• Corrosion Science and Technology
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• 제10권4호
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• pp.143-150
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• 2011

Copper electroplating has been applied to various fields such as decorative plating and through-hole plating. Technical realization of high strength copper preplating for wear-resistant tools and molds in addition to these applications is the aim of this work. Brighters and levelers, such as MPSA, Gelatin, Thiourea, PEG and JGB, were added in copper sulfate electrolyte, and the effects of these organic additives on the hardness were evaluated. All additives in this work were effective in increasing the hardness of copper electrodeposits. Thiourea increased the hardness up to 350 VHN, and was the most effective accelarator in sulfate electrolyte. It was shown from the X-ray diffraction analysis that preferred orientation changed from (200) to (111) with increasing concentration of organic additives. Crystallite size decreased with increasing concentration of additive. Hardness was increased with decreasing crystallite size, and this result is consistent with Hall-Petch relationship, and it was apparent that the hardening of copper electrodeposits results from the grain refining effect.

• Bulletin of the Korean Chemical Society
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• 제34권3호
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• pp.927-930
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• 2013

We developed an electroplating process of cobalt nanowires of which line-widths were between 70 and 200 nm. The plating electrolyte was made of $CoSO_4$ and an organic additive, dimethyldithiocarbamic acid ester sodium salt (DAESA). DAESA in plating electrolytes had an accelerating effect and reduced the surface roughness of plated cobalt thin films. We obtained void-free cobalt nanowires when the plating current density was 6.25 mA/$cm^2$ and DAESA concentration was 1 mL/L.

• Journal of Magnetics
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• 제10권3호
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• pp.118-121
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• 2005

We have investigated the magnetic properties of electroplated thin Cu/Co multilayers by using electrolytes made of copper sulphate and cobalt sulphate and by applying alternating plating voltage. While the multilayers plated with pure electrolyte showed superparamagnetism, those plated with organic additives showed ferromagnetic behavior. These changes are attributed to the so-called 'self-annealing' effect and reduction of grain size caused by the organic additives.

• 한국자기학회지
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• 제15권3호
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• pp.198-201
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• 2005

전기도금 방법으로 제작된 니켈과 니켈-구리 합금박막에 미치는 유기첨가제(organic additive)의 영향을 조사하였다. 유기첨가제를 가하여 도금하는 니켈 박막의 경우 순수한 전해액만을 이용하여 도금한 박막과는 다른 결정성을 갖는다 도금조건을 일정하게 한 후 니켈-구리의 합금 박막용 전해액에 유기첨가제를 가하면 구리와 니켈의 조성비율이 변화하는데 유기첨가제의 성분과 농도에 따라 니켈의 함유율이 $65\~95\%$ 영역에서 조절이 가능하다. 유기첨가제에 의한 이러한 물성의 변화는 자성의 변화를 유도하여 도금 박막의 자기저항의 증가와 감소에도 기여하는 것으로 나타났다.

• Corrosion Science and Technology
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• 제6권4호
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• pp.154-158
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• 2007

For the application of flexible printed circuit board (FPCB), electroplated copper is required to have low surface roughness and residual stress. In the paper, the effects of surface roughness and residual stress of electroplated copper as thick as $8{\mu}m$ were studied on organic additives such as inhibitor, leveler and accelerator. Polyimide film coated with sputtered copper was used as a substrate. Surface roughness and surface morphology were measured by 3D-laser surface analysis and FESEM, respectively. Residual stress was calculated by Stoney's equation after measuring radius curvature of specimen. The addition of additives except high concentration of accelerator in the electrolyte decreased surface roughness of electroplated copper film. Such a tendency was explained by the function of additives among which the inhibitor and the leveler inhibit electroplating on a whole surface and prolusions, respectively. The accelerator plays a role in accelerating the electroplating in valley parts. The inhibitors and the leveler increased residual stress, whereas the accelerator decreased it. It was thought to be related with entrapped additives on electroplated copper film rather than the preferred orientation of electroplated copper film. The reason why additives lead to residual stress remains for the future work.

• 한국자기학회지
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• 제17권3호
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• pp.133-136
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• 2007

퍼말로이 도금용 순수전해액에 유기첨가제(organic additive)를 첨가하여 제작된 박막의 물성과 자성의 변화를 조사하였다. 일정한 도금조건에서 특정한 유기첨가제를 첨가하여 도금한 퍼말로이 박막은 순수한 전해액으로만 제작된 박막과는 결정성과 표면 거칠기가 달라진다. 그 결과로 도금 박막의 보자력 등 자기적 특성이 변화하였다. 유기첨가제에 의한 이러한 특성 변화는 자기임피던스 비율을 최대 20%까지 증가시키는 역할을 하였다.

