CN108885922A - 层叠透明导电膜、层叠布线膜及层叠布线膜的制造方法 - Google Patents
层叠透明导电膜、层叠布线膜及层叠布线膜的制造方法 Download PDFInfo
- Publication number
- CN108885922A CN108885922A CN201780019852.7A CN201780019852A CN108885922A CN 108885922 A CN108885922 A CN 108885922A CN 201780019852 A CN201780019852 A CN 201780019852A CN 108885922 A CN108885922 A CN 108885922A
- Authority
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- China
- Prior art keywords
- film
- transparent conductive
- atom
- conductive oxide
- laminating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000010030 laminating Methods 0.000 title claims abstract description 96
- 239000012528 membrane Substances 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 36
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 32
- 229910052727 yttrium Inorganic materials 0.000 claims description 29
- 238000005530 etching Methods 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 229910052738 indium Inorganic materials 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 14
- 229910052691 Erbium Inorganic materials 0.000 claims description 13
- 229910052693 Europium Inorganic materials 0.000 claims description 13
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 13
- 229910052779 Neodymium Inorganic materials 0.000 claims description 13
- 229910052772 Samarium Inorganic materials 0.000 claims description 13
- 229910052771 Terbium Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052787 antimony Inorganic materials 0.000 claims description 13
- 229910052732 germanium Inorganic materials 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 229910052706 scandium Inorganic materials 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000002834 transmittance Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- 238000004544 sputter deposition Methods 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 208000003351 Melanosis Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000255 optical extinction spectrum Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G9/02—Oxides; Hydroxides
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
本发明的层叠透明导电膜具有由Ag或Ag合金构成的Ag膜及配置于所述Ag膜的双面的透明导电氧化物膜,所述透明导电氧化物膜由包含Zn、Ga及Ti的氧化物形成。
Description
技术领域
本发明涉及一种能够用作例如显示器或者触摸面板等透明电极膜的层叠透明导电膜、由该层叠透明导电膜构成的层叠布线膜及层叠布线膜的制造方法。
本申请主张基于2016年3月23日于日本申请的专利申请2016-058937号及2017年2月13日于日本申请的专利申请2017-024386号的优先权,并将其内容援用于此。
背景技术
在液晶显示器、有机EL(电致发光)显示器及触摸面板等中,作为透明电极膜,例如提供一种如专利文献1~4中所示的透明导电膜。在该透明导电膜中,要求可见光区域的光的透射率高,并且电阻低。
