CN1958844B - 蚀刻非传导基材表面的方法 - Google Patents
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
本发明涉及用于在金属化前蚀刻非传导基材表面，尤其是蚀刻聚酰胺或ABS塑料表面的方法以及蚀刻溶液。根据本发明，由包括卤化物和/或硝酸盐的蚀刻溶液处理待蚀刻的表面。
Description
技术领域
本发明涉及蚀刻非传导基材表面以在金属化之前制备和提供具有粘合强度的表面的方法以及相应的蚀刻溶液。
由金属涂层进行非传导基材表面，例如塑料表面的涂覆是用于形成各种基材的表面特性的常用方法。
背景技术
表面的金属化使这一表面例如成为导电的，其广泛用于集成电路，印制电路或其它电气元件或电子元件的生产领域。此外为了装饰作用，用具有相应的光学或触觉特性的金属层涂覆表面。
首先，在基材表面电沉积或自催化沉积金属层是可能的。在电沉积之前，必须通过适当的预处理将待金属化的塑料表面制成导电的。对于金属层的自催化沉积，无需这种提供表面传导性的处理。
与所述表面的电沉积或自催化沉积无关，通常必须使这一表面粗糙化以改进金属层在基材表面上的粘着性。这可以通过机械处理或通过适当的化学处理实现，例如用溶胀剂或蚀刻剂。
对于此，由现有技术可获知不同的方法。德国专利说明书DE 10124 631公开了用酸性高锰酸盐(acid permanganate)溶液处理待涂覆的塑料表面，用于非导电性基材表面的直接电解金属化方法。
德国专利DE 197 40 431 C1公开了用于非导电表面区域的金属化方法的蚀刻方法，其中通过含过氧化氢的酸性蚀刻剂制备待涂覆的表面。除过氧化氢外，此处公开的蚀刻剂还可包括酸，如磷酸，或还可包括有机化合物如丙-2-醇或-p-苯酚磺酸。
印刷出版物DE 195 10 855公开了用含有硫酸蚀刻剂的铬酸进行待涂覆的基材表面的预处理，用于非传导材料上的选择性或部分基材电解金属化方法。选择性地，公开了作为蚀刻剂的碱性高锰酸盐溶液。
国际专利申请WO 99/13696公开了通过基于过氧化氢的浸渍或蚀刻溶液进行待金属化表面的预处理，用于包括非导电表面区域的基材金属化方法。该公开的蚀刻溶液可进一步含有磷酸，甲磺酸或乙酸，其中指出所得到的氢离子浓度最大为0.5mol/kg溶液。
德国专利申请DE100 54 544也公开了通过含有铬酸盐离子的溶液进行基材表面预处理蚀刻的方法，用于表面的化学金属化方法，尤其是丙烯腈/丁二烯/苯乙烯共聚物(ABS共聚物)和这些共聚物的混合物。该溶液主要由三氧化铬和浓硫酸组成。
所有的蚀刻方法中，分解基材表面以形成待沉积金属层所要求的粘性表面是重要的。
待涂覆的基材可以是例如塑料，如聚酯，聚醚，聚酰亚胺，聚氨酯，聚酰胺，环氧树脂，聚砜，聚醚砜，聚醚酰亚胺等。
然而，特别是对于基于聚酰胺的基材，现有技术已知用于进行表面处理的方法，如用铬酸-硫酸混合物，碱溶液或酸的蚀刻，由于这些预处理方法导致聚酰胺表面不可恢复的破坏而会引起问题。
解决这些问题的一种途径是在杂志volume 59(2005)no.4的55页及其后所公开的表面蚀刻方法，该方法使用明显减少的三氧化铬部分。目前为止，现有技术中使用的三氧化铬约为400g/l，但是此处公开的方法仅用约80g/l的三氧化铬。
但是，由于铬酸盐引起的环境问题，三氧化铬的使用是困难的。
发明内容
考虑到这一点，本发明的目的在于提供一种蚀刻非传导基材表面，尤其是聚酰胺表面的方法，用于制备和提供具有粘合强度的表面，该方法能克服现有技术已知的缺点，并产生足够的表面粗糙而不使用任何铬酸盐。此外，本发明的目的在于提供了相应的蚀刻溶液。
通过在金属化前蚀刻塑料表面的方法达到了这一目的，其特征在于使所述待蚀刻的表面与蚀刻溶液接触，该蚀刻溶液含有下组的卤化物和/或硝酸盐，该组包括Na、Mg、Al、Si、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Ca和Zn。
氯化物可有利地用作卤化物。已证明FeCl3、FeCl2、TiCl3、CuCl2、CrCl3、ZnCl2、MgCl2、CaCl2、MnCl2和CuCl2以及Cr(NO3)3是特别适合的。
