• 한국재료학회:학술대회논문집
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• 한국재료학회 2003년도 춘계학술발표강연 및 논문개요집
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• pp.86-86
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• 2003

Copper has attracted much attention in the deep submicron ULSI metallization process as a replacement for aluminum due to its lower resistivity and higher electromigration resistance. Electroless copper deposition method is appealing because it yields conformal, high quality copper at relatively low cost and a low processing temperature. In this work, it was investigated that effect of the microstructure of the substrate on the electroless deposition. The mechanism of the nucleation and growth of the palladium nuclei during palladium activation was proposed. Electroless copper deposition on TiN barriers using glyoxylic acid as a reducing agent was also investigated to replace toxic formaldehyde. Furthermore, electroless copper deposition on TaN$\sub$x/ barriers was examined at various nitrogen flow rate during TaN$\sub$x/ deposition. Finally, it was investigated that the effect of plasma treatment of as-deposited TaN$\sub$x/ harriers on the electroless copper deposition.

• 한국표면공학회지
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• 제41권1호
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• pp.23-27
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• 2008

The effect of solution agitation on the copper electroless deposition process of ULSI (ultra large scale integration) interconnections was investigated by using physical, electrochemical and electrical techniques. It was found that proper solution agitation was effective to obtain superconformal copper configuration within the trenches of $130{\sim}80nm$ width. The transition of open potential during electroless deposition process showed that solution agitation induced compact structure of copper deposits by suppressing mass transfer of cuprous ions toward substrate. Also, the specific resistivity of copper layers was lowered by increasing agitation speed, which made the deposited copper particles smaller. Considering both copper deposit configuration and electric property, around 500 rpm of solution agitation was the most suitable for the homogeneous electroless copper filling within the ultra-fine patterns.

• 마이크로전자및패키징학회지
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• 제11권4호
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• pp.75-80
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• 2004

In copper metallization, resistivity of copper seed layer is very important. Conventionally MOCVD has been used for this purpose however electroless copper plating is simple process and the resistivity of copper deposit is less than that of copper prepared by MOCVD. In this study electroless copper plating was conducted on different substrate to find optimum conditions of electroless copper plating for electronic applications. To find optimum conditions, the effects and selectivity of activation method on several substrates were investigated. The effects of copper bath composition on morphology were investigated. The effects of pH and stabilizer on deposition rate were also investigated. The optimum pH of the bath was 12 with addition of stabilizer. The resistivity of copper was decreased with addition of stabilizer and alter heat treatment.

• Korean Chemical Engineering Research
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• 제43권4호
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• pp.495-502
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• 2005

무전해 도금 용액을 이용하여 구리를 직접 텅스텐(Tungsten, W) 기판 위에 도금하였다. 도금 용액의 농도는 각각 $CuSO_4$ 7.615 g/L, EDTA 10.258 g/L, glyoxylic acid 7 g/L로 하였다. 도금 용액의 pH는 11.0에서 12.8까지 변화시켰으며, 용액의 온도는 $60^{\circ}C$로 유지하였다. 도금된 필름의 특성을 조사하기 위하여 X선 회절분석기, 전계 방출 주사 전자 현미경, 주사형 원자력 현미경, X선 광전자 분석기 및 Rutherford backscattering spectroscope(RBS)를 사용하였다. 구리 도금을 위한 가장 좋은 pH 조건은 11.8이였다. 이 용액에서 10분 동안 도금한 경우 둥근 모양의 구리 입자가 균일하게 도금되었으며, 불순물 peak이 없는 순수 구리 peak이였고, 근평균 제곱 표면 거칠기는 약 11 nm가 되었다. 또한, pH 11.8에서 12분 동안 도금한 필름의 두께는 140 nm이었고 도금속도는 약 12 nm/min였다. 무전해 도금 용액의 pH를 12.8로 증가시키면 도금된 구리 필름은 Cu peak 이외에 불순물 peak인 $Cu_2O$가 나타나고 구리 입자 모양도 기다란 직사각형 모양으로 변하였다. 순수 구리의 도금을 위해서는 도금 용액에서 적당한 pH를 유지하여야 한다. 도금된 구리의 농도는 RBS로 측정한 결과 99 atom％였다. 또한, Cu/W 필름은 전기 도금하는 동안 합금 형태를 이루기 때문에 접착성도 좋았다.

• 한국표면공학회지
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• 제49권3호
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• pp.265-273
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• 2016

The effects of surface modification by nitric acid on the pre-treatment of electroless copper plating were investigated. Copper was electroless-plated on the nitric acid treated graphite activated by a two-step pre-treatment process (sensitization + activation). The chemical state and relative quantities of the various surface species were determined by X-ray photoelectron spectroscopy (XPS) after nitric acid modification or pre-treatment. The acid treatment increased the surface roughness of the graphite due to deep and fine pores and introduced the oxygen-containing functional groups (-COOH and O-C=O) on the surface of graphite. In the pre-treatment step, the high roughness and many functional groups on the nitric acid treated graphite promoted the adsorption of Sn and Pd ions, leading to the uniform adsorption of catalyst ($Pd^0$) for Cu deposition. In the early stage of electroless plating, a lot of tiny copper particles were formed on the whole surface of acid treated graphite and then homogeneous copper film with low variation in thickness was formed after 30 min.

