CN107611277B - 一种氧化镧空穴注入层有机发光器件及制备方法 - Google Patents
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Abstract
本发明公开了一种基于水溶液处理的氧化镧空穴注入层有机发光器件，所述器件的空穴注入层由水溶液处理的La2O3制备而成。另外，还公开了该器件的制备方法，所述方法至少包括如下步骤：（1）以硝酸镧六水合物和氨水为原料，采用共沉淀法制备La2O3纳米粉体颗粒；（2）将La2O3纳米粉体颗粒溶解在去离子水中，形成浓度为0.2wt％的La2O3悬浮液，然后对La2O3悬浮液过滤得到La2O3过滤液；（3）在ITO阳极玻璃基片上通过旋涂工艺旋涂La2O3过滤液形成La2O3薄膜，所述La2O3过滤液中的La浓度为0.01 mg/mL—0.03 mg/mL。本发明所述器件能有效的调节载流子的平衡，提高发光效率，同时器件的空穴注入层具有与MoOx空穴注入层几乎相当的空穴注入能力。
Description
技术领域
本发明涉及有机发光器件，具体涉及一种基于水溶液处理的氧化镧空穴注入层有机发光器件及制备方法。
背景技术
载流子平衡的调节对提高有机电致发光器件（OLED）的效率起着至关重要作用，通常在器件的阳极和空穴传输层之间引入空穴注入层用于调节空穴注入特性，从而达到调节发光层中的载流子平衡。与被广泛用于空穴注入层的有机材料相比较，无机金属氧化物（如MoOx、V2O5、WO3、NiO等）具有更优异的耐热/耐湿性和改善的器件耐久性。在器件的生产工艺方面，与传统的真空热蒸镀法相比较，溶液处理技术如卷对卷、印刷、刮涂等加快了有机电致发光器件在实际应用中的低成本、规模化生产。
发明内容
本发明的目的在于提供一种基于水溶液处理的氧化镧（La2O3）空穴注入层有机发光器件。与使用常规真空热蒸镀MoOx作为空穴注入层的参考器件相比，溶液处理的La2O3为空穴注入层的OLED能有效地调节载流子的平衡，提高器件的发光效率。空穴单载流子器件的伏安特性（I-V）曲线表明，溶液处理的La2O3空穴注入层表现出与MoOx空穴注入层几乎相当的空穴注入能力。溶液处理的La2O3空穴注入层的空穴注入机制主要由F-N遂穿理论控制，空穴注入势垒高度约为0.098eV。另外，本发明还提供了所述氧化镧空穴注入层有机发光器件的制备方法。所述制备方法至少包括了以下步骤：（1）以硝酸镧六水合物和氨水为原料，采用共沉淀法制备La2O3纳米粉体颗粒；（2）将La2O3纳米粉体颗粒溶解在去离子水中，形成浓度为0.2wt％的La2O3悬浮液，然后对La2O3悬浮液过滤得到La2O3过滤液；（3）在ITO阳极玻璃基片上通过旋涂工艺旋涂La2O3过滤液形成La2O3薄膜，所述La2O3过滤液中的La浓度为0.01 mg/mL—0.03 mg/mL。
附图说明
图1描述了不同空穴注入层OLED的发光效率-电流密度特性曲线。
图2描述了不同空穴注入层OLED的功率效率-电流密度特性曲线。
图3描述了不同空穴注入层OLED的发光效率与亮度特性。
图4描述了不同空穴注入层单空穴器件的I-V特性。
具体实施方式
一.La2O3纳米颗粒的合成。
以硝酸镧六水合物［La(NO3)3·6H 2 O］和氨水［NH4·OH］为原料，采用共沉淀法制备了氧化镧纳米颗粒（粉体）。首先，硝酸镧六水合物用纯水溶解，制成浓度为0.3 mol/L的硝酸镧溶液；随后，在溶液中边搅拌边加入少量pvp分散剂；室温条件，在剧烈搅拌状态下缓慢滴加稀释后（0.3 mol/L）的氨水，在密封的条件下沉淀4～5小时，待反应完全后pH值为9.0。过滤得到含水的浆料沉淀物，使用纯水多次洗涤以除去其中的NH4 +和NO3 -；将清洗过的浆料沉淀物在烘箱中于80～90℃条件下干燥，干燥的粉体使用氧化铝研钵粉碎；将研磨好的粉体在900℃温度下煅烧4个小时得到La2O3纳米颗粒（粉体）。
