Highly efficient polymer phosphorescent light-emitting devices based on a new polyfluorene derivative as host

Several highly efficient iridium-complex polymer light-emitting devices （PLEDs） are fabricated, with a newly synthesized blue conjugated polymer, poly[（9,9-bis（4-（2-ethylhexyloxy）phenyl）-fluorene）-co-（3,7-dibenziothiene-S,S- dioxide15）] （PPF-3,TSO15）, chosen as host. High luminous efficiencies of 7.4 cd.A-1 and 27.4 cd.A-1 are achieved in red and green PLEDs, respectively, by optimizing the doping concentrations of red phosphorescent dye iridium bis（1- phenylisoquinoline） （acetylacetonate） （Ir（piq）） and green phosphorescent dye iridium tris（2-（4-tolyl）pyridinato-N, C2＇） （Ir（mppy）3）.Furthermore, highly efficient white PLEDs （WPLEDs） with the Commission Internationale de l＇Eclairage （CIE） coordinates of （0.35, 0.38） are successfully produced by carefully controlling the doping concentration of the irid- ium complex. The obtained WPLEDs show maximal efficiencies of 14.4 cd.A-1 and 10.1 lm.W-1, which are comparable to those of incandescent bulbs. Moreover, the electroluminescent spectrum of the white device with an initial luminance of about 1000 cd.m-2 is stable, subject to constant applied current stress, indicating that good device stability can be obtained in this system.

Electrode Modifications for Polymer Light-Emitting Electrochemical Cells

The influence of different modification methods on the surface properties of indium-tin-oxide (ITO) electrodes were investigated by measurements of chemical composition,surface roughness,sheet resistance,contact angle and surface free energy.Experimental results demonstrate that oxygen plasma treatment more effectively optimizes the surface properties of ITO electrodes compared with the other treatments.Furthermore,the polymer light-emitting electrochemical cells (PLECs) with the differently treated ITO substrates as device electrodes were fabricated and characterized.It is found that oxygen plasma treatment on the ITO electrode enhances injection current,luminance and efficiency,thereby improves the device characteristics of the PLECs.

Luminescent Enhancement of Heterostructure Organic Light-Emitting Devices Based on Aluminum Quinolines

High performance organic light-emitting devices （OLEDs） have been investigated by using fluorescent bis （2-methyl-8-quinolinolato）（para-phenylphenolato）aluminum（BAlq） as an emissive layer on the performance of multicolor devices consisting of N, N＇-bis-（1-naphthyl）-N,N＇diphenyl- 1,1＇-biphenyl-4,4＇- diamine （NPB） as hole transport layer. The results show that the performance of heterostructure blue light-emitting device composed of 8-hydroxyquinoline aluminum （Alq3） as an electron transport layer has been dramatically enhanced. In the case of high performance heterostructure devices, the electroluminescent spectra has been perceived to vary strongly with the thickness of the organic layers due to the different recombination region, which indicates that various color devices composed of identical components could be implemented by changing the film thickness of different functional layers.

Highly efficient pure white polymer light-emitting devices based on poly(N-vinylcarbazole) doped with blue and red phosphorescent dyes

Efficient white-polymer-light-emitting devices (WPLEDs) have been fabricated with a single emitting layer containing a hole-transporting host polymer,poly(N-vinylcarbzole),and an electron-transporting auxiliary,1,3-bis[(4-tert-butylphenyl)-1,3,4-oxadiazolyl]-phenylene,codoped with two phosphorescent dyes:Iridium(III)bis (2-(4,6-difluorophenyl)-pyridinato-N,C2') picolinate (FIrpic) and home-made Ir-G2 for blue and red emission,respectively.With the structure of ITO/PEDOT:PSS 4083(40 nm)/emission layer(80 nm)/Ba(4 nm)/Al(120 nm),the device showed a maximal luminous efficiency (LE) of 13.5 cd A-1(corresponding to an external quantum efficiency (EQE) of 6.8%),and a peak power efficiency (PE) of 6.5 lm W-1 at 6.0 V.Meanwhile,the device exhibited pure white emission with Commission Internationale de l'Eclairage (CIE) coordinates of (0.34,0.35) at a current density of 12 mA cm-2,which is very close to the equi-energy white point with CIE coordinates of (0.33,0.33).The device performance can be further optimized when more balanced hole/electron injection is achieved by incorporating a lower conducting type anode buffer layer (PEDOT:PSS) and incorporating poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorenene)-alt-2,7-(9,9-dioctyfluorene)] (PFN) as an electron injection layer at the cathode.The optimized device showed an LE of 24.6 cd A-1 (with an EQE of 14.1%),while the peak power efficiency reached 12.66 lm W-1.Moreover,the WPLEDs showed good electroluminescence (EL) stability over a wide range of operating current density and luminance.

