Management of singlet and triplet excitons for efficient white organic light-emitting devices

Lighting accounts for approximately 22 per cent of the electricity consumed in buildings in the United States, with 40 per cent of that amount consumed by inefficient (approximately 15 lm W(-1)) incandescent lamps. This has generated increased interest in the use of white electroluminescent organic light-emitting devices, owing to their potential for significantly improved efficiency over incandescent sources combined with low-cost, high-throughput manufacturability. The most impressive characteristics of such devices reported to date have been achieved in all-phosphor-doped devices, which have the potential for 100 per cent internal quantum efficiency: the phosphorescent molecules harness the triplet excitons that constitute three-quarters of the bound electron-hole pairs that form during charge injection, and which (unlike the remaining singlet excitons) would otherwise recombine non-radiatively. Here we introduce a different device concept that exploits a blue fluorescent molecule in exchange for a phosphorescent dopant, in combination with green and red phosphor dopants, to yield high power efficiency and stable colour balance, while maintaining the potential for unity internal quantum efficiency. Two distinct modes of energy transfer within this device serve to channel nearly all of the triplet energy to the phosphorescent dopants, retaining the singlet energy exclusively on the blue fluorescent dopant. Additionally, eliminating the exchange energy loss to the blue fluorophore allows for roughly 20 per cent increased power efficiency compared to a fully phosphorescent device. Our device challenges incandescent sources by exhibiting total external quantum and power efficiencies that peak at 18.7 +/- 0.5 per cent and 37.6 +/- 0.6 lm W(-1), respectively, decreasing to 18.4 +/- 0.5 per cent and 23.8 +/- 0.5 lm W(-1) at a high luminance of 500 cd m(-2).     

掺杂对OLED发光效率的影响

概述了掺杂发光的种类、掺杂发光提高OLED发光效率的机制。     

High-efficiency fluorescent organic light-emitting devices using a phosphorescent sensitizer

To obtain the maximum luminous efficiency from an organic material, it is necessary to harness both the spin-symmetric and anti-symmetric molecular excitations (bound electron-hole pairs, or excitons) that result from electrical pumping. This is possible if the material is phosphorescent, and high efficiencies have been observed in phosphorescent organic light-emitting devices. However, phosphorescence in organic molecules is rare at room temperature. The alternative radiative process of fluorescence is more common, but it is approximately 75% less efficient, due to the requirement of spin-symmetry conservation. Here, we demonstrate that this deficiency can be overcome by using a phosphorescent sensitizer to excite a fluorescent dye. The mechanism for energetic coupling between phosphorescent and fluorescent molecular species is a long-range, non-radiative energy transfer: the internal efficiency of fluorescence can be as high as 100%. As an example, we use this approach to nearly quadruple the efficiency of a fluorescent red organic light-emitting device.     

基于复合电子传输层聚合物太阳能电池性能研究

为解决电子和空穴传输不平衡以及载流子复合对有机太阳能电池转换效率的限制问题, 提出采用聚芴材 料 PFO(poly(9,9-dioctylfluorenyl-2,7-diyl))对有机太阳能电池电子传输层 TiO 2 进行界面修饰以提高电荷传输, 进而提高太阳能电池能量转换效率。 通过表面形貌分析和功函数测量表明, PFO 界面层的引入不仅填补了 TiO 2 界面缺陷, 同时 PFO 可作为有效的电荷传输中心, 通过提高器件电子转移能力, 进而提高有机太阳能电 池器件短路电流和填充因子, 使有机电池能量转换效率从 5. 17%提升到 6. 96%。     

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

Efficient polymer light-emitting diodes (PLEDs) with violet blue emission were fabricated using blends of copolymers of paraphenylene-co-silafluorene (PSiF6-PPP) and polymer of poly (9,9'-alkyl-3,6-silafluorene) (PSiFC6C6). The performances of the devices are sensitive to the blend ratio. When the mass ratio of PSiF6-PPP to PSiFC6C6 is 1 : 3, the highest external quantum efficiency is 1.96% at luminance of 105 cd.m2, its electroluminescent (EL) spectrum peaks at 398 nm and full width at half maximum is 67 nm. The improvements of the device performances were due to the energy transfer from PSiFC6C6 to PSiF6-PPP and the balanced injection of electrons and holes.     

