CN112969819A - 电镀积层和印刷电路板 - Google Patents

电镀积层和印刷电路板 Download PDF

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CN112969819A
CN112969819A CN201980028450.2A CN201980028450A CN112969819A CN 112969819 A CN112969819 A CN 112969819A CN 201980028450 A CN201980028450 A CN 201980028450A CN 112969819 A CN112969819 A CN 112969819A
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copper
plating
build
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target
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全星郁
郑补默
朴明焕
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YMT Co Ltd
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Abstract

提供了一种电镀积层技术，用于提供印刷电路板的高粘着性内层。电镀积层技术有效地提供了含非蚀刻/低粗糙度预处理的积层或低粗糙度铜箔的无电电镀积层，以及含所述电镀积层的印刷电路板。

Description

电镀积层和印刷电路板
技术领域
本文描述的技术是关于一种用于提供印刷电路板的高粘着性内层的电镀积层技术，且更具体地是关于一种含非蚀刻/低粗糙度预处理的积层或低粗糙度铜箔的无电电镀积层，以及含所述电镀积层的印刷电路板。
背景技术
小型轻巧的电子装置以及使用更高频的电子装置的性能在电子产业中不断提升。实际上，诸如中央处理单元(CPU)和应用处理器(APs)的半导体正朝着高速和高性能发展，因此用于半导体的封装基板的线和间隔(L/S)不断变窄。
基于这些趋势，持续需要开发用于具改善粘着强度的产品的技术。代表性的技术是基于使用黑色氧化物和棕色氧化物。商用棕色氧化物产品是可从YMT获得的Brown OxidePrime Bond系列产品。这些IT系列产品用于提高与Cu粗糙度的机械结合强度，所述Cu粗糙度用黑色氧化物或棕色氧化物处理及随后的还原处理而形成，它们被称为用于IC板和高频应用的高等非蚀刻助粘剂。所述技术用于可靠的I/L粘着和阻焊层预处理，并具有许多优势，这归因于粘着力增强/非蚀刻特性而将高频信号损失降至最低，并由于机械粘着力的机制而与各类型材料具有最佳相容性。具体而言，与仅使用化学粘着促进剂相比，所述技术能够形成≤15μm的超细线，改善高频应用中的无缺陷信号性能，并实现高粘着强度。尽管具有这些优点，基于黑色氧化物或棕色氧化物的技术可能由于反应而伴随电路损失，并在还原处理不足时可能会造成残留氧化物脱附的风险。
蚀刻预处理剂作为黑色氧化物或棕色氧化物的替代物已受到关注。YMT的GMZ 20系列产品是典型的蚀刻预处理剂。这些系列产品不仅可用于封装基板，还可用于需要高可靠性的各种电子基板。然而，由于信号倾向于在常规高频基板的铜箔表面上流动，因此当铜箔表面粗糙时，信号传输可能会出现延迟。GMZ 20系列产品具有避免信号传输延迟的优点，但具有进一步需图案化以移除Cu-Sn-Ni合金的程序的缺点。
