알루미늄 위 친환경적 무전해 Ni-P 도금막 형성에 pH와 도금조 온도가 미치는 영향

지현배,빈정수,이연승,나사균,Gee, Hyun-Bae,Bin, Jung-Su,Lee, Youn-Seoung,Rha, Sa-Kyun 한국재료학회 2022 한국재료학회지 Vol.32 No.9

The overall process, from the pre-treatment of aluminum substrates to the eco-friendly neutral electroless Ni-P plating process, was observed, compared, and analysed. To remove the surface oxide layer on the aluminum substrate and aid Ni-P plating, a zincation process was carried out. After the second zincation treatment, it was confirmed that a mostly uniform Zn layer was formed and the surface oxide of aluminum was also removed. The Ni-P electroless plating films were formed on the secondary zincated aluminum substrate using electroless plating solutions of pH 4.5 and neutral pH 7.0, respectively, while changing the plating bath temperature. When a neutral pH7.0 electroless solution was used, the Ni-P plating layer was uniformly formed even at the plating bath temperature of 50 ℃, and the plating speed was remarkably increased as the bath temperature was increased. On the other hand, when a pH 4.5 Ni-P electroless solution was used, a Ni-P plating film was not formed at a plating bath temperature of 50 ℃, and the plating speed was very slow compared to pH 7.0, although plating speed increased with increasing bath temperature. In the P contents, the P concentration of the neutral pH 7.0 Ni-P electroless plating layer was reduced by ~ 42.3 % compared to pH 4.5. Structurally, all of the Ni-P electroless plating layers formed in the pH 4.5 solution and the neutral (pH 7.0) solution had an amorphous crystal structure, as a Ni-P compound, regardless of the plating bath temperature.

Influence of Phosphorous Content on Microstructure Development at the Ni-P Plating/SAC Interface

Zbigniew Huber,Joanna Wojewoda-Budka,Anna Wierzbicka-Miernik,Anna Sypien,Maciej Szczerba,Pawel Zieba 대한금속·재료학회 2016 ELECTRONIC MATERIALS LETTERS Vol.12 No.1

Studies of the commonly used Ni-P surface finish of 4.3 and 11.6 wt. %of P content electroless plated on nickel substrates followed by theirreaction with SAC305 solder were performed. It was demonstratedthat the Ni-4.3P plating was crystalline, while the Ni-11.6P wasmostly amorphous. The transformation of the Ni-P into Ni3P phasetook place at 672 K and 605 K for low and high P amount, respectively. The activation energy (Ea) of the crystallization processes in the Ni-Pplating was lower for the Ni-11.6P plating. Interaction of SAC305solder with both types of the inspected plating showed the creation of(Cu,Ni)6Sn5 phase in the form of thin layer and large scallops, whilefor Ni-11.6P/SAC305 interface also (Ni,Cu)3Sn4 phase. The thicknessof these phases was larger in the case of low phosphorous containingplating. The Ni-11.6P plating after the reaction with SAC305 totallytransformed into Ni12P5, while the enrichment in P up to 10.5 wt. %occurred in the Ni-4.3P which did not lead to the appearance of anyNixPy type phases. After the reaction of plating with solder the Ni2SnPphase was not identified. This was related to the absence of spallingphenomenon of the intermetallics into solder.

Investigation on Plated Ni/Cu Contact for Mono-Crystalline Silicon Solar Cells

김동호,이수홍 대한금속·재료학회 2013 ELECTRONIC MATERIALS LETTERS Vol.9 No.5

Silicon solar cells are required to be processed with low cost and high efficiency. Ag paste, which is frequently used for the front contact of commercial screen-printed solar cells, has high contact resistance and high cost. Therefore, it is necessary to develop an inexpensive metallization technique with improved cell performance. As an alternative, plated Ni/Cu contact was used to fabricate low cost and high efficiency solar cells in this paper. Ni/Cu metals have low cost, low contact resistance and high conductivity. Ni was formed for low contact resistance and barrier to plated Cu, which was the main contact for low cost and high conductivity. In particular, a plated Ni layer is a very crucial factor that determines performance of the contact for plated Ni/Cu solar cells. A plated Ni layer has a decisive effect on contact resistance, series resistance and fill factor. In this paper, Ni electroless plating conditions (deposition time and pH) were varied to form a well plated Ni layer. For an optimized Ni electroless plating condition (5 min of deposition time and 8.5 of pH),the efficiency of plated Ni/Cu contact solar cells recorded 18.68%.

