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.     

Polymer solar cells based on a PEDOT:PSS layer spin-coated under the action of an electric field

In the process of fabrication of polymer photovoltaic(PV) devices,poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS) thin film,acting as an anode buffer layer,is spin-coated under the action of an electric field.The PV devices with a PEDOT:PSS layer spin-coated under the action of a static electric field exhibit improved short-circuit current density(J sc) and power conversion efficiency(PCE).The investigation of morphology shows that the appropriate intensity of the electric field can increase the roughness of the surface of the PEDOT:PSS layer,which results in improved contact between the anode and hole transport layer and thus enhances the J sc of the devices.Chemical analysis is also provided by x-ray photoelectron spectroscopy(XPS) spectra.     

双功能电极改善有机发光器件效率滚降的研究

针对磷光器件存在严重的效率滚降,进而制约有机电致发光器件的实用化进程的问题,提出采用超声喷涂Poly(3,4-ethylenedioxythiophene)Polystyrene Sulfonate(PEDOT:PSS)作为透明电极,制备了红、绿、蓝三色有机电致发光器件.利用超声喷涂工艺材料利用率高的特点,起绝缘作用的水溶性PSS分子链在PEDOT:PSS透明电极中得到保留,使该透明电极具有空穴缓冲作用.这种双功能性,提高了器件在高电流密度下的载流子平衡性,降低了红、绿、蓝三色发光层中的极化子浓度,改善了红、绿、蓝三色器件的效率滚降问题,从最高外量子效率所在亮度到10000cd/m^2的电流效率滚降分别仅为14.9%、12.4%和16.0%.该结果表明,双功能性电极的引入显著改善了有机电致发光器件中载流子平衡性,具有降低三基色器件效率滚降的普适性,对实现高亮度、高效率发光器件具有重要意义.     

Effect of sorbitol doping in PEDOT:PSS on the electrical performance of organic photovoltaic devices

Organic photovoltaic cells have important advantages, such as low cost and mechanical flexibility. The conducting polymer poly(3,4 ethylenedioxy-thiophene):poly(styrene sulfonate) (PEDOT:PSS) has been widely used as an interfacial layer or a polymer electrode in polymer electronic devices, such as photovoltaic devices and light-emitting diodes. In this report, we discuss the direct current (DC) conductivity of PEDOT:PSS films containing various weight ratios of sorbitol dopant. The work function is shown to steadily decrease with increasing dopant content. With different dopant contents, illuminated current–voltage photovoltaic characteristics were observed. Ultraviolet photoelectron spectroscopy (UPS) analysis revealed that the work function of the PEDOT:PSS was affected by its sorbitol content. The morphologies of the doped PEDOT:PSS films were characterized by atomic force microscopy (AFM). For the device fabrication, we made organic photovoltaic cells by a spin-coating process and Al deposition by thermal evaporation. The sorbitol dopant is able to improve the efficiency of the device.     

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。     

White-light-emitting devices based on Nile Red and π electron rich [Zn<Subscript>4core</Subscript>] complex

A white organic light-emitting device was fabricated with a structure of ITO/PEDOT: PSS (45 nm)/PVK: Nile Red: [Zn_4core] (75 nm)/BCP (25 nm)/Al. Without Nile Red green and with Nile Red white emission was achieved. When the concentration of the Nile Red in thin film increased from 0.01 to 0.5 wt%, a white emission achieved. The electroluminescence spectra of the device cover a wide range of visible region with two peaks around 501 and 618 nm. It is noteworthy that a white and pure white OLEDs with an incomplete energy transfer from the green host [Zn_4core] to the dopant (Nile Red) was obtained in this work using a single emissive layer relative to the multi layered light emitter ones in white OLED devices. For 0.1 doped device, a maximum luminance efficiency of 2.54 cd/A with CIE coordinates of (x, y = 0.35, 0.37) at 230 mA/cm² has was achieved.     

