CN104178742B - 一种嵌入型金属/透明导电薄膜的制备方法 - Google Patents

一种嵌入型金属/透明导电薄膜的制备方法 Download PDF

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CN104178742B
CN104178742B CN201410382611.7A CN201410382611A CN104178742B CN 104178742 B CN104178742 B CN 104178742B CN 201410382611 A CN201410382611 A CN 201410382611A CN 104178742 B CN104178742 B CN 104178742B
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李保家
黄立静
任乃飞
周明
吴勃
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Dongtai Chengdong science and Technology Pioneer Park Management Co.,Ltd.
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Abstract

本发明提供了一种嵌入型金属/透明导电薄膜的制备方法,首先以TCO玻璃为基板,通过加入金属网,采用先进的激光微处理技术,获得具有凹孔结构的TCO薄膜;然后采用高真空直流磁控溅射仪溅射金属M层,获得金属M/TCO薄膜;后经退火处理得到嵌入型金属M/TCO薄膜。所得嵌入型金属M/TCO薄膜导电性得到提高的同时,透光率损失较少。本发明工艺制备方法简单、可控性好,过程中所用金属网来源广泛、易得,并且可以重复使用,实用性较好。

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一种嵌入型金属/透明导电薄膜的制备方法
技术领域
本发明涉及激光微纳加工技术及半导体材料领域,尤其涉及一种嵌入型金属/透明导电薄膜的制备方法。
背景技术
透明导电氧化物(TCO)薄膜因具有良好的导电性、在可见光区域有较高的透射率、红外区有高反射率等优点,目前被广泛应用于太阳能电池、显示器件、气敏元件以及压电器件等光电器件领域。随着人们对光电器件性能要求的不断提高,对TCO薄膜的光电性能也提出了更高的要求。
目前,针对TCO薄膜的研究主要集中于双层或多层复合薄膜,即通过引入金属或其他导电介质来提高TCO薄膜的光电性能。D.S.Ghosh等[High Figure-of-merit Ag/Al:ZnO Nano-thick Transparent Electrodes for Indium-free Flexible Photovoltaics,Solar Energy Materials&Solar Cells 2012,107,338–343.]报道了一种在制备金属/TCO双层薄膜的方法中所用的磁控溅射法,但是,这种方法只能将金属层沉积于基底表面,随着金属层厚度的增加,金属/TCO双层薄膜的透光率将会大幅度下降,影响其光电性能。
发明内容
本发明的目的是针对上述TCO薄膜随着金属层厚度的增加,透光率大幅度下降的不足,提供一种嵌入型金属/透明导电薄膜的制备方法,在提高TCO薄膜导电性的同时,尽量减少其透光率的损失,最终获得具有最佳光电性能的金属/透明导电薄膜。本发明是通过以下技术手段实现上述技术目的。
一种嵌入型金属/透明导电薄膜的制备方法,其特征在于,具体步骤包括:
(1)制备具有凹孔结构的TCO薄膜:以TCO玻璃为基板,经超声清洗、烘干后,放置在超短脉冲激光器的样品台上,调整样品台位置,使清洗烘干后的TCO薄膜表面位于所述激光器发出的激光束的焦点位;采用200~5000目的金属网作为模板,将其覆盖于清洗烘干后的TCO薄膜表面,进行激光表面处理,得到具有均匀、规则的凹孔结构的TCO薄膜,所述激光束的脉冲宽度<20ns,波长为500~1000nm,激光能量密度为0.10~0.60J/cm2,扫描速度为5~30mm/s,扫描线重叠率控制在0~20%;
(2)制备金属M/TCO薄膜:采用高真空直流磁控溅射仪在步骤(1)中具有凹孔结构的TCO薄膜表面沉积金属M层,得到金属M/TCO薄膜,所述溅射电流为60~100mA,溅射时间为2~15s,溅射气体为氩气,工作压强为0.035MPa;
(3)制备嵌入型金属M/TCO薄膜:将步骤(2)中所述的金属M/TCO薄膜置于管式炉中,进行退火处理,最终得到嵌入型金属M/TCO薄膜,所述退火处理的温度为300~600℃,时间为10~60min,退火气氛为氮气或氢气,气体流量控制为10~50sccm。
优选的,步骤(1)中所述TCO为氧化锌(ZnO)、氧化铟(In2O3)、氧化锡(SnO2)、掺铝氧化锌(AZO)、掺锡氧化铟(ITO)、掺氟氧化锡(FTO)中的一种。
优选的,步骤(1)中所述金属网不锈钢网或铜网。
优选的,步骤(1)中所述激光能量密度为0.10~0.30J/cm2
优选的,步骤(2)中所述金属M为Au、Ag、Cu、Pt、Ni和Al。
本发明具有以下优点:
(1)制备方法简单方便。过程中只需加入金属网,采用先进的激光微处理技术,就可以获得具有规则微纳凹孔结构的TCO薄膜,经溅射、退火处理后即可得导电性能好、透光率高的金属/透明导电薄膜。
(2)可控性好。采用金属网作为模板,通过调节激光能量密度、线间距、扫描速度等工艺参数,可得到不同孔径的、均匀、规则的TCO薄膜表面。
