Spectroscopic and Electrochemical Analysis of Cu(I) Complex of Copper Sulfate Electroplating Solution and Evaluation of Plated Films

Abstract

In this study, we investigated a behavior of cuprous ion (denoted as Cu(I)) in the copper sulfate plating solution and effects of the Cu(I) on a quality of Cu plating film. Through spectroscopic method, two kinds of holding structure of Cu(I) in the plating solution were firstly indicated by analyzing the kinetics of complex forming reaction between the Cu (I) and bathocuproinedisulfonic acid, disodium salt (BCS). One component is ignited from Cu(I) probably incorporated into deep inside of polyethylene glycol (PEG), and the Cu(I) must have steric hindrance of PEG to be interacted with the BCS in plating solution. Another one is a component for Cu(I) which can be instantaneously reacts to the BCS to be complex. In addition, interestingly, it has been shown that instantaneous component is affecting the roughness of Cu plating film. These results indicate that spectroscopic measurement and analysis is effective for the management and evaluation of the plating solution for high quality production.

Oxidative stress and apoptotic effects of copper and cadmium in the zebrafish liver cell line ZFL

“…5 C , F ). BCS chelated Cu(I) instead of Cu(II), and Ctr1 imported Cd [ 26 , 70 ]. The cellular Cu content increase when Cu co-exposure with BCS ( Fig.…”

Quenching characteristics of bathocuproinedisulfonic acid, disodium salt in aqueous solution and copper sulfate plating solution

“…The response to the electrolysis of the CVS and Cu(I) concentration ( : A0) shows good correlation, suggesting that the increase in Cu(I) concentration affects the roughness of the plated surface. 22) Although Cu(I) detection through a color reaction is a simple and easy method, it is not suitable for high-sensitivity detection in solution. Sensitivity due to absorption is limited to about 10 −6 mol=L and further decreases in the plating solution owing to limitations.…”

“…Electrolysis was carried out at a current density of 62.5 mA=cm 2 . 21,22) Absorbance was measured with JASCO V-630, and fluorescence measurement was performed with JASCO FR-8200 or Hamamatsu Photonics FLS920S at room temperature.…”

“…[16][17][18] We have succeeded in optically analyzing Cu(I) contained in plating solutions by monitoring the absorption of a chelate of Cu(I) with BCS. [19][20][21][22][23][24][25][26][27][28] On the basis of our method, it was shown that the Cu(I) concentration in a plating solution can be easily determined and that the holding structure of Cu(I) can also be analyzed. This information makes it possible to predict the roughness of the surface structure by electrodeposition.…”

Spectroscopic and Electrochemical Analysis of Cu(I) in Electroplating Solution and Evaluation of Plated Films

“…The disodium salt of bathocuproinedisulfonic acid (BCS) can be used to quantify the monovalent copper concentration in aqueous solutions, [6][7][8] and we have succeeded in analyzing the Cu(I) contained in plating solutions by absorption measurements of a chelate complex of Cu(I) with BCS. [9][10][11][12] Although Cu(I) in electroplating solutions is considered to be undetectable because they are oxidized immediately, in fact, a large amount of Cu(I) is contained in production line plating solutions. However, the conclusion on the relationship between the accumulation of Cu(I) in the solution and the plating surface was insufficient.…”