电场诱导空穴注入缓冲层PEDOT：PSS取向对OLED发光性能的影响

实验中以PEDOT:PSS在ITO基片上旋涂作为空穴传输层,并且在旋涂PEDOT:PSS的过程中在与ITO玻璃平面垂直的方向施加一个诱导聚合物取向的高压电场,试验着重研究了所加电场强度对双层器件:ITO/PEDOT:PSS/MEH-PPV/Al器件性能的影响。测试结果表明,旋涂时所加电场的大小对器件的发光强度和起亮电压都有明显的影响。随着所加电场的增大,器件发光强度明显增加,起亮电压减小。由此表明:在高电场作用下,聚合物分子链沿电场方向发生了取向,而且随着电场增强这种取向作用会表现得越明显,并且在PEDOT:PSS膜表层会形成一个梯度变化的PSS聚集,使得从ITO到MEH-PPV的功函数逐渐上升,降低空穴注入势垒,增强了空穴的注入效率。     

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.     

Red organic light emitting device based on TPP and a new host material

A novel coating method for fabrication of red OLEDs by using a new host material has been developed with the aid of a single furnace. The host material, zinc complex, was prepared from the reaction of zinc acetate and 2-methyl-8-hydroxyquinoline and after characterization by UV-vis, FT-IR, and ¹H NMR spectroscopes was used as an emitting material in the fabrication of OLEDs. Since meso-tetraphenylporphyrin (TPP) and zinc complex have a close molecular weight, both materials were evaporated from a single furnace. Devices with TPP and structures of ITO/PEDOT:PSS (55 nm)/PVK (90 nm)/zinc complex:TPP (65 nm)/Al (180 nm) were fabricated; Without TPP green and with TPP red emission was achieved. The device with 2 % TPP that doped into the zinc complex showed the purest red emission among all devices. The device showed the CIE coordinates of 0.70 and 0.28 at 14 V and a maximum luminance of about 94.2 cd/m². This new method is a promising candidate for fabrication of low cost red OLEDs with a more homogeneous layer.     

Metal-electrode-free inverted organic photovoltaics using electrospray-deposited PEDOT:PSS and spin-coated HAT-CN exciton blocking layer

Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) films were fabricated using an electrospray deposition (ESD) method. The ESD PEDOT:PSS films exhibited higher PSS content on the surface than spin-coated PEDOT:PSS films, which results in a higher work function. Based on this result, metal-electrode-free inverted organic photovoltaics (OPVs) were fabricated. The ESD PEDOT:PSS was used as the top electrode on the poly(3-hexythiophene-2,5-diyl) (P3HT):[6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) light-absorbing layer. The power conversion efficiency (PCE) of OPVs was significantly increased with the 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile layer. The improved PCE would be attributed to the suppression of exciton quenching at the P3HT:PCBM and PEDOT:PSS interface.     

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.     

掺杂PEDOT ∶PSS对聚合物太阳能电池性能影响的研究

研究了掺杂后poly(3,4-ethylene dioxythiophene):poly(styrenesulphonic acid)(PEDOT ∶PSS)电导率的变化以及掺杂PEDOT ∶PSS薄膜对聚合物太阳能电池器件性能的影响. 实验发现,向PEDOT ∶PSS中掺入极性溶剂二甲基亚砜(DMSO)明显提高了薄膜的电导率,掺杂后的电导率最大值达到1.25 S/cm,比未掺杂时提高了3个数量级. 将掺杂的PEDOT ∶PSS薄膜作为缓冲层应用于聚合物电池 (ITO/PEDOT ∶PSS/P3HT ∶PCBM/LiF/Al) 中,发现高电导率的PEDOT ∶PSS降低了器件的串联电阻,增加了器件的短路电流,从而提高了器件的性能. 最好的聚合物太阳能电池在100 mW/cm²的光照下,开路电压(V_oc)为0.63 V,短路电流密度(J_sc)为11.09 mA·cm^-2,填充因子(FF)为63.7%,能量转换效率(η)达到4.45%. 关键词： PEDOT ∶PSS 电导率 聚合物太阳能电池 能量转换效率     

Structural,morphological and optical properties of PEDOT:PSS/QDs nano-composite films prepared by spin-casting

This paper describes the structural, morphological and optical properties of the nano-composite of poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and quantum dots (QDs). The ZnSe and CdSe QDs have been synthesized, with the aid of Mercaptoacetic acid (MAA), by a colloidal method with an average size of ~5 to 7 nm. QDs have been embedded in PEDOT:PSS using a simple solution processing approach and has been deposited as thin films by spin coating technique. The QDs embedded PEDOT:PSS enhances the light absorption spectra of samples, prominently in terms of absorption intensity which may consequently improve sensitivity of the optoelectronic devices.     