因此，需要开发一种用于粗糙度控制的技术，所述技术提供高粘着强度同时克服上述缺点。作为参照，图1以图形方式示出了(a)与积体电路相关的关联性和(b)频率与趋肤深度之间的关联性。在实施中，图1的(a)揭示了微电路蚀刻积层预处理应用的局限性，图1的(b)揭示了粗糙度在5GHz时需控制在约1μm或更小；在10GHz时需控制在约0.66μm或更小。然而，据我们所知，迄今为止，尚未记载用于严格控制蚀刻积层预处理和高频下的粗糙度应用中的限制的技术。特别地，从经济效率和市场需求的观点来看，与电镀靶材类型无关地形成特定的粗糙度将是更期望的。
[现有技术文献]
韩国专利第1108991号。
发明内容
本发明要解决的问题
本文所述的技术旨在提供一种用于克服蚀刻积层预处理应用中的限制的技术，严格控制高频下的粗糙度并形成均匀的粗糙度，而与电镀靶材类型无关。
解决问题的手段
根据本发明的一个具体实施例，提供了一种含电镀靶材和铜膜的电镀积层，铜膜具有由无电铜电镀形成在电镀靶材上的多个晶状突起。
各晶状突起可具有下部宽度大于上部宽度的形状。
各晶状突起可形成金字塔状。
晶状突起可以是具有100nm或更小的表面粗糙度Ra的铜晶体。
金属脱模层、有机脱模层、电镀铜箔或其积层可插入电镀靶材和铜膜之间。
根据本发明的另一个具体实施例，提供了一种生产电镀积层的方法，其包含：(a)在基板上设置电镀靶材，以及(b)形成具有多个晶状突起的铜膜在电镀靶材表面上。
在步骤(b)中，具有多个晶状突起的铜膜使用含尽可能少量的铜组分和含氮组分的镀液形成，铜组分能够形成铜晶种于电镀靶材表面上，含氮组分能够扩散铜晶种，以形成多个突起于电镀靶材表面上。
铜组分可在电镀靶材表面上形成铜晶种，并可与允许晶种生长的含氮组分反应。
铜组分可选自硫酸铜、氯化铜、硝酸铜、氢氧化铜和胺基磺酸铜。含氮组分可为5元或6元环状含氮化合物。
5元或6元环状含氮化合物可以是选自嘌呤化合物、哒嗪、甲基哌啶、1,2-二(2-吡啶基)乙烯、1,2-二(吡啶基)乙烯、2,2'-二吡啶胺、2,2'-联吡啶、2,2'-联嘧啶、6,6'-二甲基-2,2'-二吡啶基、二-2-吡啶酮、N,N,N',N'-四乙二胺、萘、1,8-萘啶、1,6-萘啶、四硫富烯、三吡啶、邻苯二甲酸、间苯二甲酸和2,2'-二苯甲酸中的一种或多种类型。
步骤(a)可包含用于预处理的酸脱脂、预浸和催化处理。
在步骤(b)中，铜膜优选地由无电电镀形成。
所述方法可进一步包含在步骤(b)之后的抗腐蚀处理。
根据本发明的另一个具体实施例，提供了一种含有电镀积层的印刷电路板。
发明效果
本文所述的技术有效地克服了蚀刻积层预处理应用中的限制并严格控制了高频下的粗糙度。另外，本文所述的技术有效地形成均匀的粗糙度而与电镀靶材类型无关，从而实现显著改善的经济效率和可加工性。
附图说明
图1示出了(a)与积体电路相关的关联性以及(b)频率与趋肤深度之间的关联性的图形。
图2示出了比较(c)依本发明示例性具体实施例在其上形成了无电电镀积层的超薄铜箔表面、(a)依先前技术用棕色氧化物蚀刻的铜箔表面以及(b)依先前技术用GMZ 20蚀刻积层预处理蚀刻的铜箔表面的示意图和图像。
图3示出了比较依本发明示例性具体实施例的无电电镀积层表面的图像：(a)不含含氮组分且其粗糙度得到严格控制的无电电镀积层、(b)含特定含氮组分并均匀形成其中具有0.3μm表面粗糙度Ra的突起的无电电镀积层以及(c)含特定含氮组分并均匀形成其中具有0.6μm表面粗糙度Ra的突起的无电电镀积层。
