Publisher’s Note: Microvia Filling by Cu Electroplating over a Au Seed Layer Modified by a Disulfide [J. Electrochem. Soc., 156, D155 (2009)]

Dow, Wei‐Ping; Chiu, Yong-Da; Yen, Ming-Yao

doi:10.1149/1.3117562

Cited by 14 publications

(23 citation statements)

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“…This brightening effect on copper deposit often occurred in a copper electroplating solution containing SPS. 58,62,63 The variation trend in the grain size of the ELC deposits with the SPS concentration is consistent with that in the deposition rate except for the case without SPS addition, as shown in Fig. 10b.…”

Section: Characterization Of Modified Pi Films With Sps Additionsupporting

confidence: 82%

Modification of Cu nanoparticles with a disulfide for polyimide metallization

et al. 2010

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Copper metallization on polyimide films was carried out via a wet chemical process. This process included the chemical reaction of KOH with PI to form poly(amic acid) (PAA), ion exchange of doped K(+) with Cu(2+) to form Cu(2+)-doped PAA, doped Cu(2+) reduction by aqueous dimethylamine borane (DMAB) to form copper nanoparticles (CNPs) on PAA, and electroless copper (ELC) deposition catalyzed by CNPs on PAA. An organic additive, namely, bis(3-sulfopropyl)-disulfide (SPS), that can effectively reduce the size of CNPs and significantly enhance the chemical activity of CNPs for ELC deposition was used in this work. For comparison, doped Cu(2+) ions in the PAA were also reduced by hydrogen gas at 350 degrees C. The results show that only aqueous reductants can induce the reduced copper atoms to aggregate on the PAA surface and to form a granular copper layer that acts as a catalyst for the ELC deposition. Mechanisms for the aggregation of copper atoms and for activity enhancement of the CNPs due to SPS addition in the DMAB solution are proposed according to the evidence obtained from Fourier transform infrared spectrometry (FTIR), X-ray photoelectron spectrometry (XPS), field emission scanning electron microscopy (FESEM), cross-sectional transmission electron microscopy (TEM), and atomic force microscopy (AFM). The CNP-coated PAA films and the structures of the ELC deposits were characterized by X-ray diffraction (XRD) and UV-visible spectrophotometry (UV-Vis), respectively

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Section: Characterization Of Modified Pi Films With Sps Additionsupporting

confidence: 82%

Modification of Cu nanoparticles with a disulfide for polyimide metallization

et al. 2010

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“…4 superposed or were lower than curve ͑e͒, the MPS adlayer was completely removed from the copper surface. 20 At the same time, both the suppressor and the leveler dominated the copper deposition. The rapid drop in the polarization curves shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…In a previous work, the feasibility of this approach was demonstrated using copper and gold as seed layers, 19,20 indicating that the thiolate indeed is continuously transferable onto the surface of the as-deposited copper and exerts its accelerating effect on copper deposition in the presence of chloride. Thus, microvia filling is achievable in a plating bath without an accelerator.…”

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confidence: 98%

Copper Fill of Microvia Using a Thiol-Modified Cu Seed Layer and Various Levelers

Dow

Lin

et al. 2009

J. Electrochem. Soc.

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Microvia filling by copper electroplating was carried out using a plating bath containing a suppressor and a leveler without an accelerator. The required accelerator was adsorbed onto the copper seed layer of the microvia in a predipping bath before the filling plating. This pretreatment is similar to the self-assembled monolayer of thiol molecules that forms on a copper surface. The suppressor was poly(ethylene glycol) (PEG), and five levelers, namely, Janus green B, diazine black, methylene violet, safranine O, and Alcian blue, were employed to screen for the best plating formula suitable for a plating process in which no accelerator was present in the plating solution. The thiol molecule employed in this work was 3-mercapto-1-propanesulfonate (MPS). The electrochemical behaviors of various plating formulas were characterized using a galvanostatic measurement on a copper electrode at different rotating speeds. Results indicated that the MPS adlayer is transferable onto the surface of the copper deposit and can be displaced by the PEG-Cl-leveler. The displacement rate depends on the molecular structure of the added leveler. This plating process has the potential to greatly reduce the plating time of microvia filling

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“…29 Molecules with a −SO 3 H functionality are needed for the acceleration of Cu electrodeposition because −CH 3 -, −COOH-, and −OH-terminated thiols have been proven to be ineffective for acceleration on Cu electrodeposition. 29,30 Recently, the Cu electrodeposition mechanism that results in bottom-up filling of vias and trenches for the integrated circuit (IC) and printed circuit fabrications has been extensively studied. 30−35 A few disulfide or thiol molecules that are preadsorbed onto a Cu or Au seed layer were enough to induce bottom-up Cu filling of vias and trenches in electroplating baths containing a suppressor species only.…”

Section: Introductionmentioning

confidence: 99%

Adsorption and Desorption of Bis-(3-sulfopropyl) Disulfide during Cu Electrodeposition and Stripping at Au Electrodes

et al. 2012

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The adsorption and desorption of bis-(3-sulfopropyl) disulfide (SPS) on Cu and Au electrodes and its electrochemical effect on Cu deposition and dissolution were examined using cyclic voltammetry stripping (CVS), field-emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). SPS dissociates into 3-mercapto-1-propanesulfonate when it is contacted with Au and Cu electrodes, producing Cu(I)- and Au(I)-thiolate species. These thiolates couple with chloride ions and promote not only the reduction of Cu(2+) in Cu deposition but also the oxidation of Cu(0) to Cu(+) in Cu stripping. During Cu electrodeposition on the SPS-modified Au electrode, thiolates transfer from Au onto the Cu underpotential deposition (UPD) layer. The Cu UPD layer stabilizes a large part of the transferred thiolates which subsequently is buried by the Cu overpotential deposition (OPD) layer. The buried thiolates reappear on the Au electrode after the copper deposit is electrochemically stripped off. A much smaller part of thiolates transfers to the top of the Cu OPD layer. In contrast, when SPS preadsorbs on a Cu-coated Au electrode, almost all of the adsorbed SPS leaves the Cu surface during Cu electrochemical stripping and does not return to the uncovered Au surface. A reaction mechanism is proposed to explain these results.

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Publisher’s Note: Microvia Filling by Cu Electroplating over a Au Seed Layer Modified by a Disulfide [J. Electrochem. Soc., 156, D155 (2009)]

Abstract: not Available.

Cited by 14 publications

References 0 publications

Modification of Cu nanoparticles with a disulfide for polyimide metallization

Modification of Cu nanoparticles with a disulfide for polyimide metallization

Copper Fill of Microvia Using a Thiol-Modified Cu Seed Layer and Various Levelers

Adsorption and Desorption of Bis-(3-sulfopropyl) Disulfide during Cu Electrodeposition and Stripping at Au Electrodes

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