Improved performance of organic light-emitting diodes with dual electron transporting layers

In this study the performance of organic light-emitting diodes(OLEDs) are enhanced significantly,which is based on dual electron transporting layers(Bphen/CuPc).By adjusting the thicknesses of Bphen and CuPc,the maximal luminescence,the maximal current efficiency,and the maximal power efficiency of the device reach 17570 cd/m2 at 11 V,and 5.39 cd/A and 3.39 lm/W at 3.37 mA/cm2 respectively,which are enhanced approximately by 33.4%,39.3%,and 68.9%,respectively,compared with those of the device using Bphen only for an electron transporting layer.These results may provide some valuable references for improving the electron injection and the transportation of OLED.     

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。     

双电子传输层对有机发光二极管效率及其衰减的改善

采用Bphen和BCP制成双电子传输层(Doubleelectrontransportlayers, DETLs)的有机发光二极管器件, 与Bphen单独作ETL的器件相比, DETLs器件具有较小的空穴漏电流, 效率提升10%。与BCP独自作ETL的器件相比, 更多的电子注入使DETLs器件的效率在50~600mA/cm²的电流范围内没有衰减。BCP作ETL的器件的效率从50mA/cm²时的2.5cd/A衰减至300mA/cm²的2.1cd/A, 衰减了16%。Cs₂CO₃:BCP独自作ETL的器件效率在50~300mA/cm²的电流范围内衰减了30%, 而Bphen/Cs₂CO₃:BCP作DETLs的器件效率在50~600mA/cm²的电流范围内衰减幅度为0, 原因是Bphen阻挡了Cs原子扩散至发光层。     

基于一种新型杂化阳极修饰层的高效有机电致发光器件

设计了基于Bphen∶LiF、Al和MoO₃的杂化电荷注入层,并将其应用于有机电致发光器件中。实验研究表明,这种杂化层作为阳极修饰层是非常有效的,它可以增加器件中载流子注入的平衡性,提高器件的性能。相对参考器件,基于杂化阳极修饰层的电致发光器件的最大电流效率和最大功率效率均提高1.3倍左右。我们对器件性能及其提高的机理进行了分析。     

Tandem white organic light-emitting diodes adopting a C60：rubrene charge generation layer

Organic bulk heterojunction fullerence(C60) doped 5, 6, 11, 12-tetraphenylnaphthacene(rubrene) as the high quality charge generation layer(CGL) with high transparency and superior charge generating capability for tandem organic light emitting diodes(OLEDs) is developed. This CGL shows excellent optical transparency about 90%, which can reduce the optical interference effect formed in tandem OLEDs. There is a stable white light emission including 468 nm and 500 nm peaks from the blue emitting layer and 620 nm peak from the red emitting layer in tandem white OLEDs. A high efficiency of about 17.4 cd/A and CIE coordinates of(0.40, 0.35) at 100 cd/m2 and(0.36, 0.34) at 1000 cd/m2 have been demonstrated by employing the developed CGL, respectively.     

聚合物级联发光器件

基于溶液加工方法制备了聚乙撑二氧噻吩-聚(苯乙烯磺酸盐)(PEDOT∶PSS)/氧化锌(ZnO)/乙氧基化聚乙烯亚胺(PEIE)电荷产生层的聚合物级联发光器件, 发现PEDOT∶PSS层电导和厚度对器件的电流-电压特性影响较小, 不同PEDOT∶PSS对器件发光效率的影响主要来自于其对发光层激子不同的猝灭作用, PEDOT∶PSS厚度为60 nm的级联器件比PEDOT∶PSS 厚度为30 nm的级联器件的发光效率稍高, 原因是PEDOT∶PSS较厚时, 其表面形貌更均匀。级联器件的发光效率和驱动电压分别与发光子单元的发光效率和驱动电压之和相近, 说明在较低的电压下电荷产生层就能够有效产生电荷并注入到发光子单元中,级联器件的发光光谱中包含两个发光子单元的发光光谱,说明两个发光子单元在级联器件中都能正常工作。通过对电荷产生层的电容-电压(C-V)特性的测试, 确认了在电荷产生层中存在电荷的积累过程。证明了PEDOT∶PSS/ZnO/PEIE为有效的电荷产生层。首次报道了包含三个SY-PPV发光单元的级联器件, 三个发光子单元发光效率之和与级联器件的发光效率相当, 其最大发光效率和最大外量子效率分别为21.7 cd·A-1和6.95%。在器件亮度为5 000 cd·m-2时, 器件的发光效率和外量子效率分别为20.5 cd·A-1和6.6%。说明并没有由于发光子单元数目增加而影响级联器件的发光效率。并且其发光光谱和发光子单元的发光光谱相接近。通过 进一步降低CGL中空穴注入层对级联器件的影响有望提高级联器件的发光效率。     

