溶液法制备的金属掺杂氧化镍空穴注入层在钙钛矿发光二极管上的应用

甲脒基钙钛矿(FAPbX_3)纳米晶(NCs)具有成本低、色纯度高、吸收范围广、带隙可调等特点,在照明显示与光伏领域中表现出良好的应用前景.然而传统钙钛矿发光二极管(LEDs)的空穴注入层材料——PEDOT:PSS,由于其固有的吸湿性和酸性,严重影响着器件的稳定性,而器件的稳定性始终是阻碍钙钛矿发光器件成为实际应用的关键因素之一.本文首次使用溶液法制备的氧化镍(NiO)薄膜作为溴基甲脒钙钛矿(FAPbBr_3) NCs LEDs的空穴注入层,降低空穴注人层对钙钛矿发光层的影响,获得了高效且稳定的钙钛矿发光器件,器件寿命是基于PEDOT:PSS的器件的2.3倍.通过适当浓度的金属掺杂(Cs:NiO/Li:NiO),可以有效改善器件的电荷平衡,从而进一步提高FAPbBr_3 NCs LEDs的性能.基于掺杂2 mol%Cs的NiO的器件表现出最优异的光电性质,其最大亮度,最大电流效率,峰值EQE分别为2970 cd·m~(-2),43.0 cd·A~(-1)和11.0%;相比于传统的PEDOT:PSS基的器件,效率提高了近2倍.     

基于共价有机聚合物空穴注入层的钙钛矿发光二极管EI北大核心CSCD

卤化物钙钛矿(ABX)量子点及其发光器件具有色纯度高、外量子效率高以及在可见光范围内可调等特点,近年来在照明、显示等领域中展现出巨大潜力。然而,钙钛矿量子点发光二极管(PeQLEDs)的稳定性正成为制约其商业应用的最大障碍,除了钙钛矿发光层本身的稳定性问题之外,传输层的水氧稳定性问题也不可忽略。为了解决这一发展过程中的难题,我们提出了基于氮唑类单体构筑共价有机聚合物材料(COP-N)替代传统的PEDOT∶PSS作为空穴注入层材料的新型PeQLEDs。我们发现COP-N具有本征的水氧稳定性,且与PVK之间的空穴注入势垒更小。这些特性使得基于COP-N的PeQLED在取得比PEDOT∶PSS更好发光效率的同时实现了近2倍的稳定性提升。我们认为,这种共价有机聚合物有望成为新型的空穴注入材料,实现高效稳定的钙钛矿电致发光,促进钙钛矿发光器件的发展。     

基于改性空穴注入层与复合发光层的高效钙钛矿发光二极管

有机金属卤化钙钛矿作为发射体具有极高的色纯度和极低的成本,但钙钛矿层普遍较差的形貌制约了器件的性能.引入合适的聚合物可有效改善旋涂型钙钛矿薄膜的均匀性.本文引入聚(4-苯乙烯磺酸盐)(PSS)改性的聚(3,4-乙撑二氧噻吩):PSS(PEDOT:PSS)作为空穴注入层(HIL),结合一步旋涂制备的三溴化铅甲基胺(MAPbBr3)和聚(环氧乙烷)(PEO)复合膜作为发光层,制备了高效绿光钙钛矿发光二极管.其中,PSS增加了PEDOT:PSS功函数,降低了其与钙钛矿发光层间的注入势垒;而掺杂PEO的钙钛矿膜致密且均匀,覆盖率可以达到100%.基于改性的空穴注入层和复合发光层,我们最终获得了最大亮度为2476 cd·m^–2、最大电流效率为7.6 cd·A^–1的高效钙钛矿发光二极管.     

金纳米粒子增强钙钛矿的荧光发射

有机-无机杂化钙钛矿材料在钙钛矿发光二极管(PeLEDs)和激光器等光电器件中得到了新的应用,如何进一步提高钙钛矿薄膜的发光效率是目前的研究热点。将20nm粒径的金纳米粒子(Au NPs)掺杂至界面层PEDOT∶PSS中,可使以甲胺铅溴盐(CH3NH3PbBr3)薄膜为发光层的荧光强度提升了2.7倍。研究表明,Au NPs的引入有效增强了CH3NH3PbBr3薄膜的吸收,并提高了激子的辐射跃迁速率。同时,结合光学仿真进行分析,发现Au NPs的近场和远场表面等离激元均与钙钛矿薄膜吸收/发射区域有效耦合,从而最大程度地提高发光效率。提出利用Au NPs的近场和远场复合表面等离激元效应可最大程度地提高钙钛矿薄膜的荧光发射效率,该研究对制备高效率PeLEDs和激光器等提供了重要的理论指导和技术支持。     

