• 한국진공학회지
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• 제6권3호
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• pp.187-193
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• 1997

상온에서 polyimide 위에 증착한 Cu의 초기성장 과정과 Cu/polyimide의 계면의 형 태에 관하여 XPS를 이용하여 관찰하였다. Polyimide 위에 Cu가 증착됨에 따라, 초기단계에 는 강한 결합의 Cu-N-O complex가 주가 되어 Cu/polyimide 계명을 형성하고, Cu의 증착 두께가 증가함에 따라, 약한 결합의 Cu산화물에서 서서히 metallic Cu로서 성장하는 것을 볼 수 있었다. 이상이 결과들을 통해, Cu/polyimide의 계면은 Cu-N-O complex와 Cu산화물 이 혼합되어 있는 형태이며 polyimide 표면에 가까울수록 Cu-N-O complex가 주가 되고, Cu쪽에 가까울수록 Cu산화물이 주가 되는 형태를 이루고 있다는 것을 알 수 있었다.

• 한국진공학회지
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• 제7권2호
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• pp.135-140
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• 1998

고온($350^{\circ}C$)에서 polyimide위에 증착한 Cu의 초기성장 과정과 Cu/polyimide계면에서 의 반응물 형성에 관하여 XPS를 이용하여 관찰하였다. Polyimide 위에 고온 중에서의 Cu 증착시, 상온에서와는 달리 초기에는 Cu-C-N complex가 먼저 형성되고, 다음에 Cu-N-O complex가 주가 되어 Cu/Polyimide 계면을 형성하고, Cu의 증착두께가 증가함에 따라 Cu 산화물에서 서서히 metallic Cu로 성장하는 것을 볼 수 있었다. 그리고 반응물 형성 관점에 서, Cu 고온 증착시에 형성된 Cu/polyimide의 계면이 상온에서 이루어진 계면보다 상당히 예리함을 볼 수 있었다.

• 한국결정성장학회지
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• 제7권3호
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• pp.494-503
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• 1997

Polyimide(PI)위에서 Cu의 초기 성장과정을 설명하기 위해, PI 위에 Cu를 조금씩 증착시키면서 그리고 PI 위에 Cu 층을 쌓아놓고 이 Cu 층을 $Ar^+$ 이온으로 깍아내면서 계면에서의 변화를 XPS를 이용하여 비교ㆍ관측하였다. 상온에서 PI위에 Cu를 조금씩 증착하면서 관측하였을 때, 그 성장과정에 따르는 phase의 변화는 Cu-N-O complex에서 $Cu_2O$ phase로, 그리고 metallic Cu 순으로 성장하는 것이 관측되었다. 반면에 PI위에 증착되어 있는 Cu를 조금씩 깎아내면서 관측하였을 때, metallic Cu가 $Ar^+$ 이온으로 깍아내어 polyimide와의 계면에 도달하게 되었을 때에는 Cu$_2$O phase로서 관측되었다. 이상의 결과로부터, in-situ로 Cu를 조금씩 올리면서 계면을 조사하는 것과 Cu를 증착시킨 후, 깍으면서 계면을 조사하는 것과는 다른 결과를 얻게 된다는 것을 알 수 있었다.

• 한국재료학회지
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• 제17권12호
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• pp.664-668
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• 2007

The magnetron sputtering was used to deposit Ni buffer layers on the polyimide surfaces to increase the adhesion strength between Cu thin films and polyimide as well as to prevent Cu diffusion into the polyimide. The Ni layer thickness was varied from 100 to $400{\AA}$. The adhesion strength increased rather significantly up to $200{\AA}$ of Ni thickness, however, there was no significant increase in strength over $200{\AA}$. The XPS analysis revealed that Ni thin films could increase the adhesion strength by reacting with the polar C=O bonds on the polyimide surface and also it could prevent Cu diffusion into the polyimide. The Cu/Ni/ polyimide multilayer thin films showed a high stability even at the high heating temperature of $200^{\circ}C$, however, at the temperature of $300^{\circ}C$, Cu diffused through the Ni buffer layer into polyimide, resulting in the drastic decrease in adhesion strength.

• 한국재료학회지
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• 제17권2호
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• pp.61-67
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• 2007

The magnetron reactive sputtering was adopted to deposit CuO buffer layers on the polyimide surfaces for increasing the adhesion strength between Cu thin films and polyimide, varying $O_2$ gas flow rate from 1 to 5 sccm. The CuO oxide was formed through all the $O_2$ gas flow rates of 1 to 5 sccm, showing the highest value at the 3 sccm $O_2$ gas flow rate. The XPS analysis revealed that the $Cu_2O$ oxide was also formed with a significant ratio during the reactive sputtering. The adhesion strength is mainly dependent on the amount of CuO in the buffer layers, which can react with C-O-C or C-N bonds on the polyimide surfaces. The adhesion strength of the multi-layered Cu/buffer layer/polyimide specimen decreased linearly as the heating temperature increased to $300^{\circ}C$, even though there showd no significant change in the chemical state at the polyimide interface. This result is attributed to the decrease in surface roughness of deposited copper oxide on the polyimide, when it is heated.