图4是依本发明示例性具体实施例经由无电铜电镀形成在电镀积层的电镀靶材上的具有多个晶状突起的铜膜表面图像。
图5示出了依本发明示例性具体实施例的无电电镀积层的表面粗糙度与经由常规化学铜电镀所生产的无电电镀积层的表面粗糙度的比较图像。
图6示出了依本发明示例性具体实施例的电镀靶材的均匀粗糙度和粘着强度的图像。
附图标记：无
具体实施方式
由于本文所述技术允许各种改变和众多具体实施例，因此将在附图中示出并在书面描述中详细描述特定实施例。然而，这并不旨限制本发明为特定的实施模式，且应当理解的是，在不脱离本发明的精神和技术范围的所有改变、等同物和替代物均涵盖在本发明中。
本文所述技术克服了蚀刻积层预处理应用中的限制，严格控制了高频下的粗糙度，并形成了均匀的粗糙度，而与电镀靶材的类型无关，实现了本领域的需求以克服用于所需微电路的蚀刻积层预处理应用中的限制，严格控制粗糙度以响应高频，且无论电镀靶材的类型尽可能均匀地形成粗糙度。
图2比较了(c)依本发明示例性具体实施例在其上形成无电电镀积层的超薄铜箔表面、依先前技术用棕色氧化物(Prime bond，YMT)蚀刻的铜箔表面以及(b)依先前技术用GMZ 20系列产品(可从YMT获得)经由在30℃下蚀刻积层预处理1分钟来蚀刻铜箔表面。
在图2中，(a)示出了用棕色氧化物蚀刻的超薄铜箔表面。经由用棕色氧化物处理和随后的还原处理形成的铜粗糙度导致机械结合强度的提高。然而，由于与棕色氧化物的反应，使用棕色氧化物会导致电路还原，并且当还原处理不充分时，存在残留氧化物脱附的风险。
在图2中，(b)示出了用GMZ 20系列产品(可从YMT获得)经由蚀刻积层预处理而蚀刻的超薄铜箔表面。Cu-Sn-Ni合金的形成和随后的防腐蚀处理(用硅烷的防锈蚀处理)导致化学键结强度提高。但是，在化学键结强度提高后，应进行额外的图案化后处理以移除Cu-Sn-Ni合金。
相反的，图2的(c)示出了依本发明示例性具体实施例在其上形成无电电镀积层(正纳米粗糙度)的超薄铜箔表面。除非另有说明，否则本文所用的术语“无电电镀积层(正纳米粗糙度)”是指其中多个晶状突起不规则且连续地排列在电镀靶材上的铜膜形状。术语“多个晶状突起”是指未成形的金字塔状突起。在此，金字塔包含但不限于三角锥、四角锥、五角锥、六角锥和圆锥。在此图中，晶状突起具有下部宽度大于上部宽度的形状，但不限于此结构和排列。如有需要，至少两个金字塔的组合是可能的。如本文所用，除非另外指明，否则术语“粗糙度”是指由表面粗糙度Ra测定的值。优选地将粗糙度Ra控制在1.00μm或以下、0.66μm或以下或者0.30μm或以下，这满足了严格控制高频所需的粗糙度的需要。粗糙度的下限无特别限制，但控制在0.01μm或以上、0.05μm或以上或者0.10μm或以上，考虑到粘着强度应高于预定程度是优选的。
电镀靶材可选自本领域已知的金属箔，如电沉积的铜箔、轧辊退火(RA、HA)的铜箔和铝箔。特别地，电镀靶材可以是选自电沉积(ED)铜箔和轧辊退火(RA，HA)铜箔中的一种或多种类型。
将给出关于形成无电电镀积层(正纳米粗糙度)的详细描述，这是本发明的独特技术特征。参照图2的(c)，在铜箔表面上形成镀层。镀层具有正纳米粗糙度(形状)，其对应于上述多个晶状突起。晶状突起从其突出的表面不同于用棕色氧化物蚀刻的表面(图2的(a))和经由蚀刻积层预处理蚀刻的表面(图2的(b))。
图2的(c)中所使用的镀槽包含镀液，所述镀液的组成包含五水合硫酸铜和能够与五水合硫酸铜反应的5元或6元环状含氮组分。经由将作为靶材的载体铜箔(18μm)沉积在镀液中生产无电电镀积层。每1μm靶材施加34℃的沉积温度和15分钟的沉积时间。