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LiF修饰层的喷墨打印钙钛矿发光二极管

金属卤化物钙钛矿材料由于具有高光致发光量子产率、高色纯度、带隙可调等优良光学性能,作为发光材料广泛用于制备钙钛矿电致发光二极管(PeLEDs)。虽然已经取得了较好的研究进展,但是其大面积商业化的进程还比较缓慢,尚需进一步研究。为了实现钙钛矿薄膜发光二极管的大面积制备,本文使用喷墨打印技术,研究了不同基板结构对于钙钛矿前驱液的铺展与结晶成膜的影响及器件性能的比较,引入了具有空穴阻挡能力的无机小分子材料氟化锂(LiF)作为缓冲层沉积于空穴传输层TFB上,获得了像素化的均匀分布的钙钛矿薄膜,从而得到发光均匀的最高亮度为4 861 cd/m~2且最大电流效率为5.41 cd/A的印刷钙钛矿发光二极管。研究表明,LiF修饰层对于空穴的注入具有阻挡作用,并且有效阻止了钙钛矿发光层与TFB接触后所导致的激子猝灭现象。     

基于LiF修饰层的喷墨打印钙钛矿发光二极管EI北大核心CSCD

金属卤化物钙钛矿材料由于具有高光致发光量子产率、高色纯度、带隙可调等优良光学性能,作为发光材料广泛用于制备钙钛矿电致发光二极管(PeLEDs)。虽然已经取得了较好的研究进展,但是其大面积商业化的进程还比较缓慢,尚需进一步研究。为了实现钙钛矿薄膜发光二极管的大面积制备,本文使用喷墨打印技术,研究了不同基板结构对于钙钛矿前驱液的铺展与结晶成膜的影响及器件性能的比较,引入了具有空穴阻挡能力的无机小分子材料氟化锂(LiF)作为缓冲层沉积于空穴传输层TFB上,获得了像素化的均匀分布的钙钛矿薄膜,从而得到发光均匀的最高亮度为4861 cd/m2且最大电流效率为5.41 cd/A的印刷钙钛矿发光二极管。研究表明,LiF修饰层对于空穴的注入具有阻挡作用,并且有效阻止了钙钛矿发光层与TFB接触后所导致的激子猝灭现象。     

基于液体基质材料的有机电致发光器件的制备及性能分析

利用液体基质材料9-(2-ethylhexyl)carbazole(EHCz)掺杂有机染料分子5,6,11,12-tetraphenyl-nathacene(rubrene)制备了具有液体发光层的有机电致发光器件,其结构为:ITO/PEDOT:PSS/EH Cz:rubrene/Cs2CO3/ITO,PEDOT:PSS...     

电场变化对有机磷光器件中激子形成影响的研究

激子形成区域随电场变化的移动会使得有机电致发光器件(OLEDs)的效率和色度发生改变,从而影响器件的性能。文章首先制备了两种OLED器件,器件1为ITO/PEDOT∶PSS/PVK∶Ir(ppy)₃∶DCJTB (100∶2∶1 wt)/BCP(10 nm)/Alq₃(15 nm)/Al,器件2为ITO/PEDOT∶PSS/PVK∶Ir(ppy)₃(100∶2 wt)/BCP(10 nm)/Alq₃(15 nm)/Al,研究了电场强度对单层多掺杂结构器件激子形成的影响。实验发现在多掺杂发光层中,随着电压的增加,Ir(ppy)₃,PVK和DCJTB的发光均增强,PVK和DCJTB发光增强更快。对其发光机制进行分析,认为较高电场下,载流子获得较高能量,更容易形成高能量激子,产生宽禁带材料PVK的发光;另一方面,从能级结构分析DCJTB的带隙较窄, 俘获更多的载流子发光更强。同时,在器件的电致发光(EL)光谱发现在460 nm处一新的发射峰, 发光随着电压的增大相对减弱。为了研究460 nm发光的来源,制备了器件：ITO/PEDOT∶PSS/PVK∶BCP∶Ir(ppy)₃(x∶y∶2 wt)/Alq₃(15 nm)/Al, 改变x, y的比值研究发现,460 nm处的发光依然存在,推测此发光峰应与PVK及BCP之间有关。     

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。     

Improving efficiency of inverted perovskite solar cells via ethanolamine-doped PEDOT:PSS as hole transport layer

In order to fabricate high-performance inverted perovskite solar cells (PeSCs), an appropriate hole transport layer (HTL) is essential since it will affect the hole extraction at perovskite/HTL interface and determine the crystallization quality of the subsequent perovskite films. Herein, a facile and simple method is developed by adding ethanolamine (ETA) into poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as HTL. The doping of a low-concentration ETA can efficiently modify the electrical properties of the PEDOT:PSS film and lower the highest occupied molecular orbital (HOMO) level, which is more suitable for the hole extraction from the perovskite to HTL. Besides, ETA-doped PEDOT:PSS will create a perovskite film with larger grain size and higher crystallinity. Hence, the results show that the open-circuit voltage of the device increases from 0.99 V to 1.06 V, and the corresponding power conversion efficiency (PCE) increases from 14.68% to 19.16%. The alkaline nature of ethanolamine greatly neutralizes the acidity of PEDOT:PSS, and plays a role in protecting the anode, leading the stability of the devices to be improved significantly. After being stored for 2000 h, the PCE of ETA-doped PEDOT:PSS devices can maintain 84.2% of the initial value, which is much higher than 67.1% of undoped devices.     

