CN104812935B - 在介质上沉积金属图案的方法 - Google Patents

在介质上沉积金属图案的方法 Download PDF

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CN104812935B
CN104812935B CN201380061315.0A CN201380061315A CN104812935B CN 104812935 B CN104812935 B CN 104812935B CN 201380061315 A CN201380061315 A CN 201380061315A CN 104812935 B CN104812935 B CN 104812935B
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弗拉其苏斯·威廉默斯·玛丽亚·杰利森
劳尔·马塞利诺·佩雷斯·格拉特罗
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Abstract

在介质上沉积金属图案的方法，所述方法包括：从脉冲激光源产生脉冲激光束，其中所述介质对于所述激光束的波长来说是基本透明的；使所述激光束聚焦到目标层上，所述目标层包含分散于可激光光降解/可燃的有机基质中的无机颗粒，所述目标层产生喷出物以响应所述激光束与所述目标层之间的相互作用；在所述介质上所需的图案内累积至少一部分所述喷出物；通过无电解金属镀覆提供所述图案。本发明进一步涉及一种包含金属图案的透明介质，其中所述金属图案与所述基质之间的粘附力为至少5N/cm。

Description

在介质上沉积金属图案的方法
本发明涉及一种在介质上沉积金属图案的方法，所述方法包括：从脉冲激光源产生脉冲激光束，使激光束聚焦到目标层上，所述目标层产生喷出物以响应所述激光束与所述目标层之间的相互作用，在所述介质上所需的图案内累积至少一部分所述喷出物，通过无电解金属镀覆提供金属图案。所述方法通常用于在透明介质上产生导电图案。本发明进一步涉及包含金属图案的透明介质。
上述方法从Hanada等(Appl.Phys.A 80,111-11 5(2005))中已知。Hanada描述了通过如下使聚酰亚胺选择性金属化的方法：脉冲激光辐射在聚酰亚胺(PI)后面使用金膜目标层，接着使用无电解镀覆溶液的金属镀覆。该脉冲激光的波长是对于该波长来说PI具有优异的透明性的波长。脉冲激光首先通过PI介质，然后由目标层(无论是大块Au还是Au膜)吸收，从而从目标层表面产生激光诱导的等离子体喷出物。在目标层与PI介质之间足够短的距离内，等离子体攻击PI介质的后表面。由于等离子体和激光束之间的相互作用，在PI的后侧发生烧蚀。烧蚀过程后，表面被清洗，接着利用无电解镀覆溶液进行金属镀覆。Hanada所描述的方法的一个缺点是金属图案和介质之间的粘附力差。
US20100227133中也描述了在透明的介质上提供图案。US20100227133描述了一种在介质上沉积图案的方法，所述方法包括：从脉冲激光源产生脉冲激光束，使激光束聚焦到目标层上，所述目标层产生喷出物以响应所述激光束与所述目标层之间的相互作用，通过在所述介质上累积至少一部分所述喷射物来提供所需的图案。这种方法的缺点是，在得到导电图案之前，所述方法需要很长的时间。
本发明的目标是提供一种在介质上沉积金属图案的方法，其中金属图案与介质之间具有改善的粘附力。
根据本发明，该目标通过包含无机颗粒的目标层而达到，所述无机颗粒分散于可激光光降解/可燃的有机基质中。
作为使用包含无机颗粒目标层的结果是，金属镀层和介质之间的粘附力相对于通过本领域现有技术得到的粘附力显著提高。本发明方法的一个优点是，可以使用不同类型的无机材料，例如金属氧化物。相比Hanada所描述的纯金属目标层，可制得更薄且更精确的图案。相对于US20100227133，产生导电图案的时间显著缩短。
在本发明的方法中，目标层包含无机颗粒，其分散于可激光光降解/可燃的有机基质中。通常无机颗粒和有机基质混合并压制成片(plaque)或板，或浇铸成膜。优选地，目标层是浇铸的膜，因为相比于压缩的无机氧化物，用浇铸的膜可以制得更薄且更精确限定的图案。
所述目标层优选包含20-80wt.％的无机颗粒，更优选30-75wt.％的无机颗粒，甚至更优选40-60wt.％的无机颗粒。低于20wt.％时，响应于与激光束的相互作用而产生的喷出物的量过低，因此镀覆时间变得不期望的长。超过80wt.％的无机颗粒时，烧蚀过程变得无效。
在本发明方法中的无机材料优选包括金属颗粒、或金属氧化物、或金属盐、或其任意组合。如果无机材料包括金属，该金属优选地选自金、铂、钯、银、铜、铋、镍、铁、锑或这些金属的合金的组。金属氧化物优选选自铋、铁、铜、锑或镍的氧化物。金属盐可以选自由乙酸钯、乙酸铜或碘化铜组成的组。选择所使用的无机材料使得在无机材料中的金属的氧化还原电位比如果要镀覆金属时的氧化还原电位高。无机材料由根据D50的方法测量中值粒径小于5μm、优选小于1μm，更优选小于0.5μm的颗粒[具有粒径分布]组成。
可激光光降解/可燃的有机基质可以是热塑性或热固性聚合物。
热塑性聚合物可以选自由聚酯、聚酰胺、聚碳酸酯、聚烯烃、聚氨酯、热塑性硅酮、热塑性丙烯酸酯、PLA、PEEK、PI、聚苯乙烯、聚砜和聚醚-酰亚胺组成的组。热固性聚合物是选自如下的组的热固性树脂：聚丙烯酸酯、热固性聚酯、热固性环氧、热固性酚醛、热固性醇酸、热固性聚氨酯、热固性三聚氰胺、热固性橡胶如硅胶(silicon)或EPDM、热固性聚酰亚胺、或热固性氰酸酯。缩合(condensation)、辐射或热固化可以使有机基质固化。用UV、γ或电子束辐射固化的固化是优选的。基于有机基质的总重量，有机基质优选包含小于5wt％、更优选小于3wt％、甚至更优选小于1wt％的芳族基团。若芳族基团大于5wt％，响应于与激光束的相互作用而产生的喷出物的量过低，因此镀覆时间变得不期望的长。