• 한국진공학회지
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• 제6권S1호
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• pp.122-126
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• 1997

the Cu/polyimide system is known to be the best candidate for a multilevel interconnection system due to the low resistance of Cu and to the low dielectric constant of polyimide respectively. Ion beam mixing of Cu(40nm)/polyimide was carried out at room temperature with 80 keV Ar+ and N2+ form $1.5\times$1015 to 15$\times$1015 ions/cm2. The quantitative adhesion strength was measured by a standard scratch test. X-ray photoelectron spectroscopy and x-ray emission spectrocopy are employed to investigate the chemical bonds and the interlayer compound formation of the films Cu/Al/polyimide showed more adhesion strength than Cu/polyimide after ion beam mixing and N2+ ions are more effective in the adhesion enhancement than Ar+ with the same sample geometry. The XES results shows the formation of interlayer compound of CuAl2O4 which can reflect more adhesive Cu/Al/polyimide which has not been reported previously. The latter results is understood by the fact that N2+ ions produce more pyridinelike moiety, amide group and tertiary amine moiety whcih are known as adhesion promotors.

• Applied Microscopy
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• 제25권1호
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• pp.130-138
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• 1995

TEM specimen preparation methods have been examined to characterize Cu oxide particles in the polyimide film. Polyimide films were prepared by coating polyamic acid onto Cu films which had been deposited on TEM-mask and glass substrates and Cu foil, followed by thermal curing. In case of TEM-mask, direct observation was possible without further preparation. In other cases, TEM specimen were made by separating polyimide film from the substrate. Polyimide films were removed from glass and Cu foil by dissolving glass in HF solution and Cu foil in $H_{2}SO_{4}$ solution. TEM-mask observation confirms that fine $Cu_{2}O$ particles precipitate in the polyimide as a result of reaction of polyamic acid with Cu. However $Cu_{2}O$ particle reacts with HF and $H_{2}SO_{4}$ solution during dissolving the substrate and interpretation could be misled. It is concluded characterization of $Cu_{2}O$ particle in polyimide using TEM-mask is better than other methods.

• 한국표면공학회지
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• 제45권1호
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• pp.8-14
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• 2012

The effects of the alkali surface modification process on the adhesion strength between electroless-plated Cu and polyimide films were investigated. The polyimide surfaces were effectively modified by alkali surface treatments from the hydrophobic to the hydrophilic states, and it was confirmed by the results of the contact angle measurement. The surface roughness increased by alkali surface treatments and the adhesion strength was proportional to the surface roughness. The adhesion strength of Cu/polyimide interface treated by KOH + EDA (Ethylenediamine) was 874 gf/cm which is better than that treated by KOH and KOH + $KMnO_4$. The results of XPS spectra revealed that the alkali treatment formed oxygen functional groups such as carboxyl and amide groups on the polyimide films which is closely related to the interfacial bonding mechanism between electroless-plated Cu and polyimide films. It could be suggested that the species and contents of functional group on polyimide films, surface roughness and contact angle were related with the adhesion strength of Cu/polyimide in combination.

• 한국재료학회지
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• 제19권3호
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• pp.119-124
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• 2009

In the microelectronics packaging industry, the adhesion strength between Cu and polyimide and the thermal stability are very important factors, as they influence the performance and reliability of the device. The three different buffer layers of Cr, 50%Cr-50%Ni, and Ni were adopted in a Cu/buffer layer/polyimide system and compared in terms of their adhesion strength and thermal stability at a temperature of $300^{\circ}C$ for 24hrs. A 90-degree peel test and XPS analysis revealed that both the peel strength and thermal stability decreased in the order of the Cr, 50%Cr-50%Ni and Ni buffer layer. The XPS analysis revealed that Cu can diffuse through the thin Ni buffer layer ($200{\AA}$), resulting in a decrease in the adhesion strength when the Cu/buffer layer/polyimide multilayer is heat-treated at a temperature of $300^{\circ}C$ for 24hrs. In contrast, Cu did not diffuse through the Cr buffer layer under the same heat-treatment conditions.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2003년도 춘계학술대회 논문집 센서 박막재료 반도체 세라믹
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• pp.137-140
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• 2003

Cu+ ions drift diffusion in different dielectric materials is evaluated. The diffusion is investigated by measuring shift in the flatband voltage of capacitance/voltage measurements on Cu gate capacitors after bias temperature stressing. At a field of 1.lMV/cm and temperature $200^{\circ}C$, $250^{\circ}C$, $300^{\circ}C$ for 1H, 2H, 5H. The Cu+ ions drift rate of polyimide$(2.8{\leq}k{\leq}3.2)$ is considerably lower than thermal oxide. Also Cu+ drift rate of polyimide is similar to PECVD oxide. But, polyimide film is even more resistant to Cu drift diffusion and thermal effect than Thermal oxide, PECVD oxide: This results got a comparative reference. The important conclusion is that polyimide film is strongly dielectric material by thermal effect and Cu drift diffusion.