芴类电致发光材料研究进展

有机电致发光材料是光电信息功能材料领域的研究热点之一。相比于无机电致发光材料,有机电致发光材料具有很多的优势.芴类化合物作为一类具有刚性平面联苯结构的电致发光材料,由于具有宽的能隙、高的发光效率等特点,备受各方面的关注.本文结合作者的工作,从材料合成的角度介绍了国内外在研究该类材料方面所取得的一些最新进展,并对一些有待进一步研究的问题做了展望.     

单分子有机电致白光材料及器件

有机电致白光二极管在白光照明和背光源应用中具有材料来源广、驱动电压低、节能和环保等优点,受到了广泛关注。目前实现电致白光的方法主要有小分子掺杂、多层器件、激基复合物和缔合物发光以及单分子白光等方法。其中,单分子白光材料由于要控制能量的不完全传递、单分子实现多色同步发射和优化器件结构等,目前研究得还比较少,器件的总体性能相对还不是很理想。本文从材料合成的角度,简要综述了国内外在单分子白光材料的合成与器件性能优化方面所取得的研究进展,并对下一步需要研究的热点问题作了展望。     

有机、聚合物薄膜电致发光器件的研究进展

有机、聚合物薄膜电致发光器件是近年来国际上的一个研究热点。与无机材料相比, 有机材料具有更高的发光效率和更宽的发光颜色选择范围, 并且具有容易大面积成膜的优越性。本文介绍了有机、聚合物薄膜电致发光器件的结构和制备、发光机理以及有关材料的选择, 并对该研究领域的最新动态、器件的稳定性问题以及应用前景进行了讨论。     

Role of nonemissive quenchers for the green emission in polyfluorene

The stability of fluorene-based compounds and polymers, especially at the bridged C-9 position under photoirradiation and thermal treatment, has claimed much attention. The emission of fluorenone formed by degradation of the 9-site is regarded as the origin of the low emission band at 2.2-2.3 eV in polyfluorene-based conjugated materials. We have investigated the role of nonemissive quenchers such as alkyl ketones, which were also one of the products of polyfluorene degradation, for the low-energy emission in polyfluorenes. The spectral characteristics of a blend system of polyfluorene/nonemissive quencher/fluorenone are found to accord well with the kinetics of actual polyfluorene degradation. Our results indicate that strong green emission in degraded polyfluorene would be not caused only by fluorenone, but also by nonemissive quenchers for their effectively quenching bulk emission.     

聚合物电致发光材料及其发光颜色调节的研究进展

聚合物电致发光材料已成为功能材料研究领域的一个热点.与无机材料和有机小分子材料相比,聚合物发光材料具有来源广泛、易加工成型、通过分子结构设计可调节发光颜色等优点,成为制备大面积、低成本、全色柔性显示器件的首选材料.本文介绍了聚合物发光材料的发光机理及调节发光颜色的常用方法,综述了聚对苯乙炔类、聚对苯类、聚芴类等多种共轭聚合物发光材料的合成及发光颜色调节的研究现状,并对聚合物发光材料的发展趋势以及聚合物电致发光器件的制备进行了评述和展望.     

Photo- and electro-luminescent properties of thermotropic liquid crystalline quaterphenyl analogues comprising a 2,2'-bi-1,3,4-thiadiazole unit

Thermotropic liquid crystalline quaterphenyl analogues constituting a central 2,2'-bi-1,3,4- thiadiazole ring, the compounds 5,5'-bis(4-methoxy- and 4-octyloxy-phenyl)-1,3,4-thiadiazole, have been prepared and their photoluminescent (PL) and electroluminescent (EL) properties evaluated. The materials form enantiotropic smectic and nematic phases. The PL spectra showed that they emit blue and green fluorescence in the solid state. The octyloxy compound exhibited an EL spectrum with blue emission and is a candidate for organic EL applications.     