二.OLED的制备。
将合成的La2O3纳米颗粒（粉体）溶解在去离子水中，形成浓度为0.2wt％的La2O3悬浮液，对La2O3悬浮液进行过滤以形成La2O3过滤液，用电感耦合等离子体发射光谱法（ICP-OES，iCAP7600）测定该溶液的La浓度。采用旋涂工艺旋涂La2O3溶液形成La2O3薄膜（根据需要可以用去离子水对溶液进行稀释）。
将ITO涂覆的玻璃用作阳极并进行用于OLED制造的常规化学清洁；通过以3500rpm的转速分别旋涂其中La含量为0.01 mg/mL（器件A1）、0.02 mg/mL（器件A2）和0.03 mg/mL（器件A3）的La2O3溶液60秒；然后在空气条件下140℃热处理20分钟。将旋涂了La2O3的ITO阳极玻璃基片装载到多源淀积室中，在4.0×10-4 Pa的真空条件下采用真空热蒸镀工艺依次沉积N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺（NPB，厚度50 nm），8-羟基喹啉铝（Alq3，厚度30nm），4,7-二苯基-1,10-菲啰啉（BPhen，厚度25 nm），LiF（厚度0.7 nm）和Al（厚度>100 nm），分别用作OLED空穴传输层、发光层、电子传输层、电子注入层和反射阴极。制备传统的真空热蒸发MoOx（厚度2 nm）空穴注入层的OLED（器件B）和没有空穴注入层的OLED（器件C）作为参考器件用于比较，用石英晶振膜厚仪原位监测和控制层的厚度和沉积速率。
三.OLED测试结果。
OLED测试样品分别是：器件A1（La2O3空穴注入层，La含量0.01 mg/mL）、器件A2（La2O3空穴注入层，La含量0.02 mg/mL）、器件A3（La2O3空穴注入层，La含量0.03 mg/mL）、器件B（MoOx空穴注入层）和器件C（无空穴注入层）。
图1〜3所示，很明显，溶液处理的La2O3作为空穴注入层的OLED显示出了优异的性能。例如，器件A2显示最大发光效率为6.6 cd/A，功率效率为3.0 lm/W，分别比器件C（4.3cd/A及1.8 lm/W）提高了53.5％和66.7％；器件A2的最大发光效率也优于器件B的5.3 cd/A，而这两个器件的最大功率效率的差异可以忽略不计。此外，器件A2的亮度为1000 cd/m2时发光效率达到6.2 cd/A，与器件B的5.1 cd/A相比增强了21.6％，它明确表现出溶液处理的La2O3作为空穴注入层在构建高效OLED中的优越性。另一方面，与器件A1和A3相比，器件A2的效率更高，这表明La2O3溶液的浓度对器件性能有很大的影响，适当的La浓度更有利于空穴注入，从而更好地调节载流子平衡并提升器件的性能。
图4所示，I-V特性曲线表明溶液处理的La2O3较真空蒸镀的MoOx一样具有强大的空穴注入能力，并且可以促进从ITO阳极到NPB 空穴传输层的空穴注入。
Claims (1)
1.一种氧化镧空穴注入层有机发光器件的制备方法，包括空穴注入层的制备，其特征在于：所述空穴注入层的制备方法至少包括如下步骤：
（1）以硝酸镧六水合物和氨水为原料，采用共沉淀法制备La2O3纳米粉体颗粒；
（2）将La2O3纳米粉体颗粒溶解在去离子水中，形成浓度为0.2wt％的La2O3悬浮液，然后对La2O3悬浮液过滤得到La2O3过滤液；
（3）在ITO阳极玻璃基片上通过旋涂工艺旋涂La2O3过滤液形成La2O3薄膜，所述La2O3过滤液中的La浓度为0.01 mg/mL—0.03 mg/mL。
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