无电电镀积层经由比较形成多个突起之前和之后的表面图像而更清晰地研究(图3)。具体地，图3示出了比较形成多个突起之前和之后依本发明示例性具体实施例的无电电镀积层表面的图像。作为参照，图3的(a)、(b)和(c)分别示出了形成多个突起之前、多个突起部分生长之后直至达到0.3μm的表面粗糙度Ra以及多个突起生长之后达到0.6μm的较大表面粗糙度Ra的无电电镀积层。作为参照，在图3的(a)中使用了含五水合硫酸铜的镀槽。稍后将描述镀槽的具体组成。五水合硫酸铜的用量应使铜离子浓度至少为0.5g/L。图3的(b)和(c)中使用的镀槽还包含0.01ppm至1000ppm的至少一种能够与铜组分反应的含氮组分。含氮组分选自嘌呤化合物(包含嘌呤、腺嘌呤、鸟嘌呤、次黄嘌呤和黄嘌呤)、哒嗪、甲基哌啶、1,2-二(2-吡啶基)乙烯、1,2-二(吡啶基)乙烯、2,2'-二吡啶胺、2,2'-联吡啶、2,2'-联嘧啶、6,6'-二甲基-2,2'-二吡啶基、二-2-吡啶酮、N,N,N',N'-四乙二胺、萘、1,8-萘啶、1,6-萘啶、四硫富烯、三吡啶、邻苯二甲酸、间苯二甲酸和2,2'-二苯甲酸。图3的(b)示出了每0.3μm的靶材在34℃下沉积5分钟之后获得的结果，图3的(c)示出了每0.6μm的靶材在34℃下沉积10分钟之后获得的结果。
图4是依本发明示例性具体实施例经由无电铜电镀在电镀积层的电镀靶材上形成具有多个晶状突起的铜膜表面图像。所述图像显示可严格控制粗糙度，即可将粗糙度控制为均匀值。
每个晶状突起可形成未成形的金字塔状。例如，晶状突起可以是未成形的三角锥、四角锥、五角锥、六角锥和圆锥的各种组合。晶状突起可具有下部宽度大于上部宽度的形状。由于它们的形状，晶状突起提供了改进的粘着强度。可对突起的形状和排列进行各种修改。
金属脱模层、有机脱模层、电镀铜箔或其一种或多种的组合可插入铜膜和电镀靶材之间。如有需要，可在脱模层上使用化学铜箔积层。在此，脱模层可包含氧化硅膜、氮化硅膜、氟膜、黑色素或丙烯酸烷基酯。
可在铜膜上进一步设置一种或多种选自预浸体、粘着剂和接合片的绝缘体。
图5示出了依本发明示例性具体实施例的无电电镀积层的表面粗糙度与经由常规化学铜电镀生产的电镀积层的表面粗糙度的比较图。作为参照，图5示出了用电镀组合物处理PET树脂以排除Cu基的粗糙度之后测得的粗糙度。镀层的组成和条件与图3所示的相同。在相同厚度下观察到粗糙度的显著差异。
经由与图3所示的相同条件下用相同电镀组合物处理，使用不同电镀靶材制造依本发明示例性具体实施例的无电电镀积层。无电电镀积层具有均匀的粗糙度和粘着强度。结果如图6所示。
如上所述，依本发明一个具体实施例的用于在基板表面上形成无电电镀积层的技术与常规的预处理蚀刻技术不同，所述常规的预处理蚀刻技术用可从YMT获得的GMZ 20系列产品或可从YMT获得的Brown Oxide Prime Bond系列产品(图2)和图5所示的铜电镀技术。图2示意性示出形成无电电镀积层结构需要使用含尽可能少量的铜组分和含氮组分的镀液，铜组分能够形成铜晶种于电镀靶材表面上，含氮组分能够扩散铜晶种以形成无电电镀积层结构。
铜组分优选地选自能够在铜箔表面上形成铜晶种并与允许晶种生长的含氮组分反应的组分。
铜组分(例如选自五水合硫酸铜、氯化铜、硝酸铜、氢氧化铜和胺基磺酸铜的铜盐组分)与含氮组分(例如5元或6元环状含氮化合物)的组合是优选的，因为在不影响原料铜箔的情况下，可最大化提供所需的无电电镀积层的效果。