在此,在专利文献1中,作为透明导电膜,使用由作为透明导电氧化物的一种的ITO(In2O3+Sn)构成的ITO膜,但是在该ITO膜中,为了降低电阻,需要将膜厚形成为较厚,因此导致可见光区域的透射率下降。由此,不易兼顾高透射率和低电阻。
并且,在专利文献2中,使用了Cu等的金属网格材料,但是在该金属网格材料中,为了降低电阻,需要扩大金属部分的宽度,仍然存在导致透射率下降的问题。并且,有可能通过光的反射而视觉辨认金属网格材料,因此需要在金属网格材料的表面形成黑化膜等。
在专利文献3、4中,提出了层叠有Ag膜和透明导电氧化物膜的层叠透明导电膜。在该层叠透明导电膜中,由于通过Ag膜确保导电性,因此无需为了降低电阻而将透明导电氧化物膜形成为较厚,能够获得比较高的透射率。
专利文献1:日本特开2008-310550号公报
专利文献2:日本特开2006-344163号公报
专利文献3:日本特开昭63-110507号公报
专利文献4:日本特开平09-232278号公报
然而,近来,在显示器或者触摸面板等中,进一步推进布线及透明电极的微细化,而且因大屏幕化而布线及透明电极的长度变长,作为透明电极,与以往相比进一步要求电阻较低、并且可见光区域的透射率优异的透明导电膜。
在此,在专利文献3、4中所记载的层叠透明导电膜中,为了实现电阻的进一步下降及透射率的进一步提高,需要将Ag膜的膜厚设为较薄。然而,在仅将Ag膜设为较薄的情况下,Ag变得容易凝聚,因该Ag的凝聚而发生表面等离子体激元吸收,存在导致透射率大幅下降的问题。并且,因Ag的凝聚而Ag膜成为不连续膜,因此电阻也增加而存在导致导电性下降的问题。
并且,若透明导电氧化物膜对水分的阻隔性低,则在高湿度的环境下水分会到达至Ag膜,在Ag膜中促进Ag的凝聚,有可能导致透射率及导电性下降。
而且,为了使用上述层叠透明导电膜来作为布线膜,需要对于层叠透明导电膜形成布线图案。在该情况下,在层叠透明导电膜上形成抗蚀剂膜,通过蚀刻形成布线图案之后,去除该抗蚀剂膜。通过蚀刻形成布线图案时,优选使用蚀刻剂对层叠透明导电膜整体一并进行蚀刻,但是在Ag合金膜和ITO膜的层叠膜中,通过蚀刻形成电极图案时,与ITO膜相比,Ag合金膜的蚀刻速度较快,因此若使用相同的蚀刻液一并进行蚀刻,则有可能Ag合金膜的过蚀刻变大、或者产生ITO膜残渣。并且,去除抗蚀剂膜时,使用碱性抗蚀剂去除液,但是在以往的层叠透明导电膜中,存在耐碱性不充分,且在去除抗蚀剂膜时,导致层叠透明导电膜的特性劣化的问题。
发明内容
该发明是鉴于前述情况而完成的,且其目的在于提供一种透射率足够高,并且电阻足够低,耐环境性及耐碱性优异,通过蚀刻法形成布线图案时不易发生过蚀刻的层叠透明导电膜、由该层叠透明导电膜构成的层叠布线膜及层叠布线膜的制造方法。
为了解决上述问题,本发明的层叠透明导电膜的特征在于,具有由Ag或Ag合金构成的Ag膜、及配置于所述Ag膜的双面的透明导电氧化物膜,所述透明导电氧化物膜由包含Zn、Ga及Ti的氧化物形成。
根据本发明的层叠透明导电膜,在Ag膜的双面形成有由包含Zn、Ga及Ti的氧化物构成的透明导电氧化物膜,因此通过下表面的透明导电氧化物膜,Ag膜的润湿性有所提高,即使在将Ag膜形成为较薄的情况下,也能够抑制Ag膜中的Ag的凝聚。并且,由于上述透明导电氧化物膜的耐环境性(高温高湿环境下的耐久性)优异,因此即使在高湿度的环境下使用时,通过形成于Ag膜的上表面的透明导电氧化物膜,也能够抑制水分侵入Ag膜,能够抑制Ag的凝聚。由此,能够提供一种透射率足够高并且电阻足够低的层叠透明导电膜。
而且,在使用包含磷酸和乙酸的酸性混合液来作为蚀刻剂的情况下,Ag膜与透明导电氧化物膜的蚀刻速度之差较小,即使一并蚀刻该层叠透明导电膜,也能够以高精度形成布线图案。
并且,由于该透明导电氧化物膜的耐碱性高,因此即使在形成布线图案时,使用碱性抗蚀剂去除液来去除抗蚀剂膜,也能够抑制层叠透明导电膜的特性的劣化。
在此,在本发明的层叠透明导电膜中,优选将所述透明导电氧化物膜中所包含的所有金属元素的原子比例设为:Ga为0.5原子%以上且30.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、剩余部分为Zn。
在该情况下,将透明导电氧化物膜中所包含的所有金属元素中的Ga的含量设在0.5原子%以上且30原子%以下的范围内,因此能够抑制Ag膜的凝聚,并抑制电阻的增加。并且,将Ti的含量设在0.1原子%以上且10.0原子%以下的范围内,因此能够抑制电阻的增加,并且能够提高耐碱性及耐环境性。
而且,在本发明的层叠透明导电膜中,更优选将所述透明导电氧化物膜中所包含的所有金属元素的原子比例设为:Ga为0.5原子%以上且18.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、剩余部分为Zn。
在该情况下,将透明导电氧化物膜中所包含的所有金属元素中的Ga的含量设在0.5原子%以上且18.0原子%以下的范围内,因此能够进一步Ag膜的凝聚,能够更加进一步抑制电阻的增加。并且,将Ti的含量设在0.1原子%以上且10.0原子%以下的范围内,因此能够抑制电阻的增加,并且能够提高耐碱性及耐环境性。
而且,在本发明的层叠透明导电膜中,进一步优选将所述透明导电氧化物膜中所包含的所有金属元素的原子比例设为:Ga为0.5原子%以上且14.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、剩余部分为Zn。
在该情况下,将透明导电氧化物膜中所包含的所有金属元素中的Ga的含量设在0.5原子%以上且14.0原子%以下的范围内,因此能够进一步抑制Ag膜的凝聚,能够更加进一步抑制电阻的增加。并且,将Ti的含量设在0.1原子%以上且10.0原子%以下的范围内,因此能够抑制电阻的增加,并且能够提高耐碱性及耐环境性。
并且,在本发明的层叠透明导电膜中,形成所述透明导电氧化物膜的氧化物还可以包含Y。
在该情况下,形成透明导电氧化物膜的氧化物包含Y,因此能够抑制电阻的增加,并且能够进一步提高耐碱性及耐环境性。
在上述形成所述透明导电氧化物膜的氧化物包含Y的情况下,优选将所述透明导电氧化物膜中所包含的所有金属元素的原子比例设为:Ga为0.5原子%以上且30.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、Y为0.1原子%以上且10.0原子%以下、剩余部分为Zn。
在该情况下,将透明导电氧化物膜中所包含的所有金属元素中的Ga的含量设在0.5原子%以上且30原子%以下的范围内,因此能够抑制Ag膜的凝聚,能够抑制电阻的增加。并且,将Ti的含量设在0.1原子%以上且10.0原子%以下的范围内,因此能够抑制电阻的增加,并且能够提高耐碱性及耐环境性。而且,将Y的含量设在0.1原子%以上且10.0原子%以下的范围内,因此能够抑制电阻的增加,并且能够提高耐碱性。
而且,在本发明的层叠透明导电膜中,优选所述Ag膜由Ag合金构成,所述Ag合金以总计0.2原子%以上且10.0原子%以下含有Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上,且剩余部分由Ag及不可避免的杂质构成。
在该情况下,含有Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上,因此Ag膜的凝聚进一步得到抑制,即使将Ag膜形成为非常薄至10nm以下,也能够制成连续膜。
而且,在本发明的层叠透明导电膜中,优选将所述Ag膜的厚度设为10nm以下。
在该情况下,将Ag膜的厚度设为10nm以下,因此能够提高透射率。并且,在Ag膜的双面形成有上述透明导电氧化物膜,因此即使将Ag膜的厚度设为10nm以下,由于Ag不凝聚而成为连续膜,因此也能够降低电阻。
而且,在本发明的层叠透明导电膜中,优选波长为400~800nm的可见光区域的平均透射率为85%以上,且薄层电阻值为20Ω/sq.以下。
在该情况下,将可见光区域的平均透射率设为85%以上,并且将薄层电阻值设为20Ω/sq.以下,因此层叠透明导电膜具有足够高的透射率及足够低的电阻,能够用作经微细化的透明电极膜或透明布线膜。
本发明的层叠布线膜的特征在于,由上述层叠透明导电膜构成,且具有布线图案。
本发明的层叠布线膜由上述层叠透明导电膜构成,因此具有低电阻和高透射率。
本发明的层叠布线膜的制造方法为上述层叠布线膜的制造方法,所述方法的特征在于,具备:层叠透明导电膜形成工序,在基材的成膜面形成包含所述Ag膜及所述透明导电氧化物膜的所述层叠透明导电膜;抗蚀剂膜形成工序,在所述层叠透明导电膜上形成布线图案形状的抗蚀剂膜;蚀刻工序,将包含磷酸和乙酸的酸性混合液用作蚀刻剂,对形成有所述抗蚀剂膜的所述层叠透明导电膜一并进行蚀刻;及抗蚀剂膜去除工序,蚀刻后用碱性抗蚀剂去除液等去除所述抗蚀剂膜。
根据该结构的层叠布线膜的制造方法,在使用包含磷酸和乙酸的酸性混合液来作为蚀刻剂的情况下,Ag膜与透明导电氧化物膜的蚀刻速度之差小,因此即使一并蚀刻该层叠透明导电膜,也能够抑制产生Ag膜的过蚀刻和透明导电氧化物膜的残渣等,能够以高精度形成布线图案。并且,通过添加Ti或Ti及Y,透明导电氧化物膜的耐碱性有所提高,因此在抗蚀剂膜去除工序中,即使利用碱性抗蚀剂去除液来去除抗蚀剂膜,也能够抑制层叠布线膜的特性的劣化。
并且,本发明的层叠布线膜的制造方法为上述层叠布线膜的制造方法,所述方法的特征在于,具备:抗蚀剂膜形成工序,在基材的成膜面形成布线图案的反转图案形状的抗蚀剂膜;层叠透明导电膜形成工序,在形成有所述抗蚀剂膜的所述基材的成膜面,形成包含所述Ag膜及所述透明导电氧化物膜的所述层叠透明导电膜;及抗蚀剂膜去除工序,去除所述抗蚀剂膜。
根据该结构的层叠布线膜的制造方法,在基材的成膜面以布线图案的反转图案形状形成抗蚀剂膜,在形成有所述抗蚀剂膜的所述基材的成膜面形成所述层叠透明导电膜。由此,若在形成所述层叠透明导电膜之后,从基材去除抗蚀剂膜,则所述层叠透明导电膜仅残留于未形成抗蚀剂膜的区域,从而能够形成具有布线图案的层叠布线膜。因此,无需进行蚀刻工序,而能够以高精度形成布线图案。并且,通过添加Ti或Ti及Y,透明导电氧化物膜的耐碱性有所提高,因此在抗蚀剂膜去除工序中,即使利用碱性的抗蚀剂去除液来去除抗蚀剂膜,也能够抑制层叠布线膜的特性的劣化。
根据本发明,能够提供一种透射率足够高并且电阻足够低、耐环境性及耐碱性优异、不易发生过蚀刻的层叠透明导电膜、由该层叠透明导电膜构成的层叠布线膜及层叠布线膜的制造方法。
附图说明
图1是本发明的实施方式的层叠透明导电膜的局部放大剖视图。
图2是本发明的实施方式的层叠布线膜的局部放大剖视图。
图3是表示本发明的实施方式的层叠布线膜的制造方法的流程图。
图4是图3中所示的层叠布线膜的制造方法的说明图。
图5是表示本发明的另一实施方式的层叠布线膜的制造方法的流程图。
图6是图5中所示的层叠布线膜的制造方法的说明图。
图7是表示利用蚀刻法的图案形成试验后的结果的一例的表面观察照片。(a)是本发明例3,(b)是比较例2。
图8是表示利用蚀刻法的图案形成试验后的结果的一例的截面观察照片(本发明例3)。
具体实施方式
以下,关于作为本发明的实施方式的层叠透明导电膜,参考附图并进行说明。
本实施方式中的层叠透明导电膜10用作各种显示器及触摸面板的透明电极膜,尤其,用于平板尺寸以上的静电电容类型的触摸面板。
将作为本实施方式的层叠透明导电膜10示于图1中。该层叠透明导电膜10例如具备:第一透明导电氧化物膜11,在作为基材的基板20的一个表面作为基底层形成;Ag膜12,形成于该第一透明导电氧化物膜11上;及第二透明导电氧化物膜13,形成于该Ag膜12上。另外,作为基板20,例如能够使用玻璃基板、树脂薄膜等。
并且,在本实施方式中,层叠透明导电膜10设为:在波长为400~800nm的可见光区域的平均透射率为85%以上,薄层电阻值为20Ω/sq.以下。
另外,层叠透明导电膜10在波长为400~800nm的可见光区域的平均透射率优选为85%以上,进一步优选为86%以上。平均透射率越高越优选,因此上限值并无特别限定,但是优选为95%,更优选为90%。并且,层叠透明导电膜10的薄层电阻值优选为20Ω/sq.以下,进一步优选为5Ω/sq.以下。层叠透明导电膜10的薄层电阻值越低越优选,因此下限值并无特别限定,但是优选为0.5Ω/sq.,更优选为1Ω/sq.。
Ag膜12由Ag或Ag合金构成。作为构成Ag膜12的Ag或Ag合金,可以是纯度为99.9质量%以上的纯Ag、或者包含Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er等添加元素的Ag合金。
另外,关于添加元素的含量,从抑制Ag膜12的吸收率的增加(透射率的下降)及电阻的增加的观点考虑,优选限制在10.0原子%以下,更优选为2.0原子%以下。
另外,在本实施方式中,Ag膜12由Ag合金构成,所述Ag合金以总计0.2原子%以上且10.0原子%以下含有Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上,且剩余部分由Ag及不可避免的杂质构成。
在本实施方式中,构成Ag膜12的Ag合金所含有的Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er为具有提高Ag膜12相对于第一透明导电氧化物膜11的润湿性的作用效果的元素,即使在将Ag膜12形成为较薄的情况下,也能够抑制Ag的凝聚。
在此,在Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上的总含量小于0.2原子%的情况下,有可能无法充分地发挥上述作用效果。另一方面,若Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上的总含量超过10.0原子%,则有可能Ag膜12的透射率下降,并且电阻值上升。
就这种理由而言,在本实施方式中,将构成Ag膜12的Ag合金中的Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上的总含量规定在0.2原子%以上且10.0原子%以下的范围内。
另外,为了可靠地发挥上述作用效果,优选将构成Ag膜12的Ag合金中的Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上的总含量的下限设为0.3原子%以上,进一步设为0.5原子%以上。另一方面,为了进一步抑制透射率的下降和电阻率的上升,优选将Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上的总含量的上限设为8.0原子%以下,进一步优选设为5.0原子%以下,尤其优选设为2.0原子%以下。
并且,在本实施方式中,第一透明导电氧化物膜11及第二透明导电氧化物膜13设为包含Zn、Ga、Ti的氧化物、或包含Zn、Ga、Ti及Y的氧化物。
即,第一透明导电氧化物膜11及第二透明导电氧化物膜13设为在Zn氧化物中添加Ga、Ti、或Ga、Ti及Y而得的氧化物膜。
在本实施方式中,关于第一透明导电氧化物膜11及第二透明导电氧化物膜13,将各透明导电氧化物膜中所包含的所有金属元素中的Ga、Ti及Y的原子比例设为:Ga为0.5原子%以上且30.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、Y为0.1原子%以上且10.0原子%以下。
另外,第一透明导电氧化物膜11及第二透明导电氧化物膜13无需为相同的组成,设在上述组成的范围内即可。
在此,通过将第一透明导电氧化物膜11及第二透明导电氧化物膜13中所包含的所有金属元素中的Ga的含量(Ga相对于所有金属元素的原子比例)设为0.5原子%以上,能够抑制Ag膜12中的Ag的凝聚,能够抑制层叠透明导电膜10中的电阻的增加。另一方面,通过将Ga的含量设为30.0原子%以下,能够抑制第一透明导电氧化物膜11及第二透明导电氧化物膜13中的电阻的增加。而且,通过将Ga的含量设为18.0原子%以下,能够更加进一步抑制第一透明导电氧化物膜11及第二透明导电氧化物膜13中的电阻的增加。
另外,为了抑制Ag膜12中的Ag的凝聚,优选将Ga的含量的下限设为1.0原子%以上,进一步优选设为2.0原子%以上。并且,为了可靠地抑制第一透明导电氧化物膜11及第二透明导电氧化物膜13中的电阻的增加,优选将Ga的含量的上限设为25.0原子%以下,更优选设为20.0原子%以下,进一步优选设为18.0原子%以下,更加进一步优选设为14.0原子%以下。
并且,通过将第一透明导电氧化物膜11及第二透明导电氧化物膜13中所包含的所有金属元素中的Ti的含量设为0.1原子%以上,能够提高第一透明导电氧化物膜11及第二透明导电氧化物膜13的耐碱性及耐环境性。另一方面,通过将Ti的含量设为10.0原子%以下,能够抑制第一透明导电氧化物膜11及第二透明导电氧化物膜13中的电阻的增加。
另外,为了可靠地提高第一透明导电氧化物膜11及第二透明导电氧化物膜13的耐碱性及耐环境性,优选将Ti的含量的下限设为0.2原子%以上,进一步优选设为0.5原子%以上。并且,为了可靠地抑制第一透明导电氧化物膜11及第二透明导电氧化物膜13中的电阻的增加,优选将Ti的含量的上限设为9.0原子%以下,进一步优选设为8.0原子%以下。
而且,通过将第一透明导电氧化物膜11及第二透明导电氧化物膜13中所包含的所有金属元素中的Y的含量设为0.1原子%以上,能够提高透明导电氧化物膜的耐碱性。另一方面,通过将Y的含量设为10.0原子%以下,由此能够抑制第一透明导电氧化物膜11及第二透明导电氧化物膜13中的电阻的增加。
另外,为了可靠地提高第一透明导电氧化物膜11及第二透明导电氧化物膜13的耐碱性,优选将Y的含量的下限设为0.2原子%以上,进一步优选设为0.5原子%以上。并且,为了可靠地抑制第一透明导电氧化物膜11及第二透明导电氧化物膜13中的电阻的增加,优选将Y的含量的上限设为9.0原子%以下,进一步优选设为8.0原子%以下。
并且,为了可靠地抑制第一透明导电氧化物膜11及第二透明导电氧化物膜13中的电阻的增加,优选将Ga、Ti及Y的总含量设为35.0原子%以下,进一步优选设为30.0原子%以下,更加进一步优选设为25.0原子%以下。
在此,在本实施方式中,为了提高透射率,将Ag膜12的膜厚t2设定为10nm以下。另外,在进一步实现提高透射率的情况下,优选将Ag膜12的膜厚t2设为9nm以下,进一步优选设为8nm以下。并且,优选将Ag膜12的膜厚t2的下限设为3nm以上,进一步优选设为4nm以上。
并且,第一透明导电氧化物膜11的膜厚t1和第二透明导电氧化物膜13的膜厚t3设为如下膜厚:使用各单层膜中的光学常数(折射率及消光系数),以第一透明导电氧化物膜/Ag膜(Ag合金膜)/第二透明导电氧化物膜的3层结构进行光学模拟,通过光学干涉效应而可见光区域的透射率有所提高。
第一透明导电氧化物膜11的膜厚t1(nm)及第二透明导电氧化物膜13的膜厚t3(nm)优选设为大致如下范围的膜厚。
t1=550/(4×n1)×k1,t3=550/(4×n3)×k3
在此,n1、n3分别为第一透明导电氧化物膜11的折射率(n1)及第二透明导电氧化物膜13的折射率(n3)。并且,k1、k3分别为第一透明导电氧化物膜11的系数(k1)及第二透明导电氧化物膜13的系数(k3)。即,在上述光学模拟中,优化系数k1、k3的值而求出膜厚,以使可见光区域的透射率提高。
另外,系数k1、k3的最佳值根据透明导电氧化物而各自不同,但是系数k1、k3优选为0.2~0.8的范围,进一步优选为0.4~0.7的范围。尤其,若系数k1、k3为0.6左右,则与透明导电氧化物的种类无关,可见光区域的透射率都会有所提高。
在本实施方式中,上述光学模拟的结果,将第一透明导电氧化物膜11的膜厚t1及第二透明导电氧化物膜13的膜厚t3设定为40nm。这些膜厚为将系数k1、k3设为0.6时的膜厚。
接着,关于作为本发明的实施方式的层叠布线膜30及层叠布线膜30的制造方法,参考图2至图4进行说明。
如图2所示,作为实施方式的层叠布线膜30,在图1中所示的层叠透明导电膜10形成有布线图案。在此,作为本实施方式的层叠布线膜30中,布线图案的线宽及线之间的间隔的宽度在1μm以上且900μm以下的范围内。
在此,以如下方式制造上述层叠布线膜30。
首先,在作为基材的基板20的成膜面,形成作为本实施方式的层叠透明导电膜10(层叠透明导电膜形成工序S11)。
在该层叠透明导电膜形成工序S11中,在基板20上形成第一透明导电氧化物膜11来作为基底层。关于第一透明导电氧化物膜11,优选使用容易控制膜组成的烧结靶,并通过DC溅射(直流溅射)而形成。接着,在所形成的第一透明导电氧化物膜11上,使用Ag靶并通过DC溅射来形成Ag膜12。该Ag靶设为与所形成的Ag膜12的组成对应的组成。然后,在所形成的Ag膜12上,使用透明导电氧化物靶并通过DC溅射形成第二透明导电氧化物膜13。另外,透明导电氧化物靶优选设为容易控制膜组成的烧结靶。如此,形成作为本实施方式的层叠透明导电膜10。
接着,通过在形成于基板20的表面上的层叠透明导电膜10上形成抗蚀剂膜41,并对该抗蚀剂膜41进行曝光、显影来形成布线图案(抗蚀剂膜形成工序S12)。
接着,对形成有抗蚀剂膜41的层叠透明导电膜10,将包含磷酸和乙酸的酸性混合液用作蚀刻剂,一并进行蚀刻(蚀刻工序S13)。在此,在包含磷酸和乙酸的酸性混合液中,优选磷酸的含量为55体积%以下,且乙酸的含量为30体积%以下。除了磷酸及乙酸以外,混合液还可以包含20体积%以下的硝酸。
接着,使用碱性抗蚀剂去除液,去除抗蚀剂膜41(抗蚀剂膜去除工序S14)。
由此,位于布线图案形状的抗蚀剂膜41的下侧的层叠透明导电膜10残留,并形成具有布线图案的层叠布线膜30。
在设为如上述那样的结构的作为本实施方式的层叠透明导电膜10中,在基板20的表面形成第一透明导电氧化物膜11来作为基底层,在该第一透明导电氧化物膜11上形成有Ag膜12,因此Ag膜12的润湿性有所提高,即使在将Ag膜12形成为较薄的情况下,也可抑制Ag的凝聚。
而且,第一透明导电氧化物膜11及第二透明导电氧化物膜13的耐环境性优异,由此即使在高湿度的环境下使用时,也能够抑制水分侵入Ag膜12,能够抑制Ag的凝聚。
由此,能够防止在Ag膜12中由Ag的凝聚引起的表面等离子体激元吸收的发生,能够获得高透射率。并且,由于Ag膜12成为连续膜,因此也能够降低电阻。
并且,在本实施方式中,第一透明导电氧化物膜11及第二透明导电氧化物膜13设为在Zn氧化物中添加Ga、Ti或Ga、Ti及Y而得的氧化物膜,各透明导电氧化物膜中所包含的所有金属元素中的Ga、Ti及Y的原子比例设为:Ga为0.5原子%以上且30.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、Y为0.1原子%以上且10.0原子%以下。因此,通过添加Ga能够抑制Ag的凝聚,且能够抑制电阻的增加。并且,通过添加Ti能够提高耐碱性及耐环境性。而且,通过添加Y能够提高耐碱性。