高效蓝色有机发光材料与器件

有机半导体由于具有柔软性而可卷曲成形,具有可溶加工性而采用印刷成膜,从而使得加工成本有可能大大降低而受到广泛关注．本文针对有机发光材料中n型材料不足及宽能带与高电子传输性不可同时实现的难题,我们设计与合成了一系列的宽带电子传输材料并应用于蓝色磷光器件,实现了将近100％的内量子效率蓝色磷光．针对蓝色发光材料色度不纯的问题,我们设计了深蓝色荧光材料,其器件色度坐标CIE（0．15,0．08）,与NTSC标准蓝光相当接近,同时实现接近理论极限的外量子效率发光．针对器件中由于平面波导及表面等离激元等能量模式的损失,我们利用有机材料的自团聚现象在有机发光器件金属阴极上制备无规的纳米结构,把束缚能量转化成自由光子,使得顶出光效率提高到2．1—2．7倍,且不改变原有器件的发光光谱形状．     

ATRP法在纳米SiO_2表面接枝PBA及其对PVC的改性研究

采用原子转移自由基聚合法(ATRP)在纳米S iO2表面接枝PBA,并采用TEM及力学性能测试等手段研究了纳米S iO2及S iO2-g-PBA复合粒子的添加对聚氯乙烯(PVC)力学性能的影响.结果表明:用ATRP聚合方法有少量的PBA接枝于纳米S iO2表面;所制备的纳米复合粒子在PVC中较纳米S iO2粒子分散均匀,使纳米PVC/S iO2-g-PBA纳米复合材料的拉伸强度、断裂伸长率及断裂能均明显高于PVC及PVC/S iO2复合材料.     

嵌段共聚物PS-b-PAA的合成及其分散性能研究

以苯乙烯和丙烯酸为单体,二硫代苯甲酸苄酯为链转移剂,偶氮二异丁腈作为引发剂,采用可逆加成-断裂链转移活性自由基聚合方法合成了两亲性嵌段共聚物分散剂聚苯乙烯-b-聚丙烯酸(PS-b-PAA),探讨了影响聚合反应的主要因素,用GPC,IR,1H NMR对其结构进行了表征.结果表明,用RAFT法制得的共聚物分子量分布为1.1~1.3,聚合反应在80℃下24 h内转化率达95%.进一步的分散性能研究表明,超分散剂PS-b-PAA对S iO2粉体在水中有着较好的分散效果.     

碳点的制备及其荧光共振能量转移

以枝状聚乙烯亚胺和柠檬酸为原料,低温熔融法一步合成水溶性的氨基化碳点,碳点在紫外光激发下发出明亮的蓝光.采用傅里叶变换红外光谱和X射线粉末衍射仪对其结构进行表征,并研究其与碲化镉量子点在液相和固液界面的荧光共振能量转移.实验结果表明:液相中的荧光共振能量转移效率远大于固液界面的荧光共振能量转移,且能量转移具有一定的限度.     

聚乙二醇-g-聚天冬氨酸(阿霉素)的制备与毒性

聚天冬氨酸侧链修饰得到聚乙二醇接枝聚天冬氨酸(PEG-g-PAsp),将此载体与抗癌药物阿霉素(ADR)反应,透析后得到PEG-g-PAsp(ADR)胶束.药物ADR作为胶束的核,PEG作为外壳,药物的包封率最高可达29.7%.进行的毒性分析表明形成的纳米粒子与纯药物相比,表现出了更高的抗肿瘤活性.从而证明PEG-g-PAsp可以作为一种非常有潜力的药物载体.     