例如，五元或六元环状含氮组分可选自嘌呤化合物、哒嗪、甲基哌啶、1,2-二(2-吡啶基)乙烯、1,2-二(吡啶基)乙烯、2,2'-二吡啶胺、2,2'-联吡啶、2,2'-联嘧啶、6,6'-二甲基-2,2'-二吡啶基、二-2-吡啶酮、N,N,N',N'-四乙二胺、萘、1,8-萘啶、1,6-萘啶、四硫富烯、三吡啶、邻苯二甲酸、间苯二甲酸、2,2'-二苯甲酸及其组合。
用于提供无电电镀积层的电镀组合物可包含铜盐组分的量，使得铜离子浓度为至少0.5g/L，优选是1g/L至30g/L，更优选是1g/L至20g/L。考虑到用于生长形成在铜箔表面上的铜晶种的反应效率，如有需要，期望以适当的分批添加铜盐组分或在整个反应过程中连续添加铜盐组分。
与铜盐组分组合使用的5或6元环状含氮组分在组合物中的存在量可为0.01ppm至1000ppm，优选是0.05ppm至10ppm。
如有需要，用于提供无电电镀积层的电镀组合物可包含一种或多种螯合剂。可用的螯合剂实例包含有机酸(例如羧酸)及其盐，但不限于此。这样的羧酸包含但不限于酒石酸、柠檬酸、乙酸、苹果酸、丙二酸、抗坏血酸、草酸、乳酸、琥珀酸及其盐。盐包含有机酸的碱金属盐(如酒石酸钾钠)和罗雪盐(含酒石酸二钾)。螯合剂还可包含一种或多种选自乙内酰脲、乙内酰脲衍生物，例如1-甲基乙内酰脲、1,3-二甲基乙内酰脲和5,5-二甲基乙内酰脲、氮基三乙酸及其碱金属盐、三乙醇胺、乙二胺四乙酸(EDTA)及其碱金属盐，例如乙二胺四乙酸四钠、改质乙二胺四乙酸，例如N-羟基乙二胺三乙酸盐、羟烷基取代的二碱三胺，例如五羟基丙基二乙三胺，以及其他化合物，例如N,N-二羧甲基L-谷胺酸四钠盐、S,S-乙二胺二琥珀酸和N,N,N',N'-四(2-羟丙基)乙二胺(乙二腈)四-2-丙醇的化合物。
优选地，螯合剂选自罗雪盐、酒石酸二钾及其混合物。螯合剂可以至少0.5g/L，优选是1g/L至150g/L，更优选是10g/L至100g/L，最优选是15g/L至50g/L的总量存在于组合物中。
如有需要，用于提供无电电镀积层的电镀组合物可包含一种或多种pH调节剂。pH调节剂用于将碱组合物的pH调节至期望的pH范围，并且可以是本领域已知的化合物。碱性化合物的实例包含但不限于碱金属氢氧化物，如氢氧化钠、氢氧化钾和氢氧化锂。通常使用氢氧化钠、氢氧化钾或其混合物。碱性化合物可存在于总量中提供8或更大的pH范围，优选是10至14，更优选是11至13.5。
如有需要，用于提供无电电镀积层的电镀组合物可包含一种或多种还原剂。一般的还原材料如甲醛可用作还原剂。还原剂的其他实例包含但不限于次磷酸盐如碱金属次磷酸盐(例如，次磷酸钠)和亚磺酸盐化合物如羟甲亚磺酸钠。还原剂还可包含乙醛酸、甲醛、硼氢化盐和二甲基胺硼烷。这样的一般还原剂存在量优选为1g/L或以上，更优选是5g/L至20g/L。所述组合物不含乙醛酸和对环境有害的还原剂。更优选地，所述组合物不含对环境有害的还原剂如甲醛、氢化硼和二甲胺硼烷(DMAB)。
如有需要，可使用酸脱脂和预浸进行预处理。酸脱脂可以是用于铜箔的常规脱脂方法。清洁剂如硫酸和有机酸可用于酸脱脂，其实例包含可得自YMT的SAC-302和SAC-615系列产品。经由用浓度为100ml/L的清洁剂在45℃至55℃下处理4至6分钟，而适当地进行酸脱脂。酸脱脂条件可依使用环境和设备条件而异。
然后，优选地进行0.1至0.2μm的软蚀刻。所述过程是在Cu基表面上形成轻微的粗糙度，从而经由随后的催化过程促进Pd的吸附。用于软蚀刻的组合物可以是可从YMT获得的SE 500系列产品和硫酸溶液的混合物。经由用200ml/L浓度的SE 500系列产品和30ml/L浓度的硫酸(95％)在25℃至35℃下处理1至2分钟来适当地进行软蚀刻。软蚀刻条件可依使用环境和设备条件而异。