Photo- and electro-luminescent properties of thermotropic liquid crystalline quaterphenyl analogues comprising a 2,2'-bi-1,3,4-thiadiazole unit

Thermotropic liquid crystalline quaterphenyl analogues constituting a central 2,2'-bi-1,3,4- thiadiazole ring, the compounds 5,5'-bis(4-methoxy- and 4-octyloxy-phenyl)-1,3,4-thiadiazole, have been prepared and their photoluminescent (PL) and electroluminescent (EL) properties evaluated. The materials form enantiotropic smectic and nematic phases. The PL spectra showed that they emit blue and green fluorescence in the solid state. The octyloxy compound exhibited an EL spectrum with blue emission and is a candidate for organic EL applications.     

Synthesis of Two Blue-light-emitting Complexes with Schiff Base Calixarene as the Ligand

Two new blue luminescent zinc and beryllium complexes with Schiff base calixarene derivative as the ligand were prepared.Their luminescent properties were determined,which indicated that they had strong blue fluorescent properties.They also had good solubility and film formation.These new complexes can be used as blue organic electroluminescent materials (OELMs) in organic electroluminescent devices.     

Syntheses, characterization and fluorescent properties of two triethylene-glycol dicoumarin-3-carboxylates

Two novel triethylene-glycol dicoumarin-3-carboxylates were synthesized and characterized by element analysis, (1)H NMR, FT-IR and UV-vis absorption spectra. The photoluminescent behaviors of triethylene-glycol dibenzo[5,6]coumarin-3-carboxylate doped in PMMA were discussed. These compounds exhibit strong blue emission under ultraviolet light excitation. Compared to coumarin-3-triethylene glycol diester, the absorption and emission spectra of benzo[5,6]coumarin-3-triethylene glycol diester was bathochromically shifted due to the larger conjugation of benzene moiety. These derivatives have potential possible to explore organic electroluminescent materials.     

“CH”/N取代对BTD衍生物光电性质影响的理论研究

采用量子化学方法研究了“CH”/N杂原子取代对2,1,3-苯并噻二唑衍生物(BTD)的电子性质、光谱性质以及电荷传输性质的影响,为新型有机发光材料的设计与合成提供了可靠的理论基础和指导.研究结果表明,在基态和激发态,与母体分子相比,“CH”/N取代同时降低了最高占据轨道和最低空轨道的能量.而且,与母体分子相比,“CH”/N取代衍生物的能隙升高.“CH”/N取代使母体分子吸收和发射光谱发生了蓝移,并且使发射光谱的振子强度增大.“CH”/N取代衍生物具有较小的空穴重组能,可以作为有机发光二极管的空穴传输材料.     

聚集诱导发光分子的光电功能与器件应用

光电功能分子通常以薄膜和聚集体的形式显示功能, 聚集诱导发光（AIE）分子体系的发现为解决固态下聚集诱导荧光猝灭（ACQ）难题提供了新的思路. 本文总结了近年来本课题组发展的一系列AIE 分子, 侧重介绍这些AIE 分子的光电功能与器件应用, 特别是在有机电致发光器件和有机激光方面的应用. AIE 材料显示非常高的电致发光效率, 在显示与白光器件方面潜力巨大. 在发展电泵有机激光方面, AIE 材料特点突出, 是最有前景的一类材料.     

Progress in small-molecule luminescent materials for organic light-emitting diodes

Organic light-emitting diodes(OLEDs) have been extensively studied since the first efficient device based on small molecular luminescent materials was reported by Tang. Organic electroluminescent material, one of the centerpieces of OLEDs, has been the focus of studies by many material scientists. To obtain high luminosity and to keep material costs low, a few remarkable design concepts have been developed. Aggregation-induced emission(AIE) materials were invented to overcome the common fluorescence-quenching problem, and cross-dipole stacking of fluorescent molecules was shown to be an effective method to get high solid-state luminescence. To exceed the limit of internal quantum efficiency of conventional fluorescent materials, phosphorescent materials were successfully applied in highly efficient electroluminescent devices. Most recently, delayed fluorescent materials via reverse-intersystem crossing(RISC) from triplet to singlet and the "hot exciton" materials based on hybridized local and charge-transfer(HLCT) states were developed to be a new generation of low-cost luminescent materials as efficient as phosphorescent materials. In terms of the device-fabrication process, solution-processible small molecular luminescent materials possess the advantages of high purity(vs. polymers) and low procession cost(vs. vacuum deposition), which are garnering them increasing attention. Herein, we review the progress of the development of small-molecule luminescent materials with different design concepts and features, and also briefly examine future development tendencies of luminescent materials.     