Electroluminescence of a Multi-Layered Organic Light-Emitting Diode Utilizing Trans-4- [p-[N-met hyl-N- （hydroxymet hyl） amino] styryl]-N-Methylphridinium Tetraphenylborate as the Active Layer

Employing an organic dye salt of trans-4-[p-[N-methyl-N-（hydroxymethyl）amino]styryl]-N-methylphridinium tetraphenylbovate （ASPT） as the active layer, 8-hydrocyquinoline aluminium （Alq3） as the electron transporting layer and N, N＇-diphenyl-N, N＇-bis（3-methylphenyl）-[1,1＇-biphenyl]-4,4＇-diamine （TPD） as the hole transporting layer, respectively, we fabricate a multi-layered organic light-emitting diode and observe the colour tunable electroluminescence （EL）. The dependence of the EL spectra on the applied voltage is investigated in detail, and the recombination mechanism is discussed by considering the variation of the hole-electron recombination region.

Polarized red, green, and blue light emitting diodes fabricated with identical device configuration using rubbed PEDOT:PSS as alignment layer

Polarized red, green, and blue light emitting diodes(LEDs) are successfully fabricated using polyfluorene and its derivatives, namely, poly(9,9-dioctylfluorene)(PFO), poly(9,9-dioctylfluorene-co-benzothiadiazole)(F8BT),and poly(triphenylamine-co-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole-co-benzo[c]thiadiazole-co-9,9-dioctyl-9 Hfluorene)(Red F).Rubbed hole transport layer poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate)(PEDOT:PSS)is employed in the devices as the alignment layer to achieve fully monodomain alignment in all polymer layers.Red F is blended with F8BT to realize the polarized electroluminescence of red light(dichroic ratio ~3.3), despite having no liquid crystallinity itself.Comparing PFO/F8BT blend to F8BT, higher efficiency of polarized emission is found due to the energy transfer.All the polarized LEDs exhibit pronounced dichroism and efficient polarized emission compared to the non-alignment regular devices.

Silafluorene moieties as promising building blocks for constructing wide-energy-gap host materials of blue phosphorescent organic light-emitting devices

In this article, we reported the synthesis and characterization of a novel silafluorene-based host material, 1,3-bis（5-methyl-5H- dibenzo[b,d]silol-5-yl）benzene （Me-DBSiB）, for blue phosphorescent organic light-emitting devices （PHOLEDs）. The Me- DBSiB was constructed by linking 9-methyl-9-silafluorene units to the phenyl framework through the sp3-hybridized silica atom to maintain high singlet and triplet energy, as well as to enhance thermal and photo-stability. The calculated result shows that the phenyl core does not contribute to both the highest occupied molecular orbital and lowest unoccupied molecular orbital. Wide optical energy gap of 4.1 eV was achieved. When the Me-DBSiB was used as the host and iridium （Ⅲ） bis[（4,6-difluorophenyl）pyridinato-N,C2＇]picolate （Firpic） as the guest, a maximum current efficiency was 14.8 cd/A, lower than the counterpart of 1,3-bis（9-carbazolyl）benzene （28 cd/A）. The unbalanced barrier for electron and hole injection to host layer may be responsible for low efficiency. Even so, our results show that silafluorene moieties are promising building blocks for constructing wide-energy-gap host materials.

Efficient and Low-voltage Phosphorescent Organic Light-emitting Devices Based on Blue Iridium Complex Host

By adopting a phosphorescent host/guest system consisting of blue iridium complex as host and a series of phosphorescent dyes as guest, efficient and low-voltage monochromic organic light-emitting devices（OLEDs） were fabricated. The devices with blue iridium host have higher power efficiency than the device with the conventional host 4,4＇-N,N＇-dicarbazole-biphenyl. The enhancement of the maximum power efficiency in green phosphorescent device can reach 37.2%. Dichromatic white OLED could be achieved by simply adjusting the concentration of the orange dyes. At a brightness of 1000 cd/m2, the power efficiency of the white device is 8.4 lm/W with a color ren- dering index of 76.

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.

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.

