CN1328196C - 用于形成嵌入式电阻器的刻蚀溶液 - Google Patents

用于形成嵌入式电阻器的刻蚀溶液 Download PDF

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CN1328196C
CN1328196C CNB038035979A CN03803597A CN1328196C CN 1328196 C CN1328196 C CN 1328196C CN B038035979 A CNB038035979 A CN B038035979A CN 03803597 A CN03803597 A CN 03803597A CN 1328196 C CN1328196 C CN 1328196C
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丹·利利
王江涛
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Abstract

一种含有硫脲的电阻刻蚀溶液,它尤其适合于刻蚀由镍-铬合金组成的电阻材料。在(a)铜表面面积与(b)镍/铬表面面积的比值较大、并且期望精细特征刻蚀的情况下,电阻刻蚀溶液允许对镍铬合金进行快速而有效地刻蚀。

Description

用于形成嵌入式电阻器的刻蚀溶液
技术领域
本发明涉及一种用于刻蚀电阻薄片上的电阻层的刻蚀溶液,具体涉及一种含有硫脲的刻蚀溶液,它尤其适合于刻蚀由镍铬合金组成的电阻层。
背景技术
随着电子部件变得更小、更轻,相关的印刷电路板(PCB)需要变得更小、更薄。为了缩小PCB的尺寸,迹线作得更细,同时还要缩小PCB上电互连的间隔。在缩小PCB尺寸方面,将无源的离散元件(例如嵌入式电阻器)集成到PCB中也很有用的。将无源离散元件的功能集成到PCB的层叠基板中可以释放出用于离散元件的PCB表面面积。由此,利用嵌入式无源元件允许在不使用较多PCB表面面积的情况下通过结合更多有源元件得到增强的部件功能。此外,将无源元件嵌入到PCB中不仅可以让电子部件进一步小型化,而且也改善了可靠性以及电性能。
制造嵌入式电阻器的一种现有技术方法已经使用了电阻薄片,电阻薄片是通过在铜薄片上淀积一层电阻性材料薄膜形成的。在形成嵌入式电阻器中,具有镍(Ni)和铬(Cr)为主要成分的金属合金(此后称为“镍铬”或“Ni/Cr”合金)一般用作形成嵌入式电阻器。这样的一种金属合金是Ni/Cr/Si/Al。形成嵌入式电阻器的过程包括:(a)将电阻薄片层叠到介电层上,(b)顺序地刻蚀电阻薄片,以形成电阻器,以及(c)将形成的电阻器埋置在多层印刷电路板内。
在上述的顺序刻蚀过程中,使用第一选择性刻蚀溶液在不侵蚀Ni/Cr合金的情况下去除不想要的铜。然后利用第二选择性刻蚀溶液在不侵蚀铜的情况下去除不想要的Ni/Cr合金。在刻蚀Ni/Cr合金时,酸性铬刻蚀溶液是优选的。
已有多个对于酸性铬刻蚀溶液的专利。例如,美国专利No.2230156描述了一种含盐酸和乙二醇的铬刻蚀溶液,其中乙二醇的碳原子比羟基多,以及美国专利No.2687345描述了一种含氯化钙和乙烯醇的铬刻蚀溶液。此外,美国专利No.4160691描述了一种含盐酸和丙三醇的铬刻蚀溶液。所有这些提到的方案都是酸性铬刻蚀溶液,它们在很少侵蚀铜或不侵蚀铜的情况下有效地去除铬。因此,现有技术的刻蚀剂可用于刻蚀Ni/Cr合金层。
人们发现,前面描述的这类溶液的刻蚀速率随着下面比率的增加而显著降低:
该比例(此后称为“CSA/RSA比率”)能达到一个抑制Ni/Cr合金刻蚀的值。此外,人们发现某些Ni/Cr合金溶液会溶解掉处理剂(包括但不限于粘合促进处理剂(例如结核状处理剂)、阻热层处理剂、防污处理剂、以及树脂防腐涂层处理剂)。这些处理剂淀积在铜表面上,用以增强电阻薄片的剥离强度和贮藏寿命。
本发明针对现有技术中的这些和其它缺陷,并提供了一种含硫脲的刻蚀溶液,用于刻蚀由镍-铬合金构成的电阻层。
发明内容
