目的 研究印制电路板生产超粗化工艺中2-氨基苯并咪唑（2-AB）作为缓蚀剂对铜基材与环氧树脂界面结合力的提升效果及其机理分析。方法 采用失重法、喷淋法、真空热压法制备了铜-树脂压合物。通过剥离测试检验结合强度提升效果。通过扫描电子显微镜（SEM）、原子力显微镜（AFM）和背散射电子衍射（EBSD）等方法,从表面特征形貌、粗糙度、选择性腐蚀等角度解析界面结合力增强的微观机制。通过动电位极化测试和阻抗谱测试（EIS）验证缓蚀剂在酸性铜离子溶液中的有效性,研究了其缓蚀机理。结果 缓蚀剂的加入能够降低蚀刻液的腐蚀速率。2-AB的存在有助于在铜表面形成可提升结合力的表面结构,增大铜与树脂的接触面积,显著提升铜-树脂的结合强度。在2-AB的影响下,铜-树脂的结合强度相较于2-AB类似物1-氨基苯并三唑影响下的铜-树脂结合强度提升了2倍以上。铜表面有助于提升结合力的结构,是在2-AB影响下通过选择性保护来实现的。2-AB通过不完整的吸附层实现了表面粗化的目的。结论 2-AB作为超粗化过程中的缓蚀剂,可以显著提升铜-树脂之间的结合强度。
Abstract
2-Aminobenzimidazole (2-AB) is primarily utilized in agriculture and medicine for its bactericidal, anti-inflammatory, and anticancer properties, and it is generally not classified as an environmentally hazardous or toxic substance. Research on 2-AB in corrosion inhibition remains scarce, and its application in super-roughening processes has yet to be explored. This study investigates the enhancement effect and underlying mechanism of 2-AB as a corrosion inhibitor on the interfacial adhesion between copper substrates and epoxy resin during the super-roughening process in printed circuit board (PCB) manufacturing.
Copper-resin composites are prepared using weight loss measurements, spray etching, and vacuum hot pressing. Weight loss tests are conducted to quantify the corrosion efficiency of etching solutions containing varying 2-AB concentrations. A spray method is applied to produce uniformly etched copper foils for surface characterization and subsequent vacuum hot pressing, while vacuum hot pressing ensured homogeneous bonding between copper and resin. Pull-off strength tests are conducted according to IPC (Association Connecting Electronics Industries) standards with three valid samples per group, to directly evaluate adhesion improvement—a critical metric for super-roughening efficacy. The micro-mechanisms of adhesion enhancement are analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), and electron back scatter diffraction (EBSD), focusing on surface morphology, roughness, and selective corrosion behaviors. Potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS) tests further validate 2-AB's corrosion inhibition effectiveness and mechanisms in acidic cupric solutions.
Weight loss tests revealed that the addition of corrosion inhibitors reduces the corrosion rate of the etching solution, with 1-aminobenzotriazole, a structural analog of 2-AB, exhibiting higher corrosion inhibition efficiency. Notably, this work directly evaluates the adhesion enhancement effect of corrosion inhibitors through pull-off strength testing, a methodology rarely reported in existing literature. Pull-off strength tests demonstrate that under 2-AB treatment, the copper-resin adhesion reaches a maximum of 14 kN/m, more than doubling the adhesion strength achieved with its analog 1-aminobenzotriazole. This indicates that corrosion inhibition efficiency alone is insufficient to predict adhesion enhancement. SEM analysis shows that 2-AB promotes the formation of surface structures on copper that favor adhesion, significantly increasing the contact area between copper and resin. EBSD results further reveal that the Cu (001) crystallographic plane dominates the surface of these adhesion-enhancing structures, with its proportion substantially higher than other crystallographic orientations. This suggests that the formation of adhesion-promoting structures relies on selective protection induced by 2-AB. Potentiodynamic polarization and EIS tests demonstrate that the corrosion inhibitor exhibits suppression effects on metal corrosion when the self-corrosion current density decreases, charge transfer resistance decreases, and double-layer capacitance simultaneously reduce. However, the microscopic defects in the adsorption layer prevent the inhibitor from forming a complete coverage on the metal surface, resulting in preferential adsorption on localized region. This incomplete coverage accelerates localized corrosion in unprotected areas, thereby increasing surface roughness. The enhanced roughness promotes mechanical interlocking at the Cu-resin interface, ultimately improving the adhesion strength.
This study proposes that 2-AB, as a corrosion inhibitor in the super-roughening process, can significantly enhance the interfacial adhesion between copper and resin. In terms of adhesion enhancement, under the action of a single corrosion inhibitor, an adhesion strength of 14 kN/m is achieved. From the perspective of surface morphology, 2-AB modifies the copper surface to form a robust structural foundation that supports the improved copper-resin interfacial adhesion. Regarding practical applications, 2-AB exhibits excellent chemical stability. More importantly, the etching rate of the solution containing 2-AB remains largely unaffected, enabling rapid surface modification within a shorter time frame, thereby demonstrating high suitability for industrial-scale production. From an environmental and economic standpoint, 2-AB offers notable cost-effectiveness and environmental friendliness, further enhancing its industrial applicability.
关键词
2-氨基苯并咪唑 /
铜 /
表面结合力 /
缓蚀剂 /
超粗化 /
表面改性
Key words
2-Aminobenzimidazole /
copper /
surface adhesion strength /
corrosion inhibitor /
super roughening /
surface modification
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