고전류밀도에서 유기첨가제에 의한 구리 전착층의 전기적 특성 변화

우태규,박일송 대한금속·재료학회 2020 대한금속·재료학회지 Vol.58 No.1

Electroplating has many economic advantages in producing copper foils. The easiest way to manufacture electroplated copper foil with various properties is to add appropriate additives. This study evaluated the surface properties, mechanical and electrical properties of copper foil electroplated in electrolytes containing the leveler JGB (Janus Green B). When the leveler JGB was added as an additive, Cu crystals were distributed uniformly on the surface layer in an initial nucleation process. In the JGB-free group, dents and pinholes were observed on the surface of the electroplated Cu foil. Such surface defects were reduced with the addition of JGB. Surface roughness was decreased by 68% in the samples electroplated in electrolytes with 10 ~ 40 ppm JGB, when it is compared with a JGB-free sample. It was observed that the priority growth direction of crystal texture changed from (200), (111) to (220). Elongation decreased by 59%, while the tensile strength increased by 157% due to a decrease in crystal size by 69%. With the addition of 0 ~ 40 ppm JGB, resistivity increased due to the decrease in crystal size and changes in the crystal texture. Based on a linear regression approximation between 0 and 40 ppm the value of R2 was 91.4%. There was no statistically significant difference between 40 and 60 ppm, and the resistivity was 37.7% higher than in the JGB-free sample.

고전류밀도에서의 탄산칼륨 첨가제의 전해동박 특성에 미치는 영향

우태규,박일송 대한금속·재료학회 2023 대한금속·재료학회지 Vol.61 No.5

The amount and kind of additives in electrolytes play a very important role on the electroplatingof Cu foil, which is used as a cathode materials for secondary batteries. As the use of Cu foil increased, variousstudies on the electroplated Cu foil are urgently needed. We studied surface characteristics and changes instructural properties due to the addition of inhibitors under electroplating conditions with high currentdensity. The surface layer was observed, to analyze the effect of the amount of potassium carbonate as aninhibitor. When the potassium carbonate was added at 5~25 ppm without any other additives, the initialplating voltage was observed to decrease. To uniformly distribute crystals without agglomeration at the initialstage of electroplating, it is reasonable to add potassium carbonate within the range of 20~25 ppm. There wasno significant difference in surface roughness and specific resistance due to the amount of potassiumcarbonate, when the additives were added complexly. There was an increase in the relative strength of thepreferred growth orientation of (220) in a group with 20 ppm potassium carbonate, compared to the groupwith 10 ppm potassium carbonate. The grain size decreased with the amount of potassium carbonate addedwith 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 addpotassium carbonate in the range of 10~20 ppm.

티타늄 기지을 이용한 구리 전해도금 시 Arabic Gum 첨가제의 영향

우태규,박일송,이현우,설경원,Woo, Tae-Gyu,Park, Il-Song,Lee, Hyun-Woo,Seol, Kyeong-Won 한국재료학회 2006 한국재료학회지 Vol.16 No.12

The purpose of this study is to identify the effect of additives during copper electrodeposition. Additives such as arabic gum, chloride ions and glue were used in this study. Electrochemical experiments allied to SEM and roughness examination were performed to characterize of the copper foil in the presence of additives. In the production of electrodeposited copper foil, the surface roughness and grain size of the copper foil can be controlled by addition additives. on this study, the more uniform and hemispherical copper crystals are during the initial stages, the smaller crystal size and surface roughness of copper foil are. The surface roughness of copper foil electrodeposited at the current density of 500 $mA/cm^2$ under galvanostatic mode for 60 seconds has a minimum value of 0.136 ${\mu}$m when adding 2 ppm of arabic gum.

구리 박막의 표면형상과 물성에 대한 전류밀도 영향

우태규,박일송,정광희,설경원,Woo, Tae-Gyu,Park, Il-Song,Jung, Kwang-Hee,Seol, Kyeong-Won 한국재료학회 2010 한국재료학회지 Vol.20 No.10

This study examined the effect of current density on the surface morphology and physical properties of copper plated on a polyimide (PI) film. The morphology, crystal structure, and electric characteristics of the electrodeposited copper foil were examined by scanning electron microscopy, X-ray diffraction, and a four-point probe, respectively. The surface roughness, crystal growth orientation and resistivity was controlled using current density. Large particles were observed on the surface of the copper layer electroplated onto a current density of 25 mA/$cm^2$. However, a uniform surface and lower resistivity were obtained with a current density of 10 mA/$cm^2$. One of the important properties of FCCL is the flexibility of the copper foil. High flexibility of FCCL was obtained at a low current density rather than a high current density. Moreover, a reasonable current density is 20 mA/$cm^2$ considering the productivity and mechanical properties of copper foil.

