CN1798869A - 在衬底上制备金属导体的方法 - Google Patents

在衬底上制备金属导体的方法 Download PDF

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CN1798869A
CN1798869A CN200480015141.5A CN200480015141A CN1798869A CN 1798869 A CN1798869 A CN 1798869A CN 200480015141 A CN200480015141 A CN 200480015141A CN 1798869 A CN1798869 A CN 1798869A
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M·莱斯凯莱
M·里塔拉
S·林德罗斯
H·乌西卡尔塔诺
P·科伊武库纳斯
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Nokia Oyj
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Abstract

本发明涉及一种在衬底比如纸上制备金属导体例如作为导电部件的铜导体图案的方法，所述方法尤其适合于采用印刷或者其它类似的设备在纸上大规模制备金属导体。在该方法中，化学淀积至少分两步进行，其中，由金属起始材料或还原剂中的一种制成溶液，或者另外一种以气体或者蒸气的形式存在，然后将其依次施用到衬底上。

Description

在衬底上制备金属导体的方法
发明领域
本发明涉及在衬底比如纸上制备金属导体例如作为导电部件的铜导体图案的方法。所述方法尤其适合于采用印刷或者其它类似设备在纸上大规模制备金属导体。
现有技术
在微电子工业中，半导体器件正持续向尺寸越来越小并越来越快发展。用来制造集成电路和微芯片的金属一般是铝，但近来，开始采用越来越大量的铜和少量的银，因为它们的电阻低。铜还具有其它所希望的性能，包括高的热稳定性和低的价格。然而，在各种衬底上制备铜膜和图案经常遇到问题，而且所用的方法复杂。目前，主要用UV光刻法来制备尺度在200μm以下的铜膜图案。
用喷墨印刷的方法直接在衬底上印刷铜图案，由于下面的优点，已经进行了深入的研究：
·该方法可以采用简单廉价并且可以易于控制的设备进行，
·所述的印刷方法安全无缺点，
·印刷直接进行，不需要腐蚀或者复杂的表面处理，
·印刷只需要少量的反应物，耗能低。
专利US 5132248公开了采用胶态铜悬浮体喷墨印刷的方法，然后在高温下处理或者激光处理，并去除多余的材料。
已提出了多种用于喷墨印刷方法的铜前体，包括有机铜化合物。然而，在印刷之后，必须进行高温加热，这样该化合物的有机部分才能在该环境中蒸发。例子包括Hong，C.M.，Wagner，S.，IEEE ElectronDevice Lett.2000，21，384中描述的己烯酸铜(copper hexenoate)。
可以用称为化学淀积的方法来在衬底上制备金属膜。化学淀积定义为在溶液中由于金属盐和还原化学试剂之间的反应而在催化边界上的受控自催化形成连续膜的方法。该反应通常在30-80℃的温度下进行，反应不需要外加动力源。金属离子和还原剂处在同一溶液中，它们在催化边界，或者晶种表面处反应，一般包括钯或者锡。适合用于所述化学淀积的金属是镍，铜，金，钯和银。在这种方法中，金属均匀的覆盖在待处理的表面上，并渗透到空腔和气孔中，但是，该方法慢。需要采用络合剂稳定溶液，而所述络合剂也会降低反应速度。
专利US 5158604描述了一种适合用于化学淀积的粘性水溶液，包含金属离子，例如铜或镍，金属络合剂，例如EDTA，金属还原剂，例如甲醛或者次磷酸盐(hypophosphite)，以及增稠剂，例如黄原酸胶，硅石，或者羧甲基纤维素。将该溶液施用在加热了的催化衬底上，该衬底包括金属或者聚合物，所述衬底是固定的或者是移动的网的形式，溶液优选的在施用前也经过加热。
文献WO 00/33625公开了一种在聚合物衬底上制备导电层的方法，其中墨水中含有银铜等催化颗粒，用平版印刷的方法将墨水印刷到衬底上，然后将所述衬底浸到传统的化学淀积浴中，来制备导电层。
化学淀积是已知的用来在催化表面上淀积金属膜的溶液相方法。作为一种工艺，所述化学淀积法太慢，因此不适合大规模制造。造成该现象的原因是提高溶液中起始化合物的浓度会使溶液不稳定，由此会发生均相反应。而且，引发在衬底上的金属淀积需要将衬底表面活化，这一般用铂来实现。现有技术中已知的分层(substractive)平版印刷工艺，其中所需图案是腐蚀的，不适合大规模制造。另外，现有技术中的方法通常昂贵，并生成大量废物。
因此，明显的，迫切需要一种在衬底上制造金属导体，尤其是金属导体图案的方法，该方法尤其适合于大规模制造，并可以用印刷机或者其它类似设备高速进行。而且，该方法应该是简单，快速和廉价的。
发明目的
本发明的一个目的是提供一种在衬底上制备金属导体的方法。
本发明的另一个目的是提供一种在衬底上制备金属导体，例如铜导体图案作为导电部件的方法。
本发明的另外一个目的是提供一种尤其适合于采用印刷机或者类似设备在纸上大规模制造金属导体的方法。
本发明方法的特征在权利要求中给出。
发明简述