然后，预浸软蚀刻的铜表面。进行预浸以防止随后被催化剂溶液污染并更有效地吸附Pd。优选地经由用约90ml/L的硫酸(61.5％)处理20-40秒来进行预浸。预浸条件可依使用环境和设备条件而异。
然后，使用在钯吸附效率方面有利的催化剂溶液进行催化过程。例如，来自YMT的Cata 855系列产品适当地用作离子钯催化剂。在30℃至35℃下用30ml/L Cata 855和90ml/L硫酸(61.5％)处理2至5分钟，可使钯吸附在Cu表面上。催化过程条件可依使用环境和设备条件而异。
之后，使用本发明的非蚀刻粗糙度组合物在铜箔表面上进行无电电镀。常规的电镀时间和温度条件可应用于无电电镀。通常，铜可在20-60℃或30-40℃的温度下沉积。为此，可将铜箔浸入或喷涂非蚀刻粗糙度组合物。通常，无电电镀可进行2至30分钟或5至20分钟，但电镀时间也可依所需的金属厚度而异。电镀优选是在碱性环境中进行，以使基板上的金属覆层不被腐蚀。
本发明的方法还可用于提高透光性树脂如干膜、阻焊剂、粘着剂或聚合材料如聚合的抗腐蚀剂对通过积体电路和严格的粗糙度控制而提供的无电电镀积层表面的粘着强度。例如，可使用本发明的非蚀刻粗糙度组合物在基板表面上形成具有正纳米形状的均匀粗糙度，以增强干膜的粘着性。作为另一个实例，可使用本发明的非蚀刻粗糙度组合物在印刷电路板表面上形成具有正纳米形状的均匀粗糙度，以在施加阻焊剂之前增强阻焊剂的粘着性。
根据一个实施例，与先前开发的技术不同，本发明消除了形成黑色或棕色氧化铜层的需要。尽管在本发明中由于用少量S/E进行处理而可能引起轻微的电路损耗，但由于电镀反应导致的厚度增加可充分补偿所述电路损耗。
例如，可使用包含一种或多种铜离子源和一种或多种螯合剂的电镀溶液在铜箔表面上生产无电电镀积层。
组合物也可经由将上述组分在水溶液中，优选是在去离子水溶液中混合来制备。组合物的组分可任选地混合。组合物足够稳定，在储存和铜沉积期间不会形成氧化铜。组合物通常满足商业上可接受的无电电镀铜浴所需的工业标准，并以商业上可接受的速率用于电镀铜箔。
本发明的无电电镀积层以高频测量时具有例如为1μm或更小，优选为0.66μm或更小，更优选为0.3μm或更小的表面粗糙度Ra。作为参照，对于5GHz的频率需要1μm或更小的粗糙度，而对于10GHz的频率需要0.66μm或更小的粗糙度。
在其上形成无电电镀积层的表面来自可聚合材料(如聚酰亚胺膜)或积层在涂覆表面上的预浸层可具有至少1.00kgf/cm或以上，特别是来自电沉积铜(ED Cu)箔(参见图6)可具有1.17kgf/cm或以上的剥离强度。
根据本发明的另一个具体实施例，提供了一种生产电镀积层的方法，包含：(a)在基板上设置电镀靶材；以及(b)形成具有多个晶状突起的铜膜于电镀靶材表面上。
在步骤(b)中，使用含尽可能少量的铜组分和含氮组分的镀液形成具有多个晶状突起的铜膜，铜组分能够形成铜晶种于电镀靶材表面上，含氮组分能够扩散铜晶种，以形成多个突起于电镀靶材表面上。
铜组分可在电镀靶材表面上形成铜晶种，并可与允许晶种生长的含氮组分反应。
铜组分可选自硫酸铜、氯化铜、硝酸铜、氢氧化铜和胺基磺酸铜。含氮组分可为5元或6元环状含氮化合物。