芴基有机蓝光材料的研究进展

芴是具有刚性平面的多环芳烃化合物,由于其具有能隙宽、发光效率高和热稳定性好、分子结构易于修饰等特点,已经发展成为一类重要的蓝光材料。本文综述了芴基有机蓝光材料的研究进展,并对其未来发展趋势进行了展望。     

Synthesis of a Novel Blue—light—emitting Polymer Material Bearing Coumarin Pendants

A novel blue luminescent polymer bearing coumarin pendants was prepared. Its luminescent properties were determined indicating that it had strong blue fluorescent properies and good film formation ability. This novel polymer can be used as a blue organic electroluminescent material (OELM) in organic electroluminescent devices.     

Color-tunable ultralong organic phosphorescence materials for visual UV-light detection

Ultralong organic phosphorescence(UOP) materials have roused considerable attention in the field of photonics and optoelectronics owing to the feature of long-lived emission lifetimes. However, to develop UOP materials with color-tunability is still a formidable challenge. Here, we report a class of UOP materials containing carbonyl, amino or amide groups, exhibiting colortunable persistent luminescence ranging from blue(458 nm) to yellow-green(508 nm) under different UV wavelength excitation. Taken theoretical and experimental results together, we conclude that the excitation dependent color-tunable UOP emission is ascribed to multiple emission centers from single molecular and aggregated states in crystal. Given color-tunable UOP feature, these materials are used to successfully realize visual UV-light detection. This finding not only provides a strategy to design new organic phosphorescent molecules with colorful emission, but also extends the scope of the applications of purely organic phosphorescent materials.     

Recent Progress toward white organic light emitting diodes

An efficient and stable white organic light emitting diode (WOLED) is highly desirable in potential applications such as lighting, background light source, and full color display.A series of highly fluorescent dyes based on a dipyrazolopyridine skeleton,1,7-diphenyl-l,7-dihydrodipyrazolo[3,4-b,4′,3′-e]pyridine, were synthesized and evaluated as emitting as well as charge-transporting material in the fabrication of electroluminescent devices.Several of the blue derivatives are found to be useful as the source of blue emission in fabricating bright white-emitting devices. The choice of dopants, cathode materials, electron-transporting materials as well as the device configurations greatly affect the emission profile, efficiencies, as well as the device lifetime. The latest progress in achieving a more efficient, color stable, durable white light device will be discussed.     

基于三萘苯的溶液可加工螺旋形寡聚物的合成及其在蓝光有机电致发光器件中的应用

近年来,人们在有机电致发光材料和器件结构方面取得了巨大的进步。然而由于蓝光材料具带隙宽的内禀属性,在发光效率、色纯度和稳定性上仍然面临巨大挑战。本文将螺旋形三萘苯共轭体系引入电致发光材料领域,它独特的螺旋形分子结构和易于化学修饰的特点有利于抑制聚集体和基激缔合物的形成。通过SiCl₄催化的环三缩合反应和Suzuki偶联反应,我们设计合成了以三萘基苯为核心,萘、蒽和三苯胺为取代基团的系列螺旋形蓝光寡聚物,并系统地研究了它们的热学、光物理和电化学性质。研究发现,萘和三苯胺取代的寡聚物1, 3, 5-三(3-(1-甲氧基萘-2-基)-4-甲氧基萘-1-基)苯(TNNB)和1, 3, 5-三(3-(4-(N, N-二苯胺基)苯基)-4-甲氧基萘-1-基)苯(TPANB)具有最好的热稳定性。在溶液中,这两种材料都具有深蓝发射,发射峰分别为382和415 nm;在薄膜中, TNNB的发射峰仅有1 nm的红移,而TPANB甚至产生了6 nm的蓝移。以这些寡聚物为发光材料,通过旋涂法制备的有机电致发光器件结果表明,基于TNNB的器件获得了最大亮度达到5273 cd·m^-2,色坐标(0.17, 0.11)的纯蓝光器件。     