依照本发明,提供一种用于刻蚀包括镍-铬合金的电阻材料的电阻刻蚀溶液,该溶液包括盐酸和硫脲。
依照本发明的另一方面,提供一种由具有铜层和电阻层的电阻薄片形成嵌入式电阻器的方法,其中电阻薄片结合到介电层上,该方法包括:利用铜刻蚀剂,选择性地去除该铜层的若干部分,以形成迹线;以及利用由盐酸和硫脲组成的刻蚀剂,选择性地刻蚀电阻层。
依据本发明的再一个方面,提供一种用于由具有铜层和电阻层的电阻薄片形成嵌入式电阻器的方法,该电阻层包括具有铝和硅中至少之一的镍-铬合金,其中所述电阻薄片结合到介电层上,该方法包括:利用铜刻蚀剂,选择性地去除该铜层的若干部分,以形成迹线;以及利用由盐酸、丙三醇和硫脲组成的混合刻蚀剂,选择性地刻蚀包括镍-铬合金的该电阻层,其中所述丙三醇在5体积%到95体积%的范围内,所述硫脲在约1ppm到100克/升的范围内。
本发明的一个目的是提供一种用于刻蚀Ni/Cr合金的刻蚀剂。
本发明的另一目的是提供一种提高Ni/Cr合金之刻蚀速率的刻蚀剂。
本发明的又一目的是提供一种如上述的刻蚀剂,它适合刻蚀CsA/RsA比率较大的Ni/Cr合金。
通过下面结合附图优选实施例的描述以及所附的权利要求,将使这些和其它目的变得明显。
附图说明
在某些部件和部件布置上,本发明可采用物理形式,其优选实施例将在说明书中给出详细描述,以及在构成说明书一部分的附图中示出,其中:
图1是包含结合到介电层上的电阻薄片的层叠组件的剖视图;
图2是图1所示的层叠组件在经过刻蚀过程刻蚀掉电阻薄片的部分铜层之后的剖视图;
图3是图2所示的层叠组件在经过刻蚀过程刻蚀掉电阻薄片的部分电阻层之后的剖视图。
具体实施方式
现在参照附图,其所示内容仅为了说明本发明的优选实施例,而并非对本发明形成限制,图1表示通常包含结合到介电层60上的电阻薄片40的层叠组件10的剖视图。电阻薄片40包括铜层20和电阻层30。电阻薄片40通过将电阻层30淀积到铜层20上来形成。作为举例而并非限定,可利用溅射过程淀积电阻层30。电阻层30可采用多种合适的形式,包括但不局限于镍-铬合金,优选地,镍-铬合金包含镍、铬、铝和硅(Ni/Cr/Al/Si)。在优选实施例中,Ni/Cr/Al/Si合金由56wt%的镍/38wt%的铬/4wt%的铝/2wt%的硅组成。作为举例而并非限定,介电层60是含有玻璃丝织物的固化环氧树脂(传统称为“聚酯胶片”)。
采用顺序刻蚀过程形成电阻器。顺序刻蚀过程包括用于刻蚀铜层20的第一选择性刻蚀过程和用于刻蚀电阻层30的第二选择性刻蚀过程。
现有技术中的惯例是,在准备刻蚀铜的过程中,将光致抗蚀层50施加到铜层20上,在光致抗蚀层50上施加掩膜(未示出),以及根据掩膜固化光致抗蚀层50的选定部分。然后除掉掩膜,接着再除掉未固化的光致抗蚀剂。在将要通过刻蚀形成迹线的铜层20上保留固化的光致抗蚀剂。图2表示第一选择性刻蚀过程之后的层叠组件10,其中形成了迹线。在此,除掉铜层20的选定部分,以形成迹线22、24和26。
图3表示第二刻蚀过程之后的层叠组件10,其中除掉了电阻层30的选定部分。本领域普通技术人员可以理解的是,没有通过第二选择性刻蚀过程刻蚀的暴露的电阻层30的任何面积都必须用合适的光致抗蚀剂来覆盖。
按照上面所讨论的,可以发现:铜的存在、以及更具体地,要被刻蚀掉的暴露的铜表面面积之数量看起来会影响用于去除电阻材料的刻蚀溶液的性能。一个方面,电阻材料(一般是Ni/Cr合金)的刻蚀速率将随着CSA/RSA比例的增加而明显减小。已发现:该比值可达到一个完全禁止电阻层刻蚀的值。作为例子,在图2示出的实施例中,暴露的铜侧壁22a和24a的表面面积明显大于暴露的电阻材料30a的表面面积。同样,还可发现:暴露的铜侧壁24b和26b的表面面积明显大于暴露的电阻材料30b的表面面积。
还发现:使用刻蚀溶液的电阻材料的刻蚀速率也随着暴露的铜对将要刻蚀的电阻材料的逐渐靠近而减小。这样,在图2所示的例子中,随着迹线22、24和26之间的间隔减小,暴露的面积30a、30b相对暴露的铜侧壁22a、24a、24b和26b的尺寸及其相对侧壁22a、24a、24b、和26b的接近度也减小。结果,可以发现:传统刻蚀溶液的刻蚀速率减小。此外,还发现:传统的电阻刻蚀溶液会溶解铜层20上淀积的处理剂。
