Electrodeposition of Cu from Acidic Sulfate Solutions in the Presence of Bis-(3-sulfopropyl)-disulfide (SPS) and Chloride Ions

Bozzini, Benedetto; D’Urzo, Lucia; Romanello, V.; Mele, Claudio

doi:10.1149/1.2172555

Cited by 42 publications

(40 citation statements)

References 46 publications

(41 reference statements)

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“…7. When chloride ion is present in a Cu bath, SPS is adsorbed on Cu surface during electrodeposition, which was found by Bozzini et al from in situ Raman study [27]. We also found the CuS bonding on the Cu surface pre-modified with SPS by XPS.…”

Section: The Influence Of End-group Of Thiolate On the Pattern Shape supporting

confidence: 83%

“…3.5. Schematic mechanism for the tapered pattern shape of Cu deposit during electrodeposition in a Cu bath containing SPS and Cl À We therefore attempted to propose a mechanism, which may describe the sloped growth of Cu deposit adjacent to P/R mask and the electrochemical feature of SPS and Cl À and during electrodeposition, consistent with the available concepts of SAMs and electrochemical behavior of SPS and Cl À published in the literature [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28].…”

Section: The Influence Of End-group Of Thiolate On the Pattern Shape mentioning

confidence: 75%

“…The structure of adsorbed MPS was affected by the interaction of its sulfonate end-group, copper ion, chloride ion and Cu cathode surface during electrodeposition as shown in Fig. 7a [23,[25][26][27][28]. Furthermore, in a Cu bath containing SPS and Cl À , inclusion of MPS and Cl À was found in the Cu deposit [22].…”

Section: The Influence Of End-group Of Thiolate On the Pattern Shape mentioning

confidence: 98%

See 2 more Smart Citations

The influence of self-assembled disulfide additive on the pattern shape by Cu electrodeposition through mask

Jenq

Wan

Wang

2007

Journal of Electroanalytical Chemistry

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Section: The Influence Of End-group Of Thiolate On the Pattern Shape supporting

confidence: 83%

Section: The Influence Of End-group Of Thiolate On the Pattern Shape mentioning

confidence: 75%

Section: The Influence Of End-group Of Thiolate On the Pattern Shape mentioning

confidence: 98%

See 1 more Smart Citation

The influence of self-assembled disulfide additive on the pattern shape by Cu electrodeposition through mask

Jenq

Wan

Wang

2007

Journal of Electroanalytical Chemistry

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“…Effect of organosulfide.-For copper electrodeposition, mercaptosulfonate compounds such as 3-mercapto-1-propanesulfonic acid (MPS) 4,52,53 or bis(3-sulfopropyl) disulfide (SPS) [54][55][56][57] are commonly used as growth acceleration additives to enhance copper growth, especially at the bottom of microvias. Few articles have reported the use of ZPS and UPS as accelerators or brighteners for copper electrode- position because their accelerating and brightening effect on copper electrodeposition is much weaker than that of MPS and SPS.…”

Section: Effect Of Chloride Ion Concentration-mentioning

confidence: 99%

Characterization of Through-Hole Filling by Copper Electroplating Using a Tetrazolium Salt Inhibitor

Lin

Yan

Yen

et al. 2013

J. Electrochem. Soc.

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Through-hole (TH) filling of an advanced printed circuit board (PCB) by copper electroplating is performed using a direct current (DC) plating method and a simple copper plating formula composed of a single organic additive, namely, nitrotetrazolium blue chloride monohydrate (NTBC). Copper is preferentially deposited at the hole center to form a butterfly-shaped copper cross-section in the filled TH during plating. Three key factors are identified for enhancing the filling performance via a center protrusion deposition in the TH and are characterized by practical filling plating results and cyclic voltammetry (CV) analyzes. The filling performance of the copper plating formula for the TH is sensitive to forced convection, chloride ion concentrations and H 2 SO 4 concentrations. An appropriate forced convection combined with weak accelerators [3-(Benzothiazolyl-2-mercapto)-propylsulfonic acid, sodium salt (ZPS) or 3-S-Isothiuronium propyl sulfonate (UPS)] pre-adsorbed on the copper seed layer of the TH can effectively shorten the fill plating time from 9 h to 5 h. The center-protrusion filling mechanism and the role of NTBC in the TH filling are discussed in this work based on the plating results and electrochemical analyzes.

