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.     

Modulating the Electrochromic Performances of Transmissive and Reflective Devices Using N,N-Dimethyl Formamide Modified Poly(3,4-Ethylenedioxythiophene)/Poly(Styrene Sulfonate) Blend as Active Layers

As one of the important factors which affect the properties and applications of conducting polymers, the electrical conductivity of a poly(3,4-ethylenedoxy-thiophene)/ poly(styrene sulfonate) (PEDOT: PSS) blend was adjusted by using various amount of an organic solvent (N,N-dimethyl formamide, DMF) as an additive. The conductivities of PEDOT: PSS thin films can be increased dramatically, from 1.0 S to 32.1 S cm^?1, with a 2/1 volume ratio of PEDOT: PSS/DMF loading after totally removing the organic solvent by annealing the film at 80° for 48 h in a vacuum oven. The optical contrasts of transmissive and reflective devices assembled using DMF-modified PEDOT: PSS as active layers exhibited a close relationship with the conductivity of PEDOT: PSS. Interestingly, high conductivity of PEDOT: PSS enhanced the contrast of a transmissive device, while high conductivity of PEDOT: PSS decreased the contrasts of a reflective device. The underlying reason is related to the different electrochromic mechanisms of these two types of device configurations.     

稀释溶剂对PEDOT：PSS薄膜和有机太阳能电池性能的影响

采用喷涂技术制备聚3,4-乙撑二氧噻吩：聚苯乙烯磺酸盐（PEDOT：PSS）有机层薄膜,系统研究了乙醇、去离子水、甲醇、异丙醇和乙二醇等稀释溶剂对PEDOT：PSS薄膜形貌、透过率及导电性能的影响。将PEDOT：PSS薄膜应用于有机太阳能电池器件的制备,研究了不同溶剂对器件性能的影响。实验结果表明：采用乙醇稀释PEDOT：PSS溶液,能有效抑制PEDOT：PSS颗粒团聚,降低薄膜粗糙度,提高薄膜的透过率和导电性。以其制备的太阳能电池器件的能量转换效率明显高于其他溶剂稀释,转换效率为2.66%。     

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.     

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。     

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.     

Enhanced thermoelectric performance of PEDOT:PSS films via ionic liquid post-treatment

Thermoelectric(TE)energy harvesting can effectively convert waste heat into electricity,which is a crucial technology to solve energy concerns.As a promising candidate for energy conversion,poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)has gained significant attention owing to its easy doping,high transparency,and solution processability.However,the TE performance of PEDOT:PSS still needs to be further enhanced.Herein,different approaches have been applied for tuning the TE properties:(i)direct dipping PEDOT:PSS thin films in ionic liquid;(ii)post-treatment of the films with concentrated sulfuric acid(H₂SO₄),and then dipping in ionic liquid.Besides,the same bis(trifluoromethanesulfonyl)amide(TFSI)anion and different cation salts,including 1-ethyl-3-methylimidazolium(EMIM+)and lithium(Li+),are selected to study the influence of varying cation types on the TE properties of PEDOT:PSS.The Seebeck coefficient and electrical conductivity of the PEDOT:PSS film treated with H2SO4EMIM:TFSI increase simultaneously,and the resulting maximum power factor is 46.7μW·m^-1·K^-2,which may be attributed to the ionic liquid facilitating the rearrangement of the molecular chain of PEDOT.The work provides a reference for the development of organic films with high TE properties.     

基于石墨烯/PEDOT：PSS叠层薄膜的柔性OLED器件

石墨烯具有独特的电学性能、优异的机械延展性和良好的化学稳定性,是制备高性能导电薄膜的理想材料,但是当前石墨烯的高电阻率限制了它的实际应用。本文采用喷涂方法制备了石墨烯/聚（3,4-亚乙二氧基噻吩）-聚（苯乙烯磺酸）（PEDOT：PSS）复合导电薄膜,对复合薄膜的表面形貌与光电性能进行了研究。PEDOT：PSS的引入不仅降低了石墨烯薄膜的表面电阻,同时还平滑了薄膜表面。在此基础上,成功制备了柔性黄光有机电致发光器件,器件在12 V时达到效率最大值0.9 cd/A。器件在曲率半径为10 mm时弯曲了100次后,发光亮度并无明显变化。该复合薄膜可实际应用于柔性有机电致发光显示器件。     

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.     

