n型掺杂PTCDA复合材料对有机发光二极管性能的提高

采用碳酸锂(Li2CO3)为n型掺杂剂,苝四甲酸二酐(3,4,9,10 perylenetetracarboxylic dianhydride,PTCDA)为母体材料,通过真空热蒸发方式制备了n型掺杂的PTCDA复合材料,将其作为电子注入材料应用到NPB/Alq3异质结有机电致发光器件中.研究发现,同LI2CO3:BC...     

Study on electroluminescence processes in dye-doped organic light-emitting diodes

Electroluminescence (EL) mechanism of dye-doped organic light-emitting diodes (OLEDs) was investigated by using three familiar fluorescent dyes, i.e., 5,12-Dihydro-5,12-dimethylquino [2,3-b]acridine-7,14-dione (DMQA), 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB), and 5,6,11,12-tetraphenylnaphthacene (Rubrene). EL spectra of the doped devices with structure of indium tin oxide (ITO)/N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′- diamine (NPB) (40 nm)/tris-(8-hydroxyquinolate)-aluminum (Alq₃) (x nm, x=0–40 nm)/dye: Alq₃ (weight ratio≈1%, 2 nm)/Alq₃ (48−x nm)/MgAg indicated that direct carrier trapping (DCT) process dominated light emission of devices. As a result, investigation of carrier-recombination site via doping, which is conventionally applied in OLEDs, is questionable since the doping site and the dopant itself may significantly influence the carrier-recombination process in the doped devices.     

NPB厚度对异质结OLED载流子复合区域的调控

通过调控p型半导体N,N′-bis(naphthalen-1-y)-N,N′-bis(phenyl)benzidine(NPB)层的厚度,制备了结构为ITO/NPB/aluminum(Ⅲ)bis(2-methyl-8-quinolinato)-4-phenylphenolate(BAlq)/NPB(0~18nm)/tri-(8-hydroxyquinoline)-aluminum(Alq₃)/Mg:Ag的多层有机电致发光器件.分析结果表明,在该类异质结器件中,NPB不仅可以作为空穴传输材料,在适当的厚度范围内,它还可以起到调控载流子复合区域的作用;当NPB厚度在0~18nm之间变化时,随着其厚度增加器件发光颜色可由蓝色变为绿色.通过器件发光光谱的表征可以得知,器件的载流子复合区域相应地由BAlq层转移至Alq₃层.     

超低效率滚降顶发射白光有机电致发光器件

利用Ag/tris-（8-hydroxyquinoline） aluminum（Alq₃）/Ag/Alq₃/Ag这一金属/有机半导体多层结构作为阳极,实现了超低效率滚降的顶发射白光器件。在该器件中,我们在蓝光和橙光发光单元之间引入一个薄的4,4′-bis（9-carbazolyl）-2,2′-biphenyl（CBP）层,从而减少橙光发光层与蓝光发光层的Dexter能量传递,用以改善白光器件发光光谱及效率。通过优化微腔设计,实现了对橙光磷光材料发射的调控。最终,我们获得了在60 000 cd/m²亮度下效率滚降仅为17%的顶发射白光器件。在效率方面,虽然顶发射白光器件与底发射白光器件不相上下,但由于微腔效应的存在,顶发射白光器件的效率滚降却远低于底发射白光器件的效率滚降。     

PVK空穴传输层对有机电致发光器件性能的影响

以聚乙烯基咔唑poly(N-vinylcarbazole)(PVK)旋涂层为空穴传输层,着重研究了PVK层厚度对双层器件氧化铟锡(ITO)/PVK/tris-(8-hydroxyquinoline)aluminum(Alq₃)/Mg:Ag/Al器件性能的影响。测试结果表明,当Alq₃层厚度一定时(50nm),只有PVK层为适当厚度(18nm)时双层器件才有最优良的器件性能,即最低的起亮电压,最高的发光亮度和效率。同时对比了不同PVK层厚度的PVK/Alq₃双层器件之间以及PVK/Alq₃与N,N′-bis-(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine(NPB)/Alq₃双层器件寿命的差异。测试结果表明,尽管越厚的PVK层对应的PVK/Alq₃双层器件发光性能并不是越好,但器件寿命越长。原因是器件Alq₃层内形成的Alq³⁺越少,因此器件稳定性越好;而PVK/Alq₃与NPB/Alq₃双层器件寿命的差异来自不同空穴传输层的制备工艺和能级结构的不同。     