• 전기화학회지
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• 제11권4호
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• pp.284-288
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• 2008

박막 리튬이차전지의 고용량 음극을 개발하기 위하여, Sn(II) 아세테이트를 포함한 유기전해조 도금법을 이용하여 Sn 박막전극을 제조하였다. $Li^+$와 $Sn^{2+}$를 포함한 전해조에 대한 순환전위전류시험 결과 3종류의 환원 반응이 나타났으며, $2.0{\sim}2.5\;V$ 영역이 Ni 집전체 표면에 대한 Sn의 석출 반응에 해당한다. 수계전해액에 대한 $Sn^{2+}$의 표준환원전위는 2.91 V vs. $Li^+/Li^{\circ}$ 인데 반해 유기전해조에서는 보다 낮은 전위에서 환원반응이 일어났다. 이는 유기전해질의 고저항과 $Sn^{2+}$의 낮은 농도에 기인한 과전위의 결과로 생각된다. 제조한 전극의 물리적 특성 및 전기화학적 특성을 연구하였다. 석출한 Sn 전극을 $150^{\circ}C$로 열처리하여 보다 높은 결정성을 얻을 수 있었고, 이를 Sn/Li 전지로 구성하여 전기화학적 실험을 한 결과 0.25 V와 0.75 V에서 각각 합금화-탈합금화 과정을 확인 할 수 있었다. 제조한 전극의 두께를 전기량을 통하여 계산한 바 $7.35{\mu}m$였으며, 가역용량은 $400{\mu}Ah/cm^2$을 얻었다.

• Korean Chemical Engineering Research
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• 제54권1호
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• pp.108-113
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• 2016

A miniaturized lab-scale Cu plating cell for the metallization of electronic devices was fabricated and its deposit uniformity and profile were investigated. The plating cell was composed of a polypropylene bath, an electrolyte ejection nozzle which is connected to a circulation pump. In deposit uniformity evaluation, thicker deposit was found on the bottom and sides of substrate, indicating the spatial variation of deposit thickness was governed by the tertiary current distribution which is related to $Cu^{2+}$ transport. The surface morphology of Cu deposit inside photo-resist pattern was controlled by organic additives in the electrolyte as it led to the flatter top surface compared to convex surface which was observed in the deposit grown without organic additives.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2010년도 춘계학술발표대회
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• pp.48.1-48.1
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• 2010

Cu has been used for metallic interconnects in ULSI applications because of its lower resistivity according to the scaling down of semiconductor devices. The resistivity of Cu lines will affect the RC delay and will limit signal propagation in integrated circuits. In this study, we investigated the characteristics of electroplated Cu films according to the variation of concentration of organic additives. The plating electrolyte composed of $CuSO_4{\cdot}5H_2O$, $H_2SO_4$ and HCl, was fixed. The sheet resistance was measured with a four-point probe and the material properties were investigated with XRD (X-ray Diffraction), AFM (Atomic Force Microscope), FE-SEM (Field Emission Scanning Electron Microscope) and XPS (X-ray Photoelectron Spectroscopy). From these experimental results, we found that the organic additives play an important role in formation of Cu film with lower resistivity by EPD.

• 한국표면공학회지
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• 제57권4호
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• pp.274-284
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• 2024

In this study, copper foil was electroplated under high current density conditions. We used Polyethylene Glycol (PEG), known for its thermal stability and low decomposition rate, as an inhibitor to form a stable and smooth copper layer on the titanium cathode. The electrolyte was composed of 50 g/L CuSO₄ and 100 g/L H₂SO₄, MPSA as an accelerator, JGB as a leveler, and PEG as a suppressor, and HCl was added as chloride ions for improving plating efficiency. The copper foil electroplated in the electrolyte added PEG which induced to inhibit the growth of rough crystals. As a result, the surface roughness value was reduced, and a uniform surface was formed over a large area. Moreover, the addition of PEG led to priority growth to the (111) plane and the formation of polygonal crystals through horizontal and vertical growth of crystals onto the cathode. In addition, the grains became fine when more than 30 ppm of PEG was added. As the microcrystalline structure changed, mechanical and electrical properties were altered. With the addition of PEG, the tensile strength increased due to grain refinement, and the elongation was improved due to the uniform surface. However, as the amount of PEG added increased, the corrosion rate and resistivity increased due to grain refinement. Finally, it was possible to manufacture a copper foil with excellent electrical and mechanical properties and the best surface properties when electroplating was carried out under the condition of additives with Cl-20 ppm, MPSA 10 ppm, JGB 5 ppm, and PEG 10 ppm.