有机基质优选为热固性聚合物。热固性聚合物的结果是，与热塑性聚合物相比，图案和介质之间的粘附力更好。
在本发明的过程中，激光束首先被引导通过激光透明介质并聚焦在目标层上。目标层优选是涂布在支撑基材(由任何所需的材料制成，如玻璃或金属)上的膜。响应于所述激光束和所述目标层之间的相互作用，产生喷出物，其在与入射激光束相反的方向上往后转移，并沉积到介质上。在本发明的方法中，目标层可以与介质接触来被放置，或在距基质至多5mm、优选至多1mm、更优选至多5μm的距离内。该方法的一个优点是，它可以在透明介质上沉积金属图案。
在本文使用时，术语“激光透明的介质”是指对脉冲激光发射的激光束的组合吸收和反射小于50％、优选小于20％、最优选小于10％的介质。激光透明介质的透射率优选地大于90％。吸收、反射和透射是通过根据NIR光谱的方法使用积分球方法在Perkin ElmerSpectrum 2000中测量而限定的。优选地，激光透明介质在355-2000nm的范围内、更优选在从380-780nm的可见光范围内具有小于50％、优选小于20％、更优选小于10％的组合吸收和反射。
激光透明介质可以包括玻璃、石英、蓝宝石或含有聚合物的组合物。含有聚合物的组合物可以进一步包含填料，前提条件是该填料对于所用的激光束来说也是透明，例如像玻璃、石英、颜料或蓝宝石、或其任意组合。该介质可以是例如片材、管或瓶子。
作为激光束的来源，可以使用不同的激光器。在上述的波长范围内工作的这类激光器例子是CO2激光器(10.6μm)、Nd:YAG激光器(1064、532、355、266nm)和以下波长的受激准分子激光器：F2(157nm)、ArF(193nm)、KrCl(222nm)、KrF(248nm)、XeCl(308nm)和XeF(351nm)。优选地，使用Nd:YAG激光器和CO2激光器，因为这些类型在非常适合应用于诱导出于标记目的所应用的热过程的波长范围内工作.
在本发明的方法中，金属图案是通过由上述步骤制备的图案化介质的无电解镀覆而提供的。无电解镀覆可以根据本领域公知以及在例如Fundamental Aspects ofElectroless Copper Plating in Electroless Plating:Fundamentals andApplication by Mallory and Hajdu,1990中所述的标准程序来进行。
实施例
在下面的实施例中，目标层包含无机颗粒(A1-A5)和有机基质(R1、R2)
A1 氧化铋Bi2O3
A2 氧化铜(Cu(I)O或Cu(II)O
A3 氧化铁Fe2O3
A4 碘化亚铜(Cu(I)I
A5 金属盐(M-乙酸盐，其中M为Pd或Cu)
R1 Neorad DSM-AGI脂肪族氨基甲酸酯丙烯酸酯，用20％DPGDA(包括)稀释。
R2 Irgacure 819光引发剂Ciba Specialty Chemicals
使用如下列材料的片材作为基本上透明的介质：
P155D DSM热塑性聚碳酸酯氨基甲酸酯
P2A06101的DSM聚醚-酯-对苯二甲酸酯
P3Xantar 18R Mitsubishi Engineering-Plastics Corporation聚碳酸酯
P4Clear G350ARKEMA聚酰胺
所有量都是重量份。
目标层(TL)的制备方法
使用IKA的Ultra Turrax匀化器，产生包含吸收剂添加剂的若干涂料层。生产TL02-TL06以及作为对比例的TL01。TL的组成在表1中给出。均化器速度为1000转/min，在室温下。
表1.激光标记添加剂
使目标层固化的方法
使用来自Byk的涂料涂布器棒以预定的层厚度将涂料涂布到玻璃基板上。随后使用UV-H灯在氮气气氛下使这些样品固化。所施加的能量为2焦耳/cm2。UV固化步骤之后，在对流烘箱中在80℃下24小时来进行热后固化。
从固化的TL向介质转移金属种子的方法
通过透明介质，使用来自Trumpf型号Vectomark Compact波长为1064nm的二极管泵浦的Nd:YAG IR激光器将图案写到涂层组合物上。目标层紧靠介质。
镀覆透明介质的方法
使用可商购的镀液(Enthone Inc)在48℃下采用表2中所描述的配方将透明介质镀覆。
表2制备镀铜液的标准配方
镀覆性能的评价
标记速度(v[mm/sec])和频率(f[kHz])在给定的功率(p[％])和焦距(z＝0[焦点对准])下变化。表3中给出了关于在塑料基板的表面上铜生长以及从优秀(+++++)到差(-----)的粘附范围的镀覆性能的评价。
镀覆性能是通过观察在激光活化区上铜的沉积量和边缘锐度来目视判断的。
通过指甲划痕测试来评定粘附性能。表3中给出了关于在塑料基板的表面上铜生长以及从优秀(+++++)到差(-----)的粘附范围的镀覆性能的评价被列于表3。
表3.镀覆性能和粘附性能
也采用适用于镀覆的LDS-MID的粘附性的定量测试方法来测定粘附强度。使用Zwick/Roell剥离试验机，来进行根据DIN 51 221第1部分的剥离试验。在20℃下进行试验。现有技术样品的粘附力低于1N/cm。
通过本发明的方法制得的样品具有高于5N/cm的粘附强度，也可以获得高于10N/cm的值。本发明还涉及包含金属图案的透明介质，其中金属图案和介质之间的粘附力为至少1N/cm，优选至少5N/cm，更优选至少10N/cm。