Plasma treatment of the Mg:Ag/tris-(8-hydroxyquinoline) aluminum interface in OLEDs: effects on adhesion and performance

The adhesion of a Mg:Ag cathode to the tris-(8-hydroxyquinoline) aluminum (Alq₃) in organic light emitting devices (OLEDs) can be greatly enhanced by a remote plasma treatment of the Alq₃ layer using either air or N₂ prior to metal deposition. The altered surface properties which lead to increased sticking coefficients of Mg and Ag, as well as enhanced adhesion, are attributed to the introduction of new functional groups into the organic layer, as observed by X-ray photoelectron spectroscopy (XPS). The storage life of the plasma treated devices in air without any capping treatment, as judged by a visible deterioration of the cathode, was increased by approximately five to six times compared to untreated OLEDs. Current–voltage characteristics and EL efficiency, however, were shown to deteriorate for devices incorporating either an air or an N₂ plasma treated Alq₃ layer. For OLEDs subjected to short treatment times with an N₂ plasma, only a very slight increase in the turn-on voltage, of about 0.2 V, was observed. An investigation of black spot formation revealed that an air plasma treatment resulted in a five-fold decrease in the time required for 50% of the device to become non-emissive. N₂ treated devices on the other hand, developed black spots at a comparable rate to the non-treated devices. Thus, a short N₂ plasma treatment of the Alq₃ layer prior to metal deposition improves the adhesion at the interface, thereby reducing the oxidation and degradation of the device through exposure to ambient conditions, particularly in storage.     

Exciton–dopant and exciton–charge interactions in electronically doped OLEDs

The electronic dopants, like tetrafluorocyanoquinodimethane (F₄–TCNQ) molecules, used for p-doping of hole transport layers in organic light-emitting diodes (OLEDs) are found to quench the electroluminescence (EL) if they diffuse into the emissive layer. We observed EL quenching in OLED with F₄-TCNQ doped N,N′-diphenyl-N′N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine hole transport layer at large dopant concentrations, >5%. To separate the effects of exciton–dopant quenching, from exciton–polaron quenching we have intentionally doped the emissive layer of (8-tris-hydroxyquinoline) with three acceptors (A) of different electron affinities: F₄-TCNQ, TCNQ, and C₆₀, and found that C₆₀ is the strongest EL-quencher, while F₄-TCNQ is the weakest, contrary to intuitive expectations. The new effects of charge transfer and usually considered energy transfer from exciton to neutral (A) and charged acceptors (A⁻) are compared as channels for non-radiative Ex–A decay. At high current loads the EL quenching is observed, which is due to decay of Ex on free charge carriers, hole polarons P⁺. We consider contributions to Ex–P⁺ interaction by short-range charge transfer and describe the structure of microscopic charge transfer (CT)-processes responsible for it. The formation of metastable states of ‘charged excitons’ (predicted and studied by Agranovich et al. Chem. Phys. 272 (2001) 159) by electron transfer from a P to an Ex is pointed out, and ways to suppress non-radiative Ex–P decay are suggested.     

蓝色有机发光材料LiBq4的合成及其发光特性

蓝色有机发光材料的开发对于实现有机发光二极管(OLED)的全彩色化具有十分重要的意义.报道了蓝色有机发光材料8-羟基喹啉硼化锂(LiBq₄)的合成及提纯,研究了LiBq₄的光致发光特性,并用LiBq₄作为发光材料制备了蓝色有机发光器件,研究了电子传输层Alq₃的厚度及空穴缓冲层CuPc对器件电流-电压和亮度-电压特性的影响.结果表明,LiBq₄的光致发光峰值波长为452nm,器件ITO/PVK:TPD/LiBq₄/Alq₃/Al的电致发光光谱峰值波长位于475nm处,在25V工作电压下其最高亮度约为430cd/m².但CuPc的加入加剧了器件中载流子的不平衡注入,导致器件性能恶化.通过调整Alq₃的厚度,同时在Alq₃和Al阴极之间加入LiF薄膜以提高电子注入效率,获得了较为理想的实验结果.     