ENEPIG 표면처리에서의 Sn-Ag-Cu 솔더조인트 신뢰성: 1. 무전해 Ni-P도금의 두께와 표면거칠기의 영향

허석환,이지혜,함석진,Huh, Seok-Hwan,Lee, Ji-Hye,Ham, Suk-Jin 한국마이크로전자및패키징학회 2014 마이크로전자 및 패키징학회지 Vol.21 No.3

전자 제품의 경박 단소화 및 고집적화가 이루어 지면서 실리콘 집과 인쇄회로기판의 인터커넥션의 고신뢰도가 요구되고 있다. 본 연구는 Sn-4.0wt%Ag-0.5wt%Cu (SAC405) 솔더와 다양한 무전해 Ni-P 도금 두께에서의 high speed shear 에너지 및 파괴 모드를 연구하였다. 파괴 모드 분석을 위하여 집속이온빔(FIB) 분석이 이용되었다. 질산 기상 처리하지 않은 $1{\mu}m$ Ni-P 시편에서 낮은 shear 에너지가 나왔으며, 이는 솔더레지스트 선단에서 파단의 원인을 제공하는 것이 확인되었다. 질산 기상 처리한 시편에서 무전해 Ni-P 도금 두께가 커질수록 취성 파괴 모드는 감소한다. 또 Ni-P 도금 두께와 표면 거칠기(Ra)는 반비례 관계를 가진다. 이는 Ni-P 도금의 표면 거칠기를 낮추면 SAC405 솔더 조인트의 신뢰도를 향상시킨다는 사실을 나타낸다. By the trends of electronic package to be smaller, thinner and more integrative, the reliability of interconnection between Si chip and printed circuit board is required. This paper reports on a study of high speed shear energy of Sn-4.0wt%Ag-0.5wt%Cu (SAC405) solder joints with different the thicknesses of electroless Ni-P deposit. A high speed shear testing of solder joints was conducted to find a relationship between the thickness of Ni-P deposit and the brittle fracture in electroless Ni-P deposit/SAC405 solder. A focused ion beam (FIB) was used to polish the cross sections to reveal details of the microstructure of the fractured pad surface with and without $HNO_3$ vapor treatment. The high speed shear energy of SAC405 solder joint with $1{\mu}m$ Ni-P deposit was found to be lower without $HNO_3$ vapor, compared to those of over $3{\mu}m$ Ni-P deposit. This could be due to the edge of solder resist in $1{\mu}m$ Ni-P deposit, which provides a fracture location for the weakened shear energy of solder joints and brittle fracture in high speed shear test. With $HNO_3$ vapor, the brittle fracture mode in high speed shear test decreased with increasing the thickness of Ni-P deposit. Then the roughness (Ra) of Ni-P deposits decreased with increasing its thickness. Thus, this gives the evidence that the decrease in roughness of Ni-P deposit for Eelectroless Ni/ Electroless Pd/ Immersion Au (ENEPIG) surface play a critical role for improving the robustness of SAC405 solder joint.

Ni/Cu 금속전극 태양전지의 Ni electroless plating에 관한 연구

이재두,김민정,권혁용,이수홍,Lee, Jae-Doo,Kim, Min-Jeong,Kim, Min-Jeong,Lee, Soo-Hong 한국전기전자재료학회 2011 전기전자재료학회논문지 Vol.24 No.4

The formation of front metal contact silicon solar cells is required for low cost, low contact resistance to silicon surface. One of the front metal contacts is Ni/Cu plating that it is available to simply and inexpensive production to apply mass production. Ni is shown to be a suitable barrier to Cu diffusion into the silicon. The process of Ni electroless plating on front silicon surface is performed using a chemical bath. Additives and buffer agents such as ammonium chloride is added to maintain the stability and pH control of the bath. Ni deposition rate is found to vary with temperature, time, utilization of bath. The experimental result shown that Ni layer by SEM (scanning electron microscopy) and EDX analysis. Finally, plated Ni/Cu contact solar cell result in an efficiency of 17.69% on $2{\times}2\;cm^2$, Cz wafer.