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.     

PEDOT:PSS Schottky contacts on annealed ZnO films

Polycrystalline ZnO and ITO films on SiO₂ substrates are prepared by radio frequency (RF) reactive magnetron sputtering. Schottky contacts are fabricated on ZnO films by spin coating with a high conducting polymer, poly(3, 4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) as the metal electrodes. The current-voltage measurements for samples on unannealed ZnO films exhibit rectifying behaviours with a barrier height of 0.72 eV (n=1.93). The current for the sample is improved by two orders of magnitude at 1 V after annealing ZnO film at 850 ℃, whose barrier height is 0.75 eV with an ideality factor of 1.12. X-ray diffraction, atomic force microscopy and scanning electron microscopy are used to study the properties of the PEDOT:PSS/ZnO/ITO/SiO₂. The results are useful for applications such as metal-semiconductor field-effect transistors and UV photodetectors.     

In-situ characterization of electrochromism based on ITO/PEDOT:PSS towards preparation of high performance device

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS) is usually sandwiched between indium tin oxide(ITO) and a functional polymer in order to improve the performance of the device. However, because of the strong acidic nature of PEDOT:PSS, the instability of the ITO/PEDOT:PSS interface is also observed. The mechanism of degradation of the device remains is unclear and needs to be further studied. In this article, we investigate the in-situ electrochromism of PEDOT:PSS to disclose the cause of the degradation. X-ray photoelectron spectroscopy(XPS) was used to characterize the PEDOT:PSS films, as well as the PEDOT:PSS plus polyethylene glycol(PEG) films with and without indium ions. The electrochromic devices(ECD) based on PEDOT:PSS and PEG with and without indium ions are carried out by in-situ micro-Raman and laser reflective measurement(LRM). For comparison, ECD based on PEDOT:PSS and PEG films with LiCl, KCl, NaCl or InCl_3 are also investigated by LRM. The results show that PEDOT:PSS is further reduced when negatively biased, and oxidized when positively biased. This could identify that PEDOT:PSS with indium ions from PEDOT:PSS etching ITO will lose dopants when negatively biased. The LRM shows that the device with indium ions has a stronger effect on the reduction property of PEDOT:PSS-PEG film than the device without indium ions. The contrast of the former device is 44%, that of the latter device is about 3%. The LRM also shows that the contrasts of the device based on PEDOT:PSS+PEG with LiCl, KCl, NaCl, InCl_3 are 30%, 27%, 15%, and 18%, respectively.     

紫外臭氧处理超薄银修饰ITO电极的高效柔性有机太阳能电池

以紫外臭氧处理超薄Ag复合MoO₃或PEDOT：PSS修饰ITO电极的高效柔性有机太阳能电池。通过优化紫外臭氧处理Ag薄膜的时间,提高了以P3HT：PCBM为有源层的器件的功率转换效率,从1.68%（未经过紫外臭氧处理）提高到2.57%（紫外臭氧处理Ag 1 min）。提高的原因推测是紫外臭氧处理形成了AgO_x薄膜,提高了电荷提取并使器件具有高光学透明度、低串联电阻和优异的表面功函数等一些性能。并且,紫外臭氧处理Ag薄膜与MoO₃或者PEDOT：PSS复合修饰ITO的器件效率分别得到提高,Ag薄膜与MoO₃复合修饰ITO的器件效率从2.02%（PET/ITO/MoO₃）提高到2.97%（PET/ITO/AgO_x/MoO₃）,Ag薄膜与PEDOT：PSS复合修饰ITO的器件效率从2.01%（PET/ITO/PEDOT：PSS）提高到2.93%（PET/ITO/AgO_x/PEDOT：PSS）。此外,以PBDTTT-EFT：PC₇₁BM为有源层的柔性聚合物太阳能电池效率可达6.21%。基于ITO的柔性光电器件效率的提高主要归于ITO被Ag/PEDOT：PSS或Ag/MoO₃修饰后功函数的提高。     

Fabrication of ZnO and its enhancement of charge injection and transport in hybrid organic/inorganic light emitting devices

