CN105845752B - 一种应用于柔性光电器件的透明导电薄膜及其制备方法 - Google Patents
一种应用于柔性光电器件的透明导电薄膜及其制备方法 Download PDFInfo
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022491—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of a thin transparent metal layer, e.g. gold
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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- H01L31/02—Details
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Abstract
一种应用于柔性光电器件的透明导电薄膜,设置有第一氧化物层、金属膜夹层和位于金属膜夹层之上的第二氧化物层;第一氧化物层为单层或复合多层宽禁带一元氧化物非晶态薄膜,宽禁带一元氧化物为氧化钛、氧化铝、氧化锆或氧化镁。金属膜夹层为银或铜单质薄膜或者其合金薄膜。第二氧化物层为透明氧化物(In2O3)x(MO)y(ZnO)z非晶态薄膜。该透明导电薄膜结构简单,能够简化制备工序,所获得透明导电薄膜透光率高、导电性好、热稳定性佳。本发明的制备工艺实现了以简单步骤制备得到透光率高、导电性好、热稳定性佳的透明导电薄膜。
Description
技术领域
本发明涉及柔性光电器件技术领域,特别是涉及一种应用于柔性光电器件的透明导电薄膜及其制备方法。
背景技术
透明导电氧化物(Transparent Conductor Oxide,TCO)具有禁带宽、光透射率高和电阻率低等特点,已在太阳能电池、平面显示、特殊功能窗口涂层等领域获得了广泛的应用。目前,掺锡氧化铟、掺氟氧化锡和掺铝氧化锌等透明导电薄膜在光电领域已应用广泛。但是,随着柔性电子的高速发展,对透明导电膜在导电性、可靠性方面都提出了新的要求。近年来发展的氧化物-金属-氧化物透明导电薄膜具有透光率和导电率高等特点,而且具有制备抗弯折导电膜的潜力,正收到研究的关注,并已逐步应用到柔性太阳能电池和显示等光电领域。
因为柔性电子器件通常制作于塑料衬底之上。而塑料衬底对水氧阻隔能力远远不及传统的玻璃、不锈钢衬底。因此通常柔性电子器件在制作之前还需要制作额外的水氧阻隔层,如此一来增加了器件结构的复杂度,增加了工艺工序。
因此,针对现有技术不足,提供一种能够简化结构和工艺的透明导电薄膜及其制备方法甚为必要。
发明内容
本发明的目的在于避免现有技术的不足之处而提供一种应用于柔性光电器件的透明导电薄膜及其制备方法,在金属氧化物/金属膜/金属氧化物三层结构的透明导电膜中,通过将封装膜与导电膜相结合,合并了工序步骤,实现了结构和工艺简化,所获得的透明导电薄膜具有更好的光学、电学以及力学性能。
本发明的上述目的通过如下技术手段实现。
提供一种应用于柔性光电器件的透明导电薄膜,设置有第一氧化物层、设置于第一氧化物层之上的金属膜夹层和设置于金属膜夹层之上的第二氧化物层;
所述第一氧化物层为单层或复合多层宽禁带一元氧化物非晶态薄膜,所述宽禁带一元氧化物为氧化钛、氧化铝、氧化锆或氧化镁。
上述金属膜夹层为银或铜单质薄膜,或者为含银、铜的合金薄膜。
上述第二氧化物层为透明氧化物非晶态薄膜,所述透明氧化物为金属氧化物(In2O3)x(MO)y(ZnO)z,其中0≤x≤1,0≤y≤1,0≤z≤1,且x+y+z=1,M为镓、锡、钛、铝、镁、钽、铪、镱、锆中的一种元素或两种以上的元素的任意组合。
优选的,上述第一氧化物层的厚度为1 nm ~100 nm。
优选的,上述金属膜夹层的厚度为7 nm ~12nm。
优选的,上述第二氧化物层的厚度为5~15 nm。