Improved performance of polymer solar cells by using inorganic,organic, and doped cathode buffer layers

The interface between the active layer and the electrode is one of the most critical factors that could affect the device performance of polymer solar cells. In this work, based on the typical poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester(P3HT:PCBM) polymer solar cell, we studied the effect of the cathode buffer layer(CBL) between the top metal electrode and the active layer on the device performance. Several inorganic and organic materials commonly used as the electron injection layer in an organic light-emitting diode(OLED) were employed as the CBL in the P3HT:PCBM polymer solar cells. Our results demonstrate that the inorganic and organic materials like Cs_2CO_3, bathophenanthroline(Bphen), and 8-hydroxyquinolatolithium(Liq) can be used as CBL to efficiently improve the device performance of the P3HT:PCBM polymer solar cells. The P3HT:PCBM devices employed various CBLs possess power conversion efficiencies(PCEs) of 3.0%–3.3%, which are ca. 50% improved compared to that of the device without CBL. Furthermore, by using the doped organic materials Bphen:Cs_2CO_3 and Bphen:Liq as the CBL, the PCE of the P3HT:PCBM device will be further improved to 3.5%, which is ca. 70% higher than that of the device without a CBL and ca. 10% increased compared with that of the devices with a neat inorganic or organic CBL.     

High-efficiency p–i–n organic light-emitting diodes with a novel n-doping electron transport layer

We demonstrate p–i–n organic light-emitting diodes (OLEDs) incorporating an n-doping transport layer which comprises 8-hydroxy-quinolinato lithium (Liq) doped into 4′7-diphyenyl-1,10-phenanthroline (Bphen) as ETL and a p-doping transport layer which includes tetrafluro-tetracyano-quinodimethane (F₄-TCNQ) doped into 4,4′,4″-tris(3-methylphenylphenylamono) triphenylamine (m-MTDATA). In order to examine the improvement in the conductivity of transport layers, hole-only and electron-only devices are fabricated. The current and power efficiency of organic light-emitting diodes have been improved significantly after introducing a novel n-doping (Bphen: 33 wt% Liq) layer as an electron transport layer (ETL) and a p-doping layer composed of m-MTDATA and F₄-TCNQ as a hole transport layer (HTL). Compared with the control device (without doping), the current efficiency and power efficiency of Device C (most efficient) is enhanced by approximately 51% and 89%, respectively, while driving voltage is reduced by 29%. This improvement is attributed to the improved conductivity of the transport layers that leads to the efficient charge balance in the emission zone.     

Enhanced power efficiency for white OLED with MoO3 as hole injection layer and optimized charge balance

White OLEDs with a different hole injection layer (MoO₃ or m-MTDATA), and a different electron transport layer (Alq₃ or Bphen) have been investigated. With 9,10-bis (2-naphthyl)-2-t-butylanthracene (TBADN) doped with 3% P-bis (P-N, N-diphenyl-aminostyryl) benzene (DSA-ph) and 0.05% 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7,-tetramethyl-julolidy-9-enyl)-4H-pyran (DCJTB) as white emitting layer, the MoO₃/ /Bphen based device shows the lowest driving voltage and highest power efficiency among the referenced devices. At the current density of 20 mA/cm², its driving voltage and power efficiency are 5.43 V and 4.54 lm/W respectively, which is independently reduced 40% and improved 57% compared with those of the m-MTDATA/ / Alq₃ based one, respectively. The energy level diagram of the devices and single-carrier devices are studied to explain the reasons for the improvement. The results strongly indicate that carrier injection ability and balance shows a key significance in OLED performance.     

