铜沉积/溶解中特性吸附离子与添加剂/缓蚀剂间交互作用机制

Typical electrodeposition and corrosion systems of copper foil are selected as the research objects due to their great importance. Kinetics of copper/electrolyte interface reactions as well as the acting mechanisms of additives for electrodeposition and inhibitor for corrosion will be investigated, particularly focusing on the interactions (competitive or synergistic effect) among specific adsorbed anions and additives/inhibitors. In experimental research, the in-situ surface detection techniques, such as electrochemical scanning atomic force microscopy (ECAFM), scanning tunnel microscopy (ECSTM), Raman spectroscopy, and self-developed scanning micro-probe systems will be introduced to examine the effects of anion specific adsorption on double electric layer structure at metal/electrolyte interface through influencing the ad/desorption of additives/inhibitors or the surface film formation. The interfacial kinetic processes of copper foil electrodeposition and copper foil corrosion, together with the impact factors will be thoroughly explored to determine the controlling step and kinetic properties under different specific adsorbed anions and additives/inhibitors conditions. As the results, the existing models and mechanisms will be complemented and amended. In this work, electrochemical essence of metal deposition/corrosion processes was particularly emphasized. With the combination of experimental tests and numerical modeling studies, the intrinsic relation lies in metal deposition and corrosion (dissolution) processes is supposed to be revealed. The present fundamental study is establishing the theoretical groundwork for the development of novel additives and inhibitors and the other relevant application researches.

申请人希望在十余年界面反应动力学研究的基础上，选取电解铜箔制备及其腐蚀体系为研究落脚点，解析界面反应动力学过程及典型添加剂、缓蚀剂的作用机理，重点剖析微量存在的特性吸附离子与添加剂、缓蚀剂间或竞争、或协同的影响机制。本课题强调原位观测技术的引入，其中包括电化学原位扫描探针显微技术、电化学原位拉曼光谱技术及自制扫描微电极技术的应用，多角度聚焦特性吸附离子对添加剂、缓蚀剂吸/脱附及表面膜形成等界面双电层微观结构变化的影响，重视金属电沉积与腐蚀溶解过程的电化学本质。研究中，将试验与数字建模仿真相结合，力求贯通金属电沉积与腐蚀溶解过程间的内在联系，更深入解读电沉积铜箔及铜箔腐蚀的动力学过程及界面过程影响因素，确定不同特性吸附离子与添加剂/缓蚀剂条件下的控制性环节和相关动力学特性，对现有模型、机理进行补充与修正。本课题的研究将为新型添加剂和缓蚀剂的开发及相关应用研究奠定理论基础。

项目实现了离线分析与原位表征相结合、数值模拟与实验研究互为深入、相互印证，打通了金属沉积与溶解过程间的内在联系，揭示了Cl-与相关添加剂/缓蚀剂间的交互作用机制。主要成果包括：.在电解铜箔常用添加剂体系（GE、PEG、BTAH、SPS等）中，利用先进表征手段结合测试技术，捕捉特性吸附离子（Cl-）对添加剂在电极表面吸/脱附过程的影响，剖析Cl-与添加剂协同与竞争作用的界面动力学机制。结合对铜电沉积层性能的综合表征分析，分别在以GE和BTAH为添加剂的电沉积体系中，明确了添加剂成分与浓度、是否含Cl-、液相传质、温度、电流密度等条件对电沉积层形核生长机制的影响，及对沉积层晶体取向、晶粒平均尺寸与生长状态、内应力等的影响规律，完善了上述单一添加剂的作用机理；并利用电化学原子力显微镜、表面增强拉曼光谱等手段，原位观察了复合添加剂体系（PEG+SPS+Cl-）中电极表面上添加剂的竞争吸附及其经时变化关系，利用Matlab编程模拟了其电沉积动力学过程，拟合实验极化曲线，确定了相关动力学参数。.电沉积及腐蚀溶解是互为相反方向的电化学进程。除单独研究缓蚀剂在是否含Cl-环境下缓蚀效果差异之外，进一步研究了BTAH（含或不含Cl-）镀液中获得的沉积层在含/不含Cl-的腐蚀性环境中的耐蚀性差异，并结合前面电沉积中BTAH作用机制探讨了耐蚀性差异的内在原因；同时，针对GE+Cl-和PEG+Cl-体系，明确了添加剂成分、浓度对铜箔耐蚀性能的影响。此外，通过第一性原理计算明确了不同表面状态下Cl-对金属表面的侵蚀作用；基于Comsol二次开发模拟研究了含Cl-环境下金属表面异质性所引起的微观电偶腐蚀效应，研究第二相与基体在Cl-环境中的电化学行为差异、及其尺寸与分布情况对电偶腐蚀的影响，加深了对微区腐蚀电化学机理的理解；金属/溶液界面区内pH原位检测有助于深入了解金属沉积与腐蚀动力学，因而自制了pH监检测微型铱氧化物电极，并尝试用于腐蚀界面测量中，经适当修饰处理后该pH电极可用于含S2-等强还原性介质中的pH测定，为本项目的后续深入研究奠定了基础。