Acceleration Kinetic of Copper Damascene by Chloride, SPS, and Cuprous Concentration Computation in TSV Filling

Abstract

Copper electrodeposition occurs in two steps and a practical electrodeposition normally needs several additives that require kinetic parameters for the calculation of current density and the concentration of intermediates. The copper electrodeposition was considered as a surface reaction, the exponential part of Butler-Volmer equation contributes to the value of reaction rate constant while the exchange current density relates to both the reaction rate constant and the surface concentration of cupric and cuprous ions. Two models for the adsorption of an additive or two additives on electrode surface were supposed. Using cyclic voltammetric stripping and chronoamperometry method, the electron bridge performance of chloride and the interaction of chloride with SPS were quantitatively compared with the non-additive copper electrodeposition.

Electrochemical Behavior of 2M5S and Its Influence on Reduction of Cu Pumping and Keep-Out Zone

“…This acceleration effect of Cl − has been reported in the literature. 30,31 In contrast, addition of 2M5S to the VMS solution in the presence of 50 ppm Cl − increased the inhibition of copper electrodeposition on the negative going sweep, along with the decrease of anodic stripping peak. This indicating that addition of chloride does not disrupt the inhibition of copper deposition of 2M5S.…”

Mechanisms of Localized Pulsed Electrodeposition (L-PED) for Microscale 3D Printing of Nanotwinned Metals

“…14 Parameters in above equations were obtained from the literature. [15][16][17][18][19][20][21] Water evaporation from the meniscus surface has a significant effect on the process. Heat and mass transfer formulation was taken into account to model the evaporation.…”

The effect of quaternary ammonium salts with different chain lengths on copper filling behavior in blind holes of printed circuit board

“…In order to ensure that the micropores are filled with non-porous and are completely filled, copper needs to grow from the bottom of the blind hole step by step from the bottom to the top during the electrodeposition process, which is achieved through the coordination of several additives [5][6][7]. Currently, three types of additives including suppressor represented by macromolecular polyether compounds (such as polyethylene glycol (PEG) [8][9][10], polypropylene glycol [11,12]), accelerator represented by propane sulfonate derivatives (such as sodium 3-mercapto-1propane sulfonate [13,14] and bis (3-sulfopropyl) disulfide (SPS) [15][16][17]), levelers represented by heterocyclic or alkyl compounds (such as Janus Green B, Diazine Black and Alcian Blue [18][19][20]). Among them, suppressors with larger molecular chains combine with Cl − and are usually adsorbed on the surface of the circuit board to form a chelate with Cu 2+ or Cu + to inhibit the deposition rate of copper, thereby reducing the current density of the blind hole orifice [8].…”

“…Among them, suppressors with larger molecular chains combine with Cl − and are usually adsorbed on the surface of the circuit board to form a chelate with Cu 2+ or Cu + to inhibit the deposition rate of copper, thereby reducing the current density of the blind hole orifice [8]. Contrary to suppressors, the accelerator with small molecular mass easily enters the bottom of the blind hole with the aid of Cl − , accelerates the deposition rate of copper at the bottom of the blind hole, and increases the current density at the bottom of the blind hole [16]. In addition, to obtain a neat and level copper surface, leveler is indispensable.…”