Structural Controls of Tetraphenylbenzene-based AIEgens for Non-doped Deep Blue Organic Light-emitting Diodes

Aggregation-induced emission(AIE)has emerged as a new concept,giving highly efficient solid-state photoluminescence.Particularly,AIE luminogens(AIEgens)with deep blue emission(400–450 nm)have displayed salient advantages for non-doped organic light-emitting diodes(OLEDs).However,deep blue emitters with Commission Internationale de L’Eclairage(CIE)coordinates less than 0.08 are still rare.In this review,we outline the latest achievements in the molecular guidelines based on the AIE core of tetraphenylbenzene(TPB)for developing efficient deep blue AIEgens.We provide insights into the construction of deep blue emitters with high horizontal orientation by regulating the length of the linear molecule.We also discuss the luminescence mechanisms of these AIEgens-based OLEDs by using the magnetic field effects measurements.Finally,a summary of the challenges and perspectives of deep blue AIEgens for non-doped OLEDs is also presented.

电致蓝光芴取代聚芴的合成与光谱稳定性

为了筛选高效稳定的聚合物电致蓝光材料,设计合成了三苯胺和芴取代的二芳基芴单体,并通过Suzuki缩聚合成了交替共聚物TPAFF-co-F和TPAFF-co-P.将二辛基芴引入聚芴的9位可以增加其溶解度,同时具有屏蔽主链和减少主链芴9位被氧化的作用,三苯胺基团将有利于提高空穴在阳极界面的注入能力.200℃下空气中退火24h实验表明,在相同条件下,绿光指数(Igreen/Iblue)顺序为聚(9,9-二辛基芴)(1.07)>TPAFF-co-F(0.65)>TPAFF-co-P(0.47),证明了烷基芴引入减少了主链氧化的几率.还制作了发光二极管器件,其结构为ITO/PEDOT:PSS(40nm)/TPAFF-co-F或TPAFF-co-P(80nm)/Ba(4nm)/Al(120nm).在高电流密度下它们保持了良好的光谱稳定性,在547mA·cm-2电流密度下,TPAFF-co-F的CIE(国际发光照明委员会)坐标为(0.22,0.24),TPAFF-co-P的CIE坐标为(0.24,0.26),后者的电流效率为0.712cd·A-1.

Monoradically luminescent polymers by a super acid-catalyzed polymerization and deep-red electroluminescence

Luminescent radicals have received great attention recently due to their idiographic luminescent properties and potential 100%utilization efficiency of doublets under electrical excitation.However,luminescent radical polymers are rarely explored owing to their challenging molecular design and synthesis.Herein,we report an efficient approach to construct luminescent radical polymers by a super acid-catalyzed polymerization reaction proceeded at room temperature,which intrinsically avoid the heavy metal catalyst.The obtained polymers exhibit the unique paramagnetic signals,good thermal properties,and excellent photostability.Moreover,the quantifiable electroluminescence of such radical polymers was demonstrated for the first time.

基于长链胺及聚合物的高效蓝色发光器件

为了促进钙钛矿发光器件在显示和照明方面的应用,钙钛矿蓝光器件的研究受到广泛关注.在混卤素钙钛矿发光层MAPbBr_(2)Cl中引入长链丁基胺阳离子和聚合物添加剂聚环氧乙烷,通过减小晶粒尺寸,钝化缺陷,较好地抑制了离子迁移与非辐射复合.采用这种方法制备了发光最大波长位于484 nm、最大亮度为2876 cd/m^(2)和最高电流效率为3.7 Cd/A的天蓝色钙钛矿发光器件,较发光层为MAPbBr_(2)Cl器件的效率提高了近15倍.

Synthesis and Photophysical Properties of 9,10-Disubstituted Anthracenes

We report the synthesis and photophysical characterization of four 9,10-disubstituted dipheny-lanthracenes with specific modifications of the model backbone which involve both the 9,10 para substituents at the phenyl rings and the substitution with carbon-carbon triple bonds. The effects of such modifications on the photoluminescence and electroluminescence properties have been investigated on the basis of the diphenylanthracene molecular characteristics and in view of application to light-emitting devices. We have found that the substitution with the carbon-carbon triple bonds at the two 9,10-phenyls noticeably alters the electronic states of the reference molecule, also introducing a certain degree of sensitivity to the phenyl substituents, which improves the tunability of the optical emission. Differently, the 9,10 para substituents produce minor changes in the single-molecule properties, due to the lack of electronic conjugation across the 9,10-phenyls. However, even a single nitro substituent in the phenyl para position produces the formation of excimers, which appreciably reduces the optical quantum efficiency. These properties are maintained in solid-state blends and simple spin-coated bilayer electroluminescent devices have been fabricated.