此外，蚀刻溶液可有利地含有可溶性氟化物。此处，已证明通式M1(HF2)的配位氟化物化合物是特别适合的。这里，M可以是例如NH4基团。但所有其他可溶性的氟化物是同样适用的。
在根据本发明的方法中，使用含有下组卤化物和/或硝酸盐的蚀刻溶液，该组包括Na、Mg、Al、Si、Sc、Ti、V、Cr、Ca、Mn、Fe、Co、Ni、Cu和Zn，其浓度在至少0.1mol/l和溶解极限之间。在根据本发明的方法中，优选使用所含有金属盐的浓度在约0.5mol/l和约10mol/l之间的蚀刻溶液，更优选为在约2mol/l和约4mol/l之间。
根据本发明的方法中所用的蚀刻溶液可含有可溶性氟化物的浓度在约0.05mol/l和约10mol/l之间，优选为在约0.25mol/l和约3.6mol/l之间，更优选为在0.3mol/l和约1.8mol/l之间。
此外，根据本发明的方法所用的蚀刻溶液可含有酸。这里，pKs值≤5的有机和无机酸均可使用。
根据本发明的方法中，所用的蚀刻溶液可含有的酸浓度在约0.01mol/l和约10mol/l之间，优选在约0.1mol/l和约5mol/l之间，更优选在约0.5mol/l和约3.0mol/l之间。
为改善待处理基材表面的湿润性，根据本发明的方法中所用的蚀刻溶液可含有润湿剂。这里，在酸性介质中稳定的润湿剂证明是有利的。根据本发明的方法中所用的蚀刻溶液中含有的润湿剂的浓度在0.0001mol/l和约1.0mol/l之间，优选在约0.001mol/l和约0.5mol/l之间，更优选为在约0.01mol/l和约0.1mol/l之间。
可向根据本发明的方法中所用的蚀刻溶液中加入少量的贵金属或贵金属化合物。例如，为钯胶体的改进吸收，可将75ppm的Pd2+加入到该蚀刻溶液中。
根据本发明，使待蚀刻的塑料表面与该蚀刻溶液接触的时间在约0.1分钟和约20分钟之间，优选在约1.0分钟和约10分钟之间。这里，温度可在约15℃和约65℃之间的范围内，优选在约25℃和约35℃之间。
根据本发明的蚀刻溶液和蚀刻方法提供了基材表面金属化的方法，其特征在于方法步骤为：
用含有卤化物和/或硝酸盐的蚀刻剂蚀刻所述表面
使该蚀刻的表面与含有贵金属胶体的活化剂溶液或离子化的贵金属活化剂溶液接触
使活化的表面与促进剂溶液接触和
在自催化金属化浴中或直接金属化浴中金属化处理的表面。
从而，沉积在所述基材上的金属层以牢固粘附方式结合到表面上。这特别是由于使用根据本发明的蚀刻溶液由根据本发明的蚀刻方法进行有利的蚀刻处理。
具体实施方式
下面的实施例示例性说明了根据本发明的蚀刻方法以及根据本发明的蚀刻溶液，而无局限本发明于所述示例性实施方式之意。
实施例1
蚀刻溶液
500g/l FeCl3
50ml/l浓HCl
10g/l NH4HF2
5ml/l润湿剂
实施例2
蚀刻方法
将由聚酰胺(6)制成的聚酰胺注塑模制件与实施例1中所述的蚀刻溶液在50℃接触4分钟。在随后的自催化金属化之前漂洗该待金属化的注塑模制件。
实施例3
完成金属化工艺
如下处理在实施例2中所用的聚酰胺注塑模制件：
-50℃下FeCl3蚀刻剂4分钟
-漂洗
-在26℃用活化剂溶液，例如Enthone公司的Udique 879W处理2分钟
-漂洗
-在室温下将基材与促进剂溶液，例如Enthone公司的EnplateAccelerator 860接触2分钟
-漂洗
-通过例如使其在30℃在pH值9.0下与Udique NI 891接触10分钟，使处理的塑料表面镀镍
-漂洗
-进一步形成所述的层
根据本发明的蚀刻方法有利地与现有的许多ABS塑料金属化生产线兼容。它产生更均一粗糙化和晶核化的塑料表面，因此更快金属化并具有较少的缺陷，例如在自催化镀镍中。所得到的结果可很好地再重复且不要求熟悉实验室级金属化方法。此外，无需调整蚀刻步骤后的金属化中的稳定剂含量。
Claims (19)
1.在金属化前蚀刻非传导基材表面的方法，其特征在于，
使所述待蚀刻的表面与蚀刻溶液接触，该蚀刻溶液含有具有pKs值≤5的无机或有机酸、卤化物和/或硝酸盐以及作为可溶性氟化物的通式M1(HF2)的配位化合物，所述卤化物和/或硝酸盐选自FeCl3、FeCl2、TiCl3、CaCl2、CuCl2、CrCl3、ZnCl2、MgCl2、MnCl2或Cr(NO3)3，其中所述蚀刻溶液含有的卤化物和/或硝酸盐的浓度在至少0.1mol/l和溶解极限之间，所述可溶性氟化物的浓度在0.05mol/l和10mol/l之间，和所述酸的浓度在0.01mol/l和10mol/l之间，并且其中待蚀刻的基材表面与所述蚀刻溶液在15℃和65℃间的温度范围内接触，接触的时间在0.1分钟和20分钟之间。
