等离子体对OLED阳极进行处理的研究现状

大多数OLED都用ITO做阳极,为了提高ITO的功函数、改善ITO表面的平整度和减少C的污染,通常要在生长有机材料前对ITO表面进行处理。介绍了目前用等离子体对OLED阳极进行处理的研究现状,给出了Ar、O2、H2、N2、N2O和CF4等离子体处理ITO后对平整度、功函数、接触角和OLED特性等的影响,在他人研究基础上得出结论:用等离子体对OLED阳极进行处理其器件特性不仅与处理ITO表面的气体种类有关,也与产生等离子体的条件有关。采用正交试验方法可优化等离子体处理工艺参数,获得高性能的OLED。     

暴露空气对臭氧处理ITO表面效果的影响

文章研究了暴露空气对臭氧处理ITO表面效果的影响。结果表明,臭氧处理ITO表面显著提高了器件的空穴注入能力,暴露空气减弱了臭氧处理对空穴注入的提高效果。研究显示,暴露空气对臭氧处理效果的影响在于：不仅减小ITO表面功函数,导致空穴注入势垒重新增大,也将降低ITO表面能,减弱空穴注入层的粘附力,增加阳极界面接触电阻。     

氧等离子体处理改善ITO电极表面湿润性

采用氧等离子体处理对有机发光器件ITO电极进行表面改性,基于接触角的测量,利用几何平均法计算了ITO的表面能和极性度,研究了氧等离子体处理对ITO电极表面湿润性的影响.实验数据和计算结果表明:氧等离子体处理后,ITO表面极性度增加,表面能增大,接触角减小,其表面湿润性得到很大改善.同时,进一步研究了氧等离子体处理对有机发光器件性能的影响,结果显示:ITO电极表面湿润性的改善,提高了发光亮度和效率,降低了启亮电压和驱动电压,有效地改善了器件的光电性能.     

ITO表面处理对OLED性能的影响

根据实验,分析了表面处理对OLED性能的影响.对OLED的ITO阳极进行表面处理将改变ITO膜的表面化学组成及表面形态,这将直接影响ITO膜表面的功函数,从而影响ITO向有机层的空穴注入;同时还将间接影响有机层的成膜过程及其分子组织形态及ITO膜表面有机层之间的结合.     

有机酸修饰ITO对OLED器件性能的影响

分别采用二氯苯氧乙酸和溴乙酸对ITO表面进行修饰,研究其对OLED器件(ITO/PVK/ FIrPic:SimCP/TPBi/LiF/Al)性能的影响.结果显示,相较于未修饰的器件,采用二氯苯氧乙酸修饰后的器件最大亮度由673.4 cd/m2提升至1 875.2 cd/m2,同时器件的启亮电压由6.2V降至5.3V.研究发现,有机酸处理能够改变ITO的表面能和功函数,一方面改变ITO和后续膜层的接触性能,影响后续膜层的成膜;另一方面也可以有效减少ITO与有机层间的势垒,提升载流子注入.这种用有机酸修饰ITO阳极的方法工艺简单,能有效降低空穴注入势垒,优化ITO和有机层的接触性能,对器件性能的提升起到一定的促进作用.     

MoO3作空穴注入层的绿光有机电致发光器件制备及其性能研究

用真空热蒸镀的方法制备了绿光有机电致发光器件,并对其工艺流程进行了详细的描述。器件结构为ITO/MoO3(xnm)/N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,18-biphenyl)-4,4-diamine(NPB)(40nm)/tris(8-hydroxyquinoline)aluminum(Alq3)(60nm)/LiF(1nm)/Al(150nm),其中x=0,5nm。实验中,对ITO基片进行氧等离子体表面处理,能够有效减小ITO表面的接触角。通过对器件的光电性能测试,研究了MoO3作空穴注入层对有机电致发光器件性能的影响。实验结果表明,空穴注入层MoO3的最高占据分子轨道(HOMO)能级较好的与ITO功函数匹配,降低了空穴注入势垒,提高了器件的发光亮度和效率。当外加电压小于10V时,器件的电流密度随外加电压的增加而增加,但变化不明显;当外加电压大于10V时,器件的电流密度明显增强,发光色度几乎不随驱动电压的改变而改变,色坐标稳定在(0.36,0.55)附近。     

新型功函数测量系统的建立及其应用研究

采用接触势差法,设计并组建了功函数测量系统.该系统由信号发生单元、振动单元和检测单元组成,信号发生单元输出低频正弦信号使参比电极振动,调节振动单元偏压使检测单元输出信号为零,通过计算加载偏压和标准参比电极的偏差可得样品功函数值.用该系统测量了UV处理对ITO功函数的影响,发现ITO功函数的提高存在极限值并可改善有机电致发光器件(OLED)的性能.该系统可在空气中快速、准确测量表面功函数.     