차세대 웨어러블 디바이스를 위한 높은 기계적/전기적 특성을 갖는 CNT-Ni-Fabric 유연기판

김형구,노호균,차안나,이민정,하준석 한국마이크로전자및패키징학회 2020 마이크로전자 및 패키징학회지 Vol.27 No.2

Recently, numerous researches are being conducted in flexible substrate to apply to wearable devices. Particularly, Conductive substrate researches that can implement the wearable devices on clothing are massive. In this study, we formed fiber substrate spraying CNT and Pd mixed solution on it and plated metal layer with electroless plating. Used SEM equipment and EDS analysis to analysis structure of the plated fiber substrate and discovered Ni layer was created. For check electrical properties, mapping was performed to check surface resistance and distribution of resistance of electroless plated fiber substrate with 4-point probe. It was confirmed that conductivity was improved as the duration of electroless plating was increased, and it was found that distribution of resistance by surface location was uniform. Changes in resistance due to mechanical stress were measured through tensile, bending, and twisting tests. As a result, it was confirmed that resistance change of flexible substrate gradually disappeared as plating time increased. Using UTM (Universal testing machine), it was analyzed mechanical properties of the electroless plated substrate with respect to changes in plating time were improved. In the case of conductive fiber substrate in which electroless plating was performed for 2 hours, tensile strength was increased by 16 MPa than fiber substrate. Based on these results, we found that Ni- CNT-Fabric flexible substrate is adequate for clothing-intergrated conductive substrate and we positively expect that this experiment shows flexible substrate can adapt to and develop not only a wearable device technology but also other fields needing flexibility such as battery, catalyst and solar cell. 최근 웨어러블 장치에 적용하기 위한 유연성 기판에 대한 연구가 활발히 진행되고 있다. 특히, 유연성 기판중의복에 웨어러블 장치를 적용하기 위한 전도성 섬유기판에 대한 연구가 진행되고 있다. 본연구에서는, 면섬유 기판 표면에 CNT와 Pd복합 용액을 스프레이 법을 이용하여 형성하였고, 무전해 도금법을 이용하여 금속층을 도금하였다. 도금된섬유기판의 형상을 분석하기 위하여 SEM 장비를 이용하였고, CNT를증착한 섬유기판의 표면에 Ni 레이어가 형성된것을 확인하였다. EDS 분석을 통하여 섬유기판의 표면에 형성된 물질이 Ni임을 알 수 있었다. 전기적 특성을 확인하기 위하여 4-point probe로 무전해 도금을 진행한 섬유기판의 표면저항 및 저항 분포를 확인하기 위한 맵핑을 진행하였다. 무전해도금의진행시간이길어질수록전도성이 향상되었음을 확인할수있었고, 표면위치별저항의분포가 균일함을알수있었다. 인장력, 굽힘, 뒤틀림 시험을 통하여 기계적 스트레스로 인한 저항변화를 측정하였다. 그결과 도금 시간이길어질수록 유연성 기판의 저항변화가 점점 사라지는 것을 확인하였다. UTM(Universal testing machine)을이용하여 도금시간 변화에 대한 무전해 도금 기판의 기계적 특성 향상 여부에 대하여 분석하였다. 인장강도는 무전해 도금을 2 시간동안진행한 전도성 섬유기판의 경우, 면섬유 기판보다약 16 MPa 증가하였다. 이러한 결과들을 토대로 Ni-CNT-Fabric 유연기판은 의류 일체형 전도성 기판으로 이용되기에 충분함을 확인하였고, 이러한 연구 결과는 유연기판, 웨어러블 디바이스뿐만 아니라 유연성이 필요한 배터리, 촉매, 태양전지 등에 적용되어 발전에 기여할 수 있을 것으로 기대한다.

Electroless Ni-P metallization on palladium activated polyacrylonitrile (PAN) fiber by using a drying process

Lee, Jae-Young,Lee, Hong-Ki Elsevier 2018 Materials chemistry and physics Vol.204 No.-

<P><B>Abstract</B></P> <P>Polyacrylonitrile (PAN) fiber was metallized by nickel-phosphorus (Ni-P) in an electroless plating process. Firstly, the surface of PAN fiber was activated by palladium (Pd) nanocatalysts by using a drying process in which palladium(II) bis(acetylacetonate), Pd(acac)<SUB>2</SUB> was spontaneously reduced to Pd nanocatalysts in180 °C N<SUB>2</SUB> atmosphere without using any reducing agent. And then Ni-P alloy was coated on the Pd activated PAN fiber in an electroless Ni-P plating solution without using SnCl<SUB>2</SUB>-sensitizing solution. The morphology was observed by scanning electron microscopy (SEM) and elemental analyses were carried out by energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The composition ratio of Ni: P was 85.3: 14.7 atomic % and the growth rate of Ni-P layer decreased with increasing plating time. The thickness of Ni-P plating layers for 10, 30 and 60 min were 0.64, 1.03 and 1.22 μm, respectively. Electromagnetic interference shielding effectiveness (EMI-SE) of Ni-P plated PAN fiber (50 wt%)/epoxy composite was more than 30 dB in the frequency range from 30 MHz to 1500 MHz.</P> <P><B>Highlights</B></P> <P> <UL> <LI> A drying process is proposed to activate PAN fiber surface with Pd nanoparticles. </LI> <LI> Ni-P alloy is electrolessly plated on the Pd activated PAN surface. </LI> <LI> 1.22 μm thick Ni-P alloy was covered the PAN fiber. </LI> <LI> EMI shielding effectiveness was over 30 dB at 30–1500 MHz. </LI> </UL> </P>