多层结构的阴极修饰层对有机电致发光器件的性能改善

为提高有机电致发光器件（OLEDs）的阴极电子注入效率,我们设计了新型的阴极杂化修饰层,其结构为Bphen∶LiF/Al/MoO₃,将其应用到器件ITO/NPB/Alq₃/Al中,参考器件的电子注入层选用传统材料LiF。实验研究表明,与传统的阴极修饰层LiF相比,基于这种杂化结构的阴极修饰层非常有效。测试了器件的电致发光光谱（EL谱）,其峰值位于534 nm,发光来自于Alq₃,实验中我们可以观察到明亮的绿色发光。将其与传统参考器件的EL谱进行对比,在电流密度40 mA·cm-2下,两个器件的电致发光光谱是一致的。在0～100 mA·cm-2范围内,对器件的EL谱进行了测试。实验结果表明,随着电流密度的增加,器件的发光增强,但是EL谱的形状和谱峰的位置是固定不变的。与参考器件对比,基于杂化修饰层的器件的发光性能更好。研究表明,杂化修饰层的最佳参数为Bphen∶LiF(5 nm; 6%)/Al(1 nm)/MoO₃(5 nm),在测试范围内,器件的最大电流效率和最大功率效率分别为4.28 cd·A-1和2.19 lm·W-1,相比参考器件提高了25.5%和23.7%。器件的电流密度-电压特性曲线表明阴极杂化修饰层可以增强电子的注入,使器件中的载流子更加平衡,从而提高了器件的发光性能。从两个角度对器件效率的增强进行了理论方面的论证。一方面利用阴极杂化修饰层的作用机制来解释。在HML中,LiF能填充Bphen的电子陷阱,增强电流的注入,同时HML也能限制空穴的传输,减小空穴电流。另一方面从电荷平衡因子的角度,HML增强了电子的注入,使得器件的电荷平衡因子增大,空穴和电子的平衡性更好。实验研究表明,阴极杂化修饰层很好地增强了器件的效率。     

Optimization of a poly (p-phenylene benzobisoxazole)-based light-emitting device with a complex cathode structure

In this work,we report the preparation of a series of electroluminescent(EL)devices based on a high-performance polymer,poly(p-phenylene benzobisoxazole)(PBO),and their optoelectronic properties,which have been rarely explored.The device structure is optimised using a complex cathode structure of tris-(8-hydoxyquinoline)aluminium(Alq3)/LiF/Al.By tuning the thickness of the Alq3layer,we improve the device efficiency dramatically in an optimized condition.Further analysis reveals that the Alq3layer in the complex cathode structure acts as a hole blocker in addition to its electron-injection role.A green light emission with a maximum brightness of 8.7×103cd/m2and a moderate current efficiency of 4.8 cd/A is obtained.These values are the highest ever reported for PBO devices.The high operational stability demonstrated by the present device makes it a promising tool for display and lighting applications.A new material is added to the selection of polymers used in this field up to now.     

DPVBi空穴阻挡层对OLED性能的优化

研究了宽带隙有机小分子材料DPVBi作为空穴阻挡层对OLED器件效率和亮度的优化作用.DPVBi的引入有效地改善了以PEDOT:PSS做空穴注入层的OLED器件的空穴过剩问题.实验结果表明:通过优化DPVBi的厚度,插入30 nm厚的DPVBi空穴阻拦层可以有效地平衡OLED器件的电子和空穴浓度,降低器件的工作电压,优...     

