Adsorption Behavior of Polyoxyethyleneglycole on the Copper Surface in an Acid Copper Sulfate Bath

Yokoi, Masayuki; Konishi, Saburo; Hayashi, Tadao

doi:10.5796/kogyobutsurikagaku.52.218

Cited by 171 publications

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“…1 Specific combinations of electrolyte additives enable the formation of void-and seam-free Cu conductors in patterned trenches and vias by a superconformal film growth process known as superfilling. [2][3][4][5][6][7][8] Subsequent adsorption of sulfonate-terminated thiol or disulfide disrupts the inhibition provided by the polyether/halide complex, resulting in acceleration of the Cu electrodeposition rate. 2 Current electrolytic baths used for Cu electrodeposition purposes have at least three components: a polyether such as polyethylene glycol ͑PEG͒, a halide ion such as Cl − , and a sulfonate-terminated thiol or disulfide catalyst such as Na 2 ͓S͑CH 2 ͒ 3 SO 3 ͔ 2 ͑SPS͒ or NaSH͑CH 2 ͒ 3 SO 3 ͑MPS͒.…”

mentioning

confidence: 99%

Competitive Adsorption of PEG, Cl[sup −], and SPS/MPS on Cu: An In Situ Ellipsometric Study

Walker

Richter

Moffat

2006

J. Electrochem. Soc.

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The adsorption of Cu electrodeposition accelerating agents bis-͑3-sodiumsulfopropyl disulfide͒ ͑SPS͒ and ͑3-mercaptopropyl͒ sulfonate ͑MPS͒ on evaporated Cu thin films was examined in situ using spectroscopic ellipsometry under quiescent conditions. Both the thiol MPS and disulfide SPS resulted in definitive changes in the optical response of the interface, indicative of irreversible chemisorption. The optical responses of the films formed from the two additives were different, however, suggesting a difference in the adsorbed states. Cl − can reversibly coadsorb with either MPS or SPS. Preadsorption of either MPS or SPS inhibits the specific adsorption of polyethylene glycol ͑PEG͒ in the presence of Cl − . Both SPS and MPS adsorption displace preadsorbed PEG layers. The kinetics of the PEG displacement reaction differ significantly between the thiol and disulfide, consistent with observations of their respective effect on metal deposition kinetics.

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mentioning

confidence: 99%

Competitive Adsorption of PEG, Cl[sup −], and SPS/MPS on Cu: An In Situ Ellipsometric Study

Walker

Richter

Moffat

2006

J. Electrochem. Soc.

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“…A polyether chain is capable of surrounding copper ions and creating six coordination bonds with oxygen atoms, thus forming pseudocrown complexes of ëu + [19]. Owing to the emerged positive charge, such formations can interact with halide ions specifically adsorbed on a copper electrode.…”

Section: Methodsmentioning

confidence: 99%

Effect of Ethylene Glycol and Its Oligomers on the Copper(II) Electroreduction Kinetics in Halide-Containing Acid Sulfate Solutions

Bražinskienė¹,

Survila²

2005

Russ J Electrochem

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The kinetics of the copper electroreduction in acid sulfate solutions containing ethylene glycol derivatives (EG) with the common formula çé-(ëç 2 -ëç 2 -é) m -H is studied by means of voltammetry and impedance spectroscopy. All the EG ( m ≤ 6 ) display weak surface activity and barely effect the cathodic kinetics in the absence of halides. Halides can initiate inhibiting adsorption of EG only when the number of ether oxygen atoms in them is 3 ( m ≥ 4) , by inhibiting the first-electron transfer onto ions Cu 2+ . These effects are discussed invoking notions on the formation of pseudocrown structures in the adsorption layer.

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“…The observation of a strongly bound PEG component ͑nominally irreversible͒ via back-dilution with a Cl − -containing electrolyte ͑see Table I͒ is consistent with the observation that electrodes pretreated in a PEG/Cl − electrolyte continue to exhibit inhibition upon transfer to a PEG-free, Cl − -containing electrolyte. 15,16 While the PEG layer t m does not vary with potential in the presence of PEG in solution, the strongly adsorbed component does vary with potential, decreasing with increasingly negative potentials. It is likely that this is connected with the potential dependence of Cl − coverage.…”

Section: D279mentioning

confidence: 98%

Potential Dependence of Competitive Adsorption of PEG, Cl[sup −], and SPS/MPS on Cu

Walker

Richter

Moffat

2007

J. Electrochem. Soc.

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Potential-dependent adsorption of bis-͑3-sulfopropyl͒ disulfide ͑SPS͒, 3-mercaptopropyl sulfonate ͑MPS͒, chloride ͑Cl − ͒, and polyethylene glycol ͑PEG͒ on evaporated Cu thin films was examined using in situ spectroscopic ellipsometry at −0.65 V MSE , −0.75 V MSE , and −0.85 V MSE under quiescent conditions. The adsorption for the thiol compound was similar at all potentials examined, but the adsorption of the disulfide increased at more negative potentials. The influence of Cl − on the substrate was greatly diminished and PEG concurrently less strongly adsorbed at more negative potentials, as measured by ellipsometric responses. Both adsorbed MPS and SPS inhibited the specific adsorption of PEG in the presence of Cl − . Likewise MPS and SPS added to the electrolyte displaced preadsorbed PEG/ Cl − layers, with the displacement by the disulfide compound strongly potential dependent. At all potentials studied, the disulfide was less effective than MPS at displacement of preadsorbed PEG/ Cl − .

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Adsorption Behavior of Polyoxyethyleneglycole on the Copper Surface in an Acid Copper Sulfate Bath

Cited by 171 publications

References 0 publications

Competitive Adsorption of PEG, Cl[sup −], and SPS/MPS on Cu: An In Situ Ellipsometric Study

Competitive Adsorption of PEG, Cl[sup −], and SPS/MPS on Cu: An In Situ Ellipsometric Study

Effect of Ethylene Glycol and Its Oligomers on the Copper(II) Electroreduction Kinetics in Halide-Containing Acid Sulfate Solutions

Potential Dependence of Competitive Adsorption of PEG, Cl[sup −], and SPS/MPS on Cu

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