盲孔镀铜加速剂分子构效关系及超填孔作用机制

Accelerators are one of the key additives in blind hole copper plating technology for printed circuit boards (PCBs). At present, the single type of accelerator, the unclear relationship between molecular structure and its effect, and the lack of surface adsorption regulation model are the problems that limit the development of superfilling by copper plating. This proposal focuses on the structure-activity relationship of accelerator molecules. Firstly, the method of group comparison is employed to determine the characteristic functional groups in accelerator molecules, reveal the structure-activity relationship of accelerator molecules, and actively expand the types and quantities of accelerators. On this basis, the surface adsorption regulation model of accelerator molecules will be established by quantum chemical calculation combined with the electrochemical test results of accelerator molecule pre-adsorption and desorption on the electrode surface, which lays a foundation for designing and synthesizing a new and efficient blind hole copper plating accelerator. Finally, the rotating ring-disk electrode (RRDE) technology is used to detect Cu+, the intermediate product during copper deposition, in order to investigate the influence of accelerators on the rate-determining step (RDS) of copper deposition. And based on it, the mechanism of accelerator molecules in the process of superfilling by copper plating can be clarified by the blind hole filling experiment. It will provide theoretical basis for the design and development of efficient blind hole copper plating formula, and promote the breakthrough development of domestic PCB hole metallization process.

加速剂是印制电路板（PCB）盲孔镀铜技术中的关键添加剂之一。目前，加速剂种类单一、分子构效关系不明确、表面吸附调控模型缺失是限制超填孔镀铜技术发展的“卡脖子”问题。本项目围绕加速剂分子构效关系展开研究，首先采用分组对比研究的方法，确定加速剂分子中的特征官能团，揭示加速剂分子的构效关系，并积极拓展加速剂种类与数量；在此基础上，通过量子化学计算结合电极表面上加速剂分子预吸附-脱附的电化学测试结果建立加速剂分子的表面吸附调控模型，为设计、合成新型高效的盲孔镀铜加速剂奠定基础；最后，利用旋转环盘电极（RRDE）技术检测铜沉积的中间产物Cu+，探究加速剂对铜沉积速度控制步骤（RDS）的影响规律，结合电镀铜填盲孔实验阐明加速剂分子在超填孔镀铜过程中的作用机制，为设计开发高效的盲孔镀铜配方提供理论依据，促进国内PCB孔金属化制程的突破式发展。

加速剂是印制电路板（PCB）盲孔镀铜技术中的关键添加剂之一。目前，加速剂种类单一、分子构效关系不明确、表面吸附调控模型缺失成为限制超填孔镀铜技术快速发展的“卡脖子”问题。基于此，本项目围绕加速剂分子构效关系展开研究。.首先，在解析目标添加剂分子组成与结构特点的基础上，将常见的可能作为加速剂的目标分子分组进行对比研究，确定了其分子中的特征官能团，如-HS、-SO3Na、-S-、-C=S等。.然后，通过量化计算、分子动力学模拟、以及系统的电化学测试，揭示目标分子在铜表面的吸附行为及其对铜沉积过程的影响规律，结果表明：-S-、-C=S以及苯环可以增强五元杂环在铜层表面的吸附能力，但只有-S-和-C=S可以增强其对铜沉积的加速作用；当烷烃链上的-HS基和五元杂环中的-S-原子数量有1个增至2个时，该有机物分子对铜沉积的加速作用显著增强，且其加速作用不再依赖Cl-。.最后，通过RRDE技术揭示目标添加剂分子对铜沉积速度控制步骤（RDS）的影响规律；以加速剂与抑制剂（整平剂）之间的相互作用为基础，结合电镀铜填盲孔实验表征出的不同添加剂体系的填盲孔效果，阐明加速剂分子的作用机制。结果表明：镀铜加速剂分子中一般同时含有两个特征官能团，其中，一个官能团可与抑制剂发生竞争吸附，促使其吸附在铜层表面，另一个官能团则可加速铜沉积过程的RDS。