上述第一氧化物层具体是采用热生长或者等离子增强的原子层沉积方式,在80~250℃下生长成膜制备而成;
所述第二氧化物层具体是采用热生长或者等离子增强的原子层沉积方式,在80~250℃下生长成膜制备而成,或者采用物理气相方式制备而成。
上述金属膜夹层采用物理气相方式制备,具体是在本底真空小于5×10-3 Pa的状态下,在溅射气压为0.1 Pa~1.0 Pa、溅射功率为50 W~500 W、溅射速率为0.2 nm/s~1.0nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为20 oC ~150 oC。
本发明的另一目的在于提供一种应用于柔性光电器件的透明导电薄膜的制备方法,上述的透明导电薄膜在硬质衬底上采用片到片方式制备。
本发明的另一目的在于提供一种应用于柔性光电器件的透明导电薄膜的制备方法,上述透明导电薄膜在柔性衬底上采用卷到卷方式制备。柔性衬底包括金属箔、超薄玻璃、聚酰亚胺薄膜、聚对苯二甲酸乙二醇酯衬底、聚萘二甲酸乙二醇酯衬底、聚醚醚酮衬底或聚甲基丙烯酸甲酯衬底。
本发明的应用于柔性光电器件的透明导电薄膜,设置有第一氧化物层、金属膜夹层和位于金属膜夹层之上的第二氧化物层;第一氧化物层为单层或复合多层宽禁带一元氧化物非晶态薄膜,宽禁带一元氧化物为氧化钛、氧化铝、氧化锆或氧化镁。该透明导电薄膜通过宽禁带一元氧化物非晶态薄膜实现水氧阻隔、光学减反、薄膜增粘的作用,通过第一氧化物层、金属膜夹层和第二氧化物层的结构,实现封装膜与导电膜相结合,结构简单,能够简化制备工序,所获得透明导电薄膜透光率高、导电性好、热稳定性佳。本发明的制备工艺实现了以简单步骤制备得到透光率高、导电性好、热稳定性佳的透明导电薄膜。
附图说明
利用附图对本发明作进一步的说明,但附图中的内容不构成对本发明的任何限制。
图1是本发明一种透明导电薄膜的结构示意图。
在图1中,包括:
第一氧化物层01、
金属膜夹层02、
第二氧化物层03。
具体实施方式
结合以下实施例对本发明作进一步描述。
实施例1。
一种应用于柔性光电器件的透明导电薄膜,如图1所示,设置有第一氧化物层01、金属膜夹层02和位于金属膜夹层02之上的第二氧化物层03。
第一氧化物层01为单层或复合多层宽禁带一元氧化物非晶态薄膜,宽禁带一元氧化物为氧化钛、氧化铝、氧化锆或氧化镁。第一氧化物层01采用宽禁带一元氧化物非晶态薄膜,起水氧阻隔、光学减反、薄膜增粘的作用。第一氧化物层01的厚度为1 nm ~100 nm,优选为7 nm ~12nm。
金属膜夹层02为银或铜单质薄膜,或者为含银、铜的合金薄膜,金属膜夹层02主要起到导电作用。第二氧化物层03的厚度为5~15 nm。
第二氧化物层03为透明氧化物非晶态薄膜,透明氧化物为金属氧化物(In2O3)x(MO)y(ZnO)z,其中0≤x≤1,0≤y≤1,0≤z≤1,且x+y+z=1,M为镓、锡、钛、铝、镁、钽、铪、镱、锆中的一种元素或两种以上的元素的任意组合。
该应用于柔性光电器件的透明导电薄膜的制备方法,可以是在硬质衬底上采用片到片方式制备。
该应用于柔性光电器件的透明导电薄膜的制备方法,也可以在柔性衬底上采用卷到卷方式制备。柔性衬底包括金属箔、超薄玻璃、聚酰亚胺薄膜、聚对苯二甲酸乙二醇酯衬底、聚萘二甲酸乙二醇酯衬底、聚醚醚酮衬底或聚甲基丙烯酸甲酯衬底。
本实施例的透明导电薄膜通过宽禁带一元氧化物非晶态薄膜实现水氧阻隔、光学减反、薄膜增粘的作用,通过第一氧化物层01、金属膜夹层02和第二氧化物层03的结构,实现封装膜与导电膜相结合,结构简单,能够简化制备工序,所获得透明导电薄膜透光率高、导电性好、热稳定性佳。本发明的制备工艺实现了以简单步骤制备得到透光率高、导电性好、热稳定性佳的透明导电薄膜。
实施例2。
一种应用于柔性光电器件的透明导电薄膜,其它特征与实施例1相同,不同之处在于,还具有如下技术特征:第一氧化物层01具体是采用热生长或者等离子增强的原子层沉积方式,在80~250℃下生长成膜制备而成。