Performance improvement of MEH-PPV:PCBM solar cells using bathocuproine and bathophenanthroline as the buffer layers

In this work, bathocuproine (BCP) and bathophenanthroline (Bphen), commonly used in small-molecule organic solar cells (OSCs), are adopted as the buffer layers to improve the performance of the polymer solar cells (PSCs) based on poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV): [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojunction. By inserting BCP or Bphen between the active layer and the top cathode, all the performance parameters are dramatically improved. The power conversion efficiency is increased by about 70% and 120% with 5-nm BCP and 12-nm Bphen layers, respectively, when compared with that of the devices without any buffer layer. The performance enhancement is attributed to BCP or Bphen (i) increasing the optical field, and hence the absorption in the active layer, (ii) effectively blocking the excitons generated in MEH-PPV from quenching at organic/aluminum (Al) interface due to the large band-gap of BCP or Bphen, which results in a significant reduction in series resistance (Rs), and (iii) preventing damage to the active layer during the metal deposition. Compared with the traditional device using LiF as the buffer layer, the BCP-based devices show a comparable efficiency, while the Bphen-based devices show a much larger efficiency. This is due to the higher electron mobility in Bphen than that in BCP, which facilitates the electron transport and extraction through the buffer layer to the cathode.     

高效率的有机电致发光器件

有机电致发光器件 (OL EDs)的发光机理包括电子和空穴从电极的注入、激子的形成及复合发光 ,其中 ,空穴和电子的注入平衡是非常重要的。为了平衡载流子的注入以得到高效率和稳定性好的器件 ,人们不仅使用了电子注入更为有效的 L i F/ Al[1] 和 Cs F/ Al[2 ] 等复合电极 ,同时也使用了空穴缓冲层 ,如 S.A.Van Slyke等 [3]在ITO和 NPB之间使用 Cu Pc,使得器件的稳定性得到了明显的提高 ;A.Gyoutoku等[4 ] 用碳膜使器件的半寿命超过 3 5 0 0小时 ;最近 ,Y.Kurosaka等 [5]和 Z.B.Deng[6 ]分别在 ITO和空穴传输层之间插入一薄层 Al…     

基于器件结构提高TADF-OLED器件的发光性能

为了提高以TADF材料作为主体、天蓝色荧光材料作为客体的混合薄膜的OLED器件光电性能,我们调整了器件结构,使主体材料发挥其优势。制备了基本结构为ITO/NPB(40 nm)/DMAC-DPS∶x%BUBD-1(40 nm)/Bphen(30 nm)/LiF(0.5 nm)/Al的OLED器件。研究了主-客体材料在不同掺杂浓度下的OLED器件的光电特性。为了提高主体材料的利用率,在空穴传输层和发光层之间加入10 nm的DMAC-DPS作为间隔层;然后,在阳极和空穴传输层之间加入HAT-CN作为空穴注入层,形成HAT-CN/NPB结构的PN结,有效降低了器件的启亮电压(2.7 V)。测量了有无HAT-CN的单空穴器件的阻抗谱。结果表明,在最佳掺杂比例(2%)下,器件的外量子效率(EQE)达到4.92%,接近荧光OLED的EQE理论极限值;加入10 nm的DMAC-DPS作为间隔层,使得器件的EQE达到5.37%;HAT-CN/NPB结构的PN结有效地降低了器件的启亮电压(2.7 V),将OLED器件的EQE提高到5.76%;HAT-CN的加入提高了器件的空穴迁移率,降低了单空穴器件的阻抗。TADF材料作为主体材料在提高OLED器件的光电性能方面具有很大的潜力。     