• Korean Chemical Engineering Research
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• 제47권2호
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• pp.141-149
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• 2009

초고속 연산용 CMOS(complementary Metal Oxide Semiconductor) 배선재료로 사용되고 있는 구리(Cu)가, 기가급 메모리 소자용 금속 배선 물질에도 사용이 시작되면서 구리 박막에 대한 재료 및 공정이 새로운 조명을 받고 있다. 반도체 금속 배선에 사용하는 수 nm 두께의 구리 박막의 형성에 전해도금(electrodeposition)과 무전해 도금(electroless deposition) 같은 전기화학적 방법을 이용하게 되어서 표면 처리, 전해액 조성과 같은 중요한 요소에 대한 최신 연구 동향을 요약하였다. 구리 박막에서 구리 배선을 제작하여야 하므로 새로운 패턴 기술인 상감기법이 도입되어, 구리도금과 상감기법과의 공정 일치성 관점에서 전해도금과 무전해 도금의 요소 기술에 대해 기술하였다. 구리보다 비저항이 낮아 차세대 소자용 배선에 있어서 적용이 예상되는 은(Ag)을 전기화학적 방법으로 금속 배선에 적용하는 최신 연구에 대하여도 소개하였다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 1999년도 추계학술대회 논문집
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• pp.625-628
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• 1999

Recently. high-density printed circuit boards(PCB) become indispensable with the minaturization of components. Nickel is deposited on the copper patterns and followed by the gold deposition for improving connection reliability between the printed circuit boards and electronic components. Conventionally electrodeposition has been applied to metalization of copper patterns. However metalization by this method is not applicable for the isolated fine and concentrated patterns. Therefore, metalization technology of the fine patterns by electroless plating is required in place of electrodeposition. The application of electroless nickel plating for interconnection with solder strongly relies on the solderability and the interactions between nickel and solder. Factors such as phosphorus content of the deposit additive and bath temperature may influence solderability of the electroless nickel deposit. So solderability of electroless nickel/ gold deposits was investigated with substrates plated changing the condition of nickel solution.

• Bulletin of the Korean Chemical Society
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• 제25권2호
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• pp.167-171
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• 2004

The electroless deposition of copper on the hydrogen-terminated Si(111) surface was investigated by means of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, scanning tunneling microscopy (STM), and energy-dispersive spectroscopy (EDS). The hydrogen-terminated Si(111) surface prepared was stable under air atmosphere for a day or more. It was found from ATR-FTIR that two bands centered at 2000 and 2260 $cm^{-1}$ appeared after the H-Si(111) surface was immersed in 40% $NH_4F$ solution containing 10 mM $Cu^{2+}$. On the other hand, STM image included the copper islands with a height of 5 nm and a diameter of 10-20 nm. The EDS data displayed the presence of copper, silicon and oxygen species. The results were rationalized in terms of the redox reaction of surface Si atoms and $Cu^{2+}$ ions in solutions, which are changed into $Si(OH)_x(F)_y$ containing $SiF_6^{2-}$ ions and neutral copper islands.

• 한국세라믹학회지
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• 제52권4호
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• pp.264-268
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• 2015

Cu films were plated in an eco-friendly electroless bath (No-Formaldehyde) on Ni/screen printed Ag pattern/PET substrate. For electroless Cu plating, we used sodium-phosphinate ($NaH_2PO_2{\cdot}H_2O$) as reducing agent instead of Formaldehyde. All processes were carried out in electroless solution of pH 7 to minimize damage to the PET substrate. According to the increase of sodium-phosphinate, the deposition rate, the granule size, and rms roughness of the electroless Cu film increased and the Ni content also increased. The electroless Cu films plated using 0.280 M and 0.575 M solutions of sodium-phosphinate were made with Cu of 94 at.% and 82 at.%, respectively, with Ni and a small amount P. All electroless Cu plated films had typical FCC crystal structures, although the amount of co-deposited Ni changed according to the variation of the sodium-phosphinate contents. From these results, we concluded that a formation of higher purity Cu film without surface damage to the PET is possible by use of sodium-phosphinate at pH 7.

• 한국표면공학회지
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• 제25권4호
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• pp.173-180
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• 1992

The effects of the stabilizing additives such as NaCN, 2-MBT and Thiourea on bath decom-position, plating rate and surface morphology have been studied. Bath stability was increased in the order of an additive-free bath, and NaCN-, 2-MBT-, and Thiourea-stabilized baths. The sta-bilizing effects may be attributed to the stability of Cu(II) -complexes. The plating rate is the re-verse order of the bath stability. Accelerative effect of 2-MBT in proper quantity(0.3mg/$\ell$) may be explained by visualizing it absorbed through benzene ring or sulfur atom on portions of the sub-strates. The strong bond of the complexing part of the molecule to nearby chelated copper ions would tend to accelerate plating by making it easier for the Cu2+ -ligand bond to be broken. Sur-face morphologies of copper deposits depend on the bath additives. Electroless copper deposits from the 2-MBT stabilized baths are finer than the deposits from the NaCN- and Thiourea- stabi-lized baths due to the strong adsorption on the substrates.