Claims (9)

1.一种在介质上沉积金属图案的方法，所述方法包括：
i)从脉冲激光源产生脉冲激光束，其中所述介质对于所述激光束的波长来说是透明的；
ii)首先引导所述激光束通过激光透明介质并使所述激光束聚焦到目标层上，所述目标层包含分散于可激光光降解/可燃的有机基质中的无机颗粒，所述目标层产生喷出物以响应所述激光束与所述目标层之间的相互作用；
iii)在所述介质上所需的图案内累积至少一部分所述喷出物，其在与入射激光束相反的方向上往后转移；
iv)通过无电解金属镀覆提供所述图案。
2.根据权利要求1的方法，其中，所述有机基质中所述无机颗粒的浓度为20wt％到80wt％。
3.根据权利要求1或2的方法，其中，包含无机颗粒的所述目标层是浇铸的膜。
4.根据权利要求1或2的方法，其中，所述有机基质是热固性聚合物。
5.根据权利要求3的方法，其中，所述有机基质是热固性聚合物。
6.根据权利要求4的方法，其中，基于所述有机基质的总重量，所述有机基质包含小于5wt％的芳族基团。
7.根据权利要求5的方法，其中，基于所述有机基质的总重量，所述有机基质包含小于5wt％的芳族基团。
8.通过权利要求1-7中任意一项所述的方法得到的包含金属图案的透明介质，其特征在于，在根据DIN 51221第一部分的剥离测试中在20℃下测量，所述金属图案与所述基质之间的粘附力为至少5N/cm。
9.根据权利要求8的透明介质，其特征在于，在根据DIN 51221第一部分的剥离测试中在20℃下测量，所述金属图案与所述基质之间的粘附力为至少10N/cm。
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