Mechanism of the Electrodeposition and Dissolution of Copper in an Acid Copper Sulfate Bath I. The Behavior of Intermediate, Cu&lt;sup&gt;+&lt;/sup&gt;

Yokoi, Masayuki; Konishi, Saburo; Hayashi, Tadao

doi:10.5796/kogyobutsurikagaku.51.310

Cited by 13 publications

(4 citation statements)

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“…55 Cladsorbs to the Cu surface, catalyzing the deposition process in CuSO 4 solution. 56 The results reported here show that SPS and MPS adsorption to the Cl --decorated Cu(100) surface occurs slowly if it occurs at all. Even on the bare Cu(100) surface, there is little indication that SPS adsorbs.…”

Section: Discussionmentioning

confidence: 62%

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In Situ EC-STM Studies of MPS, SPS, and Chloride on Cu(100): Structural Studies of Accelerators for Dual Damascene Electrodeposition

Bae

Gewirth

2006

Langmuir

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Electrochemical, differential capacitance, and in situ electrochemical scanning tunneling microscopy (EC-STM) methods are used to examine the interaction of bis(3-sulfopropyl)-disulfide (SPS) and mercaptopropylsulfonic acid (MPS) with Cu(100) surfaces both in the absence and presence of chloride. Both electrochemical and differential capacitance results are weakly perturbed by the addition of either MPS or SPS in the potential region between -0.2 and -0.5 V versus Ag/AgCl relative to the additive-free case. EC-STM images obtained from solutions of MPS alone exhibit a c(2 x 2) adlattice whereas those from SPS alone yield only the (1 x 1) structure. In the presence of Cl-, both adsorbates evince only a c(2 x 2) adlattice on the Cu(100) surface. The desorption potential of these structure is identical to that found with Cl- alone. These results show that neither MPS nor SPS adsorbs strongly on Cu(100) in the presence of Cl-.

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Section: Discussionmentioning

confidence: 62%

“…The reduction of Cu 2+ to Cu + is strongly catalyzed by the presence of trace quantities of Cl - . Cl - adsorbs to the Cu surface, catalyzing the deposition process in CuSO 4 solution …”

Section: Discussionmentioning

confidence: 99%

In Situ EC-STM Studies of MPS, SPS, and Chloride on Cu(100): Structural Studies of Accelerators for Dual Damascene Electrodeposition

Bae

Gewirth

2006

Langmuir

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“…A technique well suited to study the formation of cuprous intermediates is the rotating ring-disk electrode technique [27][28][29] . In the potential region, where cuprous ions are detected at the ring, a current peak was seen in the forward (negative) potential scan at the copper disk.…”

Section: Effect Of Cu + On Copper Deposition Overpotentialmentioning

confidence: 99%

The chemistry of additives in damascene copper plating

Binstead²,

et al. 2005

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Copper plating baths used for forming integrated circuit interconnects typically contain three or four component additive mixtures which facilitate the superfilling of via holes and trench lines during damascene plating. Extensive study over the last two decades has provided researchers with an understanding of the underlying mechanisms. The role of cuprous intermediates in the copper deposition reaction has long been acknowledged, but it is not yet fully understood. In this paper we describe the results of an electrochemical study of the interaction of the organic additives used with copper and copper ions in solution. It is shown that cuprous intermediates near the copper surface affect the overpotential and the kinetics of plating. The additives regulate the presence of cuprous species on the surface; levelers and suppressors inhibit Cu þ formation, whereas accelerating additives enhance Cu þ formation. Acceleration by the bis(sodiumsulfopropyl) disulfide (SPS) additive results from accumulation of cuprous complexes near the surface. Adsorbed cuprous thiolate [Cu(I)(S(CH 2) 3 SO 3 H) ad ] is formed through interaction of Cu þ ions and SPS rather than Cu 2þ and mercaptopropane sulfonic acid (MPS).

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“…On the other hand, change of slope, which was obtained from copper sulfate, may be attributed to the reduction of Cu + and Cu +2 . M. Yokoi and T. Hayashi (12) stated that Cu + concentration can change the potential which deviates from the Nernst Equation in the low polarization range. It can be seen that deposition of copper from sulfate bath started at relatively low cathodic potentials than pyrophosphate bath.…”

Section: Characterization Of Zincate and Copper Strike Layersmentioning

confidence: 99%

Comparison of Structural Properties of Copper Deposits from Sulfate and Pyrophosphate Electrolytes

et al. 2014

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Aluminum is quite often plated to combine the advantages of the light metal with modified surface properties. In this study, copper strike electrodeposits obtained from cyanide and pyrophosphate strike baths were compared in terms of microstructure, and copper pyrophosphate strike was found to yield smoother deposits. Furthermore, about 50 µm thick copper depositions on the strike plated aluminum surface, were prepared from acid copper sulfate and copper pyrophosphate electrolytes to compare structural properties of the deposits. Comparison and characterization of copper electrodeposits from copper sulfate and pyrophosphate electrolytes were performed by potentiometry, SEM, roughness, and XRD analyses. Smoother and finer grained copper deposits were obtained from pyrophosphate electrolyte especially at low current densities.

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Mechanism of the Electrodeposition and Dissolution of Copper in an Acid Copper Sulfate Bath I. The Behavior of Intermediate, Cu<sup>+</sup>

Cited by 13 publications

References 0 publications

In Situ EC-STM Studies of MPS, SPS, and Chloride on Cu(100): Structural Studies of Accelerators for Dual Damascene Electrodeposition

In Situ EC-STM Studies of MPS, SPS, and Chloride on Cu(100): Structural Studies of Accelerators for Dual Damascene Electrodeposition

The chemistry of additives in damascene copper plating

Comparison of Structural Properties of Copper Deposits from Sulfate and Pyrophosphate Electrolytes

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