ZnO nanocrystals were synthesized by hydrolysis in methanol. X-ray diffraction and photoluminescence spectra confirm that good crystallized ZnO nanoparticles were formed. Utilizing those ZnO nanoparticles and poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV), light emitting devices with indium tin oxide (ITO)/poly(3,4-oxyethyleneoxy-thiophene):poly(styrene sulfonate) (PEDOT:PSS)/ZnO:MDMO-PPV/Al and ITO/PEDOT:PSS/MDMO-PPV/Al structures were fabricated. Electroluminescence (EL) spectra reveal that EL yield of hybrid MDMO-PPV and ZnO nanocrystals devices increased greatly as compared with pristine MDMO-PPV devices. The current-voltage characteristics indicate that addition of ZnO nanocrystals can facilitate electrical injection and charge transport. The decreased energy barrier to electron injection is responsible for the increased efficiency of electron injection.     

UV/ozone‐treated WS2 hole‐extraction layer in organic photovoltaic cells

WS₂ nanosheets obtained through a simple sonication exfoliation method are employed as a hole‐extraction layer to improve the efficiency of organic photovoltaic cells (OPVs). A reduction in the wavenumber difference in the Raman spectra, the appearance of a UV absorption peak, and atomic force microscopy images indicate that WS₂ nanosheets are formed through the sonication method. The power conversion efficiency (PCE) values of OPVs with and without untreated WS₂ layers are both 1.84%. After performing a UV‐ozone (UVO) treatment on the WS₂ surface for 15 min, the PCE increases to 2.4%. Synchrotron radiation photoelectron spectroscopy data show that the work function of WS₂ increases from 4.9 eV to 5.1 eV upon UVO treat‐ ment, suggesting that the increase in the PCE value is caused by the band alignment. Upon inserting poly(3,4‐ethylenedioxythiophene):poly(styrene‐sulfonate) (PEDOT: PSS) between the WS₂ and the active layer, the PCE value of the OPV increases to 3.07%, which is superior to that of the device employing only PEDOT:PSS (2.87%). Therefore, it is considered that the use of UVO‐treated WS₂ is able to improve the performance of OPV cells. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of the PEDOT:PSS/KDP mixture on a flexible substrates and the use in pressure sensing devices

In this work, the mixture poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with monobasic potassium phosphate (KDP), a piezoelectric salt, was studied as a novel material in the fabrication of a low cost, easy-to-make, flexible pressure sensing device. Firstly a theoretical study was carried out, followed by an experimental study where the mixture PEDOT:PSS and KDP was deposited in a flexible polyester substrate and dried. Afterwards, XRD analysis and impulse voltage measures were performed. The results showed that the KDP does not react chemically with PEDOT:PSS and this mixture acts directly responding to the pressure applied on the sample.     

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.     

基于空穴注入层摩擦定向的偏振蓝光聚合物电致发光器件

研究了利用摩擦空穴注入层3,4-乙撑二氧噻吩:聚苯乙烯磺酸(PEDOT:PSS)作为定向层实现聚芴(PFO)薄膜的偏振电致发光,蓝光的色坐标为(0.20,0.21).从聚合物薄膜的紫外可见吸收和光致发光偏振特性,研究了不同定向层摩擦强度、退火温度以及退火时间下PFO薄膜的二向色性,并证明退火温度是决定器件偏振性能的关键因素.当摩擦强度为25 mm退火温度和时间分别为200℃和30 min时,得到较好的偏振性能,器件的电致发光偏振率约为3. 关键词： 偏振发光 摩擦定向 聚合物电致发光 空穴注入层     

Conducting polymer based hybrid structure as transparent and flexible field electron emitter

An efficient cathode material with high transparency (93%) based on conducting polymer poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and single wall carbon nanotubes (SWCNTs) has been developed for the fabrication of highly transparent and flexible field electron emitters (FEE). This kind of material showed superior field emission (FE) performance with very high current density (10^–3A/cm²) at very low electric field. The FE performance of the hybrid materials was dramatically improved compared to either SWCNTs and PEDOT:PSS. Thus the hybrid structures of conducting polymer and SWCNTs might be a good choice for use as a cathode material to enhance the FE performance and for potential application in future portable displays. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)