxazine, C-N coupling polymerization of 4-(4’-bromophenyl)-4’’-butyldiphenylamine was carried out to afford a triblock copolymer, PTAA-phenoxazine-PF-phenoxazine-PTAA (PF-Ph-PTAA). Two types of random copolymers were also synthesized with fluorene and phenoxazine (PF2) by Suzuki coupling polymerization for comparison. All the polymers were soluble in common organic solvents and readily formed thin films by a solution processing. Prepared polymers exhibited similar UV absorption and PL emission in chloroform solutions. In a film state, the existence of phenoxazine unit drastically changed PL spectra. Although the content of phenoxazine unit in PF-Ph-PTAA was relatively high (13 mol%), it showed similar PL spectrum to that of PF2(phenoxazine content, 0.2 mol%) indicating that phenoxazine unit is isolated in single polymer chain nevertheless the high content. EL device based on PF-Ph-PTAA showed green-emission, suggesting that emission sites predominantly located in the vicinity of phenoxazine moiety because of its shallow HOMO level.

Triphenyl Phosphine Oxide and Carbazole-based Polymer Host Materials for Green Phosphorescent Organic Light-emitting Diodes

Four novel polymers, poly（3,6-9-decyl-carbazole-alt-1,3-benzene） （PB13CZ）, poly（3,6-9-decyl-carbazole-alt- bis（4-phenyl） （phenyl） phosphine oxide） （PTPPO38CZ）, poly（3,6-9-decyl-carbazole-alt-2,4-phenyl（diphenyl） phosphine oxide） （PTPPO13CZ） and poly（3,6-9-decyl-carbazole-alt-bis（3-phenyl） （phenyl） phosphine oxide） （PTTPO27CZ） were synthesized, and their thermal, photophysical properties and device applications were further investigated to correlate the chemical structures with the photoelectric performance of bipolar host materials for phosphorescent organic light emitting diodes. All of them show high thermal stability as revealed by their high glass transition temperatures and thermal decomposition temperatures at 5% weight loss. These polymers have wide band gaps and relatively high triplet energy levels. As a result, the spin coating method was used to prepare the green phosphorescent organic light emitting diodes with polymers PTPPO38CZ, PTPPO13CZ and PTTPO27CZ as the typical host materials. The green device of polymer PTPPO38CZ as host material shows electroluminescent performance with maximum current efficiency of 2.16 cd.A-1, maximum external quantum efficiency of 0.7%, maximum brightness of 1475 cd.m-2 and reduced efficiency roll-off of 7.14% at 600 cd.m-2, which are much better than those of the same devices hosted by polymers PTTPO27CZ and PTPPO13CZ.

Polymer light-emitting devices based on europium(Ⅲ) complex with 11-bromo-dipyrido[3,2-a:2′,3′-c]phenazine

Polymer light-emitting diodes(PLEDs) containing Eu(DBM)3(Br DPPz)(DBM is dibenzoylmethane, and Br DPPz is 11- bromo-dipyrido[3,2-a:2′,3′-c]phenazine) doped in a blend of poly(9,9-dioctylfluorene)(PFO) and 2-tert-butylphenyl-5- biphenyl-1,3,4-oxadiazole(PBD) as the host matrix were reported. Eu(DBM)3(Br DPPz) exhibited high thermal stability and intense UV-Vis absorption. Narrow-bandwidth red emission at 612 nm with a full width at half-maximum(FWHM) of 14.0 nm was observed from Eu(DBM)3(Br DPPz) in these double-layered PLEDs at dopant concentrations from 1 wt% to 8 wt%. For the PLED containing 1 wt% Eu(DBM)3(Br DPPz), a maximum luminance of 829 cd/m2 at 153.5 m A/cm2, highest external quantum efficiency of 1.70% at 2.1 m A/cm2 and maximum luminance of 0.74 cd/A at 4.31 m A/cm2 were obtained.

Blue light-emitting polyfluorenes containing dibenzothiophene-S,S-dioxide unit in alkyl side chain

Blue light-emitting polyfluorenes containing dibenzothiophene-S,S-dioxide(SO) unit in alkyl side chain(PF-FSOs and PF-CzSOs) were synthesized. All the polymers show high thermal stability with the decomposition temperatures over400 °C. The highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) energy levels of the copolymer slightly decrease with the increase of SO content in side chain. PL spectra of the polymers show slightly red shift and broadening with the increase of solvent polarities, indicating unremarkable intramolecular charge transfer(ICT) effect in the polymers containing SO unit in alkyl side chain. EL spectra of the polymers are almost unchanged in the current densities from 100 to 400 mA cm.2, indicating the superb EL stability of the resulted polymers. The EL spectra of the copolymers exhibit obvious blue-shift and narrowing with the CIE of(0.18, 0.11) for PF-FSO10 and(0.17, 0.11) for PF-CzSO10, respectively,compared with PF-SO10 containing SO unit in main chain with the CIE of(0.16, 0.17) and PFO with the CIE of(0.18, 0.18).The superior device performances were obtained with the luminous efficiency(LEmax) of 1.17 and 0.68 cd A.1 for PF-FSO15 and PF-CzSO20, respectively, compared with the LEmax of 0.37 cd A.1 for PFO. The results indicate that linking SO unit to alkyl side chain of the polyfluorene is a promising strategy for efficient blue light-emitting polymers.

