Accelerator Aging Effects During Copper Electrodeposition

Moffat, Thomas P.; Baker, Brett; Wheeler, Daniel; Josell, Daniel

doi:10.1149/1.1553936

Cited by 69 publications

(108 citation statements)

References 12 publications

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“…As with enzymes, adsorbed ligands may also influence the behavior of electrodes through both passive (e.g. selective adsorption) 14 33 and dithiocarbamates 34 have also been used to stabilize Au nanoparticles. In contrast with gas phase heterogeneous catalysis where sulfur species are generally considered poisons, these thiol-protected Au nanoclusters are particularly interesting candidates as electrocatalysts, 35,36 especially considering their unique electronic states resembling molecules rather than a metals.…”

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confidence: 99%

Electrocatalytic Reduction of CO₂at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior

Andrews

Krishna

Kumar

et al. 2015

J. Electrochem. Soc.

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Nanoscale Au electrocatalysts demonstrate the extraordinary ability to reduce CO 2 at low overpotentials with high selectivity to CO. Here, we investigate the role of surface chemistry on CO 2 reduction behavior using Au 25 and 5 nm Au nanoparticles. Onset potentials for CO 2 reduction at Au 25 nanoparticles in Nafion binders are shifted anodically by 190 mV while the hydrogen evolution reaction is shifted cathodically by 300 mV relative to Au foil. The net effect of this beneficial separation in onset potentials is relatively high Faradayic efficiencies for CO (90% at 0.8 V versus RHE) at high current densities. Experimental results show Faradayic efficiencies for CO are greatest using electrodes made with Nafion-immobilized Au 25 nanoparticles. Likewise, CO 2 reduction onset potential shifts are greater for smaller nanoparticles and when Nafion binders are used instead of (sulfonate-free) polyvinylidene fluoride. X-ray photoelectron spectroscopy analysis reveals Au nanoparticles may react with the sulfonates of Nafion binders. The results suggest sulfonate interfaces may alter the binding energies of key species or lead to favorable reconstructions, either of which ultimately results in remarkable improvements in Faradayic efficiencies relative to Au foil electrodes. The electrochemical reduction of CO 2 holds promise to generate energy-dense fuels using only atmospheric CO 2 , water and solar or wind energy. In recent works, several types of wet-synthesized metal nanoclusters (Au, Ag, Pt, Pd, Cu) have been demonstrated in electrochemical sensors 1-3 or electrolytic cells 3-5 with remarkable advantages over conventional metal (foil) electrodes. Recent works using Au 25 nanoclusters as electrochemical sensors demonstrate nanomolar sensitivity for species such as dopamine, ascorbic acid, uric acid, iodide or nitrites.6-8 Likewise composite electrodes with Au, Ag and Cu nanoclusters have shown desirable current-potential behaviors in CO 2 and O 2 reduction reactions including significantly lower onset potentials relative to their foil analogs (>100 mV). The underlying nature of activity enhancements associated with the structure or surface chemistry of composite nanocluster electrodes is not well established. As with enzymatic mechanisms, it is possible that structural effects associated with the ligated surface may facilitate specific reactant or product interactions. It is also possible that both kinetic and thermodynamic benefits originate from unique properties associated with under-coordinated (or ligated) metal atoms that result in improved binding energies or reduced transition state energies. In general, literature reports suggest decreasing particle dimensions increases catalytic activity; 9,10 however, trends in the electrochemical behavior associated with adsorbed ligands are less clear.11,12 Recent work by Liu et al. 13 shows alkyl-terminated Pt nanoparticles (2.85 nm) exhibit semiconducting behavior while phenyl-terminated Pt nanoparticles of the same size demonstrate metallic behavior and are more a...

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confidence: 99%

Electrocatalytic Reduction of CO₂at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior

Andrews

Krishna

Kumar

et al. 2015

J. Electrochem. Soc.

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“…[1][2][3] Tremendous efforts were taken to characterize chemical reactions on copper surfaces. [4][5][6][7] The results answer fundamental questions about reaction paths of the stepwise copper ion reduction and they explain the chemical behavior of various additive molecules. [8][9][10][11][12][13] However, the applicability to real copper plating processes and the phenomenon of superfilling is limited.…”

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confidence: 75%

The Influence of Adsorption Kinetics on Copper Superfilling for Dual Damascene

Liske

Krause

Uhlig

et al. 2016

J. Electrochem. Soc.

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The proceeding scaling in microelectronic devices requires smaller and smaller copper wires for energy transfer in integrated devices. Voids in the copper wires lead to a resistance increase and damage of the wiring. Copper wires are fabricated by electrochemical deposition as it enables a bottom-up, void free copper growth, so-called superfilling. The present work focuses on the mechanism of the electrochemical deposition with the goal of understanding and describing the superfilling. Electrochemical measurements and partial fill experiments under production-like conditions are carried out to study the effects of bath additives. The co-adsorption theory is adopted to explain additive interaction which is presumed to be the key for superfilling. It is shown that superfilling is a result of the synergetic adsorption behavior of at least two organic additives and a kinetic balancing between additive accumulation and copper deposition rate.

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“…27 Recently, attempts were made to attribute the increased deposition rate and the current density to the competitively adsorbed SPS from the viewpoint of the chemical reactions between the Cu ions and SPS or its reduced form ͑MPSA͒. [7][8][9][10] There is a need to pay attention to the fact that the current density recovered by SPS re-decreased by BTA addition. The current density in the presence of BTA was even lower than that of PEG-Cl − within the potential range of 0 to −400 mV.…”

Section: Resultsmentioning

confidence: 99%

“…[7][8][9][10] The accumulation of the accelerator inside the pattern brought about a locally higher concentration even after the complete filling of the pattern, which caused the topographic reversal ͑formation of bumps͒ and step formation at the densely patterned area. The step height generated by overdeposition at the active area had a strong relation to the dimension and the density of the patterns.…”

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Leveling of Superfilled Damascene Cu Film Using Two-Step Electrodeposition

Kim

Hwang

Cho

et al. 2006

Electrochemical and Solid-State Letters

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To enhance the compatibility of electrodeposition with the chemical mechanical polishing process, we attempted to prevent step formation on active areas. In the absence of benzotriazole ͑BTA͒, the step heights increased with the decrease in the pattern width and the increase in the pattern density due to the locally condensed accelerator. However, the addition of BTA significantly suppressed the deposition kinetic through the deactivation of the accelerator. The two-step electrodeposition with modulated accelerator and BTA concentrations was found to be effective in the retardation of bump formation and the prevention of bumps from growing without an impact on the superfilling.

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Accelerator Aging Effects During Copper Electrodeposition

Cited by 69 publications

References 12 publications

Electrocatalytic Reduction of CO₂at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior

Electrocatalytic Reduction of CO₂at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior

The Influence of Adsorption Kinetics on Copper Superfilling for Dual Damascene

Leveling of Superfilled Damascene Cu Film Using Two-Step Electrodeposition

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Accelerator Aging Effects During Copper Electrodeposition

Cited by 69 publications

References 12 publications

Electrocatalytic Reduction of CO2at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior

Electrocatalytic Reduction of CO2at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior

The Influence of Adsorption Kinetics on Copper Superfilling for Dual Damascene

Leveling of Superfilled Damascene Cu Film Using Two-Step Electrodeposition

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Electrocatalytic Reduction of CO₂at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior

Electrocatalytic Reduction of CO₂at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior