CN1310341C - 制造电极的蚀刻方法 - Google Patents
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Abstract
采用一种方法在基底上形成基本上透明的电极,该方法包括依次在该基底上形成高指数底层、金属导电层和导电率至少约为4008 1/平方的高指数顶层,然后对所述高指数底层、高指数顶层和导电层进行化学蚀刻处理,在该金属导电层中形成分隔的电极。
Description
技术领域
本发明涉及为用于使用在显示设备中的透明电极形成图案的湿蚀刻法。
背景
美国专利申请第09/009,391号描述了一种在基底上形成许多基本上透明的电极的方法,该文参考结合于此。该方法包括依次在基底上形成高指数底层、金属导电层和导电率至少约为4008 1/平方(4008 1/square)的高指数顶层。对该高指数顶层和导电层,以及可能还对高指数底层,都可采用激光烧蚀法形成图案,以便在金属导电层中形成许多分隔的电极。激光束在基底上以光栅模式扫描,并在来自光栅影像处理器的数字信号的控制下进行调制。在激光烧蚀步骤完成后,电极组合件上有表面残留物和再沉积的碎屑。用含有表面活性剂的水溶液清洗该组合件的表面,或再轻微擦拭,去除残留物和碎屑。
概要
对电极组合件的高指数顶层、导电层以及可能还对高指数底层进行烧蚀来成形图案是很准确而有效的。但是,这种方法不可能适用于所有的材料和结构。也并不是所用的图案成形操作都需要在激光烧蚀装置中使用高分辨率图像文件。此外,将激光烧蚀装置加到现有的生产设备中也不是件易事。
一方面,本发明是一种形成电极的方法,该方法包括依次在基底上形成高指数底层、导电层和导电率至少为4008 1/平方的高指数顶层;然后化学蚀刻该高指数底层、顶部高蚀刻层和导电层,在导电层中形成电极。
另一方面,本发明是一个基本上透明的电极组合件,该组合件包括一个基底,在其上面依次沉积高指数底层、金属导电层和导电率至少为4008 1/平方的高指数顶层。该导电层包括许多分隔的电极,这些电极是化学蚀刻该高指数底层、高指数顶层和导电层而形成的。
又一方面,本发明是一种包括有基本上透明电极组合件的显示设备。该电极组合件包括一个基底,在其上面依次沉积高指数底层、金属导电层和导电率至少为4008 1/平方的高指数顶层。该导电层包括许多分隔的电极,这些电极是化学蚀刻该高指数底层、高指数顶层和导电层而形成的。
另一方面,本发明是一种有这种基本上透明电极组合件的电子设备。
下面的说明书中将给出本发明一个或多个实施方式的详细描述。从这些描述和权利要求书,将可理解本发明的其它特征、目标和优点。
详细的描述
用于本发明方法的基底,可由具有足够机械完整性和足够光滑的表面,便于在其上面形成电极的任何材料制得。所述基底,与电极组合件的其它层一样,较佳是足够地透明,因此可用于液晶显示器中。可使用玻璃基底,但通常较佳的是由合成的树脂制得基底。为此目的的优选树脂包括如聚醚砜、聚(烷基)丙烯酸酯、纤维素二乙酸酯、聚碳酸酯、聚酯、从Lonza AG(Basel,瑞士)得到的名为“POKALON HT”的高玻璃转变温度(Tg)聚碳酸酯共聚物,以及聚(二(环戊二烯)缩合物),如从Lonza AG(Basel,瑞士)购得的名为“TRANSPHAN”的材料。这种材料是由日本合成橡胶有限公司(Japan Synthetic Rubber Co.Ltd.,东京,日本)名为“ARTON”的聚合物制得的膜,它的式子由制造者给出如下:
(其中X是极性基团)
可在该基底的一个或两个表面上施加涂层,提供防止气体或水分的屏障,和/或改进该基底的硬度和抗刮伤性能,和/或增强高指数层对基底的附着。例如,可将一种硬的聚合物涂覆到基底的一个或两个表面上。这种硬涂层的厚度一般约为1-15φm,较佳约为2-4φm。可采用适当的聚合材料的游离基聚合(热引发或紫外辐照引发)使该涂层聚合。特别优选的硬涂层用的是Tekra公司(New Berlin,WI)的名为“TERRAPIN”的丙烯酸树脂涂料。
可在基底的一个或两个表面上施加薄的氧化硅(SiOx)层(通常为10-40nm,较佳约为30nm),此层可作为最终形成的液晶显示装置的气体和水分的屏障,并作为附着促进剂,以改善高指数底层的附着。术语“氧化硅”在本文中指式SiOx的物质,其中x并不一定等于2。可采用化学蒸气沉积法将这些氧化硅沉积,或者在氧气气氛中溅射硅,因此沉积的物质并不能准确符合纯二氧化硅的化学计量式SiO2。当将硬涂层和氧化硅层都施加到基底上时,可以任何顺序施加两个层。在一优选的实施方式中,将第一氧化硅层施加到基底的表面上,接着依次是硬涂层和第二氧化硅层。
在本方法中,依次将下列层沉积到基底上:高指数底层、金属导电层和顶部高深刻层。可采用各种技术沉积这些层,例如电子束和热蒸发技术,但是,较佳采用溅射或化学蒸气沉积法沉积这些层。特别优选采用dc溅射法,但也可采用RF、磁控管以及反应性溅射和低压等离子体增强和激光增强的化学蒸气沉积法。当使用优选的塑料基底时,这三层中的每一层都应在不高于约170EC的温度下沉积到基底上,以免对塑料基底造成损伤。过程的温度限制随所使用的确切基底材料而异。例如,对于TRANSPHAN基底,沉积温度应不大于约160-165EC。
靠近基底的高指数底层可以是电绝缘的或导电的。一般优选绝缘材料,因此,如果高指数底层的任何部分在形成图案步骤后仍保留在邻近的两个电极之间,则所保留的部分不会引起电极间的短路。这种短路当然是不可以的,因为它在效果上将会使两个邻近的电极变成一个电极,会不利地影响使用了电极组合件的液晶显示器或触摸屏的质量。但是,如果形成图案的条件确保高指数底层在形成图案后没有留下,则可使用导电性的高指数层。
不管是绝缘的还是导电的,高指数底层通常是由金属氧化物形成。可用于高指数底层的氧化物有氧化铟(In2O3)、二氧化钛(TiO2)、氧化镉(CdO)、氧化镓铟、五氧化二铌(Nb2O5)和氧化铌锡(ITO)。优选ITO。正如形成液晶显示组合件用的电极这一领域里熟练的技术人员所周知的〔例如,可参见Patel等人,《监测和控制采用DC溅射法将反应性ITO沉积在柔性基底上的方法》(Methods of monitoring andcontrol of reactive ITO deposition process on flexible substrates with DC sputtering),真空涂层学会第39界年会技术会议汇刊(Society of Vacuum Coaters 39th AnnualTechnical Conference Proceedings),441-45(1996);和Gibbons等人,《用于显示应用的ITO涂层》,真空涂层学会第40界年会技术会议汇刊,216-220(1997)〕,改变氧化物层沉积的条件,可在几个数量级范围内控制这些金属氧化物层的导电率。对于优选的dc溅射沉积法,相关的条件包括温度、反应器压力、氧的分压、dc偏置和沉积速率。也可使用掺杂法来控制绝缘层的导电性。通常,绝缘层的厚度约为20-80nm。
邻近基底的高指数底层(以及高指数顶层)中所需的折射指数,在一定程度上根据装上本发明电极组合件的最终装置中存在的其它层而改变。通常,在550nm测量的高指数层的折射率要超过1.6,可容易地将该优选的金属氧化物高指数层制成折射率超过1.9,如上述文献中所述。
导电层由能采用所使用的沉积法沉积并具有足够的导电率能在最终的电极组合件中产生所需低电阻的任何材料制得。较佳的是,该导电层是金属或金属合金,最佳是包含金、银中的至少一种和金/银合金(例如美国专利第4,234,654号中所述的合金)。由于金会提高导电层的抗腐蚀性,所以一般需要这个层是在一个面或两个面上涂有较薄的金层的一层银。例如,已发现,10nm厚的银层夹在两层1nm厚的金层之间可产生良好的效果。导电层的总厚度一般约为5-20nm。
形成高指数顶层的优选材料和方法与形成高指数底层的一样,不同的是顶部层沉积的条件要改变,使该顶部层具有相当大的导电率。通常在组合件的整个表面上测量电极组合件中使用的层的电阻,导电率至少约为4008 1/平方的高指数顶层可产生满意的结果,优选的是导电率约为100-2008 1/平方的高指数层。高指数顶层的厚度优选约为20-100nm。
表1列出高指数底层、导电层和高指数顶层的组合的实施例。
表1
高指数底层 | 导电层 | 高指数顶层 |
ITO,40nm | Ag,10nm | ITO,47nm |
ITO,40-42nm | Ag,9-10nm/Au,1-1.5nm | ITO,47nm |
ITO,40-42nm | Au,1nm/Ag,10nm/Au,1nm | ITO,47nm |
SnO2,42nm | Ag,10-12nm | ITO,47nm |
SnO2,42nm | Ag,9-10nm/Au,1-1.5nm | ITO,47nm |
SnO2,42nm | Au,1nm/Ag,10nm/Au,1nm | ITO,47nm |
将高指数底层、导电层和高指数顶层沉积好后,采用湿蚀刻法在高指数顶层和导电层上形成图案,从而在导电层上形成许多分隔的电极。图案的形成较佳应完全延伸贯穿高指数顶层和导电层,以确保导电层上形成的邻近电极间没有短路。在实践上,图案的形成通常完全贯穿到邻近基底的高指数底层,但是,如先前所述,较佳的是,高指数底层具有足够的电阻,以防止图案形成后如果有高指数底层保留的话,会导致邻近电极间不利的电流短路。
在本发明的湿蚀刻法中,将已在其上依次涂上高指数底层、导电层和高指数顶层的基底在一蚀刻浴中进行处理。湿蚀刻法可以包括多个步骤,也可以是一个步骤。蚀刻浴的组成可根据高指数顶层和高指数底层以及导电层的材料而有很大的差别。较佳的是,蚀刻液的组成应选择能除去高指数底层、高指数顶层和导电层,以便在导电层中形成电极。
例如,如果电极结构体中使用表1中的那些物质,并且高指数底层是ITO,则蚀刻液可包括含H2SO4的第一浴、含FeCl3的第二浴和含H2SO4的第三浴。然后首先将电极结构体浸入第一H2SO4浴中,对高指数顶层进行蚀刻,接着浸入第二FeCl3浴中,对导电层进行蚀刻,最后浸入第三H2SO4浴中,对高指数底层进行蚀刻。
但较佳的是,蚀刻浴是包含H2SO4与FeCl3在内的一个浴。此蚀刻浴中H2SO4和FeCl3的比例可根据溶液温度和电极结构体在该溶液中的停留时间而有极大的变化。例如,假设基底涂覆了表1中各层的材料,则可制备约3重量%浓度为37%H2SO4的原液和约0.01重量%FeCl3的原液。这些原液可以特定的比例组合,产适当的蚀刻液。3%H2SO4原液和0.01%FeCl3原液的比例范围较佳应约为1∶1到约1∶6,较佳约为2∶1到5∶1,最佳约为4∶1到5∶1。
蚀刻液的温度也可有很大的不同,但蚀刻温度稍微高于室温是较佳的,这样将要获得满意的蚀刻而需要的溶液成分的浓度以及停留时间减少到最小程度。使用上述浓度的优选成分,溶液的温度较佳应约为20-60℃,更佳应约为30-40℃,最佳应约为35℃。蚀刻溶液的温度较佳应维持在约±5℃的范围内。
停留时间也可根据蚀刻液中的成分、浓度和蚀刻液的温度而有较大的不同,但是停留时间应尽可能地减到最短,以便在一生产规程中完成蚀刻过程。使用上述优选的成分和温度,停留时间应约为1-10分钟,一般是约1-5分钟,较佳约为3-5分钟,更佳约为3.5-5分钟。
蚀刻浴较佳要搅拌,以帮助从电极组合件上除去残留物。可采用已知的任何技术搅拌蚀刻浴,如使用搅拌棒或超声波搅拌。优选采用频率约为40-50kHz的超声波搅拌,对于上述列出的蚀刻液成分,频率约为40的超声波搅拌特别合适。
可用几种方法评估使用上述蚀刻浴获得的蚀刻质量。可将所需的蚀刻线宽与实际的蚀刻线宽比较,蚀刻的线可以肉眼观察,以确定残留物的存在与否。此外,可测量蚀刻区域的导电率,低导电率表明所测量的区域蚀刻得更为完全。
蚀刻过程结束后,还可以用水或其它清洗液清洗样品,去除残留物并使样品表面洁净。在此可用的清洗步骤后,将许多导体附着到在图案形成步骤中形成的分隔的电极上的高指数顶层上。这些导体就通过导电的顶层而与电极呈电接触。由此形成的电极组合件可用于无源型液晶显示器、触摸显示屏或其它平板显示器。
已发现,可容易地形成在550nm具有约80%透明度、小于约20欧姆/方块的薄层电阻(20ohms per square sheet resistance)的本发明电极组合件。这种电极组合件很容易装入商业质量的显示装置,如液晶显示器、触摸显示屏、场致发光显示屏和胆甾醇型显示器中。这些显示器可用在许多电子装置,如计算机、电话、寻呼机、手持电子指挥器等中。
实施例
制备了依序具有下述层结构的电极组合件:硬涂层/TRANSPHAH基底/硬涂层/30nm厚SiOx/38.5nm厚ITO高指数底层/1nm厚Au导电层/8nm厚Ag/1nm厚Au/35nm厚ITO高指数顶层。建立了一个包括改变的温度、H2SO4(3%)和FeCl3(0.01%)的浓度比和时间的实验矩阵,并评估了所获得的实际蚀刻线宽的质量与所需的(光致抗蚀间隙)蚀刻线宽相比。所试验的温度为30℃、35℃和40℃;浓度比为2∶1、4∶1和5∶1,停留时间是1分钟、3分钟和5分钟。所有的溶液都从相同的H2SO4(3%)和FeCl3(0.01%)原液配制。在40kHz或47kHz的超声波装置中对电极组合件蚀刻。
2∶1的H2SO4(3%)和FeCl3(0.01%)之比被证明在本实施例的条件下太浓了,导致过分蚀刻,无论与温度、时间和超声波浴频率如何。
4∶1的H2SO4(3%)与FeCl3(0.01%)之比在本实施例的一些条件下产生良好的结果,但是,在此比例下进行的蚀刻,其所产生的结果对温度和时间非常敏感。
对于5∶1的溶液,温度有10度的变化也看不出蚀刻质量有多大改变(对于相同的时间间隔)。最好的结果出现在3.5分钟和5分钟。
对于本实施例的电极组合件,最优的蚀刻溶液是5∶1的H2SO4(3%)和FeCl3(0.01%)。溶液应在超声波浴中维持在35±5℃,导体浸入的停留时间应为3.5到5分钟。在这些条件下,我们没有观察到过分蚀刻或有残留物的情况。使用频率为40kHz和47kHz的两种超声波浴,都产生良好的结果。
已描述本发明的一些实施例。但是,应理解在不偏离本发明的实质和范围的情况下可作出各种改动。
Claims (20)
1.一种形成电极的方法,该方法包括:
在基底上依次形成高指数底层、导电层和导电率至少为4008 1/平方的高指数顶层;
用含有H2SO4和FeCl3的蚀刻液对所述高指数底层、高指数顶层和导电层进行化学蚀刻,在导电层中形成电极。
2.如权利要求1所述的方法,其特征在于,所述蚀刻步骤在含有H2SO4和FeCl3的一个浴中进行。
3.如权利要求2所述的方法,其特征在于,所述浴含比例为2∶1到5∶1的3%H2SO4溶液与0.01%FeCl3溶液。
4.如权利要求2所述的方法,其特征在于,浴中的所述比例为4∶1到5∶1。
5.如权利要求2所述的方法,其特征在于,所述高指数顶层和高指数底层以及导电层停留在浴中的停留时间为1-5分钟。
6.如权利要求2所述的方法,其特征在于,所述高指数顶层和高指数底层以及导电层在浴中的停留时间为3-5分钟。
7.如权利要求2所述的方法,其特征在于,所述浴的温度为30-40℃。
8.如权利要求2所述的方法,其特征在于,所述方法还包括对该浴进行搅拌。
9.如权利要求2所述的方法,其特征在于,所述浴是个超声波浴。
10.如权利要求1所述的方法,其特征在于,所述方法还包括将许多导体连接到位于分隔的电极上的所述高指数顶层的部分。
11.如权利要求1所述的方法,其特征在于,所述基底是选自醚砜、聚(烷基)丙烯酸酯、纤维素二乙酸酯、聚碳酸酯、聚酯、聚碳酸酯共聚物和聚(二(环戊二烯)缩合物)的材料。
12.如权利要求1所述的方法,其特征在于,所述基底还包括在其至少一个表面上的氧化硅层。
13.如权利要求1所述的方法,其特征在于,所述基底在其表面上包括下述顺序的层:第一氧化硅层、硬涂层和第二氧化硅层。
14.一种基本上透明的电极组合件,它包括:
具有依次沉积于其上的高指数底层、金属导电层和导电率至少为4008 1/平方的高指数顶层的基底,所述导电层中有由化学蚀刻所述高指数底层、高指数顶层和导电层而形成的许多分隔的电极,其中,该电极组合件在550nm具有80%透明度、小于20欧姆/方块的薄层电阻。
15.如权利要求14所述的电极组合件,其特征在于,所述基底是选自醚砜、聚(烷基)丙烯酸酯、纤维素二乙酸酯、聚碳酸酯、聚酯、聚碳酸酯共聚物和聚(二(环戊二烯)缩合物)的材料。
16.如权利要求14所述的电极组合件,其特征在于,所述化学蚀刻在含有H2SO4和FeCl3的一个浴中进行。
17.如权利要求14所述的电极组合件,其特征在于,所述基底还包括在其至少一个表面上的氧化硅层。
18.如权利要求14所述的电极组合件,其特征在于,所述基底在其表面上依次形成有第一氧化硅层、硬涂层和第二氧化硅层。
19.一种显示装置,它包括基本上透明的电极组合件,该电极组合件包括具有依次沉积在其上的高指数底层、金属导电层和导电率至少为4008 1/平方的高指数顶层的基底,所述导电层中有由化学蚀刻所述高指数底层、高指数顶层和导电层而形成的许多分隔的电极,其中,该电极组合件在550nm具有80%透明度、小于20欧姆/方块的薄层电阻。
20.一种电子装置,它包括权利要求19所述的显示装置。
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KR101397200B1 (ko) | 2008-02-28 | 2014-05-20 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 저 가시성 도체를 구비한 터치 스크린 센서 |
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- 2000-05-12 US US09/570,310 patent/US6652981B2/en not_active Expired - Fee Related
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- 2001-04-13 EP EP01928536A patent/EP1284023A2/en not_active Withdrawn
- 2001-04-13 CN CNB018093361A patent/CN1310341C/zh not_active Expired - Fee Related
- 2001-04-13 JP JP2001584497A patent/JP2003533890A/ja active Pending
- 2001-04-13 AU AU5538301A patent/AU5538301A/xx active Pending
- 2001-04-13 KR KR1020027015090A patent/KR20030007605A/ko active IP Right Grant
- 2001-04-13 AU AU2001255383A patent/AU2001255383B2/en not_active Ceased
- 2001-04-13 WO PCT/US2001/012208 patent/WO2001088998A2/en active IP Right Grant
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EP0265110A1 (en) * | 1986-10-06 | 1988-04-27 | CPFilms, Inc. | Transparent electrode |
EP0421429A2 (en) * | 1989-10-03 | 1991-04-10 | Sharp Kabushiki Kaisha | Electrode pattern forming method |
JPH11282383A (ja) * | 1998-01-13 | 1999-10-15 | Toppan Printing Co Ltd | 電極基板およびその製造方法 |
Also Published As
Publication number | Publication date |
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KR20030007605A (ko) | 2003-01-23 |
US6652981B2 (en) | 2003-11-25 |
WO2001088998A3 (en) | 2002-11-28 |
CN1429409A (zh) | 2003-07-09 |
JP2003533890A (ja) | 2003-11-11 |
EP1284023A2 (en) | 2003-02-19 |
AU5538301A (en) | 2001-11-26 |
WO2001088998A2 (en) | 2001-11-22 |
AU2001255383B2 (en) | 2005-09-29 |
US6838013B2 (en) | 2005-01-04 |
US20020182386A1 (en) | 2002-12-05 |
US20030129424A1 (en) | 2003-07-10 |
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