CN106868470A - 一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法 - Google Patents
一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法 Download PDFInfo
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Abstract
一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法，属于透明导电电极制备技术领域。首先是将透明基底进行清洁处理，再用氮气吹干；然后透明基底的同一侧表面粘贴两条相互分立的保护膜，两条保护膜对称地位于基底表面靠近边缘处的位置，得到图形化透明基底，然后将该图形化透明基底送入原子层沉积设备的反应室中进行透明铜薄膜的生长；最后将透明基底及其上沉积生长的透明铜薄膜高温退火，退火温度为200～300℃，退火时间为20～30min，从而在透明基底上得到图形化的均匀透明铜薄膜导电电极。本发明制备的透明铜薄膜导电电极均匀性好，光电性能优异，可用于制造太阳能电池、发光二极管、LCD以及手机等光电器件。
Description
技术领域
本发明属于透明导电电极制备技术领域，具体涉及一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法。
背景技术
透明导电电极被广泛应用于平板显示、固态照明、微小显示器、太阳能电池及光电探测器等领域，是光电器件的关键组件。目前，透明导电电极最常用的薄膜材料是通过磁控溅射技术制备在玻璃或者其他透明基质上的ITO薄膜，然而ITO薄膜虽然具有比较好的透光率，但其应用也存在诸多限制，例如：a)导电性相对较差；b)制备ITO薄膜所需要的铟属于稀有金属，在地壳中含量较少，且铟材料有毒，在制备和应用过程中对人体有害；c)ITO薄膜延展性较差，不适用于柔性基底。与之相反的是，金属电极虽然具有较好的导电性，延展性以及较为丰富的来源，但是金属电极的透光性较差，很难制备出透明的金属导电电极。
制备透明导电电极的主要方法为真空物理法和化学方法。其中，真空物理法主要指磁控溅射法，该种方法可以制备致密均匀、物理附着性好的透明导电膜，但是对仪器设备及生长环境要求高，且制备出来的金属薄膜电极透光性较差。化学方法主要为溶胶-凝胶法，该方法的优点是生产设备简单，易于实现多组分的均匀掺杂，但是导电膜和基底间物理附着性差且高温处理使得透明导电电极的基底受到限制。
原子层沉积(ALD)是一种基于自限制性和自饱和性的改性技术，在沉积过程中，通过将气相前驱体(即反应源)脉冲交替地通入反应室并在沉积基体上发生表面化学吸附反应形成薄膜的一种方法。在沉积过程中，通过将气相前驱体(即反应源)脉冲交替地通入反应室并在沉积基体上发生表面化学吸附反应形成薄膜的一种方法。脉冲时间决定通入前驱体源的用量，当通入另一种气相前驱体脉冲时，需要将前面的前驱体排除干净，方式是用氮气将前驱体运送排出，排空时间就是氮气的通入时间,/循环是指气相前驱体(即反应源)脉冲交替地通入反应室并在沉积基体上发生表面化学吸附反应形成的一个循环。
相比于传统的真空物理法和化学法，原子层沉积技术因为其自限制的生长模式，可以生长均匀、高保型性、高高宽比的薄膜；而且由于逐层生长的特点，能精确的控制生长薄膜的厚度，可以用来制备超薄透明导电金属薄膜电极，因此越来越受到人们的重视。
发明内容
本发明的目的在于克服现有技术的不足，结合原子层沉积技术的优势，提供一种基于原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法。采用原子层沉积技术制备透明铜薄膜导电电极解决了同时具有高导电性、透光率及延展性的透明导电电极的难点，由于制备的是Cu薄膜导电电极，因此其具有较好的延展性，当使用柔性基底时，还可以制备成柔性器件。
本发明所述的一种基于原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法，其具体步骤如下：
1)将透明基底依次用丙酮、乙醇及去离子水擦拭，并依次用丙酮、乙醇及去离子水超声清洗，然后用氮气吹干；
2)在步骤1)得到的透明基底的同一侧表面粘贴两条相互分立的保护膜，两条保护膜对称地位于基底表面靠近边缘处的位置(保护膜的作用在于控制发光区域的面积以避免阳极和阴极接触短路)，得到图形化透明基底，然后将该图形化透明基底送入原子层沉积设备的反应室中；
3)向原子层沉积设备的反应室内依次通入反应物前驱体二乙基锌(ZnEt2)和二(六氟乙酰丙酮)铜(Cu(hfac)2)，在步骤2)得到的图形化透明基底上沉积生长厚度为10～12nm的透明铜薄膜，生长完成后揭下保护膜；由于保护膜的存在，生长在透明基底上的透明铜薄膜的横向或纵向尺寸小于透明基底的横向或纵向尺寸，即在透明铜薄膜横向或纵向的边缘处位置露出部分透明基底；