二苯基氧磷修饰的不对称三嗪主体材料的理论研究

近年来,电致磷光器件因其在全色显示和固体照明领域的潜在应用而备受关注.文中针对电致磷光器件中的主体材料,设计了基于二苯氧磷的一系列三嗪衍生物,并通过密度泛函理论（DFT）对三嗪衍生物进行了系统的量子化学理论研究.研究发现：三嗪核决定了该类材料具有较高的三线态能级（2.84 eV～3.02eV）,而其前沿轨道能级可通过二苯氧磷和咔唑修饰单元数量及其比例来逐级调控,最高占据轨道（HOMO）由咔唑决定,维持在-5.85 eV;而最低未占据轨道（LUMO）受二苯氧磷影响,可以从-1.42 eV降低到-2.33 eV,从而具有独立可调的LUMO能级.综合比较发现,具有两个咔唑和一个二苯氧磷的不对称三嗪（DCzPT）比较适合作为蓝光客体的主体材料,这是因为DCzPT不仅具有高的三线态能级（3.02 eV）和低的LUMO值（-1.74 eV）,而且具有较高的电子和空穴的传输能力.     

包裹姜根油的多种纳米颗粒的制备及质量评价

以大豆磷脂、聚乙交酯丙交酯(PLGA)和聚乙二醇(PEG)3种原料成功制备了包裹难溶于水的植物提取物姜根油(GRO)的纳米脂质体、PLGA纳米颗粒和PEG纳米颗粒,并对3种不同载体制备的纳米制剂的形貌、大小、Zeta电位,包封率及物理稳定性等进行了考察.研究结果表明3种纳米颗粒各有优缺点,可以根据不同的条件和不同的需要制备不同的颗粒,为开发新型的难溶药用植物提取物的理想药剂提供了实验依据.     

聚合物双层结构实现稳定的白光发射

通过聚乙烯咔唑(PVK)和发绿光的9’9-二辛基芴(DOF)与硒芬(SeH)的共聚物(PFSeH)形成聚合物双层器件结构(ITO/PEDOT/PVK/PFSeH/Ba/A l)实现白光发射.通过优化PVK和PFSeH各层的厚度,得到了光谱稳定的白光发射.在电压为13V时该器件的最大发光效率为0.51 cd/A,相应的亮度为750 cd/m2和色坐标C IE1931为(0.32,0.32).在10~18 V的电压范围内双层器件的白光发射光谱稳定不变.双层器件发白光的原因是由于PVK层的蓝光发射和PFSeH层的绿光发射及PFSeH与PVK双层界面间形成基激复合物的红光发射.     

Synthesis and energy transfer of model conjugate of phycobilisome rods

The conjugate of R-phycoerythrin (R-PE) and C-phycocyanin (C-PC) was synthesized through a heterobifunctional coupling reagent, N-succinimidyl 3-(2-pyridyldithio) propionate. The molar ratio of R-PE to C-PC was determined by absorption spectra, and the result was 2:1. The energy transfer phenomena were observed from steady-state fluorescence spectra. The calculated result showed that the energy transfer efficiency from R-PE to C-PC was 88%. The energy transfer kinetics was determined by picosecond time-resolved fluorescence spectra. The time constant of energy transfer from R-PE to C-PC was 80 ps, which was much longer than that in the rod of native phycobilisomes.     

PET/PEN共混物的热分解行为及其动力学

研究了惰性气氛下聚对苯二甲酸乙二酯(PET)/聚对萘二甲酸乙二酯(PEN)共混物的非等温热分解行为及其动力学.研究发现,不同PET/PEN共混物的热降解为一个主要的热分解过程,热分解反应为一级反应.随着共混物中PEN质量分数的增加,共混物的起始分解温度逐渐升高,共混物的热稳定性逐渐提高,而且共混物的热分解反应活化能也逐渐增加,这是由于PEN分子链中萘环的热分解温度比PET中苯环高,因此分子链的热稳定性比PET要高.共混物中萘环的化学组成含量越高,则热稳定性愈高.     

