Kim S-H, Braun T M, Lee H-J, Moffat T P, Josell D
Department of Materials Science and Engineering, Dong-A University, Saha-Gu, Busan 49315 Korea.
Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 USA.
J Electrochem Soc. 2022;169(3). doi: 10.1149/1945-7111/ac5ad8.
The microstructure and crystallographic texture of copper electrodeposits in millimeter scale through silicon vias are characterized using electron backscatter diffraction. The deposits obtained from additive-containing CuSO-HSO electrolytes are characteristic of the superconformal deposition process, with growth textures and columnar grains consistent with previous findings in smaller TSV. The microstructure, like the filling evolution it records, changes substantially with chloride concentration for the concentrations of polymer suppressor used. With chloride concentrations of 80 μmol·L and less, columnar grains of Cu capture the linear motion of the local growth front during filling with a strong <110> orientation along the elongated grain axes typical of deposition in chloride-containing Cu electrolytes. In the mid- and upper- via locations these columnar grains are angled upward from the sidewalls toward the center of the v-shaped growth front. In a limited region adjacent to the via bottom they extend vertically from the bottom surface. With millimolar chloride concentration, deposition also exhibits columnar grains with preferred <110> growth orientation in the lower region of the via and adjacent to the sidewalls. However, separation of the central deposit from the sidewalls results in a convex geometry of the growth front and spatially varying texture in most of the deposit.
通过电子背散射衍射对毫米尺度硅通孔中的铜电沉积物的微观结构和晶体织构进行了表征。从含添加剂的CuSO-HSO电解质中获得的沉积物具有超共形沉积过程的特征,其生长织构和柱状晶粒与先前在较小通孔中的发现一致。微观结构,就像它所记录的填充演变一样,对于所使用的聚合物抑制剂浓度,会随着氯化物浓度的变化而发生显著变化。当氯化物浓度为80 μmol·L及以下时,铜的柱状晶粒在填充过程中捕获局部生长前沿的线性运动,沿着含氯铜电解质中典型沉积的细长晶粒轴具有强烈的<110>取向。在通孔的中部和上部位置,这些柱状晶粒从侧壁向上倾斜朝向v形生长前沿的中心。在与通孔底部相邻的有限区域中,它们从底部表面垂直延伸。当氯化物浓度为毫摩尔级时,在通孔下部区域和靠近侧壁处的沉积也呈现出具有优选<110>生长取向的柱状晶粒。然而,中心沉积物与侧壁的分离导致生长前沿呈凸形几何形状,并且在大部分沉积物中存在空间变化的织构。