On the origin of exciton formation in dye doped Alq3 OLEDs

Electrically Detected Magnetic Resonance (EDMR) was used to investigate the influence of dye doping on spin-dependent exciton formation in aluminum (III) 8-hydroxyquinoline (Alq₃) based Organic Light Emitting Diodes (OLEDs) with different device structures. 4-(dicyanomethylene)-2-methyl-6-{2-[(4-diphenylamino)-phenyl]ethyl}-4H-pyran (DCM-TPA) and 5,6,11,12-tetraphenylnaphthacene (Rubrene) were used as dopants. Results at room temperature show significant differences on the EDMR spectra (g-factor and linewidth) of doped and undoped devices. Signals from DCM-TPA and Rubrene dye doped OLEDs showed strong temperature dependence, with signal intensity increasing by 2 orders of magnitude below 200 K for DCM-TPA dye doped OLEDs and increasing by ～1 order of magnitude below 225 K for the Rubrene dye doped device, while undoped devices shows almost no temperature dependence. By adding a “spacer” layer of undoped Alq₃ at the recombination zone, changes in bias voltage were used to shift the recombination from doped to undoped region and correlate that with changes in the EDMR spectrum. Our results are indicating that charge trapping on the dopant followed by recombination is the main mechanism of light emission in the investigated devices.     

Effect of dye dopants in poly(methylphenyl silane) light-emitting devices

To investigate the inter-molecular energy transfer between polysilane and dye dopants, poly(methylphenylsilane)(PMPS) was used as a host material and perylene as the blue dopant. The structure of the devices is indium–tin oxide (ITO)/PEDOT:PSS(30 nm)/PMPS:perylene(dye dopant 0.1–1.0 mol%)(60 nm)/Alq₃(20 nm)/LiF(0.5 nm)/Al(100 nm). Poly(3,4-ethylenedioxythiophene) (PEDOT):poly(4-styrenesulfonate) (PSS) is used as a buffer layer, tris(8-hydroxyquinoline)aluminum (Alq₃) as hole transporting layer, LiF as hole injection layer. The device shows a luminance 810 cd/m² at current density of 28 mA/cm², luminous efficiency of 0.14 lm/W. The external quantum efficiency (EQE) is about 0.5% and EQE increased up to 0.52% by doping with single wall carbon nanotubes (SWNT) into the emissive layer. We found an efficient inter-molecular energy transfer from polysilane to dye dopants. Furthermore, using the polysilane and energy-matched dye dopants enable to fabricate the electroluminescence devices through wet processes.     

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...     

Influence of the thickness of N,N′-Bis(naphthalene-1-yl)-N,N′-bis(phenyl) benzidine layer on the performance of organic light-emitting diodes

We investigated the influence of the thickness of hole-transport layer, N,N′-biphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB), on the performance of the typical bi-layer organic light-emitting diodes (OLEDs). It was found that both the current efficiency and the power efficiency of bi-layer OLEDs were improved when the thickness of the hole-transport layer varied from 30 to 120 nm. By investigating the hole-injection efficiency of ITO/NPB contact with various thicknesses of NPB film, we found that the hole-injection efficiency was reduced with the thickness of NPB layer increasing from 60 to 180 nm, which improved the injected carriers balance in devices and increased the efficiency of the bi-layer OLEDs.     