现在，已惊奇的发现，现有技术方案所遇到的问题和缺点，可以用本发明的方法消除或者至少显著减少，在所述方法中，化学淀积至少分两步进行。金属起始材料和还原剂分处在不同的溶液里，或者其中一种以气态或蒸气的形式存在。然后将所述溶液或气体或蒸气依次喷涂或者施用到衬底需要成膜的位置上。
发明详述
在依据本发明的方法中，化学淀积至少分两步进行。在所述的化学淀积中，由金属起始材料和还原剂中的至少一种形成溶液，或者其中的一种作为气体或蒸气存在，然后将它们依次施用到衬底上。这样，总是由金属起始材料和还原剂构成单独的溶液，或者其中一种作为气体或蒸气存在，将所述溶液或气体或蒸气依次喷涂或者施用到衬底上需要成膜的位置。与传统的化学淀积相反，起始材料分处在不同的溶液中，或者其中的一种作为气体或蒸气存在，因而金属膜的生长可以通过提高起始材料的浓度来提高，而不会同时引起所不希望的均相反应。在依据本发明的方法中，至少一种起始材料是存在于溶液中的，将其喷涂到纸上或者其它衬底上的需要成膜的位置。所述溶液优选的是水溶液，但其中也可以包含有机溶剂比如醇类。
适合用于该方法中的金属选自Cr，Mn，Fe，Co，Ni，Cu，Zn，Ga，As，Se，Tc，Ru，Rh，Pd，Ag，Cd，In，Sn，Sb，Te，Re，Os，Ir，Pt，Au，Hg，Tl，Pb，Bi以及它们的合金。铜，银，金，铬，铁，钴，镍，钯和铂以及它们的合金是优选的。尤其优选的是铜，银和镍，其中可以得到高电导率和合适的价格。适宜用盐的形式将金属引入到水溶液中，优选的是硫酸盐或者氯化物。所述金属溶液含有的所述金属盐的浓度在0.005M到饱和溶液对应的浓度之间变化，优选的为0.1-0.5M。所述金属溶液优选的是水溶液。
可选的，所述金属溶液还含有一种或者多种络合化合物，其优选的选自EDTA，柠檬酸，乙二胺。络合化合物的相对含量至少要与金属成化学计量比。
如有必要，调节金属溶液的pH值，合适的pH范围依据所用的金属。可以将铜的EDTA络合物作例子，这时pH的下限为6，优选范围在12-13。可以用任何合适的碱来进行pH调节，优选的氢氧化钠。
适用的还原剂包括碱金属和碱土金属的硼氢化物，例如NaBH4和次磷酸盐，例如NaH2PO2，甲醛NCON，水合肼N2H4和氨基硼烷类R2NHBH3，其中R可以是烷基，优选的是甲基，乙基或者丙基。还原剂优选的以水溶液使用。
而且，如果必要，在含有金属的溶液和含有还原剂的溶液中，可以使用表面活性剂和控制表面张力的试剂，例如，聚乙二醇，十二烷基硫酸钠。
衬底是固定的，或者是移动的网，进一步的，其可包括纸，板，其它纤维材料，聚合物材料或者用聚合物涂覆的金属。在施用之前，不必对衬底进行催化活化。
起始材料溶液，气体和蒸气的数量可以多于一种。
在第一步中，采用合适的施用方法将起始材料溶液中的一种应用到衬底表面上要制作图案的位置，或者可选的整个表面上，施用方法适用传统印刷方法，例如照相凹版印刷，苯胺印刷，胶版印刷，丝网印刷或者喷墨印刷方法，其中优选的是喷墨印刷方法，起始材料溶液是金属溶液或还原剂溶液。在第二步中，随后采用合适的施用方法将另一种起始材料(即金属或还原剂)以溶液的形式施用到衬底表面上，施用方法适用传统印刷方法，包括照相凹版印刷，苯胺印刷，胶版印刷，丝网印刷或者喷墨印刷方法，其中优选的是喷墨印刷方法，由此或者喷射形成图案，或者覆盖整个表面，或者可选的汽化或作为气体施用。尤其优选的是采用数控喷墨印刷方法。起始材料的施用顺序是不重要的，还可以分别重复多次将起始材料施用到衬底上。
该施用可以用合适的辊到辊(roll to roll)印刷方法在衬底或者板上进行，而且，衬底可以包括纸，板，其它纤维材料，聚合物材料或者用聚合物涂覆的金属。辊到辊印刷方法是优选采用的。
该施用进行的温度依赖于工艺。例如，在铜工艺中，温度在20-200℃，优选的在20-140℃。
本发明方法具有几个优点。用来形成图案的化学淀积通过将起始组分中的一种或者全部以各自溶液的形式施用到需要淀积金属的位置。依据本发明方法的反应由于不需要稳定剂而是快速的。采用这种方法，可以用另外的方法在衬底所需位置上制造具有所需形状的导电图案，并且图案的厚度可以在很宽的范围内变化。这种方法可以在室温常压下进行，不需要保护气体。溶液是水基的，在室温下是稳定的，而且，起始材料廉价。与现有技术中的腐蚀方法相反，在该方法中没有废料。
现在，用下面的实施例对本发明进行说明，但不会以任何方式限制本发明的范围。
实施例
实施例1
在纸上淀积铜
在本实施例中，采用乙二胺四乙酸(EDTA)络合的硫酸铜(0.25MCuSO4·5H2O+0.25M EDTA)溶液作铜起始材料，硼氢化钠(2.0M NaBH4)作还原剂。在使用前，用氢氧化钠(NaOH)将铜溶液的pH值调节到碱性(pH 12-13)。在140℃，在空气中，将铜起始材料溶液和还原剂溶液交替施用到纸上，让铜溶液在纸上扩散大约20秒，然后添加还原剂溶液。将纸在140℃下保持大约2分钟。结果，通过以100μl的量将两种溶液分别施用三次，在滤纸(Whatman)上得到了导电的(大约4-20Ω)铜层。
总反应为：
实施例2
在纸上淀积银
在本实施例中，采用氨(NH3)络合的硝酸银(0.04M AgNO3+0.01MNH3)溶液作银起始材料，硼氢化钠(2.0M NaBH4)作还原剂。在使用前，银溶液的pH值为12-13。在160℃，在空气中将银溶液和还原剂交替施用到纸上。让银溶液在纸上扩散大约20秒，然后添加还原剂溶液。将纸在160℃下保持大约2分种。结果，通过使用100μl的施用，在滤纸(Whatman)上得到了导电的(大约1-10Ω)银层。
总反应为：