4)将步骤3)得到的透明基底及其上沉积生长的透明铜薄膜高温退火，退火温度为200～300℃，退火时间为20～30min，从而在透明基底上得到图形化的均匀透明铜薄膜导电电极。
上述方法步骤1)所述的透明基底为普通抛光玻璃，也可以是聚萘二甲酸乙二醇酯polyethylene naphthalate(PEN)、聚对苯二甲酸乙二醇酯polyethylene terephthalate(PET)、聚醚酰亚胺polyetherimide(PEI)等柔性商用透明聚酯膜基底。
上述方法步骤2)所述的保护膜是硅片保护膜。硅片保护膜为双层结构，由基底层和胶黏层组成，基底层为双轴拉伸聚氯乙烯，胶黏层为经过处理的丙烯酸酯乳胶。保护膜可以被轻易地从基底上撕除而无胶黏剂残留。
上述方法步骤3)所述的沉积是在原子层沉积系统中进行的，反应室内沉积压力为0.1～1Torr，沉积温度为100～130℃。
上述方法步骤3)ZnEt2脉冲时间0.02s～0.03/循环，氮气(N2)排空时间80s/循环以上；Cu(hfac)2脉冲时间0.08～0.1s/循环，氮气(N2)排空时间120s/循环以上。
本发明制备工艺简单，沉积过程易于控制。本发明制备的透明铜薄膜导电电极均匀性好，光电性能优异，电阻率可低至6.2Ω/cm2(电极厚度12nm)，而透光率可达80％左右。可用于制造太阳能电池、发光二极管、LCD以及手机等光电器件。
附图说明
图1为本发明方法得到的图形化均匀透明铜薄膜导电电极示意图。图中1为保护膜，2为ALD生长的透明铜薄膜导电电极；
图2为本发明实施例1制备的10nm透明铜薄膜导电电极的光学透过率曲线；
图3为本发明实施例1制备的10nm透明铜薄膜导电电极的方块电阻随薄膜厚度的变化曲线；
图4为实施例1制备的10nm透明铜薄膜导电电极的XRD图；
图5为实施例2制备的有机电致发光器件的亮度测试曲线。曲线1为ITO电极制备的有机电致发光器件的亮度测试曲线，曲线2为12nm透明铜薄膜导电电极制备的有机电致发光器件的亮度测试曲线。从曲线2可以看出，其亮度高于曲线1，表明制备的器件效果良好。
图6为实施例2制备的有机电致发光器件各层结构示意图，竖线区域为Cu阳极层，斜线区域为有机层，横线区域为Al阴极层。
具体实施方案
本发明中所述的原子层沉积系统为北京英作纳米技术股份有限公司设计的，型号为LabNano 9100系列ALD沉积设备。
实施例1
我们采用原子层沉积通过置换反应制备了方块电阻可低至6.2Ω/cm2、而透光率可达80％左右的均匀透明铜薄膜导电电极。
具体过程如下：
1)将25×25mm的玻璃基底用丙酮、乙醇及去离子水擦拭并依次用丙酮、乙醇及去离子水超声清洗，然后用氮气吹干；
2)在步骤1)清洗过的玻璃基底的同一侧表面上粘贴两条相互分立的硅片保护膜，保护膜结构与尺寸如图1所示，位于基底同一侧表面的上下两侧靠近边缘端面处为保护膜的位置，其尺寸为25×5mm，中间部分为生长铜膜区域，其尺寸为25×15mm，其作用在于控制发光区域的面积以避免阳极和阴极接触短路，得到图形化的透明基底，然后将图形化的透明基底送入原子层沉积设备的反应室；
3)将反应室抽真空至真空度为0.15Torr后，将得到的图形化透明基底加热至120℃，首先每循环先通入前驱体反应物ZnEt2，脉冲时间为0.02s/循环，紧接着通入清洗气体N2，排空时间为80s/循环；然后通入前驱体反应物Cu(hfac)2，脉冲时间为0.08s，N2排空时间为120s/循环。每个循环生长铜薄膜厚度约为0.2nm，生长500～600个循环，得到10～12nm的透明铜薄膜导电电极，透明铜薄膜生长完成后从层沉积设备的反应室中取出，并揭下保护膜。
4)将生长在玻璃基底上的透明铜薄膜进行高温退火，退火温度为200℃，退火时间为30min，得到透明铜薄膜导电电极；
对得到的10nm(500个循环)透明铜薄膜导电电极在可见光范围内的光学透过率进行测试，如图2所示，可以看出其透过率在80％左右，对利用原子层沉积生长不同循环得到的不同厚度)的透明铜薄膜导电电极进行了方块电阻的测试，如图3所示，结果表明其具有良好的导电性能，对利用原子层沉积生长2500循环得到的50nm透明铜薄膜导电电极进行X射线衍射分析(XRD)，其XRD如图4所示，结果表明该实验条件下制备的铜薄膜样品其结构性能良好，杂质较少。
实施例2
我们利用原子层沉积技术通过置换反应原理制备了12nm(600个循环)厚的图形化均匀透明铜薄膜导电电极，并且在此基础上制备了结构为A：玻璃/ITO/HAT-CN(5nm)/TAPC(50nm)/Ir(ppy)3：CBP 5％(百分数的单位是摩尔量)(15nm)/TPBI(30nm)/Liq(1nm)/Al和结构为B：玻璃/Cu(本发明制备的透明铜薄膜导电电极，12nm)/HAT-CN(5nm)/TAPC(50nm)/Ir(ppy)3：CBP 5％(15nm)/TPBI(30nm)/Liq(1nm)/Al的OLED器件，其中，HAT-CN为空穴注入层，TAPC为空穴传输层，Ir(ppy)3：CBP为发光层，TPBI为电子传输层，Liq为缓冲层，Al为阴极。