2.根据权利要求1的方法，其特征在于所用的蚀刻溶液含有氯化铁。
3.根据权利要求1的方法，其特征在于M是NH4基团。
4.根据权利要求1的方法，其特征在于所用的蚀刻溶液含有润湿剂。
5.根据权利要求4的方法，其特征在于所用的蚀刻溶液含有的润湿剂对于酸是水解稳定的。
6.根据权利要求4或5的任一项的方法，其特征在于所用的蚀刻溶液含有润湿剂的浓度在0.0001mol/l和1.0mol/l之间。
7.根据权利要求1的方法，其特征在于基材是下组的塑料，该组包括聚酯，聚醚，聚酰亚胺，环氧树脂，聚砜或聚酰胺。
8.根据权利要求7的方法，其中塑料为聚氨酯、聚醚砜或聚醚酰亚胺中的一种。
9.塑料表面的金属化方法，其特征在于所述方法的步骤为：
-用含有如下组分的蚀刻溶液蚀刻所述表面，所述组分为具有pKs值≤5的有机或无机酸、卤化物和/或硝酸盐以及作为可溶性氟化物的通式M1(HF2)的配位化合物，所述卤化物和/或硝酸盐选自FeCl3、FeCl2、TiCl3、CaCl2、CuCl2、CrCl3、ZnCl2、MgCl2、MnCl2和Cr(NO3)3，其中所述蚀刻溶液含有的卤化物和/或硝酸盐的浓度在至少0.1mol/l和溶解极限之间，所述可溶性氟化物的浓度在0.05mol/l和10mol/l之间，和所述酸的浓度在0.01mol/l和10mol/l之间，并且其中待蚀刻的基材表面与所述蚀刻溶液在15℃和65℃间的温度范围内接触，接触的时间在0.1分钟和20分钟之间，
-使该蚀刻的表面与含有贵金属胶体的活化剂溶液或离子化的贵金属活化剂溶液接触，
-使活化的表面与促进剂溶液接触，
-在自催化金属化浴中或直接金属化浴中使处理表面金属化。
10.根据权利要求9的方法，其特征在于待金属化的塑料表面在25℃和35℃之间的温度下蚀刻。
11.根据权利要求9或10的任一项的方法，其特征在于所述的塑料表面的蚀刻时间在1.0分钟和10分钟之间。
12.根据权利要求9或10的任一项的方法，其特征在于所述的塑料表面是聚酰胺表面或ABS表面。
13.用于对待金属化的塑料表面预先处理的蚀刻溶液，其特征在于该蚀刻溶液含有下组的卤化物和/或硝酸盐，该组包括FeCl3、FeCl2、TiCl3、CaCl2、CuCl2、CrCl3、ZnCl2、MgCl2、MnCl2和Cr(NO3)3，作为可溶性氟化物的通式M1(HF2)的配位化合物，以及pKs值≤5的有机或无机酸，其中所述蚀刻溶液含有的卤化物和/或硝酸盐的浓度在至少0.1mol/l和溶解极限之间，所述可溶性氟化物的浓度在至少0.05mol/l和10mol/l之间，和所述酸的浓度在0.01mol/l和10mol/l之间。
14.根据权利要求13的蚀刻溶液，其特征在于该蚀刻溶液含有氯化亚铁作为卤化物。
15.根据权利要求13的蚀刻溶液，其中在所述可溶性氟化物的通式中的M是NH4。
16.根据权利要求13的蚀刻溶液，其特征在于该蚀刻溶液含有润湿剂。
17.根据权利要求16的蚀刻溶液，其特征在于该蚀刻溶液含有的润湿剂的浓度在0.0001mol/l和1.0mol/l之间。
18.根据权利要求16或17的任一项的蚀刻溶液，其特征在于该蚀刻溶液含有抗酸性水解的润湿剂。
19.根据权利要求13的蚀刻溶液，其特征在于该蚀刻溶液含有贵金属或贵金属化合物。
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| EP1785507B1 (en) | 2009-10-14 |
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| DE602006009746D1 (de) | 2009-11-26 |
| EP1785507A2 (en) | 2007-05-16 |
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