• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1603-1607
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• 2012

The effects of plating process on the surface coverage of the accelerator were investigated in terms of Cu superfilling for device metallization. When a substrate having 500 nm-wide trench patterns on it was immersed in an electrolyte containing poly (ethylene glycol) (PEG)-chloride ion ($Cl^-$)-bis(3-sulfopropyl) disulfide (SPS) additives without applying deposition potential for such a time of about 100s, voids were generated inside of the electrodeposit. In time-evolved electrochemical analyses, it was observed that the process (immersion without applying potential) in the electrolyte led to the build-up of high initial coverage of SPS-Cl on the surface, resulting in the fast saturation of the coverage. Repeated experiments suggested that the fast saturation of SPS-Cl failed in superfilling while a gradual increase in the SPS-Cl coverage through competition with initially adsorbed PEG-Cl enabled it. Consequently, superfilling was achievable only in the case of applying the plating potential as soon as the substrate is dipped in an electrolyte to prevent rapid accumulation of SPS-Cl on the surface.

• Korean Chemical Engineering Research
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• v.52 no.1
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• pp.26-39
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• 2014

Cu interconnection in electronic devices is fabricated via damascene process including Cu electrodeposition. In this review, Cu electrodeposition and superfilling for fabricating Cu interconnection are introduced. Superfilling results from the influences of organic additives in the electrolyte for Cu electrodeposition, and this is enabled by the local enhancement of Cu electrodeposition at the bottom of filling feature formed on the wafer through manipulating the surface coverage of organic additives. The dimension of metal interconnection has been constantly reduced to increase the integrity of electronic devices, and the width of interconnection reaches the range of few tens of nanometer. This size reduction raises the issues, which are the deterioration of electrical property and the reliability of Cu interconnection, and the difficulty of Cu superfilling. The various researches on the development of organic additives for the modification of Cu microstructure, the application of pulse and pulse-reverse electrodeposition, Cu-based alloy superfilling for improvement of reliability, and the enhancement of superfilling phenomenon to overcome the current problems are addressed in this review.

• Journal of the Korean Electrochemical Society
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• v.2 no.4
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• pp.237-241
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• 1999

The characteristics of copper thin films and via hole filling capability were investigated by pulsed electrodeposition method. Especially, the effects of additives on the properties of copper thin films were studied. Copper films, which were deposited by pulsed electrodeposition using commercial additives, had low tensile stress value under 83.4 MPa and high preferred Cu (111) texture. Via holes with $0.25{\mu}m$ in diameter and 6 : 1 aspect ratio were successfully filled without any defects by superfilling. It was observed that copper microstructure deformed by twining. After heat treatment at $500^{\circ}C$ for 1 k in vacuum furnace, grain size was 1 or 2 times as large as film thickness and the bamboo structure was formed. Heat treated copper films showed good resistivities of $1.8\~2.0{\mu}{\Omega}{\cdot}cm$.

• Korean Chemical Engineering Research
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• v.54 no.6
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• pp.723-733
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• 2016

Intensive researches have been focused on the 3-dimensional packaging technology using through silicon via (TSV) to overcome the limitation in Cu interconnection scaling. Void-free filling of TSV by the Cu electrodeposition is required for the fabrication of reliable electronic devices. It is generally known that sufficient inhibition on the top and the sidewall of TSV, accompanying the selective Cu deposition on the bottom, enables the void-free bottom-up filling. Organic additives contained in the electrolyte locally determine the deposition rate of Cu inside the TSV. Investigation on the additive chemistry is essential for understanding the filling mechanisms of TSV based on the effects of additives in the Cu electrodeposition process. In this review, we introduce various filling mechanisms suggested by analyzing the additives effect, research on the three-additive system containing new levelers synthesized to increase efficiency of the filling process, and methods to improve the filling performance by modifying the functional groups of the additives or deposition mode.

• Journal of the Korean Electrochemical Society
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• v.5 no.3
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• pp.153-158
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• 2002

The effects of leveler on the copper trench filling were investigated during damascene plating process. To investigate the trench filling effect with the addition of a leveler, a cross-section images of the electroplated trenches with the width of$0.37{\mu}m,\;and\;0.18{\mu}m$ were observed by field emission scanning electron microscope (FE-SEM). Polyethylene glycol(PEG), 3-mercapto-1-propanesulfonic acid and Janus Green B were used as a carrier, an accelerator and a leveler. $0.37{\mu}m$ trenches were superfilled without voids, but there was voids formation in $0.18{\mu}m$ trenches when the leveler was not added into the electrolyte. On the other hand $0.18{\mu}m$ trenches were superfilled without voids with the addition of the leveler due to the reduction growth rate of copper at protrusions and edges, which yield smooth final deposit surface. The leverer effect becomes more significant as the width of trenches becomes smaller when trenches are filed.