Behaviour of poly(ethylene glycol) during electrodeposition of bright copper coatings in sulfuric acid electrolytes

Stoychev, D.; Tsvetanov, Christo B.

doi:10.1007/bf00241515

Cited by 126 publications

(127 citation statements)

References 19 publications

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“…Complexation of Cu +2 with PEG in aqueous solutions was suggested by Stoichev and Tsvetanov on the basis of conductivity measurements 15,22 according to the stoichiometry…”

Section: Resultsmentioning

confidence: 99%

Chemical Mechanism of Suppression of Copper Electrodeposition by Poly(ethylene glycol)

Hebert¹,

Adhikari²,

Houser³

2005

J. Electrochem. Soc.

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Poly͑ethylene glycol͒ ͑PEG͒ is an important additive to electroplating baths used for the deposition of copper interconnects on semiconductor wafers. In an earlier paper, Yokoi et al., Denki Kagaku oyobi Kogyo Butsuri Kagaku, 52, 218 ͑1984͒ found a direct relationship between the deposition rate in the presence of PEG and chloride ions with the open-circuit potential measured after plating, suggesting that the rest potential reflects the chemical state of reactive copper ions within a surface polymer film. Here, these measurements were corroborated and then interpreted in terms of a proposed mechanism of copper deposition in the presence of PEG. In this mechanism, aqueous Cu 2+ ions are reduced to an intermediate complex at the PEG-Cu interface detected earlier by Raman spectroscopy ͓Z. V. Feng et al., J. Phys. Chem. B, 107, 9415 ͑2003͔͒, in which Cu + ions associate with adsorbed Cl − ions and ether oxygen ligands of PEG. The rest potential measurements are quantitatively explained on the basis of competition for these ligands at open circuit with Cu 2+ ions absorbing from solution. The results indicate that deposition is mediated though ions partially solvated with the polymer, the concentration of which is controlled by the PEG concentration and molecular weight. PEG then behaves as a polymer electrolyte film as opposed to a passive barrier.

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“…Complexation of Cu +2 with PEG in aqueous solutions was suggested by Stoichev and Tsvetanov on the basis of conductivity measurements 15,22 according to the stoichiometry…”

Section: Resultsmentioning

confidence: 99%

Chemical Mechanism of Suppression of Copper Electrodeposition by Poly(ethylene glycol)

Hebert¹,

Adhikari²,

Houser³

2005

J. Electrochem. Soc.

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“…The synergy of these additives stemmed from the adsorptive and transport characteristics of chloride ions and from the competitive interaction between the suppressor, accelerator, and leveler. 13,[35][36][37][38][39][40][41][42][43][44][45][46][47] In order to further analysis the function of Polyquaternium-2 in TH electroplating process, the addition sequence was changed again (the addition sequence followed the description in Table 1) and the result was shown in Fig. 9.…”

Section: Resultsmentioning

confidence: 99%

Polyquaternium-2: A New Levelling Agent for Copper Electroplating from Acidic Sulphate Bath

Chen

Wang

et al. 2016

Electrochemistry

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Poly[bis(2-chloroethyl)ether-alt-1,3-bis [3-(dimethylamino)propyl]urea] (Polyquaternium-2) was employed as a leveler in the through-hole (TH) electroplating experiments from an acidic sulphate bath. The interaction between Polyquaternium-2 and copper surface was investigated using Field Emission Scanning Electronic Microscope (FE-SEM) and X-ray Photoelectron Spectra (XPS). The electrochemical behavior of Polyquaternium-2 and its interaction with other additives, such as a suppressor and an accelerator were characterized using rotating disk electrode. Polyquaternium-2 could absorb on copper surface to form an adsorption layer and inhibit the copper electrodeposition. As shown in the TH electroplating experiments, a copper deposit with uniform thickness was obtained when 0.17 µmol/L Polyquaternium-2 was added. The addition of Polyquaternium-2 could also increase the cathodic polarization, which is attributed to the adsorption of Polyquaternium-2 on the cathode in the process of TH electroplating. The results indicate that Polyquaternium-2 is an effective leveler used for TH electroplating, having a good synergy with SPS, PEG and Cl − .

