Synthesis of Conjugated Polymers for Light Emitting and Photovoltalc Applications

1 Results The initial report of polymeric light-emitting diodes (PLEDs) based on poly(p-phenylenevinylene) gave birth to an intense research effort in conjugated polymers, primarily focused on the development of optoelectronic and electrochemical devices. Significant developments in modern synthetic chemistry, especially the chemistry of carbon-carbon bond formation have allowed the synthesis of various well-defined conjugated polymers and oligomers with optimized physical properties.Meanwhile, these re...

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.

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.

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.

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.

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.

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%,55nm)/TPBI(38 nm)/Ca:Ag;device II:ITO/PEDOT:PSS(45 nm)/PVK:OXD-7:EML(3:1:3 wt%,55 nm)/TPBI(38nm)/Ca:Ag).The device II of P2 shows the best performances,affording a maximum luminance of 6500 cd/m2and a high peak efficiency of 2.11 cd/A.

Alkali metal salts doped pluronic block polymers as electron injection/transport layers for high performance polymer light-emitting diodes

A series of alkali metal salts doped pluronic block copolymer F127 were used as electron injection/transport layers (ETLs) for polymer light-emitting diodes with poly[2-(4-(3′,7′-dimethyloctyloxy)-phenyl)-p-phenylenevinylene] (P-PPV) as the emission layer. It was found that the electron transport capability of F127 can be effectively enhanced by doping with alkali metal salts. By using Li2CO3 (15%) doped F127 as ETL, the resulting device exhibited improved performance with a maximum luminous efficiency (LE) of 13.59 cd/A and a maximum brightness of 5529 cd/m2, while the device with undoped F127 as ETL only showed a maximum LE of 8.78 cd/A and a maximum brightness of 2952 cd/m2. The effects of the doping concentration, cations and anions of the alkali metal salts on the performance of the resulting devices were investigated. It was found that most of the alkali metal salt dopants can dramatically enhance the electron transport capability of F127 ETL and the performance of the resulting devices was greatly improved.

Germafluorene conjugated copolymer——synthesis and applications in blue-light-emitting diodes and host materials

A germafluorene-fluorene copolymer was successfully obtained via Suzuki polymerization.The ger-manium containing copolymer has an efficient blue light emission under the ultraviolet irradiation and its single layer EL device showed the highest brightness of 2630 cd/m2 at 7.8 V and the highest effi-ciency of 0.301 lm/W at 6.2 V.The copolymer can also serve as the host material for phosphorescent metal complexes with the maximum brightness of 15600 cd/m2 and the quantum efficiency of 8.5%.The results are quite promising and promise that as its analogs of fluorene and silafluorene,germafluorene is an excellent building block for blue light-emitting polymers and host materials.

High-efficiency conjugated-polymer-hosted blue phosphorescent light-emitting diodes

Highly-efficient blue phosphorescent light-emitting diodes were fabricated based on a conjugated-polymer host by doping bis(2-(4,6-difluorophenyl)-pyridinato-N,C2') picolinate(FIrpic) into poly(9,9-dioctylfluorene)(PFO).Previously,conjugated polymers were not considered as potential hosts for blue phosphorescent dyes because of their low-lying triplet energy levels.Energy back transfer would occur and lead to poor luminescent efficiency in both photoluminescence(PL) and electroluminescence(EL) processes.However,by inserting a hole-transporting layer of poly(N-vinylcarbazole)(PVK),the energy back transfer was suppressed.At low FIrpic-doping concentrations,PFO emissions were completely quenched;with 8 wt% FIrpic,a maximum luminous efficiency of 11.5 cd/A was achieved.

Novel Bipolar Conjugated Polymer Containing Both Triphenylamine and Oxadizole Units

A novel bipolar conjugated polymer containing triphenylamine and 1, 3, 4-oxadiazole units was synthesized by Suzuki reaction. Its structure and properties were characterized by NMR, IR, UV-Vis, PL spectroscopy and electrochemical measurement. The photoluminescent spectroscopy and cyclic voltammograms measurement demonstrated that the resulting polymer shows blue emission (477 nm) and possesses both electron and hole-transporting property.

一步法合成固态荧光氮掺杂碳化聚合物点及多色LEDs的构建

以柠檬酸、尿素和丙烯腈为原料,乙醇为溶剂,通过一步溶剂热法制备了氮掺杂碳化聚合物点(NCPDs),其粒径分布范围约为12~22 nm.NCPDs粉末不仅可发射黄色荧光(λem=570 nm),而且荧光强度和发射峰位置具有显著的浓度依赖性.将NCPDs分散在硅溶胶中制备成NCPDs质量分数为0.15%~45%的NCPDs/硅溶胶复合薄膜,该复合材料的固态荧光发射波长随NCPDs的浓度增加逐渐从蓝色红移至红色(453~638 nm),且具有良好的稳定性.将NCPDs应用于发光二极管(LEDs),可构建蓝光到红光的多色LEDs.此外,NCPDs优异的固态荧光性能使其在指纹识别领域展示出潜在的应用前景,因此评估了其在指纹识别中的适用性.

