Mechanism of the Electrodeposition and Dissolution of Copper in an Acid Copper Sulfate Bath IV. Acceleration Mechanism in the Presence of Cl&lt;sup&gt;-&lt;/sup&gt; Ions

Yokoi, Masayuki; Konishi, Saburo; Hayashi, Tadao

doi:10.5796/kogyobutsurikagaku.51.460

Cited by 37 publications

(20 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Small amounts of chloride ion are known to have an accelerating effect on the deposition of copper. This supports the hypothesis that chloride ions act as binding sites for surfactants such as PEG to the electrode surface [88][89][90]. Excess chloride can produce insoluble copper chlorides at the anode surface, hindering the deposition process [91].…”

Section: Chloridesupporting

confidence: 76%

Electrodeposition of Copper

Dini

Snyder

2010

Modern Electroplating

View full text Add to dashboard Cite

Polyethylene oxides, glycols, and amines U.S.5,024,736 6/18/91 Clauss et al. Disubstituted ethane sulfonic compounds U.S.4,990,224 2/5/91 Mahmoud Urea, sodium lauryl sulfate, and tosyl or mesyl sulfonic acid U.S.4,975,159 12/4/90 Dahms Alkoxylated lactam amides U.S.4,954,226 9/4/90 Mahmoud Urea and glycerin U.S.4,948,474 8/14/90 Miljkovic Alkylarylene U.S.4,897,165 1/30/90 Bernards et al. Copper/sulfuric acid ratios U.S.4,781,801 11/1/88 Frisby Polyether surfactants þ sulfurized benzene þ grain refiner U.S.4,673,467 6/16/87 Nee Polyethers þ mercaptoimidazole þ sulfurized benzene U.S.4,555,315 11/26/85 Barbieri et al. Polyethers þ organic divalent sulfur compound þ tertiary alkyl amine with polyepichlorohydrin U.S.4,551,212 11/5/85 Rao et al. Phenazine dyestuffs U.S.4,540,473 11/22/83 Bindra et al. S-containing anions other than SO 4 U.S.4,521,282 7/11/84 Tremmel Sulfamic acid U.S.4,490,220 12/25/84 Houman Nitrogen-carbon-sulfur compound U.S.4,430,173 2/7/84 Boudot et al. Sodium salt of W-sulfo-n-propyl N,N-diethyldithiocarbamate, PEG, and crystal violet U.S.4,376,685 6/24/81 Watson Alkylated polyalkyleneimine U.S.4,347,108 8/31/82 Willis Nitrogen-and sulfur-containing compounds U.S.4,336,114 6/22/82 Mayer et al. Phthalocyanine, tertiary alkyl amine with polyepichloro hydrin, polyethyleneimine U.S.4,334,966 12/2/81 Beach et al. Polyether, mercaptoimidazole, sulfurized benzene U.S.4,310,392 1/12/82 Kohl Phenolphthalein U.S.4,272,335 2/19/80 Combs Substituted phthalocyanine radical U.S.4,242,181 12/30/80 Malak Regular coffee U.S.4,134,803 1/16/79 Eckles et al. Disulfides, sulfonic acids, and aliphatic aldehyde U.S.4,110,176 8/29/78 Creutz et al.

show abstract

Section: Chloridesupporting

confidence: 76%

Electrodeposition of Copper

Dini

Snyder

2010

Modern Electroplating

View full text Add to dashboard Cite

show abstract

“…This is discussed next. [19,30,31]. Figure 5 shows the effect of the different copper plating additives on the copper deposition current and on the ring current for cuprous ion formation.…”

Section: Effect Of Cu + On Copper Deposition Overpotentialmentioning

confidence: 99%

The chemistry of additives in damascene copper plating

Binstead²,

et al. 2005

View full text Add to dashboard Cite

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).

show abstract

“…In prototypical acidic CuSO 4 electrolytes, Cl – is an essential additive influencing the co-adsorption and operation of both polyether inhibitors and sulfonate-terminated alkyl disulfide accelerator species. − In situ scanning tunneling microscopy (STM) and surface X-ray scattering (SXS) measurements have revealed a great deal about the structure and step dynamics associated with potential-dependent phase transitions of the chemisorbed anions, SO 4 2– and Cl – , on low-index Cu surfaces. − At technically relevant concentrations, Cl – displaces SO 4 2– from the Cu surface and facilitates an increase in the rate of the Cu 2+ /Cu + inner sphere electron-transfer reaction. , The addition of PEG ( M w = 3400 g/mol) to the electrolyte suppresses the Cu deposition rate by 2 orders of magnitude relative to the H 2 SO 4 –CuSO 4 –Cl – solution. − However, in the absence of halide, negligible inhibition of metal deposition is observed, demonstrating that Cl – is required for the polyether suppressor to function. − …”

Section: Introductionmentioning

confidence: 99%

SEIRAS Study of Chloride-Mediated Polyether Adsorption on Cu

et al. 2018

View full text Add to dashboard Cite

Surface-enhanced infrared absorption spectroscopy is used to examine the co-adsorption of a selection of polyethers with Cl– under conditions relevant to superconformal Cu electrodeposition in CuSO4–H2SO4 electrolytes. In 0.1 mol/L H2SO4, a potential-dependent mixed SO4 2––H3O+/H2O layer forms on weakly textured (111) Cu thin-film surfaces. With the addition of 1 mmol/L NaCl, the SO4 2––H3O+/H2O adlayer is displaced and rapidly replaced by an ordered halide layer that disrupts the adjacent solvent network, leading to an increase in non-hydrogen-bonded water that makes the interface more hydrophobic. The altered wetting behavior facilitates co-adsorption of polyethers, such as poly(ethylene glycols), polyoxamers, or polyoxamines. Interfacial water is displaced by co-adsorption of the hydrophobic polymer segments on the Cl–-terminated surface, while the hydrophilic ether oxygens are available for hydrogen bond formation with the solvent. The combined polyether–Cl– layer serves as an effective suppressor of the Cu electrodeposition reaction by limiting access of Cuaq 2+ to the underlying metal surface. This insight differs from previous work which suggested that polymer adsorption is mediated by Cu+–ether binding.

show abstract

Mechanism of the Electrodeposition and Dissolution of Copper in an Acid Copper Sulfate Bath IV. Acceleration Mechanism in the Presence of Cl<sup>-</sup> Ions

Cited by 37 publications

References 0 publications

Electrodeposition of Copper

Electrodeposition of Copper

The chemistry of additives in damascene copper plating

SEIRAS Study of Chloride-Mediated Polyether Adsorption on Cu

Contact Info

Product

Resources

About