In situ STM imaging of bis-3-sodiumsulfopropyl-disulfide molecules adsorbed on copper film electrodeposited on Pt(111) single crystal electrode

Hsinling Tu, Poyu Yen, Sihzih Chen, Shuehlin Yau, Wei Ping Dow, Yuh-Lang Lee

Research output: Contribution to journalArticle

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Abstract

The adsorption of bis-3-sodiumsulfopropyldi-sulfide (SPS) on metal electrodes in chloride-containing media has been intensively studied to unveil its accelerating effect on Cu electrodeposition. Molecular resolution scanning tunneling microscopy (STM) imaging technique was used in this study to explore the adsorption and decomposition of SPS molecules concurring with the electrodeposition of copper on an ordered Pt(111) electrode in 0.1 M HClO 4 + 1 mM Cu(ClO4)2 + 1 mM KCl. Depending on the potential of Pt(111), SPS molecules could react, adsorb, and decompose at chloride-capped Cu films. A submonolayer of Cu adatoms classified as the underpotential deposition (UPD) layer at 0.4 V (vs Ag/AgCl) was completely displaced by SPS molecules, possibly occurring via RSSR (SPS) + Cl-Cu-Pt → RS--Pt+ + RS- (MPS) + Cu2+ + Cl -, where MPS is 3-mercaptopropanesulfonate. By contrast, at 0.2 V, where a full monolayer of Cu was presumed to be deposited, SPS molecules were adsorbed in local (4 × 4) structures at the lower ends of step ledges. Bulk Cu deposition driven by a small overpotential (η < 50 mV) proceeded slowly to yield an atomically smooth Cu deposit at the very beginning (<5 layers). On a bilayer Cu deposit, the chloride adlayer was still adsorbed to afford SPS admolecules arranged in a unique 1D striped phase. SPS molecules could decompose into MPS upon further Cu deposition, as a (2 × 2)-MPS structure was observed with prolonged in situ STM imaging. It was possible to visualize either SPS admolecules in the upper plane or chloride adlayer sitting underneath upon switching the imaging conditions. Overall, this study established a MPS molecular film adsorbed to the chloride adlayer sitting atop the Cu deposit.

Original languageEnglish
Pages (from-to)6801-6807
Number of pages7
JournalLangmuir
Volume27
Issue number11
DOIs
Publication statusPublished - 2011 Jun 7

Fingerprint

disulfides
Scanning tunneling microscopy
Sulfides
Disulfides
scanning tunneling microscopy
sulfides
Copper
Single crystals
Imaging techniques
copper
Electrodes
Molecules
electrodes
single crystals
Chlorides
molecules
chlorides
Deposits
deposits
Electrodeposition

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

Cite this

Tu, Hsinling ; Yen, Poyu ; Chen, Sihzih ; Yau, Shuehlin ; Dow, Wei Ping ; Lee, Yuh-Lang. / In situ STM imaging of bis-3-sodiumsulfopropyl-disulfide molecules adsorbed on copper film electrodeposited on Pt(111) single crystal electrode. In: Langmuir. 2011 ; Vol. 27, No. 11. pp. 6801-6807.
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abstract = "The adsorption of bis-3-sodiumsulfopropyldi-sulfide (SPS) on metal electrodes in chloride-containing media has been intensively studied to unveil its accelerating effect on Cu electrodeposition. Molecular resolution scanning tunneling microscopy (STM) imaging technique was used in this study to explore the adsorption and decomposition of SPS molecules concurring with the electrodeposition of copper on an ordered Pt(111) electrode in 0.1 M HClO 4 + 1 mM Cu(ClO4)2 + 1 mM KCl. Depending on the potential of Pt(111), SPS molecules could react, adsorb, and decompose at chloride-capped Cu films. A submonolayer of Cu adatoms classified as the underpotential deposition (UPD) layer at 0.4 V (vs Ag/AgCl) was completely displaced by SPS molecules, possibly occurring via RSSR (SPS) + Cl-Cu-Pt → RS--Pt+ + RS- (MPS) + Cu2+ + Cl -, where MPS is 3-mercaptopropanesulfonate. By contrast, at 0.2 V, where a full monolayer of Cu was presumed to be deposited, SPS molecules were adsorbed in local (4 × 4) structures at the lower ends of step ledges. Bulk Cu deposition driven by a small overpotential (η < 50 mV) proceeded slowly to yield an atomically smooth Cu deposit at the very beginning (<5 layers). On a bilayer Cu deposit, the chloride adlayer was still adsorbed to afford SPS admolecules arranged in a unique 1D striped phase. SPS molecules could decompose into MPS upon further Cu deposition, as a (2 × 2)-MPS structure was observed with prolonged in situ STM imaging. It was possible to visualize either SPS admolecules in the upper plane or chloride adlayer sitting underneath upon switching the imaging conditions. Overall, this study established a MPS molecular film adsorbed to the chloride adlayer sitting atop the Cu deposit.",
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In situ STM imaging of bis-3-sodiumsulfopropyl-disulfide molecules adsorbed on copper film electrodeposited on Pt(111) single crystal electrode. / Tu, Hsinling; Yen, Poyu; Chen, Sihzih; Yau, Shuehlin; Dow, Wei Ping; Lee, Yuh-Lang.

In: Langmuir, Vol. 27, No. 11, 07.06.2011, p. 6801-6807.

Research output: Contribution to journalArticle

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