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The amount and kind of additives in electrolytes play a very important role on the electroplating of Cu foil, which is used as a cathode materials for secondary batteries. As the use of Cu foil increased, various studies on the electroplated Cu foil are urgently needed. We studied surface characteristics and changes in structural properties due to the addition of inhibitors under electroplating conditions with high current density. The surface layer was observed, to analyze the effect of the amount of potassium carbonate as an inhibitor. When the potassium carbonate was added at 5~25 ppm without any other additives, the initial plating voltage was observed to decrease. To uniformly distribute crystals without agglomeration at the initial stage of electroplating, it is reasonable to add potassium carbonate within the range of 20~25 ppm. There was no significant difference in surface roughness and specific resistance due to the amount of potassium carbonate, when the additives were added complexly. There was an increase in the relative strength of the preferred growth orientation of (220) in a group with 20 ppm potassium carbonate, compared to the group with 10 ppm potassium carbonate. The grain size decreased with the amount of potassium carbonate added with other additives. However, there was no significant difference in tensile strength and elongation (p-value: 0.000). To ensure uniform properties with a combination of 4 kinds of additives it is reasonable to add potassium carbonate in the range of 10~20 ppm.

Extremely thin film high quality copper foil is required to ensure high performance in electronics and slimness in secondary batteries. During the electroplating of copper foil, Janus Green B(JGB) and Collagen were introduced as additives to the electrolytes to study their effects. The structural and electrical properties of the electroplated copper foil were evaluated. When each additive was added individually, the potential was increased. Specifically, the potential of the group with 30 ppm added collagen was about 27% higher rather than the non-additive group. When Cl- ions and MPSA(3-mercapto-1-propane sulfonic acid) were added to the electrolytes without collagen and JGB, the surface roughness(Rz) increased by about 136% to 2.24 μm compared to the non-additive group. This was the highest value among all groups. However, a uniform layer with a surface roughness value below 0.3 μm was formed when less than 30 ppm and 10 ppm collagen and JGB were added, respectively, to the electrolyte. The direction of crystal growth with the JGB additives tended to go forward to the (220) direction, and the crystal size was reduced by 10~27% compared to the non-additive group. The addition of Collagen is necessary to reduce the difference in resistivity of the shiny layer and right matte layer. JGB additives were required to reduce the deviation in grain size. The results confirmed that the accelerators, inhibitors and leveler need to be properly added to form a copper plating layer with low surface roughness and to reduce differences in crystal texture of the shiny layer and right matte layer. Copper foil can be safely and uniformly deposited from electrolytes with JGB below 10 ppm and collagen below 30 ppm.

In this study, we studied the surface and mechanical properties of multiple additives as well as the initial plating properties of individual additives. With the individual additive groups, copper crystals tended to converge at a stage above the critical amount of additive. When chloride ions were added, large crystals formed at several places on the surface. Thereafter, small crystals were attached to and grew on the surface of the large crystals. When collagen and JGB (Janes Green B) were added individually, the crystals were more uniformly distributed on the surface as compared with the group with added chloride ions. In addition, starlike crystals were grown depending on the amount of addition. It was necessary to use multiple additives, which is why it is difficult to make a uniform surface layer with individual additives. Large crystals of more than 10 μm formed unevenly on the surface treated with multiple additives of chloride ions and MPSA (3-mercapto-1-propane sulfonic acid). Large crystals disappeared on the surface treated with additional collagen along with multiple additives. However, valley like shapes were observed on this surface, due to the large crystals. But, addition of JGB additives to this reduced the valley and formed a uniform plating layer. MPSA and 20 ppm of collagen were added as multiple additives, grain sizes increased by 93.5% (220 peak) and 172.3% (311 peak) compared with the non-additive group. As a result, tensile strength decreased by 24.5% and elongation increased by 17.8%. The crystal size was reduced 25.0% on average by the addition of 10 ppm JGB, which contributed to a 5.4% increase in tensile strength and a 16.0% decrease in elongation. The grain size and surface properties could be controlled by adding multiple combinations of additives. As a result, It was confirmed that mechanical properties could be controlled by the proper amount and the optimum combination of additives.

This study represents the results of the peel strength and surface morphology according to the preprocessing times of polyimide (PI) in a Cu/Ni/PI structure flexible copper clad laminate production process based on the polyimide. Field emission scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopywere used to analyze the surface morphology, crystal structure, and interface binding structure of sputtered Ni, Cu, and electrodeposited copper foil layers. The surface roughness of Ni, Cu deposition layers and the crystal structure of electrodeposited Cu layers were varied according to the preprocessing times. In the RF plasma times that were varied by 100-600 seconds in a preprocessing process, the preprocessing applied by about 300-400 seconds showed a homogeneous surface morphology in the metal layers and that also represented high peel strength for the polyimide. Considering the effect of peel strength on plastic deformation, preprocessing times can reasonably be at about 400 seconds. (Received March 4, 2011)

This study examined the effect of copper and sulfuric acid concentrations on the surface morphology and physical properties of copper plated on a polyimide (PI) film. Electrochemical experiments with SEM and a four-point probe were performed to characterize the morphology and mechanical characteristics of copper electrodeposited in the composition of an electrolyte. The resistivity and peel strength were controlled using a range of electrolyte compositions. A lower resistivity and high flexibility were obtained when an electrolyte with 20 g/l of copper was used. However, a uniform surface was obtained when a high current density that exceeded 20 mA/cm was applied, which was maintained at copper concentrations exceeding 40 g/l. Increasing sulfuric acid to >150 g/l decreased the peel strength and flexibility. The lowest resistivity and fine adhesion were detected at a Cu: H2SO4 ratio of 50:100 g/l. (Received March 23, 2010)