Bipolar Blue Light-emitting Polyfluorenes Containing Dibenzothiophene-S,S-dioxide/Carbazole Units

Bipolar blue light-emitting polyfluorenes（PFSO-Cz） containing electron-deficient dibenzothiophene-S,S- dioxide（SO） and electron-rich carbazole（Cz） unit were synthesized. All the polymers show a high thermal stability with the decomposition temperatures over 400 ℃ and higher photoluminescence quantum yields. The highest occupied molecular orbital energy levels（EHMH＇s） slightly enhance and the lowest unoccupied molecular orbital energy levels（ELuMo＇S） gently depress with the increase of Cz content in the polymers. PL spectra of the polymers display remarkable red shift and broadening with the increase of solvent polarities, indicating significant intramolecular charge transfer（ICT） effect in the polymers. Electroluminescence（EL） spectra of the polymers exhibit a broadening tendency with increasing the content of Cz unit in the polymers. The superior device performances were obtained with the maximum lumhlous efficiency（LEmax） of 5.2 cd/A, the maximum external quantum efficiency（EQEmax） of 4.8% and the Internationale de I＇Eclairage（CIE）（x,y） coordinates of （0.16, 0.17） for PFSO15-Cz10 based on the single-layer device of ITO/PEDOT：PSS/EL/CsF/A1. The results indicate that the efficient bipolar blue light-emitting polyfluorenes are also constructed by Suzuki copolymerization using the monomers in common use.

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.

Synthesis and characterization of novel red-emitting copolymers containing fluorene,diketopyrrolopyrrole,and phenothiazine units

A novel three-component copolymer (PFDP), derived from 9,9-dihexylfluorene, diketopyrrolopyrrole( DPP), and 10-octylphenothiazine, was synthesized through palladium-catalyzed Suzuki polycondensation in good yields. PFDP possessed moderate molecular weight and polydispersity, well-defined structure, and excellent thermal properties with an onset decomposition temperature at 357°C. PFDP in thin film exhibited red photoluminescence from DPP chromophore exclusively, with a peak at 602 nm. Electron-rich phenothiazine units sighificantly improved the injection and transport of holes by incorporating into polymer backbone. Light-emitting device was fabricated in the ITO/PEDOT: PSS/PVK/ polymer/Ba/Al configuration using PFDP as the emitting layer. The device based on PFDP showed red emission [CIE coordinate value (0.62, 0.38)] that was close to the standard red (0.66, 0.34). The results on electroluminescent performance revealed that PFDP may be a promising candidate for the red emitter with a maximum brightness of 259 cd/m2 and a maximum external quantum efficiency of 0.25%.

Synthesis of Thieno[3,4-b]pyrazine-based Alternating Conjugated Polymers via Direct Arylation for Near-infrared OLED Applications

Three alternating conjugated polymers,namely PFTP,PCz TP,and PSi TP,which combine a thieno[3,4-b]pyrazine(TP)unit with different benzene-based donor units such as 9,9-dioctylfluorene,9-heptadecyl-9H-carbazole and 5,5-dioctyl-5H-dibenzo[b,d]silole,were synthesized in good yield(>85%)and high molecular weight up to Mn=5.82×10^(4) via direct arylation polymerization(DAr P).All the resultant polymers exhibit moderate bandgap of about 1.80 e V and strong deep red/near-infrared emitting in the solid state.Among them,the PSi TP-based electroluminescence(EL)devices with an architecture of ITO/PEDOT:PSS/PTAA/emitting layer/TPBi/Li F/Al give the best performance with a maximum luminance of 2543 cd/m^(2) at 478 m A/cm^(2).This work expands the application scope of high-performance conjugated polymers which can be synthesized by DAr P.

Electrospun Supramolecular Hybrid Microfibers from Conjugated Polymers:Color Transformation and Conductivity Evolution

A type of novel electrospun supramolecular hybrid microfibers comprising poly(9-(4-(octyloxy)-phenyl)-2,7-fluoren-9-ol)(PPFOH)and poly(A/-vinylcarbazole)(PVK)are successfully prepared for intriguing multi-color emission properties.The supramolecular tunable PPFOH aggregation in PVK matrix endows the complex with a smart energy transfer behavior to obtain the multi-color emissions.In stark contrast to PVK fibers,the emission color of PPFOH/PVK fibers with an efficient dispersion of PPFOH fluorophores at a proper dope ratio can be tuned in a wide spectrum of blue(0.1%),sky blue(0.5%),nearly white(1%),cyan(2%),green(5%)and yellow(10%).Besides,conductive behaviors of the microfiber were demonstrated in accompany with the increment of the doping ratio of PPFOH to PVK.Successful fabrication of polymer light-emitting diode(PLED)based on the blended electrospun fiber provided a further evidence of its excellent electrical property for potential applications in optoelectronic devices.