可以理解的是,通过在利用铜刻蚀剂去掉了不想要的铜之后不从铜层20上去除固化的光致抗蚀剂,可以减小CSA/RSA比值。因而,光致抗蚀剂覆盖着铜层20,同时利用Ni/Cr刻蚀溶液刻蚀掉电阻层30(例如Ni/Cr合金)之不想要的部分。铜层20上的固化光致抗蚀剂减小了暴露的铜的表面面积。
在高密度互联PCB情况中(其中PCB上需要更细的线和更小的间隔用于电互联),线和其间间隔的尺寸变得更小。但是,人们发现:在将要刻蚀小于大约2-6密耳的间隔时,由于铜相对电阻材料的量很大,因此很难采用传统的电阻刻蚀溶液对电阻材料进行合适的刻蚀。
依照本发明的优选实施例,提供了一种电阻刻蚀溶液,它能在高CsA/RsA比率的情况下,以及在刻蚀间隔很小、例如宽度小于约2-6密耳的情况下提高刻蚀速率。优选的刻蚀溶液尤其适合于刻蚀由镍-铬合金如Ni/Cr/Al/Si合金(举例而非限制)构成的电阻材料。
依照本发明的优选实施例,提供了一种由HCl和硫脲构成的刻蚀溶液。在优选实施例中,电阻刻蚀溶液是由HCl、丙三醇和硫脲组成的溶液。可观察到:硫脲能明显地提高镍一铬合金的刻蚀速率,尤其在高CsA/RsA比率的情况下更是如此。即便在电阻刻蚀过程中铜上没有光致抗蚀剂的情况下,在电阻刻蚀溶液中加入硫脲也可以实施合适的细微特征刻蚀(例如,在暴露面积30a、30b<6密耳的情况下刻蚀镍-铬合金电阻材料)。
优选的电阻刻蚀溶液包括:范围为5体积%到95体积%(优选约43体积%)的盐酸(按重量计37%的HCl),范围为5体积%到95体积%(优选约46体积%)的丙三醇,范围在0.1ppm到100克/升(更优选是1ppm到2ppm)的硫脲,以及足以补足100%(总体积%)的水。优选电阻刻蚀溶液的温度范围为室温(约68°F到约77°F)到大约刻蚀溶液的沸点温度(220°F附近),优选在120°F到180°F范围内,更优选在140°F到150°F范围内。优选地,通过喷射施加电阻刻蚀溶液。
现在通过以下例子进一步描述本发明,其中利用两份类似的刻蚀溶液(一份有硫脲,一份没有硫脲)刻蚀相同的电阻材料。现在参照例1和2,示出有硫脲和没有硫脲的刻蚀时间比较。
例1
刻蚀溶液:      HCl(43体积%)
                丙三醇(46体积%)
                硫脲(2ppm)
                水(11体积%)
刻蚀溶液温度:  150
铜薄片(每单位面积的重量):1 oz./ft2
电阻材料:Ni(56wt%)/Cr(38wt%)/Al(4wt%)/Si(2wt%)
电阻材料厚度:0.1μm
相邻迹线之间的间隔:2-4密耳
刻蚀时间
    无硫脲     有2ppm的硫脲
    用光致抗蚀剂     6分钟     3分钟
    不用光致抗蚀剂     未刻蚀     5分钟
例2
刻蚀溶液:    HCl(43体积%)
              丙三醇(46体积%)
              硫脲(2ppm)
              水(11体积%)
刻蚀溶液温度:150
铜薄片(每单位面积的重量):1 oz./ft2
电阻材料:Ni(56wt%)/Cr(38wt%)/Al(4wt%)/Si(2wt%)
电阻材料厚度:0.03μm
相邻迹线之间的间隔:2-4密耳
刻蚀时间
    无硫脲     有2ppm的硫脲
    用光致抗蚀剂     4分钟     2分钟
    不用光致抗蚀剂     未刻蚀     3分钟
从例1和2示出的刻蚀时间可以看出,在电阻刻蚀过程中存在光致抗蚀剂时,含硫脲的电阻刻蚀溶液具有明显较高的刻蚀速率。在此,刻蚀时间缩短了大约50%。在去除光致抗蚀剂的情况下,有硫脲的电阻刻蚀溶液促进了电阻刻蚀,而这在不含硫脲的电阻刻蚀溶液情况下是不可能的。
其它人在阅读并理解本说明书的基础上,可以作出其它改进和替换。目的在于,所有这些改进和替换都落在要求保护的本发明的范围或其等效范围。