(3)实用性好。该处理方法使用的金属网容易获得,并且可以重复使用。
附图说明
图1嵌入型金属/透明导电薄膜制备过程流程图。
图2为实施例1和对比例1中Ag/FTO双层薄膜Ag嵌入型和非嵌入型透光率谱图。
图3为实施例2和对比例2中Cu/AZO双层薄膜Cu嵌入型和非嵌入型透光率谱图。
具体实施方式
下面结合附图以及具体实施例对本发明作进一步的说明,但本发明的保护范围并不限于此。
对比例1:
(1)FTO薄膜的准备:采用FTO玻璃为基底,并将其裁切为面积为2.0cm×2.0cm的小块,依次在去离子水、丙酮、乙醇中超声波清洗10分钟后用高纯氮气吹干,置于80℃以下的烘箱中烘干1小时,得清洁干净的FTO薄膜;
(2)制备金属M/FTO薄膜:采用高真空直流磁控溅射仪在步骤(1)得到FTO薄膜表面沉积金属Ag层(Ag靶纯度为99.99%),得到Ag/FTO薄膜,所述溅射电流为60mA,溅射时间为5s,溅射气体为氩气,工作压强为0.035MPa;
(3)制备非嵌入型金属M/TCO薄膜:将步骤(2)中的Ag/FTO薄膜置于管式炉中,在氮气气氛中,500℃下保持20分钟,气体流速为10sccm,冷却至室温取出,得非嵌入型Ag/FTO薄膜。
实施例1:
图1为嵌入型金属/透明导电薄膜过程流程图,如图1所示:
(1)制备具有凹孔结构的FTO薄膜:采用FTO玻璃为基底,并将其裁切为面积为2.0cm×2.0cm的小块,依次在去离子水、丙酮、乙醇中超声波清洗10分钟后用高纯氮气吹干,置于80℃以下的烘箱中烘干1小时,得清洁干净的FTO薄膜;随后将FTO薄膜放置在超短脉冲激光器的样品台上,调整样品台位置,使FTO薄膜表面位于所述激光器发出的激光束的焦点位;取400目的不锈钢网作为模板,将其覆盖于FTO薄膜表面,进行激光表面处理,得到具有均匀、规则的凹孔结构的FTO薄膜,所述激光束的脉冲宽度1ns,波长为532nm,重复频率为1kHz,激光能量密度为0.10J/cm2,扫描速度为10mm/s,扫描重叠率为15%,扫描线宽为70μm,扫描间距为60μm,设定各线扫描次数为1次,控制激光光束运动,使激光光束垂直于薄膜表面扫描;
(2)制备金属M/FTO薄膜:采用高真空直流磁控溅射仪在步骤(1)中具有凹孔结构的FTO薄膜表面沉积金属Ag层(Ag靶纯度为99.99%),得到Ag/FTO薄膜,所述溅射电流为60mA,溅射时间为5s,溅射气体为氩气,工作压强为0.035MPa;
(3)制备嵌入型金属M/TCO薄膜:将步骤(2)中的Ag/FTO薄膜置于管式炉中,在氮气气氛中,500℃下保持20分钟,气体流速为10sccm,冷却至室温取出,得嵌入型Ag/FTO薄膜,经检测,所得嵌入型Ag/FTO薄膜的方块电阻为5.6Ω/sq,与原始FTO(方块电阻为8.5Ω/sq)相比,其导电性得到提高。由图2可以看出,嵌入型的Ag/FTO薄膜的透光率明显高于非嵌入型,说明嵌入型的薄膜透光性能优于非嵌入型的。
对比例2:
(1)AZO薄膜的准备:以AZO玻璃为基底,并将其裁切为面积为2.0cm×2.0cm的小块,依次在去离子水、丙酮、乙醇中超声波清洗10分钟后用高纯氮气吹干,置于80℃以下的烘箱中烘干1小时,得清洁干净的AZO薄膜;
(2)制备金属M/AZO薄膜:采用高真空直流磁控溅射仪在步骤(1)中具有凹孔结构的AZO薄膜表面沉积金属Cu层(Cu靶纯度为99.99%),得到Cu/AZO薄膜,所述溅射电流为100mA,溅射时间为12s,溅射气体为氩气,工作压强为0.035MPa;
(3)制备非嵌入型金属M/AZO薄膜:将步骤(2)中的Cu/AZO薄膜置于管式炉中,在氮气气氛中,500℃下保持20分钟,气体流速为10sccm,冷却至室温取出,得非嵌入型Cu/AZO薄膜。
实施例2:
图1为嵌入型金属/透明导电薄膜过程流程图,如图1所示:
(1)制备具有凹孔结构的AZO薄膜:采用AZO玻璃为基底,并将其裁切为面积为2.0cm×2.0cm的小块,依次在去离子水、丙酮、乙醇中超声波清洗10分钟后用高纯氮气吹干,置于80℃以下的烘箱中烘干1小时,得清洁干净的AZO薄膜;随后将AZO薄膜放置在超短脉冲激光器的样品台上,调整样品台位置,使AZO薄膜表面位于所述激光器发出的激光束的焦点位;取400目的不锈钢网作为模板,将其覆盖于AZO薄膜表面,进行激光表面处理,得到具有均匀、规则的凹孔结构的AZO薄膜,所述激光束的脉冲宽度16ns,波长为800nm,重复频率为1kHz,激光能量密度为0.50J/cm2,扫描速度为25mm/s,扫描重叠率为5%,扫描线宽为90μm,扫描间距为85μm,设定各线扫描次数为1次,控制激光光束运动,使激光光束垂直于薄膜表面扫描;
(2)制备金属M/AZO薄膜:采用高真空直流磁控溅射仪在步骤(1)中具有凹孔结构的AZO薄膜表面沉积金属Cu层(Cu靶纯度为99.99%),得到Cu/AZO薄膜,所述溅射电流为100mA,溅射时间为12s,溅射气体为氩气,工作压强为0.035MPa;
(3)制备嵌入型金属M/AZO薄膜:将步骤(2)中的Cu/AZO薄膜置于管式炉中,在氮气气氛中,500℃下保持20分钟,气体流速为10sccm,冷却至室温取出,得嵌入型Cu/AZO薄膜,经检测,所得嵌入型Cu/AZO薄膜的方块电阻为26.3Ω/sq,与原始AZO(方块电阻为85.6Ω/sq)相比,其导电性得到提高。由图3可以看出,嵌入型的Cu/AZO薄膜的透光率明显高于非嵌入型,说明嵌入型的薄膜透光性能优于非嵌入型的。
所述实施例为本发明的优选的实施方式,但本发明并不限于上述实施方式,在不背离本发明的实质内容的情况下,本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。