Optimization of barrel plating process for electroless Ni–P plating

홍인권,이승범,김형진 한국공업화학회 2014 Journal of Industrial and Engineering Chemistry Vol.20 No.5

A plating test was carried out with changes in the concentration of nickel sulfate (NiSO4) and sodium hypophosphite (NaH2PO2) to analyze the plating characteristics depending on the balance of the electroless Ni–P plating solution. The coating thickness increased with the concentrations of NiSO4 and NaH2PO2. The optimum concentrations for electroless Ni–P plating were 27.0 g/L for NiSO4, and 24.0 g/L for NaH2PO2. The coating thickness was thicker at up to pH 4, but it was thinner after that. The deviations in the coating thickness decreased at up to pH 4, but it was increased after that. So the optimum pH of the plating solution was 4. Barrel plating was carried out while varying the open pore ratio, barrel rotation speed, plating temperature, and plating time, which revealed that the coating thickness was increased with the open pore ratio and barrel rotation speed. Therefore, the optimum open pore ratio and barrel rotation speed in electroless Ni–P plating were 22.5% and 2.5 rpm, respectively.

문전해 Ni-Cu-P 도금층의 자성에 미치는 도금조건과 도금속도의 영향

오이식(I. S. Oh),이태희(T. H. Lee) 한국동력기계공학회 2005 한국동력기계공학회 학술대회 논문집 Vol.- No.-

The effect of bath composition, plating condition and plating rate on the magnetic properties of electroless Ni-Cu-P deposits were investigated. With increasing CuSo₄ concentration in the bath, plating rate increased, while the Br value of deposits decreased Sharply. Plating rate increased up to 34% with the addition of 200ppm of NaF and 0.8ppm of Thiourea to the bath. Plating reaction had been ceased by the increase of pH above 11.3, bath temperature higher than 90℃ and under 70℃. The Br value of deposit was uniform with various concentration of complexing agent (Sodium citrate, Ethylenediamine) in the bath. The Br Value of deposit was almost equal to that found by the addition of stabilizer(Thiourea) and accelerator(NaF). The Br value of deposit was uniform in plating time(120 min) and heat treatment temperature(below 200℃), and were confirmed to have adequate bath stability for practical use.

전해도금에 의한 Ni-C 복합층의 내식성 및 표면 전기저항

박제식,이성형,정구진,이철경,Park, Je-Sik,Lee, Sung-Hyung,Jeong, Goo-Jin,Lee, Churl-Kyoung 한국재료학회 2011 한국재료학회지 Vol.21 No.5

Simultaneous Ni and C codeposition by electrolysis was investigated with the aim of obtaining better corrosion resistivity and surface conductivity of a metallic bipolar plate for application in fuel cells and redox flow batteries. The carbon content in the Ni-C composite plate fell in a range of 9.2~26.2 at.% as the amount of carbon in the Ni Watt bath and the roughness of the composite were increased. The Ni-C composite with more than 21.6 at.% C content did not show uniformly dispersed carbon. It also displayed micro-sized defects such as cracks and crevices, which result in pitting or crevice corrosion. The corrosion resistance of the Ni-C composite in sulfuric acid is similar with that of pure Ni. Electrochemical test results such as passivation were not satisfactory; however, the Ni-C composite still displayed less than $10^{-4}$ $A/cm^2$ passivation current density. Passivation by an anodizing technique could yield better corrosion resistance in the Ni-C composite, approaching that of pure Ni plating. Surface resistivity of pure Ni after passivation was increased by about 8% compared to pure Ni. On the other hand, the surface resistivity of the Ni-C composite with 13 at.% C content was increased by only 1%. It can be confirmed that the metal plate electrodeposited Ni-C composite can be applied as a bipolar plate for fuel cells and redox flow batteries.