双亲性嵌段共聚物P4VP-b-PMAA的合成

以三[(2-二甲基氨基)乙基]胺为配体,α-氯代丙酸乙酯为引发剂,在异丙醇中引发4-乙烯吡啶(4VP)进行原子转移自由基聚合(ATRP),得到了端基为氯原子、相对分子质量在1 500～5 610之间的聚4-乙烯吡啶(P4VP-Cl)大分子引发剂.进而使P4VP-Cl引发甲基丙烯酸叔丁酯(tBMA)进行ATRP反应,得到了P4VP-b-PtBMA嵌段共聚物,其转化率可达60%以上.傅里叶变换红外光谱和核磁共振的分析结果表明,所得嵌段共聚物的结构明确.通过对P4VP-b-PtBMA进行水解,得到了P4VP-b-PMAA双亲性嵌段共聚物.     

Pure and stable white organic light-emitting device with an ultra-thin layer

Due to high brightness, low viewing angle, low driving voltage and short response time, organic light-emitting display is appraised as one of the most promising flat displays in the near future. Full-color technology is the bottle neck for industrializati…     

体硅阳极和薄膜微晶硅阳极聚合物顶发光白光器件

分别以p型体硅和p型薄膜微晶硅为阳极, 以掺入MEH-PPV的PFO为发光层, 以透明金属Sm/Au为阴极, 制作了顶发光白光器件。器件结构是: 硅阳极/PEDOT:PSS/MEH-PPV:PFO/Cs₂CO₃/Sm/Au。通过调节MEH-PPV在PFO中的质量百分比, 改进了白光器件的发射色度。当MEH-PPV的质量百分比为0.13%时, 发光在白光范围, CIE色坐标为(0.372, 0.391)。研究了器件发光效率对体硅阳极电阻率的影响, 当体硅阳极电阻率为0.079 Ω•cm时, 器件电流效率和功率效率都达到极大, 分别是0.191 cd/A和0.131 lm/W。以金属Ni诱导硅晶化的薄膜微晶硅为阳极, 通过调节Ni层厚度, 优化器件效率。当Ni层厚度为2 nm时, 薄膜硅阳极器件的电流效率和功率效率分别达到最大值: 0.371 cd/A和0.187 lm/W, 相对于最佳电阻率体硅阳极器件分别提高了94%和43%。     

Vibrational excitation through tug-of-war inelastic collisions

Vibrationally inelastic scattering is a fundamental collision process that converts some of the kinetic energy of the colliding partners into vibrational excitation(,). The conventional wisdom is that collisions with high impact parameters (where the partners only 'graze' each other) are forward scattered and essentially elastic, whereas collisions with low impact parameters transfer a large amount of energy into vibrations and are mainly back scattered. Here we report experimental observations of exactly the opposite behaviour for the simplest and most studied of all neutral-neutral collisions: we find that the inelastic scattering process H + D(2)(v = 0, j = 0, 2) --> H + D(2)(v' = 3, j' = 0, 2, 4, 6, 8) leads dominantly to forward scattering (v and j respectively refer to the vibrational and rotational quantum numbers of the D(2) molecule). Quasi-classical trajectory calculations show that the vibrational excitation is caused by extension, not compression, of the D-D bond through interaction with the passing H atom. However, the H-D interaction never becomes strong enough for capture of the H atom before it departs with diminished kinetic energy; that is, the inelastic scattering process is essentially a frustrated reaction in which the collision typically excites the outward-going half of the H-D-D symmetric stretch before the H-D(2) complex dissociates. We suggest that this 'tug of war' between H and D(2) is a new mechanism for vibrational excitation that should play a role in all neutral-neutral collisions where strong attraction can develop between the collision partners.     

苯乙炔封端超支化聚醚醚酮的合成及性能

采用亲核取代反应, 通过A₂+B₃方法制备含联苯结 构氟封端超支化聚醚醚酮(HPDEEK-F), 用4-苯乙炔苯酚与得到的氟封端聚合物反应, 制得苯乙炔封端的超支化聚醚醚酮(HPDEEK-PEP), 并研究了其结构和性能. 结果表明, 苯乙炔封端聚合物的玻璃化转变温度高于氟封端聚合物的玻璃化转变温度, 热稳定性好于氟封端聚合物, 两种聚合物在极性溶剂中都具有良好的溶解性.