而且,在本实施方式中,将Ag膜12的厚度t2设定为10nm以下,因此能够提高透射率。并且,在基板20的表面形成有第一透明导电氧化物膜11来作为基底层,因此即使将Ag膜12的厚度设为10nm以下,Ag也不会凝聚而成为连续膜,能够降低电阻。
并且,在本实施方式中,由Ag合金构成Ag膜12,所述Ag合金以总计0.2原子%以上且10.0原子%以下含有Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上,且剩余部分由Ag及不可避免的杂质构成,因此Ag膜12的凝聚进一步得到抑制,即使将Ag膜12形成为进一步较薄,也成为连续膜,能够兼顾高透射率和低电阻值。
而且,在本实施方式中,层叠透明导电膜10在波长为400~800nm的可见光区域的平均透射率设为85%以上,且薄层电阻值设为20Ω/sq.以下,具有足够高的透射率及足够低的电阻,能够用作经微细化的透明电极膜或透明布线膜。
并且,在作为本实施方式的层叠透明导电膜10形成有布线图案,因此作为本实施方式的层叠布线膜30具有低电阻和高透射率。
而且,在本实施方式中,在蚀刻工序S13中,在使用包含磷酸和乙酸的酸性混合液来作为蚀刻剂的情况下,Ag膜12与第一透明导电氧化物膜11及第二透明导电氧化物膜13的蚀刻速度之差较小,因此即使一并蚀刻该层叠透明导电膜10,也能够抑制发生Ag膜12的过蚀刻、第一透明导电氧化物膜11及第二透明导电氧化物膜13的残渣等,能够以高精度形成布线图案。
并且,在本实施方式中,通过添加Ti或Ti及Y,第一透明导电氧化物膜11及第二透明导电氧化物膜13的耐碱性有所提高,因此在抗蚀剂膜去除工序S14中,即使利用碱性抗蚀剂去除液来去除抗蚀剂膜,也能够抑制层叠布线膜30的特性的劣化。
以上,对本发明的实施方式进行了说明,但是本发明并不限定于此,在不脱离该发明的技术思想的范围内能够适当进行变更。
例如,在本实施方式中,对由Ag合金构成的Ag膜12进行了说明,所述Ag合金以总计0.2原子%以上且10.0原子%以下含有Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上,且剩余部分由Ag及不可避免的杂质构成,但是Ag膜12并不限定于此,可以是纯Ag、含有固溶于Ag中的其他金属元素的Ag合金。
并且,在本实施方式中,将第一透明导电氧化物膜11及第二透明导电氧化物膜13的膜厚设为40nm左右而进行了说明,但是并不限定于此,可以设为其他膜厚。其中,如本实施方式中所记载那样,优选进行光学模拟,选择通过光干涉效应而透射率有所提高的膜厚。
而且,在本实施方式中,通过蚀刻法制造层叠布线膜30而进行了说明,但是并不限定于此,如图5及图6所示,可以通过剥离法来制造层叠布线膜30。
在图5及图6中所示的层叠布线膜30的制造方法中,首先,在基板20的成膜面上形成抗蚀剂膜41,并对该抗蚀剂膜41进行曝光、显影,由此形成反转布线图案而得的反转图案(抗蚀剂膜形成工序S21)。
接着,通过溅射法,在形成有具有反转图案的抗蚀剂膜41的基板20上,依次形成第一透明导电氧化物膜11、Ag膜12、第二透明导电氧化物膜13。由此,在抗蚀剂膜41及基板20上形成层叠透明导电膜10(层叠透明导电膜形成工序S22)。
接着,使用碱性抗蚀剂去除液,去除抗蚀剂膜41(抗蚀剂膜去除工序S23)。
由此,去除形成于反转图案形状的抗蚀剂膜41上的层叠透明导电膜10,形成具有布线图案的层叠布线膜30。
根据该结构的层叠布线膜30的制造方法,无需进行蚀刻工序,而能够以高精度形成布线图案。并且,通过添加Ti或Ti及Y,第一透明导电氧化物膜11及第二透明导电氧化物膜13的耐碱性有所提高,因此在抗蚀剂膜去除工序S23中,即使使用碱性抗蚀剂去除液来去除抗蚀剂膜,也能够抑制层叠布线膜30的特性的劣化。
实施例
关于对本发明所涉及的层叠透明导电膜的作用效果进行确认而得的确认实验的结果进行说明。
通过溅射法,在玻璃基板(无碱玻璃:50mm×50mm×1mmt)的表面形成了表1、表2、表3及表4中所示的结构的层叠透明导电膜。另外,在比较例A,B中,通过溅射法形成了ITO单层膜。并且,只有比较例B中,将玻璃基板加热至200℃而成膜。
在此,关于透明导电氧化物膜的膜厚,进行在实施方式中说明的光学模拟,选择通过光学干涉效应而可见光区域的透射率有所提高的膜厚,在本发明例中,均设为40nm。
另外,关于本发明的实施例及比较例中的Ag膜及透明导电氧化物膜的膜厚,使用膜厚仪(ULVAC,Inc.制造的DEKTAK)来进行了测量。
并且,关于透明导电氧化物膜及Ag合金膜的组成,通过使用ICP发光分光装置(Hitachi High-Tech Science Corporation.制造的ICP发光分光分析装置STS-3500DD)进行元素的定量分析来求出。
制作透明导电氧化物膜时,使用了表1、表2、表3及表4中所记载的组成的氧化物烧结体靶。
制作Ag膜时,使用了表1、表2、表3及表4中所记载的组成的Ag靶。以下示出各个膜的形成条件。
另外,在比较例中,ITO膜(在In2O3中添加了Sn的氧化物)的组成为In:35.6原子%、Sn:3.6原子%、O:60.8原子%。
GZO膜(在ZnO中添加Ga而得的氧化物)的组成为Zn:47.3原子%、Ga:2.2原子%、O:50.5原子%。
<透明导电氧化物膜的形成条件>
溅射装置:DC磁控溅射装置(ULVAC,Inc.制造的CS-200)
磁场强度:1000Gauss(靶的正上方、垂直分量)
极限真空度:5×10-5Pa以下
溅射气体:Ar+O2的混合气体(O2的混合比:1%)
