Superfilling and the Curvature Enhanced Accelerator Coverage Mechanism

Moffat, TP; Wheeler, Donald R.; Josell, Daniel

doi:10.1149/2.f07044if

Cited by 35 publications

(35 citation statements)

References 27 publications

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“…1,2 For submicrometer features, superconformal growth involves competitive adsorption between polyethers (e.g., poly(ethylene glycol) (PEG) and/or its derivatives) that suppress metal deposition and sulfonate-terminated alkyl disulfides and/or related thiols that accelerate Cu deposition. 3,4 For larger-scale features, such as TSV, extreme bottom-up filling can occur due to disruption of the polymer suppressor layer by positive feedback with the metal deposition reaction itself. 5−8 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.…”

Section: ■ Introductionmentioning

confidence: 99%

“…5−8 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. 3−20 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. 21−31 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.…”

Section: ■ Introductionmentioning

confidence: 99%

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SEIRAS Study of Chloride-Mediated Polyether Adsorption on Cu

et al. 2018

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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.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

SEIRAS Study of Chloride-Mediated Polyether Adsorption on Cu

et al. 2018

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“…To date, most of the site-selective Li deposition approaches have been based on the above idea: that is, modifying the chemistry of substrates. However, less attention has been paid to the effect of local geometry of substrates, which can also influence the metal electrodeposition behaviors. , In fact, on a nonplanar surface, concave structures such as pores and cavities are expected to be the preferred nucleation sites for metals. − Therefore, the geometry effect is speculated to play a role in site-controlled Li deposition for achieving dendrite-free anodes. Nevertheless, little work has focused on this aspect.…”

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confidence: 99%

Lithium Storage in Bowl-like Carbon: The Effect of Surface Curvature and Space Geometry on Li Metal Deposition

Wang

Yin

et al. 2021

ACS Energy Lett.

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Dendrite growth severely hinders the practical use of lithium metal as an ideal battery anode. To realize controlled Li plating, tremendous efforts have been focused on modifying the lithiophilicity chemistry of the anode hosts. Instead, we attempt to address this issue from a geometry perspective. We herein adopt carbon nanobowls (CBs) as a model host to study the geometry-guided Li growth behaviors by in situ electron microscopy. The strong effect of surface curvature is clearly demonstrated: Li metal is always guided to deposit on the concave surface of an isolated CB instead of the convex surface. The fully confined hollow cavity is more favorable for Li deposition in comparison to the partially confined spaces, such as the hemispherical concavity of a CB and interstitial voids between neighboring CBs. Density functional theory calculations elucidate that the geometry-guided Li growth is driven by the energy minimization associated with the formation of low-energy Li/C interfaces.

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“…NIST developed a quantitative process model on this basis-curvature-enhanced accelerator coverage (CEAC)that has guided development [658]. The basic idea is that (a) the growth velocity of the infilling copper is proportional to the local accelerator, or catalyst, coverage, and (b) the catalyst remains segregated at the metal-electrolyte interface during metal deposition.…”

Section: Part F Copper Plating In Microelectronicsmentioning

confidence: 99%

Electrodeposition of Copper

Dini

Snyder

2010

Modern Electroplating

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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.

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Superfilling and the Curvature Enhanced Accelerator Coverage Mechanism

Abstract: State-of-the-art manufacturing of semiconductor devices involves the electrodeposition of copper for on-chip wiring of integrated circuits.

Cited by 35 publications

References 27 publications

SEIRAS Study of Chloride-Mediated Polyether Adsorption on Cu

SEIRAS Study of Chloride-Mediated Polyether Adsorption on Cu

Lithium Storage in Bowl-like Carbon: The Effect of Surface Curvature and Space Geometry on Li Metal Deposition

Electrodeposition of Copper

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