Improved outcoupling of light in organic light emitting devices, utilizing a holographic DFB-structure

In this work organic light emitting devices (OLEDs) were fabricated implementing gratings, in order to extract waveguided electroluminescence (EL). The gratings were recorded by exposing thin films of the molecular azo glass N, N′-bis (4-phenyl)-N, N′-bis [(4-phenylazo)-phenyl] benzidine (AZOPD) to holographic light patterns. The photopatterned AZOPD serves as hole transport material for devices with aluminum-tris(8-hydroxyquinoline) doped with 1% of 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (Alq₃:DCM) as emissive/electron transport layer. The corrugated devices showed enhanced emission in the forward direction. The emitted light is polarized preferably parallel to the grating lines. In addition, we have found a doubling in the total luminance with respect to the unstructured device.     

TBVB用作蓝光发光层的非掺杂有机电致蓝光和白光器件

利用一种来源于PPV的发蓝光的齐聚物材料2,5,2',5'-tetra(4'-biphenylenevinyl)-biphenyl(TBVB)制作非掺杂的有机电致蓝光和白光器件。蓝光器件的结构为ITO/NPB/TBVB/Alq₃/LiF/Al,其中TBVB用作发光层;白光器件的结构为ITO/NPB/TBVB/rubrene/Alq₃/LiF/Al,其中TBVB与超薄层(平均“厚度”0.05~0.20nm)的Rubrene相结合用作发光层,二者分别发蓝光和黄光。在蓝光器件中,当TBVB的厚度为30nm时,器件发出色坐标为(0.20,0.26)的蓝光,其最大亮度和效率分别达到2154cd/m²和1.62cd/A。在白光器件中,可通过调节TBVB和Rubrene的厚度实现对器件发光色度的调节。当TBVB和Rubrene的厚度分别为10,0.15nm时,器件在亮度为4000cd/m²时发光色坐标为(0.33,0.34),非常接近白光等能点,且随着电压的变化始终处于白光区。当电压为16V时该器件达到最高亮度4025cd/m²;当电压为6V时器件有最高的效率3.2cd/A。     

钙铝镁合金阴极对WOLED器件性能的影响

采用Ca/Al/Mg合金作为器件的阴极,基于红绿/蓝双发光层制作了6种白色磷光OLED器件,器件结构为ITO/MoO₃ (30 nm)/NPB (40 nm)/mCP:Firpic (8%,40 nm)/CBP:R-4B (2%):Ir(ppy)₃ (14%,5 nm)/TPBi (10 nm)/Alq₃(40 nm)/Ca:Al:Mg (x%,100 nm) (x=0,5,10,15,20,25)。通过改变Mg的掺杂比例,研究了不同比例的Ca/Al/Mg合金阴极对器件性能的影响。结果表明:Mg质量分数为15%的Ca/Al/Mg阴极具有良好的电子注入特性,有效改善了器件的发光特性,最大发光亮度可达1 504 cd/m²,效率达到最大值14.3 cd/A,色坐标接近(0.46, 0.42)。     

基于MoO3/Ag/MoO3透明阳极的顶发射OLED的模拟计算与制备

运用传输矩阵法和正交分析法模拟计算出MoO₃/Ag/MoO₃透明电极的最佳厚度,采用镀膜实验验证模拟计算的准确性,制备了一系列不同MoO₃膜厚度和Ag膜厚度的透明电极。然后,制备了一系列顶发射有机电致发光器件:铝/氟化锂(LiF)/三(8-羟基喹啉)铝(Alq₃)/N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺/三氧化钼(MoO₃)/银(Ag)/三氧化钼(MoO₃),来进一步验证模拟计算运用在器件制备中的准确性。MoO₃(10 nm)/Ag(10 nm)/MoO₃(25 nm)在532 nm处的透射率达到最大值88.256%,以该透明电极制备的器件与参考器件相比,性能有了明显提高,最大亮度和最大效率分别为20 076 cd/m²和4.03 cd/A,提高了18.5%和56%。器件性能的提高归因于顶发射OLED器件透射率的提高和MoO₃对空穴注入能力的提升。     