空穴传输层对有机电致发光器件性能的影响

制备了结构为ITO/MoO₃(40 nm)/空穴传输层/CBP:Ir(ppy)₂acac(8%)(30 nm)/BCP(10 nm)/Alq₃(40 nm)/LiF(1 nm)/Al(100 nm)的器件,其中Ir(ppy)₂acac为绿色磷光染料,空穴传输层分别为TAPC(50 nm)、TAPC(40 nm)/TCTA(10 nm)、NPB(50 nm)、NPB(40 nm)/TCTA(10 nm)。通过使用4种不同结构的空穴传输层,对器件的发光性能进行了研究。结果表明,空穴传输层对器件的发光性能有较大影响。在电压为6 V、电流密度为2 mA/cm²的条件下,4种结构的器件的电流效率分别为52.5,67.8,35.6,56.6 cd/A。其原因是TAPC/TCTA及NPB/TCTA能级结构更有利于空穴对发光层的注入而且TAPC拥有较高的空穴迁移率;另外,TAPC及TCTA拥有较高的LUMO和三线态能量,可以有效地将电子和三线态激子束缚在发光层内,增加绿光染料的复合发光几率。所制备的器件均表现出良好的色坐标稳定性。     

Improving the performance of perovskite solar cells with glycerol-doped PEDOT:PSS buffer layer

In this paper, we investigate the effects of glycerol doping on transmittance, conductivity and surface morphology of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate))(PEDOT:PSS) and its influence on the performance of perovskite solar cells.. The conductivity of PEDOT:PSS is improved obviously by doping glycerol. The maximum of the conductivity is 0.89 S/cm when the doping concentration reaches 6 wt%, which increases about 127 times compared with undoped. The perovskite solar cells are fabricated with a configuration of indium tin oxide(ITO)/PEDOT:PSS/CH_3NH_3PbI_3/PC_(61)BM/Al, where PEDOT:PSS and PC_(61)BM are used as hole and electron transport layers, respectively. The results show an improvement of hole charge transport as well as an increase of short-circuit current density and a reduction of series resistance, owing to the higher conductivity of the doped PEDOT:PSS. Consequently, it improves the whole performance of perovskite solar cell. The power conversion efficiency(PCE) of the device is improved from 8.57% to 11.03% under AM 1.5 G(100 mW/cm~2 illumination) after the buffer layer has been modified.     

Poly(3,4-ethylene dioxythiophene): Poly(styrene sulfonate)的共振拉曼光谱研究

通过拉曼光谱方法分别对PEDOT:PSS掺杂和去掺杂状态进行了详细分析. 实验结果表明, 去掺杂的PEDOT:PSS由于其在激发波长附近的吸收增强而引起了共振效应, 拉曼信号得到大幅度增强, 可见, 以633 nm(He-Ne)激光为激发波长的拉曼光谱是研究PEDOT:PSS掺杂状态的有效方法. 此外, 显微拉曼光谱也是分析聚合物发光二极管器件内各层材料的有效手段.     

Pentacene as a hole transport material for high performance planar perovskite solar cells

A cost-effective and efficient organic semiconductor pentacene was developed as a hole transport layer (HTL) material to replace classical PEDOT:PSS for planar perovskite solar cells (PSCs). As expected, the pentacene based device exhibits power conversion efficiency (PCE) of 15.90% (J_sc of 19.44 mA/cm², V_oc of 1.07 V, and FF of 77%), comparable to the PEDOT:PSS based device (PCE of 15.65%, J_sc of 18.78 mA/cm², V_oc of 1.07 V, and FF of 77%) under the same experimental conditions. The excellent performance of vacuum deposited pentacene is mainly attributed to the high efficient charge extraction and transfer in device due to the high-quality perovskite film grown on the top of pentacene substrate and a favorable energy-level alignment together with a desired downward band bending formed at the perovskite/pentacene interface. Our research has confirmed that pentacene could be served as a promising HTL material to achieve effective and potentially economical planar type PSCs.     

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...     

Improvement in performance of organic light-emitting devices by inclusion of multi-wall carbon nanotubes

Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) was modified by different concentrations of multi-wall carbon nanotubes (MWNTs), and the nanocomposites of PEDOT:PSS and MWNTs were firstly used as hole-injection layer in fabrication of organic light-emitting devices (OLEDs) by using a double-layer structure with hole-injection layer of doped PEDOT:PSS and emitting/electron transport layer of tris(8-hydroxyquinolinato) aluminum (Alq₃). PEDOT:PSS solution doped with MWNTs was spin-coated on clean polyethylene terephthalate (PET) substrate with indium tin oxide (ITO). It was found that the electroluminescence (EL) intensity of the OLEDs were greatly improved by using PEDOT:PSS doped with MWNTs as hole-injection layer which might have resulted from the hole-injection ability improvement of the nanocomposites. Higher luminescence intensity and lower turn-on voltage were obtained by these devices and the luminance intensity obtained from the device with the hole-injection layer of PEDOT:PSS doped by 0.4 wt.% MWNTs was almost threefolds of that without doping.