Carbazole-containing lightemitting polymers:Properties of excited states

A series of light-emitting conjugated polymers alternatively involving carbazole and bivinylene arylene moieties in the main chain were synthesized via Wit-tig-Horner type copolymerization. The photoinduced charge transfer process relating to these polymers was investigated by using the technique of fluorescence spectroscopy. The interaction between excited copolymers and C60 in benzene solution was studied. The fluorescence quenching can be well described by the 搒phere-of-action?mechanism. It is be-lieved that two basic steps are involved in the quenching process, i.e. the diffusion of excitation within the conjugated polymers and the dissociation of the exctions trapped by fullerene. The radius of the sphere-of-action can be related to the excitation diffusion length, which depends on the lifetime of the exciton. The dynamic fluorescence quenching of the copolymers by another quencher, 1,4-dicyanobenzene (DCB) was also surveyed. Copolymers with different chain confor-mations show different temperature effects in the dynamic quenching. A planar conformation is beneficial for the quenching via bimolecular collision.

基于PEDOT:PSS导电聚合物的透明电极制备及其光电性能研究

通过掺杂改性,在玻璃和柔性塑料衬底上采用旋涂法制备了高导电性和高透明性的PEDOT:PSS薄膜。然后以此为基础,研究了PEDOT:PSS为阳极的绿光OLED标准器件和黄光电致磷光器件性能。以CBP掺杂磷光材料(MPPZ)2Ir(acac)为发光层制备了柔性和平面OLED器件,考察了以ITO、PEDOT:PSS/玻璃、PEDOT:PSS/PET三种不同阳极器件的性能。实验结果表明,以PEDOT:PSS/玻璃阳极的器件启动电压为3.83 V,最大亮度可达18632 cd/m^(2),最大电流效率可达21.61 cd/A,显示了PEDOT:PSS透明导电薄膜作为OLED阳极材料具有很大的发展潜力。

Stability study of saturated red polymer light-emitting diodes

Saturated red polymer light-emitting diodes have been fabricated with a single emitting polymer blend layer of poly[2-(2-ethylhexyloxy)-5-methoxy-1,4-phenylenevinylene] (MEH-PPV) and poly[9,9-dioc- tylfluorene-co-4,7-di-2-thienyl-2,1,3-benzothiadiazole] (PFO-DBT15). Saturated red emission with the Commission Internationale de l’Eclairage (CIE) coordinates of (0.67, 0.33) was obtained. The device stability was investigated. The results showed that energy transfer occurred from MEH-PPV to PFO-DBT15, and MEH-PPV improved the hole injection and transportation.

High efficient light-emitting diodes using polystyrene as matrix

High efficient polymer light-emitting diodes(PLEDs) were obtained by using a blend of conjugatedpolymer G-PF, a copolymer of fluorene and thiophene, andpolystyrene (PS). The maximum electroluminescent (EL)efficiency of the device is 12 cd/A when G-PF/PS weight ratiois at 80/20, while that of pure G-PF device is 6.5 cd/A. Studieson photoluminescence and electroluminescence of the blendsindicate that inter-chain interactions were tremendouslysuppressed due to the dilution effect. However, after PS con-centration exceeds 20% the EL efficiency of the devices de-creases with further increase of PS concentration. This maybe due to the decrease of the recombination probability ofelectrons and holes with the excessive addition of PS insulator.

Efficient polymer light-emitting diodes with violet blue emission based on blends of PSiF6-PPP and PSiFC6C6

有效聚合物有紫蓝排放的轻射出的二极管(PLEDs ) 用 paraphenylene-co-silafluorene (PSiF6-PPP ) 和聚合物的共聚物的混合被制作 poly (9,9''-alkyl-3,6-silafluorene )(PSiFC6C6 ) 。设备的表演对混合比率敏感。当到 PS1FC6C6 的 PS1F6-PPP 的集体比率是 1 时：3，最高的外部量效率在 105 cd-m~ 的发光性是 1.96%(-2), 它的电镀物品光(EL ) 光谱在 398 nm 达到顶点，在半最大值的完整的宽度是 67 nm。设备表演的改进由于从 PSiFC6C6 的精力转移到 PS1F6-PPP 和电子和洞的平衡注射。

New applications of poly(arylene ether)s in organic light-emitting diodes

Compared with conventional π-conjugated polymers,poly（arylene ether）s（PAEs） may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,their applications have been extended from engineering plastics to optoelectronic materials.In this review,various kinds of functional PAEs used as fluorescent polymers,host polymers and phosphorescent polymers in organic light-emitting diodes（OLEDs） are outlined,and their molecular design,synthesis and device performance are overviewed.

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.

OLED驱动器的发展和应用

介绍了OLED/PLED的特点和目前其驱动器的发展状态。应用Solomon公司集行驱动、列驱动和控制器为一体的SSD1301芯片和低电压、低功耗的单片机W78LE58芯片,成功地驱动了96×64点阵的PLED显示屏,给出了硬件接口电路图和软件流程图。