5元或6元环状含氮化合物可以是选自嘌呤化合物(包含嘌呤、腺嘌呤、鸟嘌呤、次黄嘌呤和黄嘌呤)、哒嗪、甲基哌啶、1,2-二(2-吡啶基)乙烯、1,2-二(吡啶基)乙烯、2,2'-二吡啶胺、2,2'-联吡啶、2,2'-联嘧啶、6,6'-二甲基-2,2'-二吡啶基、二-2-吡啶酮、N,N,N',N'-四乙二胺、萘、1,8-萘啶、1,6-萘啶、四硫富烯、三吡啶、邻苯二甲酸、间苯二甲酸和2,2'-二苯甲酸中的一种或多种类型。
铜组分可使铜离子浓度为至少0.5g/L的量存在于镀槽中。
五元或六元环状含氮组分可以0.01ppm至1000ppm的量存在于镀槽中。
步骤(a)可包含用于预处理的清洁、酸脱脂、预浸和活化。
在步骤(b)中，铜晶种优选地由无电电镀形成。
所述方法可进一步包含在步骤(b)之后的防腐处理。
根据本发明的另一个具体实施例，提供了一种含电镀积层的印刷电路板。
用于提供印刷电路板的高粘着性内层的电镀积层技术有效地提供了含非蚀刻/低粗糙度预处理的积层或低粗糙度铜箔的无电电镀积层，以及含所述电镀积层的印刷电路板。本说明书和所附附图仅示出了包含于上述技术中的一些技术思想，并且本领域技术人员可轻易地理解各种修改而不会脱离本文所述技术的说明书和附图中的技术思想范围。

Claims (15)

1.一种电镀积层，其特征在于，包含电镀靶材和铜膜，所述铜膜具有由无电铜电镀在所述电镀靶材上形成的多个晶状突起。
2.根据权利要求1所述的电镀积层，其特征在于，各所述晶状突起具有下部宽度大于上部宽度的形状。
3.根据权利要求1所述的电镀积层，其特征在于，各所述晶状突起形成金字塔状。
4.根据权利要求1所述的电镀积层，其特征在于，所述晶状突起是具有100nm或更小的表面粗糙度Ra的铜晶体。
5.根据权利要求1所述的电镀积层，其特征在于，金属脱模层、有机脱模层、电镀铜箔或其积层插入所述电镀靶材和所述铜膜之间。
6.根据权利要求1所述的电镀积层，其特征在于，一个或多个绝缘体进一步设置在所述铜膜上。
7.一种生产电镀积层的方法，其特征在于，包含(a)在基板上设置电镀靶材，以及(b)形成具有多个晶状突起的铜膜在所述电镀靶材表面上。
8.根据权利要求7所述的方法，其特征在于，在步骤(b)中，具有多个晶状突起的所述铜膜使用含尽可能少量的铜组分和含氮组分的镀液形成，所述铜组分能够形成铜晶种于所述电镀靶材表面上，所述含氮组分能够扩散所述铜晶种以形成多个突起于所述电镀靶材表面上。
9.根据权利要求8所述的方法，其特征在于，所述铜组分形成铜晶种在所述电镀靶材表面上，并与允许所述晶种生长的所述含氮组分反应。
10.根据权利要求9所述的方法，其特征在于，所述铜组分选自硫酸铜、氯化铜、硝酸铜、氢氧化铜和胺基磺酸铜，且所述含氮组分为5元或6元环状含氮化合物。
11.根据权利要求10所述的方法，其特征在于，所述5元或6元环状含氮化合物是选自嘌呤化合物、哒嗪、甲基哌啶、1,2-二(2-吡啶基)乙烯、1,2-二(吡啶基)乙烯、2,2'-二吡啶胺、2,2'-联吡啶、2,2'-联嘧啶、6,6'-二甲基-2,2'-二吡啶基、二-2-吡啶酮、N,N,N',N'-四乙二胺、萘、1,8-萘啶、1,6-萘啶、四硫富烯、三吡啶、邻苯二甲酸、间苯二甲酸和2,2'-二苯甲酸中的一种或多种类型。
12.根据权利要求7所述的方法，其特征在于，步骤(a)包含用于预处理的酸脱脂、预浸和催化处理。
13.根据权利要求7所述的方法，其特征在于，在步骤(b)中，所述铜膜由无电电镀形成。
14.根据权利要求7所述的方法，其特征在于，还包含在步骤(b)之后的抗腐蚀处理。
15.一种印刷电路板，其特征在于，包含根据权利要求1至6中任一项所述的电镀积层。
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