Chain length variation to probe the mechanism of accelerator additives in copper electrodeposition

Schmitt, Kevin G.; Schmidt, Ralf; Gaida, Josef; Gewirth, Andrew A.

doi:10.1039/c9cp00839j

Cited by 24 publications

(55 citation statements)

References 72 publications

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“…In principle, in situ vibrational spectroscopies including Raman, − infrared (IR), , and sum-frequency generation (SFG) spectroscopies are able to provide the structural information on adsorbates on Cu electrodes. Among these in situ techniques, SFG merits a unique interfacial specificity, but it depends upon high-performance laser and well-trained professionals with the detectable frequencies limited usually to more than 1000 cm –1 .…”

supporting

confidence: 63%

“…In addition, electrochemical SFG results are often too complicated to be explained. Electrochemical surface-enhanced Raman spectroscopy (SERS) merits the low-frequency detection with high surface sensitivity, and it has been used most widely for characterizing the adsorption configurations of additives on a Cu surface. − Nevertheless, the oxidation–reduction cycling (ORC) pretreatment of Cu in a chloride-containing solution for the SERS effect may complicate the surface structure and composition . In addition, the local high power density of laser irradiation may cause an unwanted photochemical reaction.…”

mentioning

confidence: 99%

“…In situ SERS measurement requires the ORC pretreatment of a Cu electrode in KCl solution. Based on previous SERS spectral results, mixed trans and gauche modes of MPS-thiolate were assumed on Cu electrode. , In the gauche mode, the sulfonate group was assumed closer to the Cu surface, in favor of accelerating the deposition of copper. Nevertheless, the above ORC pretreatment involves the dissolution and redeposition of Cu atoms in KCl solution, and the resulting SERS-active Cu electrode contains lots of complex surface defects and clusters, which are likely responsible for partial conversion of MPS-thiolate from trans mode to gauche mode; thus, the structural information about MPS-thiolate on Cu electrode may be distorted with an in situ SERS measurement.…”

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confidence: 99%

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In Situ Wide-Frequency Surface-Enhanced Infrared Absorption Spectroscopy Enables One to Decipher the Interfacial Structure of a Cu Plating Additive

Mao

et al. 2022

J. Phys. Chem. Lett.

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In situ spectroscopic characterization of the interfacial structure of an organic additive at a Cu electrode is essential for a mechanistic understanding of Cu superfilling at the molecular level. In this work, we demonstrate wide-frequency attenuated total reflection surface-enhanced infrared absorption spectroscopy (wf-ATR-SEIRAS) to elucidate the dissociative adsorption of bis(sodium sulfopropyl)-disulfide (a typical accelerator) on a Cu electrode in conjunction with the electrochemical quartz crystal microbalance measurement and modeling calculations. The wf-ATR-SEIRAS clearly identifies the peaks featuring the sulfonate and methylene groups as well as the C–Ssulfonate and C–Sthiol vibrations of the adsorbate. Analysis of relative peak intensities from 1100 to 650 cm–1 reveals a more tilted alkyl chain axis for the thiolate on Cu than that on Au, which is supported by comparative density functional theory calculations. This work opens a new avenue for the wf-ATR-SEIRAS to study interfacial structures of electroplating additives related to advanced microelectronics manufacture.

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confidence: 63%

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confidence: 99%

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confidence: 99%

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In Situ Wide-Frequency Surface-Enhanced Infrared Absorption Spectroscopy Enables One to Decipher the Interfacial Structure of a Cu Plating Additive

Mao

et al. 2022

J. Phys. Chem. Lett.

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“…It has been claimed by some authors [ 1 , 7 ] that the formation of very stable complex Cu(I)ClMPS − is responsible for the acceleration of copper deposition. Some more recent studies [ 8 ] showed that sulfonate groups help to partially remove the hydration shell of Cu 2+ that accelerates the reduction of Cu 2+ to Cu + and transfer the latter species to a chloride adlayer. In that way, SPS or MPS acts as an efficient factor for the desolvation step while chloride ions are important for forming Cu–Cl complexes that are reduced to Cu by single electron transfer.…”

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confidence: 99%

Studies of Bis-(Sodium-Sulfopropyl)-Disulfide and 3-Mercapto-1-Propanesulfonate on/into the Copper Electrodeposited Layer by Time-of-Flight Secondary-Ion Mass Spectrometry