溅射气压:0.4Pa
溅射功率:DC100W
<Ag膜的形成条件>
溅射装置:DC磁控溅射装置(ULVAC,Inc.制造的CS-200)
磁场强度:1000Gauss(靶的正上方、垂直分量)
极限真空度:5×10-5Pa以下
溅射气体:Ar
溅射气压:0.5Pa
溅射功率:DC100W
关于所获得的层叠透明导电膜及ITO单层膜,对成膜后的薄层电阻及透射率进行了评价。
并且,对恒温恒湿试验后的薄层电阻及透射率以及耐碱性试验后的薄层电阻及透射率进行了评价。
而且,关于所获得的层叠透明导电膜,进行了利用蚀刻法的图案形成试验及利用剥离法的图案形成试验。
以下示出评价方法。
<薄层电阻>
使用表面电阻测量器(Mitsubishi Petrochemical Co.,Ltd.制造的Loresta APMCP-T400),并通过四探针法测量了薄层电阻。将薄层电阻的测量结果分别示于表5、表6、表7及表8中。
<透射率>
使用分光光度计(Hitachi High-Technologies Corporation.制造的U4100),对400nm至800nm的波长范围内的透射率光谱进行测量,并求出平均透射率(透射率)。将透射率的测量结果分别示于表9、表10、表11及表12中。
<恒温恒湿试验>
在温度85℃、湿度85%的恒温恒湿槽中放置250小时,测量试验后的透射率及薄层电阻并对自试验前的变化率进行了评价。
<耐碱性试验>
在温度为40℃的碱性抗蚀剂去除液(pH9,Tokyo Ohka Kogyo Co.,Ltd.制造的TOK-104)中浸渍10分钟,对浸渍后的透射率及薄层电阻进行测量,并对自浸渍前的变化率进行了评价。
<利用蚀刻法的图案形成试验>
关于上述层叠透明导电膜,通过光刻法(Photolithography method),在层叠透明导电膜上以线宽/间隔宽度:30μm/30μm的布线图案形状形成了抗蚀剂膜。对该抗蚀剂膜,使用包含磷酸和乙酸的混合液(KANTO CHEMICAL CO.,INC.制造的SEA-5)来作为蚀刻剂,一并进行了蚀刻。另外,关于蚀刻,在未加热的状态下分别进行了适当的蚀刻时间(20秒至120秒)。并且,将混合液中的磷酸的含量设为55体积%以下,且将乙酸的含量设为30体积%以下。
然后,使用碱性抗蚀剂去除液(pH9,Tokyo Ohka Kogyo Co.,Ltd.制造的TOK-104)来去除抗蚀剂膜之后,通过光学显微镜(KEYENCE公司制造的激光显微镜VK-X200)以倍率50倍观察所形成的布线图案,确认了透明导电氧化物膜的残渣的有无。详细而言,在确认到有未被蚀刻而以针状或粒状等形状残留的透明导电氧化物膜的情况下,判断为有透明导电氧化物膜的残渣,将除此以外的情况判断为没有透明导电氧化物膜的残渣。将本发明例3及比较例2的观察结果分别示于图7的(a)、图7的(b)中。另外,在图7的(a)、图7的(b)中,对线附加了符号P,对间隔附加了符号S,对过蚀刻附加了符号O,对残渣附加了符号R。
并且,使用扫描电子显微镜(Hitachi High-Technologies Corporation.制造的SU8000)以倍率50000倍观察了去除抗蚀剂膜之前的图案的截面(与线及间隔正交且与基板20的成膜面垂直的截面)。将本发明例3的截面形状的观察结果示于图8中。将蚀刻至抗蚀剂膜41的内部的部分设为过蚀刻的长度,根据它们的观察像,测量并求出从抗蚀剂膜41的端部至内部的层叠透明导电膜10的端部为止的长度L(与基板20的成膜面平行的方向的长度)。另外,将在与基板20之间层叠透明导电膜10本来应残留的抗蚀剂图案的边界部(边缘部)设为抗蚀剂膜41的端部,在抗蚀剂图案与基板20之间残留的层叠透明导电膜10的内侧的端部中将在与基板20的成膜面平行的方向上离抗蚀剂膜41的端部最远的点设为层叠透明导电膜10的端部而测量了长度L。将本发明例及比较例的各样品的过蚀刻的长度分别示于表5、表6、表7及表8中。另外,表5、表6、表7及表8的过蚀刻的长度为观察一个截面而获得的长度L的值。
并且,剥离抗蚀剂而以肉眼观察了层叠膜的表面。
<利用剥离法的图案形成试验>
首先,将抗蚀剂液涂布于基板上,附上形成有线宽/间隔宽度:30μm/30μm的布线图案的光掩膜并用曝光机照射紫外线之后,用显影液去除被感光的部分,并通过光刻法形成了反转图案。
接着,在形成有反转图案的基板上,如上所述那样使用溅射装置形成了层叠透明导电膜。
接着,浸渍于抗蚀剂去除液(pH9,Tokyo Ohka Kogyo Co.,Ltd.制造的TOK-104)中,并去除形成于抗蚀剂膜上的层叠透明导电膜之后,通过光学显微镜(KEYENCE公司制造的激光显微镜VK-X200)以倍率50倍观察所形成的布线图案,确认了电极图案的精度。另外,在线(P)确认到膜的剥离或抗蚀剂的残渣的情况下,判断为未以高精度形成电极图案,将除此以外的情况判断为以高精度形成了电极图案。
[表1]
[表2]
[表3]
[表4]
[表5]
[表6]
[表7]
[表8]
[表9]
[表10]
[表11]
[表12]
在本发明例中,成膜后的平均透射率均超过85%,而且成膜后薄层电阻均为20Ω/sq.以下,确认到可获得透射率优异并且电阻足够低的层叠透明导电膜。
另一方面,在比较例中,成膜后的平均透射率均为85%以下,若与Ag膜的膜厚相同的样品进行比较,成膜后的薄层电阻高于本发明例。推测是因为在Ag膜中发生了Ag的凝聚。
并且,在比较例A中,通过将ITO单层膜形成为较厚,为600nm,薄层电阻成为10Ω/sq.以下,但是平均透射率大幅劣化至76.4%。
而且,在比较例B中,通过将玻璃基板加热至200℃,膜厚成为180nm且薄层电阻成为10Ω/sq.以下,但是平均透射率为85%以下。