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“…24 Inhibitors prevent plating by forming a thin, passivating film at the substrate surface that obstructs and envelopes the copper ions. [37][38][39] The inhibiting capability is dependent on the molecular weight of the polymer, and has the ability to reduce deposition kinetics by as much as two orders of magnitude. 40 Therefore, a sufficiently large cathodic potential is required for copper ion reduction.…”

Section: The Additives-assisted Electrodeposition Modelmentioning

confidence: 99%

Modeling Macro-Sized, High Aspect Ratio Through-Hole Filling by Multi-Component Additive-Assisted Copper Electrodeposition

Childers

Johnson

Ramírez‐Rico

et al. 2013

J. Electrochem. Soc.

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A multi-element, time-dependent model is used to examine additive-assisted copper electroplating in macro-channels. This model is an adaptation of the work of Akolkar and Landau [J. Electrochem. Soc., 156, D351 (2009)], used to describe plating in micro-vias for integrated circuits. Using their method for describing species movement in the channel, the model has been expanded to include transport and adsorption limitations of the inhibitor and accelerator, as well as the copper ions in solution. The model is used to investigate copper plating as an infiltration method across many size scales and aspect ratios. Biomorphic graphite scaffolds produced from wood are used as a representative system and the results of a two-additive bath are used to characterize the behavior of the additives and determine the effectiveness of the plating. The results indicate that at macro-scales, channel dimensions play an increasingly important role in dictating the behavior of additive-assisted plating. Because additive systems are designed to establish differential surface coverage within the channel, the success of which is determined by the additive's rates of diffusion and adsorption, certain size scale/aspect ratio combinations preclude such coverage. A guide for sample geometries that may be successfully infiltrated with a two-additive bath is provided. Electrodeposition is a common method of producing multicomponent material systems.1,2 This technique is useful in overcoming common melt-based composite processing constraints, such as high melting points, fragile scaffolds, non-wetting components, and significant coefficient of thermal expansion (CTE) mismatch. Unlike melt infiltration or reactive wetting, electrodeposition is a low-temperature, non-reactive process. While electroformed copper is employed in the fabrication of items such as musical instruments, reflectors, and heat exchangers, 1 the electronics sector is responsible for the majority of advancements in the field, especially in terms of use as an infiltration method. Electrodeposition is used for interconnect metallization in integrated circuits, where small channels in a silicon wafer, known as vias, are filled with high purity copper. IBM pioneered this technique in 1998 to replace aluminum vapor deposition.3,4 While the microvias used in current integrated circuit technology can reach several hundred microns in dimension, channel size is trending toward nanosized, closely packed channels. [5][6][7] In other functional composites, one might contend with larger length scales and aspect ratios compared to metal interconnects. With this as motivation, we explore the feasibility of using existing electroplating techniques for composite processing of non-interconnect systems through a multi-component, time-dependent model. Specifically, we investigate infiltration of a metal into highly porous ceramic scaffolds with macro-sized channels.As a macro-porous system for study, we examine biomorphic SiCand graphite-Cu composites produced by electrodeposition, which may ...

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Behaviour of poly(ethylene glycol) during electrodeposition of bright copper coatings in sulfuric acid electrolytes

Cited by 126 publications

References 19 publications

Chemical Mechanism of Suppression of Copper Electrodeposition by Poly(ethylene glycol)

Chemical Mechanism of Suppression of Copper Electrodeposition by Poly(ethylene glycol)

Polyquaternium-2: A New Levelling Agent for Copper Electroplating from Acidic Sulphate Bath

Modeling Macro-Sized, High Aspect Ratio Through-Hole Filling by Multi-Component Additive-Assisted Copper Electrodeposition

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