Ion-pair chromatography of bis (sodium-sulfopropyl) disulfide brightener in acidic copper plating baths

Palmans, Roger; Claes, Steven; Vanatta, L.E.; Coleman, David E.

doi:10.1016/j.chroma.2005.02.042

Cited by 18 publications

(17 citation statements)

References 4 publications

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“…This reaction was also confirmed by Palmans et al 18 who observed that, as soon as Cu 2+ was present in the plating bath, more than 99% of the MPSA was converted into SPS. In addition, such a dimerization reaction was reported by Suarez and Olson 19 for thiourea, a widely used additive in copper electrorefining processes, that dimerizes to FDS, a disulfide compound.…”

supporting

confidence: 81%

Influence of the Anode and the Accelerator on Copper Bath Aging in the Damascene Process

Moçotéguy

Gabrielli

Perrot

et al. 2006

J. Electrochem. Soc.

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Electrochemical impedance spectroscopy and cyclic voltammetry were used to characterize the aging of copper plating baths used in damascene process for superfilling of trenches and vias in the semiconductor industry. The effects of copper anode composition, anodic current density, and accelerator nature and concentration were studied. Phosphorus added to copper anodes has a prominent impact on the evolution of current/voltage curves and impedance spectra during bath aging. The observed evolutions were explained by the formation of a Cu I -accelerator complex in the bulk of the bath that adsorbs at the copper surface to act as an accelerating species, and by the increase of its concentration during aging with undoped copper anode. The Cu I -accelerator complex formation is limited by the phosphorus contained in the Cu-P anode, which traps electrogenerated cuprous ions in the black anodic film. Differences observed between baths containing SPS ͑bis͑3-sulfopropyl͒disulfide͒ or MPSA͓͑3-mercaptopropane͒sulfonic acid͔ are also attributed to the existence of two different Cu I -accelerator complexes, both of which exhibit different formation equilibrium constants.

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supporting

confidence: 81%

Influence of the Anode and the Accelerator on Copper Bath Aging in the Damascene Process

Moçotéguy

Gabrielli

Perrot

et al. 2006

J. Electrochem. Soc.

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“…3-5 A move to explore other polyethers is underway, 6,7 and several studies report using ͑3-mercaptopropyl͒sulfonate ͑MPS͒ in place of SPS, although the former is known to be unstable with respect to oxidative dimerization to SPS in the presence of Cu 2+ . 3,4,[8][9][10][11][12] Steady-state and transient electrochemical experiments have been used to establish the two-step model for Cu deposition Cu 2+ + e − = Cu + ͓1͔Cu + + e − = Cu ͓2͔where the rate constant for the first reaction step is thought to be on the order of a thousand times slower than the second step, such that the latter is often considered to be at a local equilibrium. 13-15 The fully solvated Cu aq + intermediate has been unambiguously measured by rotating ring-disk experiments, and the delicate interplay among Cu/Cu + /Cu 2+ equilibria has been examined.…”

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confidence: 99%

Accelerator Surface Phase Associated with Superconformal Cu Electrodeposition

Moffat

Liu

2010

J. Electrochem. Soc.

132

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Superconformal film growth is a key process in state-of-the-art Cu metallization of electronic devices. Superfilling of recessed surface features results from the competition between electrolyte additives that accelerate or inhibit Cu electroplating. In situ scanning tunneling microscopy is used to image the accelerating bis-͑3-sodiumsulfopropyl disulfide͒ ͑SPS͒-Cl − surfactant phase that is responsible for disrupting and preventing the formation of the inhibiting poly͑ethylene glycol͒-Cl − layer. Various aspects of competitive and coadsorption of Cl − and SPS on Cu͑100͒ were examined for industrially relevant additive concentrations. At potentials associated with superfilling, a saturated, c͑2 ϫ 2͒ Cl − ordered adlayer forms on the surface. When as-received SPS is added, individual SPS and ͑3-mercaptopropyl͒sulfonate ͑MPS͒ molecules are imaged as a mobile two-dimensional gas diffusing on the Cl − adlattice. The SPS-Cl − surfactant accounts for many aspects of the additive function previously observed and stipulated by the curvature enhanced accelerator model of superconformal film growth. SPS-derived species of differing mobility and tunneling contrast appear with exposure time. The lattice gas species are sensitive to the imaging conditions with tip-molecule interactions particularly evident at higher tunneling currents. At negative potentials, the c͑2 ϫ 2͒ Cl − adlayer is disrupted by an order-disorder transition, followed by desorption at more negative potentials. This allows direct access of SPS to the Cu metal whereupon irreversible sulfide formation occurs.In the past decade, Cu electrodeposition has become the dominant technology for fabricating interconnects for microelectronic devices over length scales ranging from those of damascene processing of submicrometer logic and memory circuitry to through silicon vias ͑TSVs͒ for chip stacking and circuit board metallization. 1 Central to the success of this technology is its ability to generate voidand seam-free bottom-up filling of trenches and vias by additive derived superconformal growth. 2 The desired bottom-up superconformal growth mode derives from a competition between rateaccelerating and rate-inhibiting two-dimensional ͑2D͒ phases for the available surface area within filling features. Area change is a key aspect that accompanies deposition on any nonplanar interface. 3,4 Feature filling behavior is well described by a mass balance construct known as the curvature enhanced adsorbate coverage ͑CEAC͒ model. 3,4 In this model, the coverage of the more strongly bound accelerator surface phase increases during area reduction accompanying deposition within recessed features, thereby giving rise to the bottom-up superfilling dynamic. For a prototypical acid CuSO 4 electrolyte, the suppressing or inhibiting phase involves coadsorption of chloride with polyether, whereas the accelerating phase derives from the combination of chloride with either a sulfonate-terminated disulfide or thiol. The most widely discussed additive system to date is chloride ͑Cl − ͒, ...

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“…Ion chromatography has been applied for the determination of sulfuric and oxalic acids in aluminum anodizing solutions [9] and for quantitative determination of the brightener bis(sodium-sulfopropyl) disulfide in acidic copper plating baths [10]. Gas chromatography (GC) has been used for the determination of volatile constituents in an anodic electrolytic plating bath [11] or for the quantitation of hydrogen in metals, based on hot extraction and gas chromatography [12].…”

Section: Introductionmentioning

confidence: 99%

Gas chromatography with flame ionization detection for determination of additives in an electrolytic Zn bath

Barriola

Ostra

Ubide

2012

Journal of Chromatography A

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Ion-pair chromatography of bis (sodium-sulfopropyl) disulfide brightener in acidic copper plating baths

Cited by 18 publications

References 4 publications

Influence of the Anode and the Accelerator on Copper Bath Aging in the Damascene Process

Influence of the Anode and the Accelerator on Copper Bath Aging in the Damascene Process

Accelerator Surface Phase Associated with Superconformal Cu Electrodeposition

Gas chromatography with flame ionization detection for determination of additives in an electrolytic Zn bath

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