MgF2缓冲层对蓝光OLED性能的影响

为了提高蓝光有机电致发光器件(OLED)的发光性能,将MgF2缓冲层插入ITO阳极与空穴传输层NPB之间,通过优化MgF2的厚度,制备了结构为ITO/MgF2(x nm)/NPB(50nm)/DPVBi:DSA-ph(30nm)/Alq3(30nm)/LiF(0.6nm)/Al(100nm)的高性能蓝光器件。实验结果表明,MgF2厚为1.0nm时,器件性能最佳,对应的器件最大电流效率达到5.51cd/A,最大亮度为23 290cd/m2(10.5V),与没有MgF2缓冲层的标准器件相比,分别提高47.3%和25.2%。对ITO表面的功函数测量结果表明,MgF2缓冲层可以有效修饰ITO表面,降低ITO与NPB之间的势垒高度差,改善空穴的注入效率,从而导致电子和空穴的注入更加平衡,激发机制更高效,实现了高性能的蓝光发射,为实现高效而稳定的全彩显示和白光照明奠定了基础。     

基于有机电致发光显示的透明导电膜ITO

介绍了ITO作为OLED器件阳电极时，ITO各参数对OLED整体性能，如发光亮度、效率、寿命和稳定性的影响，并以溅射ITO工艺为例，分析了制备与处理环境对ITO的方阻、透过率、表面平整度及功函数的影响。针对其成因．提出了一些改进措施。对高性能平板显示OLED器件用透明导电阳极的研制具有一定的参考价值。     

干冰微粒喷射法清洗ITO玻璃及其对有机电致发光器件性能的影响

采用干冰微粒喷射法对ITO玻璃表面进行了清洁处理,并与浸泡式低频超声波湿法清洗的ITO玻璃进行了对比测量,结果表明:干冰微粒喷射法处理后,ITO薄膜表面的接触角减小,表面污染物颗粒数量下降,ITO薄膜表面上碳的含量较之未处理时降低了48.5%,锡、铟的含量分别增加了533.33%和267.57%,说明干冰微粒法对ITO薄膜表面的有机污染物和杂质颗粒的清洗效果超过了超声波湿法。此后,制备了干冰微粒法清洗ITO阳极的有机电致发光器件(OLED)器件,以及结构相同但ITO电极是用超声波湿法清洗的OLED器件,对这两种器件的参数进行了测量,其结果表明:干冰微粒喷射法清洗器件的启亮电压、亮度和电流效率与超声波湿法清洗的相比较均有所改善。     

Influence of electrode characteristics on the performance of organic light-emitting devices

Indium-tin oxide (ITO) substrates were treated by oxygen plasma for organic light-emitting devices (OLEDs). Using the ITO substrates aged for various times as hole-injecting electrodes, the double-layered OLEDs were fabricated by the vacuum sublimation technique, and the aging effect of treated ITO anodes on the performance of OLEDs was studied with respect to the electroluminescence efficiency, brightness and driving voltage. Experimental results reveal that the luminescent and electrical characteristics of the OLEDs are strongly dependent on the properties of the ITO anodes, and the ITO anodes aged for various times result in significant differences in device performance, which become worse with the increment of the aging time. The measurements of X-ray photoelectron spectroscopy (XPS) and surface energy show that carbon concentration increases, oxygen concentration reduces and surface energy decreases, and thereby the improved surface properties of ITO tend to decay, as the aging time increases. It indicates that the device performance of the OLEDs is closely related to the surface characteristics of the ITO anodes.     