第二氧化物层03具体是采用热生长或者等离子增强的原子层沉积方式,在80~250℃下生长成膜制备而成,或者采用物理气相方式制备而成。
金属膜夹层02采用物理气相方式制备,具体是在本底真空小于5×10-3 Pa的状态下,在溅射气压为0.1 Pa~1.0 Pa、溅射功率为50 W~500 W、溅射速率为0.2 nm/s~1.0 nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为20 oC ~150 oC。
本实施例的透明导电薄膜通过宽禁带一元氧化物非晶态薄膜实现水氧阻隔、光学减反、薄膜增粘的作用,通过第一氧化物层01、金属膜夹层02和第二氧化物层03的结构,实现封装膜与导电膜相结合,结构简单,能够简化制备工序,所获得透明导电薄膜透光率高于84%,方阻值不高于10Ω/□,水氧阻隔性能良好、热稳定性佳。
实施例3。
一种应用于柔性光电器件的透明导电薄膜,如图1所示,设置有第一氧化物层01、金属膜夹层02和位于金属膜夹层02之上的第二氧化物层03。
第一氧化物层01,其材料为氧化锆,厚度为40 nm。金属膜夹层02为银膜,厚度为9nm。第二氧化物层03,其材料为氧化铟锡,厚度为10nm。衬底基板为透明柔性聚酰亚胺(PI)衬底。
第一氧化物层01采用原子层沉积方式制备,采用热生长或者等离子增强的原子层沉积方式,在250℃下生长成膜制备而成。
银膜采用磁控溅射方式制备,具体是在本底真空小于5×10-3 Pa的状态下,在溅射气压为1.0 Pa、溅射功率为300 W、溅射速率为0.8 nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为150 oC。
第二氧化物层03采用物理气相沉积方法制备,具体是本底真空小于5×10-3 Pa的状态下,在溅射气压为0.6 Pa、溅射功率为300 W、溅射速率为2 nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为250 oC。
该实施例制备的透明导电薄膜的方阻值为9.5 Ω/□,可见光透过率大于84.5%,水氧阻隔性能(WVTR)达到4*10-4 cm2/g day。薄膜在100 oC环境温度下放置24小时,未有退化现象发生。
可见,本实施例的透明导电薄膜结构简单,能够简化制备工序,所获得透明导电薄膜透光率高、导电性好、热稳定性佳。
实施例4。
一种应用于柔性光电器件的透明导电薄膜,如图1所示,设置有第一氧化物层01、金属膜夹层02和位于金属膜夹层02之上的第二氧化物层03。
第一氧化物层01,其材料为氧化钛,厚度为50 nm。金属膜夹层02为铜膜,厚度为10nm。第二氧化物层03,其材料为氧化铟镓锡,厚度为10nm。衬底基板为透明柔性聚对苯二甲酸乙二醇酯衬底。
第一氧化物层01采用原子层沉积方式制备,采用热生长或者等离子增强的原子层沉积方式,在200℃下生长成膜制备而成。
铜膜采用磁控溅射方式制备,具体是在本底真空小于5×10-3 Pa的状态下,在溅射气压为0.8 Pa、溅射功率为400 W、溅射速率为0.6 nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为100 oC。
第二氧化物层03采用物理气相沉积方法制备,具体是本底真空小于5×10-3 Pa的状态下,在溅射气压为0.8 Pa、溅射功率为320 W、溅射速率为2 nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为200 oC。
该实施例制备的透明导电薄膜的方阻值为9.45 Ω/□,可见光透过率大于84.5%,水氧阻隔性能(WVTR)达到3.96*10-4 cm2/g day。薄膜在100 oC环境温度下放置24小时,未有退化现象发生。
可见,本实施例的透明导电薄膜结构简单,能够简化制备工序,所获得透明导电薄膜透光率高、导电性好、热稳定性佳。
实施例5。
一种应用于柔性光电器件的透明导电薄膜,如图1所示,设置有第一氧化物层01、金属膜夹层02和位于金属膜夹层02之上的第二氧化物层03。