Claims (14)

1.在衬底上制备金属导体的方法，其特征在于在所述方法中，化学淀积至少分两步进行，其中，至少由金属起始材料或由还原剂制成溶液，或者另一种以气体或蒸气的形式存在，然后将它们依次施用到衬底上。
2.依据权利要求1中的方法，其特征在于金属起始材料中的金属选自Cr，Mn，Fe，Co，Ni，Cu，Zn，Ga，As，Se，Tc，Ru，Rh，Pd，Ag，Cd，In，Sn，Sb，Te，Re，Os，Ir，Pt，Au，Hg，Tl，Pb，Bi以及它们的合金。
3.依据权利要求1或2中的方法，其特征在于金属是铜，银，金，铬，铁，钴，镍，钯和铂以及它们的合金。
4.依据任意权利要求1-3的方法，其特征在于金属是铜，银或者镍。
5.依据任意权利要求1-4的方法，其特征在于金属以可溶于水的盐的形式引入到金属溶液中，优选作为硫酸盐或者氯化物，所述金属溶液含有的金属盐的浓度在0.005M到饱和溶液对应的浓度之间变化，优选的为0.1-0.5M。
6.依据任意权利要求1-5的方法，其特征在于所述金属溶液中还含有一种或者多种络合剂，优选的为EDTA，柠檬酸，或乙二胺。
7.依据任意权利要求1-6的方法，其特征在于所述的还原剂是碱金属或碱土金属的硼氢化物或者次磷酸盐，甲醛，水合肼或者氨基硼烷R2NHBH3，其中R代表烷基。
8.依据任意权利要求1-7的方法，其特征在于所述的还原剂是硼氢化钠，甲醛，次磷酸钠，水合肼或者氨基硼烷R2NHBH3，其中R代表甲基，乙基或者丙基，所述的还原剂优选的是作为水溶液。
9.依据任意权利要求1-8的方法，其特征在于衬底是固定的，或者是移动的网，其可包括纸，板，其它纤维材料，聚合物材料或者用聚合物涂覆的金属。
10.依据任意权利要求1-9的方法，其特征在于采用印刷的方法将起始材料中的一种作为溶液施用到衬底表面上需要形成图案的位置，或者可选的整个表面上，并且当使用印刷方法将另一种起始材料作为溶液施用到衬底表面上时，或者通过喷射形成图案，或者喷涂覆盖整个表面。
11.依据权利要求10中的方法，其特征在于印刷方法是照相凹板印刷，苯胺印刷，胶版印刷，丝网印刷或者喷墨印刷方法。
12.依据权利要求10或11中的方法，其特征在于所述的印刷方法是喷墨印刷法。
13.依据任意权利要求10-12的方法，其特征在于所述的印刷方法是辊到辊印刷法。
14.依据任意权利要求10-13的方法，其特征在于所述的印刷方法是数控喷墨印刷法。
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