Ultraviolet photoelectron spectroscopy investigation of interface formation in an indium-tin oxide/fluorocarbon/organic semiconductor contact

It has been demonstrated that hole-injection in organic light-emitting devices (OLEDs) can be enhanced by inserting a UV-illuminated fluorocarbon (CF_x) layer between indium-tin oxide (ITO) and organic hole-transporting layer (HTL). In this work, the process of interface formation and electronic properties of the ITO/CF_x/HTL interface were investigated with ultraviolet photoelectron spectroscopy. It was found that UV-illuminated fluorocarbon layer decreases the hole-injection barrier from ITO to α-napthylphenylbiphenyl diamine (NPB). Energy level diagrams deduced from the ultraviolet photoelectron spectroscopy (UPS) spectra show that the hole-injection barrier in ITO/UV-treated CF_x/NPB is the smallest (0.46 eV), compared to that in the ITO/untreated CF_x/NPB (0.60 eV) and the standard ITO/NPB interface (0.68 eV). The improved current density-voltage (I-V) characteristics in the UV-treated CF_x-coated ITO contact are consistent with its smallest barrier height.     

TBPe与MEH-PPV共掺杂的有机电致发光器件的优化研究

采用有机小分子TBPe（2,5,8,11-tetratertbutylperylene）以不同比例掺入MEH-PPV（poly ）作为发光层,研究了TBPe不同掺杂比例对器件性能的影响,进而对发光强度进行优化。对于所制备的ITO/PEDOT：PSS/MEH-PPV/TBPe/Al有机电致发光器件,TBPe的最优蒸镀厚度为0.5 nm,其发光强度相对于标准器件提高了325%。ITO/PEDOT：PSS/MEH-PPV：TBPe/TBPe/Liq/Al有机电致发光器件的最优掺杂比例为MEH-PPV：TBPe=100：30（质量比）,其发光亮度相比于未掺杂器件提高了44%。在上述器件的基础上增加Alq₃层提高电子注入,分别制作了Liq和LiF作为修饰层的ITO/PEDOT：PSS/MEH-PPV：TBPe/TBPe/Alq₃/Liq/Al和ITO/PEDOT：PSS/MEH-PPV：TBPe/TBPe/Alq₃/LiF/Al多层器件,发光亮度分别达到4 162 cd/m²和4 701 cd/m²。所有器件的电致发光波长均为580 nm,为MEH-PPV的发光,TBPe的掺杂对MEH-PPV的发光起到了增强作用。     

Intensity-dependent photocurrent generation at the anode in bulk-heterojunction solar cells

The efficiency that a solar cell can reach is ultimately limited by the number of photons absorbed in its active layer and the efficiency with which these photons are converted into electrical current. In this study we seek to quantify and separate the optical and electrical efficiencies in photovoltaic devices based on mixtures of [6,6]-phenyl C61-butyric acid methyl ester (PCBM) and regio-regular poly(3-hexylthiophene) (P3HT). The optical efficiency is determined by comparing the measured external quantum efficiency (EQE) and the maximum possible EQE (EQEmax) as determined by modeling the fractional dissipation of light in the active layer at a given wavelength and layer thickness (d_active). We determine, by examining the difference between EQE and EQEmax, that a significant contribution (up to 35%) of the total losses are electrical in nature. Comparison of the internal quantum efficiency (IQE) and the optical intensity distribution as a function of d_active shows photocurrent generation is anti-correlated to light intensity in the vicinity of the PEDOT:PSS/active layer interface. The magnitude of this effect is modeled using standard optical tools and a half Gaussian shaped reduced generation zone (RGZ) centered at this interface. Illumination-intensity (I₀) dependent measurements of the short-circuit-current density allows us to exclude vertical segregation and bi-molecular recombination as potential explanations for the RGZ. Examination of the work functions of P3HT and PEDOT:PSS gives evidence that in the devices positive charges build up at the interface due to permanent redox chemistry, leading to the formation of a dipolar layer with holes on the P3HT. The dependence of EQE on I₀ at low illumination intensities gives evidence for correlation of the charge build up and the size change of the reduced generation zone. We argue that the only physical phenomenon that explains a region-specific reduction in photocurrent generation and is consistent with a build up of positive charge at the interface is a reduced probability of exciton separation or quenching. In support of our findings, we show that reduction of the light intensity yields increased quantum efficiency consistent with our model. PACS  42.25.bs; 72.40.tw; 72.80.le