第一氧化物层01,其材料为氧化镁,厚度为30 nm。金属膜夹层02为铜薄膜,厚度为9nm。第二氧化物层03,其材料为氧化铟钽锡,厚度为11nm。衬底基板为透明柔性聚萘二甲酸乙二醇酯衬底。
第一氧化物层01采用原子层沉积方式制备,采用等离子增强的原子层沉积方式,在190℃下生长成膜制备而成。
铜膜采用磁控溅射方式制备,具体是在本底真空小于5×10-3 Pa的状态下,在溅射气压为0.9 Pa、溅射功率为390 W、溅射速率为0.6 nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为90 oC。
第二氧化物层03采用物理气相沉积方法制备,具体是本底真空小于5×10-3 Pa的状态下,在溅射气压为0.9 Pa、溅射功率为300 W、溅射速率为2 nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为200 oC。
该实施例制备的透明导电薄膜的方阻值为9.4 Ω/□,可见光透过率大于84.5%,水氧阻隔性能(WVTR)达到4.02*10-4 cm2/g day。薄膜在100 oC环境温度下放置24小时,未有退化现象发生。
可见,本实施例的透明导电薄膜结构简单,能够简化制备工序,所获得透明导电薄膜透光率高、导电性好、热稳定性佳。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (8)
1.一种应用于柔性光电器件的透明导电薄膜,其特征在于:设置有第一氧化物层、设置于第一氧化物层之上的金属膜夹层和设置于金属膜夹层之上的第二氧化物层;
所述第一氧化物层为单层或复合多层宽禁带一元氧化物非晶态薄膜,所述宽禁带一元氧化物为氧化钛、氧化铝、氧化锆或氧化镁;
所述金属膜夹层为银或铜单质薄膜,或者为含银、铜的合金薄膜;
所述第二氧化物层为透明氧化物非晶态薄膜,所述透明氧化物为金属氧化物(In2O3)x(MO)y(ZnO)z,其中0≤x≤1,0≤y≤1,0≤z≤1,且x+y+z=1,M为镓、锡、钛、铝、镁、钽、铪、镱、锆中的一种元素或两种以上的元素的任意组合。
2.根据权利要求1所述的应用于柔性光电器件的透明导电薄膜,其特征在于:所述第一氧化物层的厚度为1nm~100nm。
3.根据权利要求2所述的应用于柔性光电器件的透明导电薄膜,其特征在于:所述金属膜夹层的厚度为7nm~12nm。
4.根据权利要求3所述的应用于柔性光电器件的透明导电薄膜,其特征在于:所述第二氧化物层的厚度为5~15nm。
5.根据权利要求1至4任意一项所述的应用于柔性光电器件的透明导电薄膜,其特征在于:所述第一氧化物层具体是采用热生长或者等离子增强的原子层沉积方式,在80-250℃下生长成膜制备而成;
所述第二氧化物层具体是采用热生长或者等离子增强的原子层沉积方式,在80-250℃下生长成膜制备而成,或者采用物理气相方式制备而成。
6.根据权利要求5所述的应用于柔性光电器件的透明导电薄膜,其特征在于:所述金属膜夹层采用物理气相方式制备,具体是在本底真空小于5×10-3Pa的状态下,在溅射气压为0.1Pa~1.0Pa、溅射功率为50W~500W、溅射速率为0.2nm/s~1.0nm/s的的条件下进行溅射成膜,溅射成膜过程中,衬底的温度为20℃~150℃。
7.一种如权利要求1至6任意一项所述的应用于柔性光电器件的透明导电薄膜的制备方法,其特征在于:所述透明导电薄膜在硬质衬底上采用片到片方式制备。
8.一种如权利要求1至6任意一项所述的应用于柔性光电器件的透明导电薄膜的制备方法,其特征在于:所述透明导电薄膜在柔性衬底上采用卷到卷方式制备;所述柔性衬底包括金属箔、超薄玻璃、聚酰亚胺薄膜、聚对苯二甲酸乙二醇酯衬底、聚萘二甲酸乙二醇酯衬底、聚醚醚酮衬底或聚甲基丙烯酸甲酯衬底。
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