Effects of surface treatment of ITO anode layer patterned with shadow mask technology on characteristics of organic light-emitting diodes

We investigated the effects of various surface treatments of indium tin oxide (ITO) on the electrical and optical characteristics of organic light-emitting diodes (OLEDs). A 150-nm-thick ITO anode layer was patterned directly with a shadow mask during the sputtering process without the use of a conventional photolithography patterning method. The sputtered ITO layer was subjected to thermal and oxygen plasma treatments to reduce the sheet resistance and improve surface roughness. The thermal treatment was performed for 1 h at temperatures of 250 and 380 °C, which were chosen so that the glass substrates would not deform from thermal damage. The measured sheet resistance decreased from 30.86 Ω/sq for the as-sputtered samples to 8.76 Ω/sq for the samples thermally treated at 380 °C for 1 h followed by oxygen plasma treatment. The root-mean-square surface roughness measured by atomic force microscopy considerably decreased to 3.88 nm with oxygen plasma treatment. The thermal treatment considerably decreased the sheet resistance of the ITO anode layer patterned with the shadow mask. The spike-like structures that are often formed and observed in shadow mask-patterned ITO anode layers were almost all removed by the oxygen plasma treatment. Therefore, a smooth surface for shadow mask-patterned ITO layers with low sheet resistance can be obtained by combining thermal and oxygen plasma treatments. A smooth surface and low sheet resistance improves the electrical and optical characteristics of OLEDs. The surface-treated ITO layer was used to fabricate and characterize green phosphorescent OLED devices. The typical characteristics of OLED devices based on surface-treated shadow mask-patterned ITO layers were compared with those fabricated on untreated and photolithography-patterned ITO layers to investigate the surface treatment effects. The OLED devices fabricated by thermal treatment at 380 °C for 1 h followed by oxygen plasma treatment for 180 s showed the highest luminance and current density. Furthermore, the leakage current that might be induced by the rough ITO surface was dramatically reduced to 0.112 mA/cm². Our study showed that the shadow mask-patterned ITO anode layer treated by heat and plasma and having a low sheet resistance and surface roughness yielded excellent electrical and optical properties for OLEDs compared to those based on an untreated ITO layer. The fabricated OLED devices using the surface-treated shadow mask-patterned ITO layer exhibited comparable characteristics to those obtained from a conventional photolithography-patterned ITO anode.     

Direct Threat of a UV‐Ozone Treated Indium‐Tin‐Oxide Substrate to the Stabilities of Common Organic Semiconductors

Ultraviolet‐ozone treated indium‐tin‐oxide (UV‐ITO) glass substrates have been widely and unquestioningly used in the field of organic electronics to improve both device performance and stability. Evidence is presented here for rapid decay of common organic films such as N,N′‐bis(naphthalen‐1‐ yl)‐N,N′‐bis(phenyl)‐benzidine (NPB), tris(8‐hydroxy‐quinolinato)aluminum (Alq₃), and rubrene when they are in contact with an UV‐ITO substrate. While the photoluminescence (PL) of these organic films deposited on an UV‐ITO substrate decay rapidly under illumination; those on quartz substrates are comparatively much more stable. Results from X‐ray and UV photoemission spectroscopies (XPS and UPS) further suggest that degradations of the rubrene films on UV‐ITO substrate are mainly attributed to active oxygen species generated upon UV‐ozone treatment. These reactive oxygen species on the UV‐ITO surface behave as a reservoir of oxygen that interacts with rubrene and shifts its highest occupied molecular orbital (HOMO) level away from the Fermi level. This interaction induces a gap‐state in the energy gap of rubrene, which acts as a charge recombination center. More importantly, enhanced stabilities of rubrene‐based organic photovoltaic (OPV) devices are demonstrated when they are fabricated on gold‐coated or trifluoromethane (CHF₃) plasma‐treated ITO. The presented works shows that the commonly used UV‐ITO substrate is a threat to the stability of addlayer organic semiconducting films.     

A surface modification layer capable of tolerating substrate contamination on transparent electrodes of organic electronic devices

An organic molecule, hexaazatriphenylene hexacarbonitrile (HAT-CN), is found that it can be used not only as a hole-injecting material but also a surface modification material to clean contaminated substrate electrodes for the fabrication of organic electronic devices. As an example, HAT-CN can modify or “clean” indium-tin-oxide (ITO) anode surface in organic light-emitting diodes (OLEDs). Negative effect from ITO surface contamination on the electroluminescence performance of OLEDs can be dramatically reduced with this modification layer. As a result, the OLEDs with the same device architecture but with different ITO surface conditions, even with intentional contamination, can all exhibit substantially identical and superior electroluminescence performance. The surface modification function of this material is feasibly useful for the real fabrications of OLEDs as well as for advanced research on other organic electronic devices.     