Seed 금속의 종류와 두께에 따른 구리 전착층의 표면형상에 미치는 영향

우태규,박일송,설경원,Woo, Tae-Gyu,Park, Il-Song,Seol, Kyeong-Won 한국재료학회 2007 한국재료학회지 Vol.17 No.5

This study aimed to investigate the effects of the seed layer with copper electroplating on the surface morphology of copper foil. Three kinds of seed metal such as platinum, palladium, Pt-Pd alloy were used in this study. Electrodeposition was carried out with the constant current density of 200 $mA/cm^2$ for 68 seconds. Electrochemical experiments, in conjunction with SEM, XRD, AFM and four-point probe, were performed to characterize the morphology and mechanical characteristics of copper foil. Large particles were observed on the surface of the copper deposition layer when a copper foil was electroplated on the 130 nm thickness of Pd, Pt-Pd seed layer. However, a homogeneous surface, low resistivity was obtained when the 260 nm thickness of Pt, Pt-Pd alloy seed layer was used. The minimum value of resistivity was 2.216 ${\mu}{\Omega}-cm$ at the 260 nm thickness of Pt-Pd seed layer.

첨가제에 의한 구리 박막의 기계적 특성 변화

우태규,박일송,정광희,손규송,송람,이만형,황영규,설경원 대한금속·재료학회 2012 대한금속·재료학회지 Vol.50 No.3

The objective of this study is to investigate the effect of additives on the mechanical and electrical characteristics of electrodeposited copper foils. Additives A(leveler) and B(brightener) were used in this study and Cl ions were used as an accelerator. In case of using these additives A and B, it showed a disadvantage that decreased the elongation of electrodeposited layer due to decreased grain sizes and increased tensile strength. On the other hand, the Cl ions decreased the specific resistance of the copper layer and increased elongation owing to increasing grain sizes. The highest elongation and lowest resistivity were measured in the group added only Cl ions, whose values were 21.9% and 3.11 μΩ-cm, respectively.

구리 전해도금 변수의 기계적 특성 및 표면 특성에 미치는 주 효과 분석

우태규,박일송,설경원 대한금속·재료학회 2018 대한금속·재료학회지 Vol.56 No.6

Electroplated copper has been used as wiring in electronic circuit boards and as cathode materials for secondary batteries, and its usage has expanded into the construction industry because of its convenient production and high economic value. During the electroplating process, various parameters, such as crystal phase and size, can affect its mechanical properties and surface characteristics. Electroplating parameters were applied with the Taguchi experimental design method, and the electroplated copper layer was analyzed to observe changes in properties with various parameters. Among the parameters, current density significantly affected mechanical properties such as tensile strength and elongation. The size of the crystal grain decreased with the current density, which resulted in a 47% increase in tensile strength. Tensile strength and elongation tended to decrease when SPS(bis(3-sulfopropyl)disulfide)) was added as additives, and high elongation was observed when the hydroxyethyl cellulose(HEC)/SPS ratio was three times or more. When the concentration of sulfuric acid was high, the strongly preferred direction of crystal growth was parallel to the (111) plane.

고전류밀도 구리전해도금에서 첨가제의 주요효과

우태규,박일송 한국재료학회 2025 한국재료학회지 Vol.35 No.5

This study investigates the changes in the surface characteristic, electrical and mechanical properties of copper foils electrodeposited in electrolytes with added various additives (Janus Green B (JGB), 3–mercapto–1–propane sulfonic acid (MPSA), Polyethylene glycol (PEG) and Chloride ion) under high current density. The main effect of additives on these properties was analyzed. In the group with added JGB, the crystal size on the surface became finer, and a homogeneous surface was observed. However, dented areas were observed, which decreased with an increase in chloride ions. When 100 ppm of PEG and 10 ppm of JGB were added, the fine dents on the surface increased. When a certain amount or more of additives were added, defects on the surface occurred due to competition between additives. The addition of JGB induced crystal growth in the direction of the (111) plane. Copper foils with excellent yield strength, tensile strength, and elongation could be obtained with an appropriate crystal size. The addition of JGB mainly affected crystal size and the direction of crystal growth, which is an important factor for controlling mechanical properties. PEG mainly affected elongation, and chloride ions had a primary effect on surface roughness, resistivity, and corrosion rate. Therefore, controlling additives is an effective way to significantly affect the manufacture of copper foil and produce various suitable properties in high demand.

JGB 첨가제에 의한 동박의 미세구조변화와 전기적 특성

우태규,박일송 대한금속·재료학회 2021 대한금속·재료학회지 Vol.59 No.6

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.

고전류밀도에서의 첨가제 초기 거동 및 동박의 기계적 특성

우태규,박종재,박일송 대한금속·재료학회 2021 대한금속·재료학회지 Vol.59 No.5

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.