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“…[23][24][25] Bozzini et al also revealed that SPS is absorbed on Cu surface during electrodeposition by in situ Raman study, when chloride ion is present in Cu bath. 26 In addition, the interactions between SPS, Cu ion, chloride ion, and electrode surface play an important role in depolarization during electrodeposition. 27 Schultz et al detected the CuCl coordination to sulfonate end group of SPS from vibrational spectroscopic and mass spectrometric studies.…”

Section: Resultsmentioning

confidence: 99%

Tapered Cu Pattern Metallization by Electrodeposition Through Mask

Jenq

Wan

Wang

et al. 2006

Electrochem. Solid-State Lett.

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A tapered shape of Cu pattern by electrodeposition through mask is preferred for fabricating metal line on thin-film transistors ͑TFTs͒. The influence of individual organic additive ͓polyethylene glycol ͑PEG͒, bis-3-sodiumsulfopropyl disulfide ͑SPS͔͒ on the sidewall shape of the Cu pattern was identified. A compromising effect shows up when both PEG and SPS are added owing to the competition of the behavior of two different organic additives during Cu electrodeposition. Therefore, a method has been developed for the fabrication of copper pattern used in TFTs, which forms a tapered pattern in one single Cu deposition step.With increasing demand for large panels with high resolution, the signal delay of the gate and data lines of thin-film transistors ͑TFTs͒ resulting from high resistance of very fine metal lines becomes crucial. 1 Therefore, how to reduce the signal delay by replacing Al or Al alloy currently employed with metals of lower resistivity has been under intensive study. [2][3][4][5] Lately, copper metallizations for active matrix-liquid crystal displays ͑AM-LCDs͒ have attracted much attention because of the successful experience in fabricating ultralarge scale integrated ͑ULSI͒ circuits. 3-7 However, there are several unsolved issues for copper metallization on TFTs, which are different from ULSI circuits owing to the differences in structure and feature size between TFTs and ULSI circuits. One of the key issues is how to form the Cu pattern. Electrodeposition and chemical mechanical polishing ͑CMP͒ are two key technologies used in the damascene process of ULSI circuits. However, the area of TFTs substrate is greatly larger than that of a 12 in. wafer. It is difficult to apply the CMP method to prepare Cu pattern on TFTs. 8 Therefore, current methods for forming Cu pattern for TFTs tend to focus on Cu metallization plus etching. Common methods for Cu metallization include physical vapor deposition ͑PVD͒, chemical vapor deposition ͑CVD͒, and electrodeposition. Cu electrodeposition has become an increasingly attractive method because it requires a relatively low working temperature and yields a high deposition rate with low cost. 9,10 Few details about copper electrodeposition for pattern metallization on TFTs have been revealed in published literature. In brief, there are two major methods for forming Cu pattern by electrodeposition. One is the subtractive process including panel deposition and etching of copper, and the other is the additive process consisting of Cu deposition through mask and etching of conductive layer. 11 Current studies of Cu pattern for TFTs focus on the subtractive process. 3-8 However, the additive process for electrodeposition has the feature of selectively forming metal deposit and etching conductive layer rather than panel deposition and etching of full metal layers as the subtractive process requires.

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Electrodeposition of Cu from Acidic Sulfate Solutions in the Presence of Bis-(3-sulfopropyl)-disulfide (SPS) and Chloride Ions

Cited by 42 publications

References 46 publications

The influence of self-assembled disulfide additive on the pattern shape by Cu electrodeposition through mask

The influence of self-assembled disulfide additive on the pattern shape by Cu electrodeposition through mask

Characterization of Through-Hole Filling by Copper Electroplating Using a Tetrazolium Salt Inhibitor

Tapered Cu Pattern Metallization by Electrodeposition Through Mask

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