Low-cost supercritical CO2/H2O2 treatment on ITO anodes of fluorescent organic light-emitting diodes

A simple and cost-effective approach is proposed as an alternative to conventional oxygen plasma treatment to modify surface property of Indium tin oxide (ITO) anode of a fluorescent organic light-emitting diode (OLED). This was achieved by treating the ITO anode in supercritical CO₂ (SCCO₂) fluids with hydrogen peroxide (H₂O₂). The SCCO₂/H₂O₂ treatment yielded an ITO work function of 5.35 eV after 15 min treatment at 85 °C and 4000 psi, which was significant higher than 4.8 eV of the as-cleaned ITO surface and was slightly less than 5.5 eV of the ITO surface treated by oxygen plasma. The highest work function achieved was 5.55 eV after 45 min SCCO₂/H₂O₂ treatment. The SCCO₂/H₂O₂ treatment can be used to tailor the ITO work function through changing the operation pressure of the treatment. In addition, the correlated dependence of OLED performance on the ITO anodes with and without the treatments was investigated. The maximum power efficiency of 1.94 lm/W was obtained at 17.3 mA/cm² for the device with 15 min SCCO₂/H₂O₂ treatment at 4000 psi. This power efficiency was 19.3% and 33.8% higher than those of the oxygen plasma treatment and as-clean, respectively. The improvement in device efficiency by the SCCO₂/H₂O₂ treatments can be attributed to enhanced hole injection and balance in charge carriers due to increased work function and surface energy of the ITO anodes.     

Effect of parylene layer on the performance of OLED

An organic light-emitting device structure with a thin parylene layer deposited by low-temperature chemical vapour deposition at the anode-organic interface was fabricated. Such a structure gives higher luminescence efficiency when operated at the same current density compared to one without the parylene layer. In addition, the devices with a thin parylene layer also show a smaller number and smaller size dark non-emissive areas, slower growth rate of the dark areas and a longer device lifetime. The modified surface of the indium tin oxide (ITO) shows an increased work function compared to that of the ITO surface alone and a reduced surface roughness, which contributes to the device performance improvement. The parylene layer is a conformal coating on the ITO surface, which could significantly stabilise the interface leading to a more uniform current density. It also provides a good barrier for blocking oxygen and moisture diffusion and hence reducing dark spot occurrence.     

Optoelectrical characteristics of organic light-emitting devices fabricated with different cathodes

Organic light-emitting devices (OLEDs) with various cathode structures were prepared on indium tin oxide (ITO) substrates by vacuum sublimation technique, and the effects of the device cathodes on the electroluminescence (EL) characteristics of OLEDs were studied in terms of the luminance, efficiency, driving voltage and threshold voltage. The results demonstrate that the optical and electrical performance of OLEDs depend on the properties of the devices' cathodes and the characteristics of the cathode–organic interface and the organic–organic interface. The optoelectrical performance of a device with composite cathodes is better than that of the devices with metal alloy and pure metal cathodes. The improvement in the device performance can be attributed to a more efficient electron injection at the cathode–organic interface, a better balanced hole and electron recombination in the light-emitting layer and fewer accumulated charges near the organic–organic interface.     

Photo-degradation of the indium tin oxide (ITO)/organic interface in organic optoelectronic devices and a new outlook on the role of ITO surface treatments and interfacial layers in improving device stability

This work focuses on the effect of light exposure on ITO/organic interface in organic optoelectronic devices, including organic light emitting devices (OLEDs), organic photo-detectors (OPDs) and organic solar cells (OSCs). The results show that irradiation by light in the visible and UV range leads to a gradual deterioration in charge injection and extraction across the interface. A correlation between the performance stability of the devices and the photo-stability of the ITO/organic contacts is established. Studies also show that this photo-induced degradation can be significantly reduced by means of ITO surface treatment or through the insertion of interfacial layers between ITO and the organic layers. X-ray Photoelectron Spectroscopy (XPS) measurements reveal detectable changes in the interface characteristics after irradiation, indicating that the photo-degradation of the ITO/organic contacts is chemical in nature. Changes in XPS characteristics after irradiation suggest a possible reduction in bonds between ITO and its adjacent organic layer. The results shed light on a new material degradation mechanism that appears to have a wide presence in ITO/organic contacts in general, and which may play a key role in limiting the stability of various organic optoelectronic devices such as OLEDs, OSCs and OPDs.