Optimized Performances of Thick Film Organic Lighting-Emitting Diodes

The performance of organic light-emitting diodes (OLEDs) with thick film is optimized. The alternative vanadium oxide (V₂O₅) and N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (NPB) layers are used to enhance holes in the emissive region, and 4,7-dipheny-1,10-phenanthroline (Bphen) doped 8-tris-hydroxyquinoline aluminium (Alq₃) is used to enhance electrons in the emissive region, thus ITO/V₂O₅ (8nm)/NPB (52nm)/V₂O₅ (8nm)/NPB (52nm)/Alq₃ (30 and 45nm)/Alq₃:Bphen (30wt%, 30 and 45nm)/LiF (1nm)/Al (120nm) devices are fabricated. The thick-film devices show the turn-on voltage of about 3V and the maximal power efficiency of 4.5lm/W, which is 1.46 times higher than the conventional thin-film OLEDs.     

Highly efficient bipolar connecting layers for tandem organic light-emitting devices

A highly efficient tandem organic light-emitting device (OLED) has been fabricated by using an effective bipolar connecting layer structure. The connecting layers were made up of a layer of magnesium (Mg): 2,7-dipyrenyl-9,9-diphenyl fluorene (N-DPF) and a layer of tungsten trioxide (WO₃). Such a connecting layer structure permits efficient opposite holes and electrons flowing into two adjacent emitting units. The current efficiency of the two-unit tandem device can be dramatically enhanced by more than four times compared with that of the conventional single-unit device. At 60 mA/cm², the current efficiency of the tandem OLED using the connecting layers of Mg: N-DPF/WO₃ was about 8.15 cd/A. The results can be marked as a breakthrough approach to improve the current efficiency and brightness of OLEDs. Furthermore, a model of the carrier tunneling into light-emitting units is proposed based on carrier balance and field-assisted tunneling. It indicates that the connecting layer structure functions as the origin of high efficiency for the tandem OLEDs.     

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...     

空穴注入层对蓝色有机电致发光器件性能的影响

以DPVBi为发光层,NPB为空穴传输层,在阳极ITO和NPB之间分别插入不同的空穴注入层CuPc和PEDOT:PSS,制备了两种结构的蓝色有机电致发光器件(OLEDs):ITO/CuPc/NPB/DPVBi/BCP/Alq3/Al和ITO/PEDOT:PSS/NPB/DPVBi/BCP/Alq3/Al,研究了不同空穴注入材料对蓝色OLEDs发光性能的影响,并与没有空穴注入层的器件进行了比较.其中CuPc分别采用旋涂和真空蒸镀两种丁艺,比较了不同成膜工艺对器件发光特性的影响.结果表明:加入空穴注入层的器件比没有空穴注入层器件性能要好,其中插入水溶性CuPc的器件,其发光亮度和效率虽然比蒸镀CuPc器件要低,但比插入PEDOT:PSS 器件发光性能要好.又由于水溶性CuPc采用旋涂工艺成膜,与传统CuPc相比,制备工艺简单,所以为一种不错的空穴注入材料.     

基于新型电荷生成层的P-i-N结构白色有机叠层电致发光器件

采用2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline(BCP): 5 wt.% cesium carbonate(Cs₂CO₃)和N, N'-Bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine(NPB): 20 wt.% molybdenum oxide(MoO₃)分别作为器件的电子注入层和空穴注入层,研究了N型和P-i-N结构有机电致发光器件的载流子传输特性.载流子传输层中BCP: Cs₂CO₃和NPB:MoO₃的引入有效增强了载流子注入能力,从而降低了器件的驱动电压.基于新型电荷生成层BCP: 5 wt.% Cs₂CO₃/ NPB: 20 wt.% MoO₃制备了色稳定、高效率P-i-N结构有机叠层器件.与单元器件相比,引入新电荷生成层有机叠层器件的最大电流效率增大了2.5倍,表明该电荷生成层可以有效地将电子和空穴分别注入到相邻发光单元中.采用该电荷生成层制备了P-i-N结构白色有机叠层器件,器件的上下发光单元分别为橙光和蓝光发射.当发光亮度从500增加到5 000 cd/m²时,器件的色坐标稳定在(0.33, 0.29)附近,接近白光等能点.利用单色发光单元堆叠制备白色有机叠层器件的方法为实现色稳定、高效率的白色有机电致发光器件提供了一种有效的途径.     

