Grup d'Enginyeria de Materials (GEMAT), IQS-School of Engineering, Ramon Llull University , Via Augusta 390, 08017 Barcelona, Spain.
Centro de Investigación Biomédica en Red en Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN) , 50018 Zaragoza, Spain.
ACS Appl Mater Interfaces. 2017 Jan 11;9(1):1057-1065. doi: 10.1021/acsami.6b12119. Epub 2016 Dec 30.
Due to continuous miniaturization and increasing number of electrical components in electronics, copper interconnections have become critical for the design of 3D integrated circuits. However, corrosion attack on the copper metal can affect the electronic performance of the material. Superhydrophobic coatings are a commonly used strategy to prevent this undesired effect. In this work, a solventless two-steps process was developed to fabricate superhydrophobic copper surfaces using chemical vapor deposition (CVD) methods. The superhydrophobic state was achieved through the design of a hierarchical structure, combining micro-/nanoscale domains. In the first step, O- and Ar-plasma etchings were performed on the copper substrate to generate microroughness. Afterward, a conformal copolymer, 1H,1H,2H,2H-perfluorodecyl acrylate-ethylene glycol diacrylate [p(PFDA-co-EGDA)], was deposited on top of the metal via initiated CVD (iCVD) to lower the surface energy of the surface. The copolymer topography exhibited a very characteristic and unique nanoworm-like structure. The combination of the nanofeatures of the polymer with the microroughness of the copper led to achievement of the superhydrophobic state. AFM, SEM, and XPS were used to characterize the evolution in topography and chemical composition during the CVD processes. The modified copper showed water contact angles as high as 163° and hysteresis as low as 1°. The coating withstood exposure to aggressive media for extended periods of time. Tafel analysis was used to compare the corrosion rates between bare and modified copper. Results indicated that iCVD-coated copper corrodes 3 orders of magnitude slower than untreated copper. The surface modification process yielded repeatable and robust superhydrophobic coatings with remarkable anticorrosion properties.
由于电子设备中电子元件的数量不断增加和尺寸不断缩小,铜互连已成为三维集成电路设计的关键。然而,铜金属的腐蚀会影响材料的电子性能。超疏水涂层是一种常用的策略,可以防止这种不良影响。在这项工作中,采用无溶剂两步法,通过化学气相沉积(CVD)方法在铜基底上制备超疏水铜表面。通过设计微/纳尺度的分级结构,实现了超疏水状态。在第一步中,对铜基底进行 O 和 Ar 等离子体刻蚀,以产生微粗糙度。然后,通过引发 CVD(iCVD)在金属表面上沉积共聚物 1H,1H,2H,2H-全氟癸基丙烯酸酯-乙二醇二丙烯酸酯[p(PFDA-co-EGDA)],以降低表面能。该共聚物的形貌呈现出非常独特的纳米蠕虫状结构。聚合物的纳米形貌与铜的微粗糙度相结合,实现了超疏水状态。原子力显微镜(AFM)、扫描电子显微镜(SEM)和 X 射线光电子能谱(XPS)用于研究 CVD 过程中形貌和化学组成的演变。改性铜的水接触角高达 163°,滞后角低至 1°。该涂层能够在长时间内耐受腐蚀性介质的侵蚀。Tafel 分析用于比较裸铜和改性铜的腐蚀速率。结果表明,iCVD 涂层铜的腐蚀速率比未处理的铜慢 3 个数量级。表面改性工艺得到了具有优异耐腐蚀性的可重复且稳定的超疏水涂层。