A Novel Deep Blue LE-Dominated HLCT Excited State Design Strategy and Material for OLED

Deep blue luminescent materials play a crucial role in the organic light-emitting diodes (OLEDs). In this work, a novel deep blue molecule based on hybridized local and charge-transfer (HLCT) excited state was reported with the emission wavelength of 423 nm. The OLED based on this material achieved high maximum external quantum efficiency (EQE) of 4% with good color purity. The results revealed that the locally-excited (LE)-dominated HLCT excited state had obvious advantages in short wavelength and narrow spectrum emission. What is more, the experimental and theoretical combination was used to describe the excited state characteristic and to understand photophysical property.     

Dual fluorescence of graphene oxide: a time-resolved study

The fluorescence properties of graphene oxide (GO) was studied by recording the fluorescence lifetime, fluorescence emission, and excitation spectra, as well as UV-visible and near-IR absorption spectra. For the first time, we showed that a blue band (ca. 440 nm) and a long wavelength (LW) band (ca. 700 nm) are coexistent, which can be recorded simultaneously by controlling concentration, excitation wavelength, and pH values. Two bands are closely related by the protonation or deprotonation of GO. The blue band is favored by low GO concentration, short excitation wavelength, and high pH value, while the LW band is favored by low pH and long excitation wavelength. To reveal the nature of the dual emission of GO, the fluorescence lifetimes under various conditions were also measured. The blue band contains three emitting components; one of them has a lifetime as long as 10 ns, and its emitting intensity is fairly sensitive to pH, showing the potential for applications in sensing H(+) and fluorescence lifetime imaging. Combining the results under various conditions, we conclude that the electronic transition for this component is very likely due to n-π* transition. The LW band contains two main emitting components (0.2 and 2.1 ns) that also appear in the blue band as minor contributors; the related emission is assigned to π-π* transition. In summary, GO emission is of broadband (300-1250 nm), long-lived, pH sensitive, and excitation wavelength dependent. This makes it easily tailored for versatile applications.     

Exciplex Formation and Electromer Blocking for Highly Efficient Blue Thermally Activated Delayed Fluorescence OLEDs with All-Solution-Processed Organic Layers

Highly efficient solution-processable emitters are greatly desired to develop low-cost organic light-emitting diodes (OLEDs). The recently developed thermally activated delayed fluorescence (TADF) materials are promising candidates, but blue TADF materials compatible with the all-solution-process have still not been achieved. Here, a series of TADF materials, named X-4CzCN, are developed by introducing the bulky units through an unconjugated linker, which realizes high molecular weight to enhance the solvent resistance ability without disturbing the blue TADF feature. Meanwhile, the peripheral wrapping groups efficiently inhibit the triplet–triplet and triplet–polaron quenching by isolating the energy-transfer and charge-transporting channels. The photophysical measurements indicate that a small variation in peripheral unit will have a noticeable effect on the luminescence efficiency. The enlarged volume of peripheral units will make the electroluminescent spectra blueshift, while enhancing the energy transfer of exciplex and blocking the energy leakage of electromer can facilitate the exciton utilization. As a result, the fully solution-processed blue OLED achieves a CIE of (0.16, 0.27), a low turn on voltage of 2.9 eV, and a high external quantum efficiency of 20.6 %. As far as we known, this is the first report of all-solution-processed TADF OLEDs with blue emission, which exhibits a high efficiency even comparable to the vacuum-deposited devices.