Alkyl-chain branched effect on the aggregation and photophysical behavior of polydiarylfluorenes toward stable deep-blue electroluminescence and efficient amplified spontaneous emission

The control of the condensed superstructure of light-emitting conjugated polymers(LCPs)is a crucial factor to obtain high performance and stable organic optoelectronic devices.Side-chain engineering strategy is an effective platform to tune inter chain aggregation and photophysical behaviour of LCPs.Herein,we systematically investigated the alkyl-chain branched effecton the conformational transition and photophysical behaviour of polydiarylfluorenes toward efficient blue optoelectronic devices.The branched side chain will improve materials solubility to inhibit interchain aggregation in solution according to DLS and optical analysis,which is useful to obtain high quality film.Therefore,our branched PEODPF,POYDPF pristine film present high luminance efficiency of 36.1%and 39.6%,enhanced about 20%relative to that of PODPF.Compared to the liner-type sides'chain,these branched chains also suppress chain planarization and improve film morphological stability effectively.Interestingly,the branched polymer also had excellent stable amplified spontaneous emission(ASE)behaviour with low threshold(4.72μJ/cm2)and a center peak of 465 nm,even thermal annealing at 220℃in the air atmosphere.Therefore,side-chain branched strategy for LCPs is an effective means to control interchain aggregation,film morphology and photophysical property of LCPs.

Non-conjugated Polynorbornene Hosts with High Triplet Energy Levels for Solution-processed Narrowband Blue OLEDs

Three polymer hosts(namely PNB-tBuCz,PNB-Ac,PNB-TAc)containing non-conjugated polynorbornene(PNB)backbone and hole-transporting arylamine segments(carbazole,acridan and dendritic teracridan)in side chains are developed for solution-processed narrowband blue organic light-emitting diodes(OLEDs).It is found that the non-conjugated polynorbornenes can keep high triplet energy(ET)levels in range of 3.12-3.20 eV by interrupting the conjugation of repeating units,making them capable as host materials for blue emitters.Meanwhile,by increasing the electron-donating capability of side chain arylamine from carbazole to acridan and dendritic teracridan,the highest occupied molecular orbital(HOMO)levels for the polymer hosts are elevated from-5.50 eV to-5.11 eV,beneficial for reducing the hole injection barrier from anode to emissive layer.As a result,solution-processed OLEDs employing polynorbornenes with dendritic teracridan side chain(PNB-TAc)as host and boron,selenium,nitrogen-containing multiple resonance thermally activated delayed fluorescence emitter as dopant reveal efficient narrowband blue electroluminescence with emission peak at 474 nm,full-width at half maximum of 30 nm,together with maximum external quantum efficiency of 20.2%,representing the state-of-the-art device efficiency for solution-processed OLEDs with narrowband blue emission.

Blue emitting exciplex for yellow and white organic light‑emitting diodes

White organic light-emitting diodes(WOLEDs)have several desirable features,but their commercialization is hindered by the poor stability of blue light emitters and high production costs due to complicated device structures.Herein,we investigate a standard blue emitting hole transporting material(HTM)N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine(NPB)and its exciplex emission upon combining with a suitable electron transporting material(ETM),3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole(TAZ).Blue and yellow OLEDs with simple device structures are developed by using a blend layer,NPB:TAZ,as a blue emitter as well as a host for yellow phosphorescent dopant iridium(III)bis(4-phenylthieno[3,2-c]pyridinato-N,C2')acetylacetonate(PO-01).Strategic device design then exploits the ambipolar charge transport properties of tetracene as a spacer layer to connect these blue and yellow emitting units.The tetracene-linked device demonstrates more promising results compared to those using a conventional charge generation layer(CGL).Judicious choice of the spacer prevents exciton difusion from the blue emitter unit,yet facilitates charge carrier transport to the yellow emitter unit to enable additional exciplex formation.This complementary behavior of the spacer improves the blue emission properties concomitantly yielding reasonable yellow emission.The overall white light emission properties are enhanced,achieving CIE coordinates(0.36,0.39)and color temperature(4643 K)similar to daylight.Employing intermolecular exciplex emission in OLEDs simplifes the device architecture via its dual functionality as a host and as an emitter.

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

A novel red-emitting binuclear platinum complex （dfppy）zPtz（C^OXT）z was synthesized and characterized, in which dfppy represents 2-（4＇,6＇-difluorophenyl）pyridinato unit and CsOXT 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）2Ptz（CsOXT）2 as emitter exhibited a satu- rated red emission peaked at 620 nm. The best device performances were obtained in the device at 8 wt% dopant concentration, with a maximum external quantum efficiency of 8.4%, a current efficiency of 4.2 cd/A and brightness of 3228 cd/m~. This work provides an effective approach to obtain high-efficiency red emission through construction of new binuclear platinum complex and its doped SEL devices.