基于混合空穴注入层的湿法制备高效蓝光热激活延迟有机发光二极管

在溶液法制备有机电致发光器件(OLEDs)的研究中, PEDOT∶PSS由于具有较好的成膜性与高透光性而常被用作器件的空穴注入层。但相关研究表明, PEDOT∶PSS本身稳定性较差以及功函数较低,这使得溶液法制备OLEDs的性能差且不稳定。蓝色作为全彩色的三基色之一,制备高效的蓝光器件对于实现高质量显示器件和固态照明装置必不可少。而目前溶液法制备蓝光OLEDs的器件效率普遍较差,针对此问题,本文利用传统的蓝光热激活延迟荧光发光(TADF)材料DMAC-DPS作为发光层,用溶液法制备了蓝光TADF OLEDs,通过在PEDOT∶PSS中掺杂PSS-Na制备混合空穴注入层(mix-HIL)来提高空穴注入层的功函数,研究其对于蓝光TADF OLEDs器件性能的影响。首先在PEDOT∶PSS水溶液中掺入不同体积的PSS-Na溶液,在相同条件下旋涂制膜,进行器件制备。通过观测各个实验组器件的电致发光(EL)光谱,发现掺入PSS-Na后器件EL谱存在光谱蓝移的现象,这是由于掺入PSS-Na水溶液后, mix-HIL层的厚度有所降低,使得在微腔效应作用下, EL光谱发生蓝移。通过对比各组器件的电流密度-电压-亮度(J-V-L)曲线及其计算所得器件的电流效率,结果显示随着PSS-Na的掺入,器件的亮度和电流都有所增大,器件的电流效率也得到了提升,当掺杂比例为0.5∶0.5(PEDOT∶PSS/PSS-Na)时提升幅度最大(亮度提升86.7%,电流效率提升34.3%)。通过在瞬态电致发光测试过程中施加或撤去驱动电压观测了器件EL强度的变化,分析了在混合空穴注入层/发光层(mix-HIL/EML)界面处的电荷积累情况。实验证明,通过在PEDOT∶PSS中掺杂PSS-Na制备mix-HIL获得了蓝光TADF OLEDs器件性能的提升,这是一个获得高效率溶液法制备OLEDs的可行方法。     

Tandem organic light-emitting diode with a molybdenum tri-oxide thin film interconnector layer

A 10-nm-thick molybdenum tri-oxide(MoO3) thin film was used as the interconnector layer in tandem organic lightemitting devices(OLEDs).The tandem OLEDs with two identical emissive units consisting of N,N-bis(naphthalen-1-yl)N,N-bis(phenyl)-benzidine(NPB) /tris(8-hydroxyquinoline) aluminum(Alq3) exhibited current efficiency-current density characteristics superior to the conventional single-unit devices.At 20 mA/cm2,the current efficiency of the tandem OLEDs using the interconnector layers of MoO3 thin film was about 4.0 cd/A,which is about twice that of the corresponding conventional single-unit device(1.8cd/A).The tandem OLED showed a higher power efficiency than the conventional single-unit device for luminance over 1200cd/m2.The experimental results demonstrated that a MoO3 thin film with a proper thickness can be used as an effective interconnector layer in tandem OLEDs.Such an interconnector layer can be easily fabricated by simple thermal evaporation,greatly simplifying the device processing and fabrication processes required by previously reported interconnector layers.A possible explanation was proposed for the carrier generation of the MoO3 interconnector layer.     

不同电极对蓝光有机电致发光器件性能的影响

利用高真空多源型有机分子沉积系统分别制备了不同负电极为Al、LiF/Al和Mg:Ag的有机小分子多层电致发光器件,比较了不同负极对以五苯基环戊二烯（PPCP）为发光层的蓝光有机电致发光器件性能的影响,发现以LiF/Al作负极的器件在综合性能上优于其它器件。其中器件ITO／TPD／PPDP／Alq/LiF/Al蓝光发射的最大发光亮度达2375cd/m^2,最大发光效率为0.26lm/W.