有机发光材料DPVBi的空穴阻挡特性

讨论了有机发光材料4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl(DPVBi),在结构为ITO/N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine(NPB)/DPVBi/tris-(8-hydroxyquinoline)aluminum(Alq₃)/LiF/Al的有机电致发光器件中所表现出来的空穴阻挡特性。通过实验可以看到,当NPB的厚度小于DPVBi的厚度时,DPVBi对空穴的阻挡作用和其自身的厚度有关,厚度越大阻挡能力越强。DPVBi的厚度一定(120nm)且不足以将空穴完全限制于DPVBi层内时,其对空穴的阻挡能力,随着NPB厚度(30~60nm)的增加而相对减弱。当NPB的厚度大于DPVBi的厚度时,进入DPVBi层的空穴,随着它们之间厚度差别的增大而增加,从而使器件的光谱半峰全宽加大。这几条规律对于制作基于DPVBi的有机蓝光和有机白光器件具有一定的指导意义。     

效率增强的新型蓝色有机发光器件

使用一种新型空穴传输材料J003制备了不同结构、不同发光层厚度的两组蓝色发光器件,其结构为:ITO/CuPc/J003/JBEM:perylene/Al_q3/LiF/Al和ITO/CuPc/J003/JBEM:perylene/TPBi/Al_q3/LiF/Al,这里CuPc(Copper phthalocyanine)和LiF分别为空穴注入层(HIL)和电子注入层(EIL),J003为空穴传输层(HTL),JBEM(9,10-bis(3,5'-diaryl)phenylylanthracene)为发光层(EML),TPBj(1,3,5-tri(phenyl-2-benzimidazole)-benzene)为空穴阻挡层(HBL),Al_q3(tris(8-quinolinolato)aluminium complex)为电子传输层(ETL).两种结构中前者为无阻挡层的普通型结构,后者在发光层和电子传输层中加入了空穴阻挡层,是新型阻挡层结构.研究了空穴阻挡层的引入在不同厚度发光层时对器件发光性能的影响,结果表明,新型阻挡层结构能明显提高器件的亮度和效率,但依赖于发光层厚度,利用能级图分析了其中的原因.     

Aggregation of phthalocyanine derivatives in liquid solutions and human blood

The aggregation of the copper (II) 4,4′,4′′,4′′′-tetrasulfonated phthalocyanine anion (Cu(tsPc)⁻⁴) has been studied in aqueous solutions, DMSO and in human blood by UV–VIS absorption spectroscopy and resonance Raman spectroscopy (RRS). The vibrational mode ν₄ (1530 cm⁻¹) has been used as a probe in RRS. It has been shown that the dimerization equilibrium constant K is shifted significantly towards monomeric forms when human blood is added to the solution. The life-time of the singlet excited state S_n of (Cu(tsPc)⁻⁴) in aqueous solution has been estimated to be shorter than 500 fs using femtosecond pump-probe absorption spectroscopy.     

阴极修饰层CuPc、ZnPc、C60对OLED光电性能的影响

采用真空蒸镀法分别制备了以CuPc、ZnPc、C₆₀为阴极修饰层的OLED,对比研究了它们对OLED光电性能的影响。从能级结构、表面形貌、折射率及纳米界面等方面对载流子注入和输运进行了探讨。结果表明:修饰层使器件性能显著提高,它不仅降低OLED开启电压（最低至4.2 V）、提高OLED电流密度及发光效率（最高至13.49 lm/W）,同时增强了器件的发光稳定性（180 s后光强保持在90%以上）,其中以CuPc为阴极修饰层的器件表现的性能最好。发光光谱方面,以CuPc和ZnPc作为修饰层的器件对550~650 nm的红光部分略有吸收,而C₆₀作为修饰层的器件光谱则无太大变化,这是由修饰层材料的吸收系数随不同波长而变化所致。实验结果说明,若想较大程度地提高器件电性能,酞菁材料是不错的选择;若对光谱有要求,可用C₆₀做阴极修饰层。