Effects of Additives on Copper Electrodeposition in Submicrometer Trenches

Hasegawa, Masaya; Negishi, Yoshinori; Nakanishi, Tetsuya; Osaka, Tetsuya

doi:10.1149/1.1867672

Cited by 108 publications

(89 citation statements)

References 27 publications

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“…This combination of additives has been commonly used for via-filling or superfilling. 13,14,16,20,21 Although smooth surface morphologies were obtained, MWCNTs were barely observed in the films. This shows that the simple addition of a typical combination of additives does not yield ideal Cu-MWCNT composite films.…”

Section: Methodsmentioning

confidence: 97%

Effects of Additives on Cu-MWCNT Composite Plating Films

Arai¹,

Saitō²,

Endo

2010

J. Electrochem. Soc.

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The effects of plating bath additives on copper-multiwalled carbon nanotube ͑MWCNT͒ composite platings were studied. An acidified cupric sulfate electrolyte containing MWCNTs and polyacrylic acid as a dispersing agent was used as the base plating bath. Chloride ions ͑Cl − ͒, poly͑ethylene glycol͒, bis͑3-sulfopropyl͒disulfide ͑SPS͒, and Janus green B ͑JGB͒ were examined as additives. The surface morphologies and cross-sectional microstructures of the electrodeposited films were investigated, and the MWCNT content of the films was determined. Furthermore, the electrical resistivity and field emission properties of the films were evaluated. The simultaneous addition of Cl − , SPS, and JGB to the base plating bath was effective for forming smooth Cu-MWCNT composite films with a high MWCNT content over a wider range of current densities. The optimal bath composition was 0.85 mol dm −3 CuSO 4 ·5H 2 O + 0.55 mol dm −3 H 2 SO 4 + 100 ppm PA5000 + 2 g dm −3 MWCNTs + 2 ppm SPS ϩ 2 ppm JGB ϩ50 ppm Cl Ϫ . Cu-MWCNT composite films containing 0.15-0.33 mass % MWCNTs with smooth surface morphologies were formed in the current density range of 0.5-5 A dm −2 . The electrical resistivity of the films was around 2 ⍀ cm, and they showed obvious field emission properties.

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Section: Methodsmentioning

confidence: 97%

Effects of Additives on Cu-MWCNT Composite Plating Films

Arai¹,

Saitō²,

Endo

2010

J. Electrochem. Soc.

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“…generic, plating solutions (GPS). The GPS's are formulated with various mixtures of chemicals of the type that are known to be indispensable in super conformal Cu plating: Cu sulfate, sulfuric acid, Cl -ions and organic additives, such as polyethylene glycol (PEG) [17][18][19][20]. The morphology and organic impurity levels of selected plated Cu samples are examined.…”

mentioning

confidence: 99%

Influence of plating parameters and solution chemistry on the voiding propensity at electroplated copper–solder interface

Liu

Wang

Yin³

et al. 2008

J Appl Electrochem

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Interfacial voiding in solder joints formed with Sn-Ag-Cu solder alloys and electroplated Cu was examined as a function of the plating solution chemistry and parameters. Galvanostatic Cu plating of *10 lm thick Cu films was performed in a commercially available plating solution, and in model generic plating solutions. Analysis of the current voltage behavior along with Secondary Ion Mass Spectrometry studies of organic impurity content of two plated and a wrought copper samples, yielded a conclusion that for certain chemistry solutions (e.g., H 2 SO 4 + CuSO 4 + Cl -+ PEG) and current density ranges above 2.5 mA cm -2 , organic impurities were incorporated into the growing Cu. Solder joints were produced with a variety of electroplated Cu samples. These joints were, then, annealed at a temperature of 175°C for 1 week, cross sectioned and examined. In general, it was observed that interfacial voiding in laboratory electroplated Cu layers was qualitatively similar to the unexplained voiding observed in some industrially plated Cu products. More specifically, it was found that the propensity for voiding could be correlated with specific electroplating parameters that in turn were associated with significant incorporation of organic impurities in the Cu deposit.

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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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Effects of Additives on Copper Electrodeposition in Submicrometer Trenches

Cited by 108 publications

References 27 publications

Effects of Additives on Cu-MWCNT Composite Plating Films

Effects of Additives on Cu-MWCNT Composite Plating Films

Influence of plating parameters and solution chemistry on the voiding propensity at electroplated copper–solder interface

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

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