Claims (5)

1.一种嵌入型金属/透明导电薄膜的制备方法,其特征在于,包括下列步骤:
(1)制备具有凹孔结构的TCO薄膜:以TCO玻璃为基板,经超声清洗、烘干后,放置在超短脉冲激光器的样品台上,调整样品台位置,使清洗烘干后的TCO薄膜表面位于所述激光器发出的激光束的焦点位;采用200~5000目的金属网作为模板,将其覆盖于清洗烘干后的TCO薄膜表面,进行激光表面处理,得到具有均匀、规则的凹孔结构的TCO薄膜,所述激光束的脉冲宽度<20ns,波长为500~1000nm,激光能量密度为0.10~0.60J/cm2,扫描速度为5~30mm/s,扫描线重叠率控制在0~20%;
(2)制备金属M/TCO薄膜:采用高真空直流磁控溅射仪在步骤(1)中具有凹孔结构的TCO薄膜表面沉积金属M层,得到金属M/TCO薄膜,所述溅射电流为60~100mA,溅射时间为2~15s,溅射气体为氩气,工作压强为0.035MPa;
(3)制备嵌入型金属M/TCO薄膜:将步骤(2)中所述的金属M/TCO薄膜置于管式炉中,进行退火处理,最终得到嵌入型金属M/TCO薄膜,所述退火处理的温度为300~600℃,时间为10~60min,退火气氛为氮气或氢气,气体流量控制为10~50sccm。
2.根据权利要求1所述一种嵌入型金属/透明导电薄膜的制备方法,其特征在于,步骤(1)中所述TCO为氧化锌(ZnO)、氧化铟(In2O3)、氧化锡(SnO2)、掺铝氧化锌(AZO)、掺锡氧化铟(ITO)、掺氟氧化锡(FTO)中的一种。
3.根据权利要求1所述一种嵌入型金属/透明导电薄膜的制备方法,其特征在于,步骤(1)中所述金属网为不锈钢网或铜网。
4.根据权利要求1所述一种嵌入型金属/透明导电薄膜的制备方法,其特征在于,步骤(1)中所述激光能量密度为0.10~0.30J/cm2
5.根据权利要求1所述一种嵌入型金属/透明导电薄膜的制备方法,其特征在于,步骤(2)中所述金属M为Au、Ag、Cu、Pt、Ni和Al。
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