Claims (15)

1、一种用于由具有铜层和电阻层的电阻薄片形成嵌入式电阻器的方法,该电阻层包括具有铝和硅中至少之一的镍-铬合金,其中所述电阻薄片结合到介电层上,该方法包括:
利用铜刻蚀剂,选择性地去除该铜层的若干部分,以形成迹线;以及
利用由盐酸、丙三醇和硫脲组成的混合刻蚀剂,选择性地刻蚀包括镍-铬合金的该电阻层,其中所述丙三醇在5体积%到95体积%的范围内,所述硫脲在约1ppm到100克/升的范围内。
2、根据权利要求1所述的方法,其中,将光致抗蚀剂施加到该铜层上,以限定所述迹线。
3、根据权利要求2所述的方法,其中,在选择性地刻蚀电阻层之前不除去所述光致抗蚀剂。
4、根据权利要求2所述的方法,其中,在选择性地刻蚀掉电阻层之前,除去所述光致抗蚀剂。
5、根据权利要求1所述的方法,其中,所述盐酸的范围是约43体积%。
6、根据权利要求1所述的方法,其中,所述硫脲的范围为1ppm到20ppm。
7、根据权利要求1所述的方法,其中,所述丙三醇为大约46体积%。
8、根据权利要求1所述的方法,其中,所述混合刻蚀剂还包括水。
9、根据权利要求8所述的方法,其中,所述水的量足以补足100%的总体积%。
10、根据权利要求1所述的方法,其中,所述混合刻蚀剂的温度范围为室温到大约所述混合刻蚀剂的沸点温度。
11、根据权利要求10所述的方法,其中,所述混合刻蚀剂的温度范围为120到180。
12、根据权利要求11所述的方法,其中,所述混合刻蚀剂的温度范围为140到150。
13、根据权利要求1所述的方法,其中,所述镍-铬合金包括铝和硅。
14、根据权利要求13所述的方法,其中,所述镍-铬合金由56重量%的镍、38重量%的铬、4重量%的铝和2重量%的硅制成。
15、根据权利要求1所述的方法,其中,所述硫脲在约1ppm到2ppm的范围内。
CNB038035979A 2002-02-11 2003-02-03 用于形成嵌入式电阻器的刻蚀溶液 Expired - Fee Related CN1328196C (zh)

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