其中，A组器件ITO作为OLED阳极，B组器件12nm透明铜薄膜导电电极作为OLED阳极，具体过程如下：
1)A组器件基底为带有ITO电极的玻璃，首先依次用丙酮、乙醇及去离子水擦拭并依次用丙酮、乙醇及去离子水超声清洗，然后用氮气吹干，玻璃的尺寸为25×25mm。
B组器件基底为25×25mm的普通玻璃，按照实施例1的方法，在玻璃上制备图形化的12nm透明铜薄膜导电电极，透明铜薄膜导电电极的尺寸为25×15mm。
2)将步骤1)处理好的A、B组器件的ITO电极和透明铜薄膜导电电极面朝上，置于多源有机分子气相沉积系统中。系统的真空度可达到10-5Pa，在薄膜生长的过程中系统的真空度维持在4×10-4Pa左右。以玻璃基底的中心为中心，利用尺寸为20×20mm的有机掩膜版依次制备面积为20×20mm的有机电子器件的各个层(HAT-CN(5nm)/TAPC(50nm)/Ir(ppy)3：CBP 5％(15nm)/TPBI(30nm)/Liq(1nm)/Al)，蒸镀Al电极的掩膜版形状为工字形结构(外部形状的尺寸为17×25mm)，得到的Al接触电极即为二个分立的凸字形结构(大区域的长24mm，大区域的宽4mm，小区域的长10mm，小区域的宽4mm)位于基底的左、右两侧靠近端面处，其器件生长各层如图6所示，竖线区域为Cu阳极层，斜线区域为有机层，横线区域为Al阴极层。有机材料生长速率控制在Liq的生长速率控制在蒸镀Al电极采用的镀料为铝粒，将铝粒放在一根钨丝蒸发源上，钨丝两端通电，利用热蒸发的原理蒸镀Al电极，其生长速率控制在从而得到OLED器件。
3)进行A、B二组器件亮度测试的对比，测试仪器为便携式分光辐射亮度计PR-655，所有的亮度-电压曲线测试都是在室温大气环境中进行的。
ITO和透明铜薄膜导电电极分别作为阳极的OLED亮度测试图为图5，曲线1为ITO电极制备的有机电致发光器件的亮度测试曲线，曲线2为12nm透明铜薄膜导电电极制备的有机电致发光器件的亮度测试曲线。其结果表明利用原子层沉积技术通过置换反应原理制备的12nm图形化透明铜薄膜导电电极作为OLED器件的阳极具有良好的电学性能和光学性能。
综上所述，基于原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法，解决了同时具有高导电性、透光率及延展性的透明导电电极的难点，由于制备的是Cu电极层，因此其具有较好的延展性，当使用柔性基底时，还可以制备成柔性透明电极，可用于制造太阳能电池、发光二极管、LCD以及手机等光电器件。
Claims (5)
1.一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法，其步骤如下：
1)将透明基底依次用丙酮、乙醇及去离子水擦拭，并依次用丙酮、乙醇及去离子水超声清洗，然后用氮气吹干；
2)在步骤1)得到的透明基底的同一侧表面粘贴两条相互分立的保护膜，两条保护膜对称地位于基底表面靠近边缘处的位置，得到图形化透明基底，然后将该图形化透明基底送入原子层沉积设备的反应室中；
3)向原子层沉积设备的反应室内依次通入反应物前驱体二乙基锌和二(六氟乙酰丙酮)铜，在步骤2)得到的图形化透明基底上沉积生长厚度为10～12nm的透明铜薄膜，生长完成后揭下保护膜；
4)将步骤3)得到的透明基底及其上沉积生长的透明铜薄膜高温退火，退火温度为200～300℃，退火时间为20～30min，从而在透明基底上得到图形化的均匀透明铜薄膜导电电极。
2.如权利要求1所述的一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法，其特征在于：步骤1)中所述的透明基底为抛光玻璃、聚萘二甲酸乙二醇酯、聚对苯二甲酸乙二醇酯或聚醚酰亚胺。
3.如权利要求1所述的一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法，其特征在于：步骤2)中所述的保护膜为硅片保护膜。
4.如权利要求1所述的一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法，其特征在于：步骤3)中所述的沉积是在原子层沉积系统中进行的，反应室内沉积压力为0.1～1Torr，沉积温度为100～130℃。
5.如权利要求1所述的一种利用原子层沉积技术通过置换反应制备透明铜薄膜导电电极的方法，其特征在于：步骤3)中二乙基锌的脉冲时间为0.02s～0.03/循环，氮气排空时间80s/循环以上；二(六氟乙酰丙酮)铜的脉冲时间0.08～0.1s/循环，氮气排空时间120s/循环以上。
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