• Journal of the Korean Vacuum Society
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• v.6 no.3
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• pp.187-193
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• 1997

We investigated the initial growth mode of Cu deposited on polyimide at room temperature using x-ray photoelectron spectroscopy. We could find that when Cu is sputter-deposited on the polymide, Cu-N-O complex of strong interaction is mainly formed first, Cu-oxide of weak interaction is formed successively, and then finally metallic Cu grow. From these results, we could conclude that Cu/polyimide interface consists of Cu-N-O complex and Cu-oxide.

• Journal of the Korean Vacuum Society
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• v.7 no.2
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• pp.135-140
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• 1998

We investigated the initial growth mode of Cu deposited on polyimide at high temperature($350^{\circ}C$) using x-ray photoelectron spectroscopy. We could find that when Cu is sputter-deposited on the polyimide at high temperature, Cu-C-N complex is formed first, Cu-N-O complex and Cu-oxide are mainly formed successively, and then funally metallic Cu grows. In the chemical reaction point of view, the interface of Cu/polyimide at high temperature is than that at room temperature.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.7 no.3
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• pp.494-503
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• 1997

We investigated the initial stages of formation of the Cu/polyimide interface using another two methods by X-ray photoelectron spectroscopy. : One, in-situ measurement with increasing of Cu deposition thickness onto polyimide(PI), the other, measurement with decreasing of Cu thickness of Cu/pI film by $Ar^+$ ion etching. From these results, we find that the chemical reactions exist in Cu/PI interface. However, the measured chemical reactions were different according to experimental method.

• Korean Journal of Materials Research
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• v.17 no.12
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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.

• Korean Journal of Materials Research
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• v.17 no.2
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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.

• Journal of the Korean Vacuum Society
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• v.6 no.S1
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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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• v.25 no.1
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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.

• Journal of the Korean institute of surface engineering
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• v.45 no.1
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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.

• Korean Journal of Materials Research
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• v.19 no.3
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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.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.05c
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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.