2022

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Interactions of functional additives SPS (bis-(sodium-sulfopropyl)-disulfide), MPS (3‑Mercapto-1-Propanesulfonate), and Cl accumulated and incorporated on/into a copper electrodeposited layer were studied using time-of-flight secondary-ion mass spectrometry (TOF-SIMS) in combination with cyclic voltammetry measurements (CV). It was shown that the Cl and MPS surface coverage is dependent on the applied overpotential and concentration of Cl, SPS, or MPS in the solution. Detailed discussion on the mechanism of yielding CH2SO3−, C3H5SO3−, CuSC3H6SO3−, and CuS− fragments and their assignment to the gauche or trans conformation was proposed. The mechanism of the process of incorporation and re-adsorption of MPS on/into a copper surface under electrochemical conditions without and with chloride ions and its impact on electrochemical properties was proposed. Moreover, it was shown that the presence of chloride ions, the ratio gauche/trans of MPS molecules, as well as the ratio chloride/thiols demonstrate a high impact on the accelerating abilities. Comparative studies conducted under open circuit potential conditions on the nitinol and copper substrate allowed for the identification of specific reactions/interactions of MPS, or SPS and Cl ions on the nitinol and copper surface.

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“…This work aims to evaluate the structure and order of SAM in relation to the polarization of the electrode. We focus on a mixed-component SAM consisting of membrane-anchoring long-chain thiol WC14 and backfiller deuterated 2-mercaptoethanol (ME-D 4 , SH–C2D 2 –C1D 2 –OH), adsorbed on a gold electrode, probed by using in situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS) technique. − Usage of isotopically labeled short backfiller molecules allowed us to discriminate between spectroscopic features of ME-D 4 and WC14 and provided the opportunity to track structural alterations induced by the change in bias potential.…”

Section: Introductionmentioning

confidence: 99%

Potential-Induced Structural Alterations in the Tethered Bilayer Lipid Membrane-Anchoring Monolayers Revealed by Electrochemical Surface-Enhanced Raman Spectroscopy

2020

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Mixed self-assembled monolayers (SAMs) are widely used to anchor tethered lipid bilayer membranes (tBLMs) that mimic biological membranes and are useful platforms for fundamental studies and construction of biosensors. Electrode potential is an important variable in the construction of biosensors based on tBLMs and fundamental studies. In this work, potential-induced structural changes in mixed SAMs composed of lipid-like long-chain WC14 molecules and short surface backfiller 2-mercaptoethanol (ME-D4) was probed in situ by isotope-edited electrochemical surface-enhanced Raman spectroscopy (EC-SERS) coupled with first-principles calculations, reductive desorption voltammetry, and generalized two-dimensional correlation spectroscopy (2DCOS). We show that negative electrode polarization leads to the lengthening of Au–S and Au–O bonds and reorganization of molecules in the headgroup region. Calculations predicted the preferential formation of Au–O bonds of ME-D4 at more positive electrode potentials. Alkane chains of WC14 form potential-induced clusters at more negative electrode polarization in mixed monolayers, a phenomenon that is witnessed from all-trans vibrations of the C–C group at 1129 cm–1. The evidence of the formation of tBLM on mixed WC14/ME-D4 SAMs is documented by SERS. Specifically, the peak position of olefin group stretching vibration suggests a fluid-like structure of tBLM. This work provides vibrational spectroscopy evidence for the potential-induced formation of phase-segregation clusters of the hydrophobic thiols in mixed monolayers, a phenomenon that should be considered in preparation of tBLMs, construction of membrane-based biosensors, bioengineering developments, and studies of biomolecular processes using model membranes.

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Chain length variation to probe the mechanism of accelerator additives in copper electrodeposition

Abstract: We evaluate the effect of chain length for a series of alkyl sulfonic acid additives on Cu electrodeposition by using a combination of electrochemical and Raman spectroscopic methods.

Cited by 24 publications

References 72 publications

In Situ Wide-Frequency Surface-Enhanced Infrared Absorption Spectroscopy Enables One to Decipher the Interfacial Structure of a Cu Plating Additive

In Situ Wide-Frequency Surface-Enhanced Infrared Absorption Spectroscopy Enables One to Decipher the Interfacial Structure of a Cu Plating Additive

Studies of Bis-(Sodium-Sulfopropyl)-Disulfide and 3-Mercapto-1-Propanesulfonate on/into the Copper Electrodeposited Layer by Time-of-Flight Secondary-Ion Mass Spectrometry

Potential-Induced Structural Alterations in the Tethered Bilayer Lipid Membrane-Anchoring Monolayers Revealed by Electrochemical Surface-Enhanced Raman Spectroscopy

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