并且,恒温恒湿试验的结果确认到,在本发明例中,恒温恒湿试验后的透射率及薄层电阻的变化率较小,耐环境性优异。
另一方面,在比较例中,除A、B以外,恒温恒湿试验后的透射率或薄层电阻的变化率较大,耐环境性不充分。
而且,耐碱性试验的结果确认到,在本发明例中,耐碱性试验后的透射率及薄层电阻的变化率较小,耐碱性优异。
另一方面,在比较例中,在比较例13~比较例24的样品中,耐碱性试验后的透射率及薄层电阻的变化率较大,耐碱性不充分。
并且,利用蚀刻法的图案形成试验的结果确认到,在本发明例中,如表5、表6、表7及图7的(a)所示,能够以高精度形成层叠膜的过蚀刻的长度为1μm以下,且没有透明导电氧化物膜的残渣的布线图案。
另一方面,在比较例中,如表8及图7的(b)所示,层叠膜的过蚀刻O的长度均大于1μm,并且还产生透明导电氧化物膜的残渣R,通过一并蚀刻,很难以高精度形成布线图案。
并且,剥离抗蚀剂而以肉眼观察层叠膜的表面的结果,在本发明例中,与试验前相比,未观察到变化,相对于此,将未添加Y、Ti的GZO膜作为透明导电氧化物的比较例13~比较例24的层叠膜中,剥离抗蚀剂之后,到处观察到有膜剥离。
并且,利用剥离法的图案形成试验的结果确认到,在本发明例中,能够以高精度形成布线图案。
另一方面,在将未添加Y、Ti的GZO膜作为透明导电氧化物的比较例13~比较例24的层叠膜中,去除抗蚀剂之后,到处观察到有膜的剥离。
根据以上确认到,根据本发明例,能够提供一种即使将Ag膜形成为较薄也没有Ag的凝聚、透射率高且电阻值低的层叠透明导电膜。
产业上的可利用性
关于本发明的层叠透明导电膜,透射率足够高,并且电阻足够低,耐环境性及耐碱性优异,不易发生过蚀刻,因此适于显示器或者触摸面板等的透明电极膜。
符号说明
10-层叠透明导电膜,11-第一透明导电氧化物膜(透明导电氧化物膜),12-Ag膜,13-第二透明导电氧化物膜(透明导电氧化物膜),20-基板,30-层叠布线膜,41-抗蚀剂膜。
Claims (12)
1.一种层叠透明导电膜,其特征在于,具有由Ag或Ag合金构成的Ag膜及配置于所述Ag膜的双面的透明导电氧化物膜,
所述透明导电氧化物膜由包含Zn、Ga及Ti的氧化物形成。
2.根据权利要求1所述的层叠透明导电膜,其特征在于,
将所述透明导电氧化物膜中所包含的所有金属元素的原子比例设为:Ga为0.5原子%以上且30.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、剩余部分为Zn。
3.根据权利要求2所述的层叠透明导电膜,其特征在于,
将所述透明导电氧化物膜中所包含的所有金属元素的原子比例设为:Ga为0.5原子%以上且18.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、剩余部分为Zn。
4.根据权利要求3所述的层叠透明导电膜,其特征在于,
将所述透明导电氧化物膜中所包含的所有金属元素的原子比例设为:Ga为0.5原子%以上且14.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、剩余部分为Zn。
5.根据权利要求1所述的层叠透明导电膜,其特征在于,
形成所述透明导电氧化物膜的氧化物还包含Y。
6.根据权利要求5所述的层叠透明导电膜,其特征在于,
将所述透明导电氧化物膜中所包含的所有金属元素的原子比例设为:Ga为0.5原子%以上且30.0原子%以下、Ti为0.1原子%以上且10.0原子%以下、Y为0.1原子%以上且10.0原子%以下、剩余部分为Zn。
7.根据权利要求1至6中任一项所述的层叠透明导电膜,其特征在于,
所述Ag膜由Ag合金构成,所述Ag合金以总计0.2原子%以上且10.0原子%以下含有Cu、Sn、Sb、Ti、Mg、Zn、Ge、In、Al、Ga、Pd、Au、Pt、Bi、Mn、Sc、Y、Nd、Sm、Eu、Gd、Tb及Er中的一种或两种以上,且剩余部分由Ag及不可避免的杂质构成。
8.根据权利要求1至7中任一项所述的层叠透明导电膜,其特征在于,
将所述Ag膜的厚度设为10nm以下。
9.根据权利要求1至8中任一项所述的层叠透明导电膜,其特征在于,
波长为400~800nm的可见光区域的平均透射率为85%以上,且薄层电阻值为20Ω/sq.以下。
10.一种层叠布线膜,其特征在于,其由权利要求1至9中任一项所述的层叠透明导电膜构成,且具有布线图案。
11.一种层叠布线膜的制造方法,其特征在于,其为权利要求10所述的层叠布线膜的制造方法,该制造方法具备:
层叠透明导电膜形成工序,在基材的成膜面形成包含所述Ag膜及所述透明导电氧化物膜的所述层叠透明导电膜;
抗蚀剂膜形成工序,在所述层叠透明导电膜上形成布线图案形状的抗蚀剂膜;
蚀刻工序,将包含磷酸和乙酸的酸性混合液用作蚀刻剂,对形成有所述抗蚀剂膜的所述层叠透明导电膜一并进行蚀刻;及
抗蚀剂膜去除工序,蚀刻后去除所述抗蚀剂膜。
12.一种层叠布线膜的制造方法,其特征在于,其为权利要求10所述的层叠布线膜的制造方法,该制造方法具备:
抗蚀剂膜形成工序,在基材的成膜面形成布线图案的反转图案形状的抗蚀剂膜;
层叠透明导电膜形成工序,在形成有所述抗蚀剂膜的所述基材的成膜面,形成包含所述Ag膜及所述透明导电氧化物膜的所述层叠透明导电膜;及
抗蚀剂膜去除工序,去除所述抗蚀剂膜。
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JP2020090707A (ja) | 2018-12-05 | 2020-06-11 | 三菱マテリアル株式会社 | 金属膜、及び、スパッタリングターゲット |
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