Effect of thiourea, benzotriazole and 4,5-dithiaoctane-1,8-disulphonic acid on the kinetics of copper deposition from dilute acid sulphate solutions

Farndon, E. E.; Walsh, Frank C.; Campbell, S. A.

doi:10.1007/bf00573215

Cited by 135 publications

(114 citation statements)

References 25 publications

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“…There are several matured techniques that can fabricate the Cu wire/interconnect, such as sputtering, evaporation, and electrochemical deposition, among which electrochemical deposition (also known as electroplating) is a cost-effective method capable of making uniform and hole-filling Cu metallization [1,[4][5][6]. In addition to basic constitutes such as sulfuric acid and copper sulphate, it is necessary to add several functional additives in the plating bath to assist or modulate the deposition of Cu atoms on non-planar substrates [7][8][9][10][11][12][13][14]. For example, in TSV Cu-filling process, two typical organic additives are usually used, one is polyethylene glycol (PEG) the electrodeposition of Cu, and therefore, the impurity effect becomes more and more significant.…”

Section: Introductionmentioning

confidence: 99%

Impurity Effects in Electroplated-Copper Solder Joints

Lee

Chen

2018

Metals

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Copper (Cu) electroplating is a mature technology, and has been extensively applied in microelectronic industry. With the development of advanced microelectronic packaging, Cu electroplating encounters new challenges for atomic deposition on a non-planar substrate and to deliver good throwing power and uniform deposit properties in a high-aspect-ratio trench. The use of organic additives plays an important role in modulating the atomic deposition to achieve successful metallic coverage and filling, which strongly relies on the adsorptive and chemical interactions among additives on the surface of growing film. However, the adsorptive characteristic of organic additives inevitably results in an incorporation of additive-derived impurities in the electroplated Cu film. The incorporation of high-level impurities originating from the use of polyethylene glycol (PEG) and chlorine ions significantly affects the microstructural evolution of the electroplated Cu film, and the electroplated-Cu solder joints, leading to the formation of undesired voids at the joint interface. However, the addition of bis(3-sulfopropyl) disulfide (SPS) with a critical concentration suppresses the impurity incorporation and the void formation. In this article, relevant studies were reviewed, and the focus was placed on the effects of additive formula and plating parameters on the impurity incorporation in the electroplated Cu film, and the void formation in the solder joints.

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Section: Introductionmentioning

confidence: 99%

Impurity Effects in Electroplated-Copper Solder Joints

Lee

Chen

2018

Metals

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“…The electrochemical reaction for the reduction of TU was also reported. 24,25 As mentioned above, here we propose a reaction scheme for the electrodeposition of Cu in the presence of TU. In addition, the proposed reaction model does not consider TU-Cu complexes because of the low concentration of TU in the experiment and assumes that the adsorption and desorption reactions of TU are affected by overvoltage.…”

Section: Measurement Of Impedance Spectra Of Cu Electrodementioning

confidence: 99%

“…The small amounts of additives are added to the main electrolyte solution to control the electrodeposition rate of Cu and improve the electrical properties of the deposited Cu layer. 2,3 The roles of additives can be divided into four groups: (1) accelerator (Cl ¹ ), [4][5][6][7][8][9] (2) polymer (Polyethyleneglycol and polypropyleneglycol), [10][11][12][13][14][15][16] (3) brightener, (Bis(sodiumsulfopropyl)disulfide and 3-mercapto-1-propanesulfonate sodium salt), [17][18][19][20][21] and (4) leveler (Thiourea (TU), [22][23][24] benzotriazol, [25][26][27] and Janus Green B [28][29][30] ). An electrochemical impedance spectroscopy (EIS) has been widely employed to clarify the Cu electrodeposition mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Interpretation of Negative Resistance Observed in Electrochemical Impedance during Copper Electrodeposition Containing Thiourea

et al. 2015

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The effect of the thiourea on the electrochemical impedance during copper electrodeposition was investigated using a rotating ring disk electrode. The rest potential of the copper electrode measured in the solution containing thiourea was shifted to less noble due to the adsorption of thiourea. The cathode polarization curve of the copper electrode demonstrated that the current density of the copper electrode decreased remarkably because of an increase in the concentration of thiourea. The Nyquist plot of impedance spectrum in the presence of the thiourea described the capacitive loop, which was related to the time constant of the charge transfer resistance and the electric double layer capacitance, in the high frequency range and a part of the large locus crossing the imaginary axis in the low frequency range. This low frequency locus is related to negative resistance which contributes to "leveler" effect. In order to clarify the negative resistance, the theoretical equations of the Faraday impedance were derived. We proposed the four steps of the copper electrodepostion reactions in the presence of thiourea.

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“…An extensive list of additives used in acid copper plating prior to 1959 can be found in the literature [5] and in the acid copper chapter in a previous edition of this book [6]. Additives covered in patents granted in recent years are listed in Table 2 [84,85,93,94], cadmium [95], casein [96], cobalt [97], dextrin [96], dimethylamino derivatives [98], disulfides [98,99], 1,8-disulfonic acid [93], disodic 3,3-dithiobispropanesulfonate [100], 4,5-dithiaoctane-l,8 disulfonic acid [93], dithiothreitol [101], ethylene oxide [100], gelatin [102], glue [76,96], gulac [76], lactose benzoylhydrazone [103], 2-mercaptoethanol [104], molasses [96], sulfonated petroleum [76], o-phenanthroline [95,105], polyethoxy ether [106], polyethylene glycol [87,107,108], polyethylene imine [107], poly N,N 0 -diethylsaphranin [100], polypropylene ether [109,110], propylene oxide [100], sugar [96], thiocarbamoyl-thio-alkane sulfonates [111], and thiourea [76,81,…”

Section: Addition Agentsmentioning

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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Effect of thiourea, benzotriazole and 4,5-dithiaoctane-1,8-disulphonic acid on the kinetics of copper deposition from dilute acid sulphate solutions

Cited by 135 publications

References 25 publications

Impurity Effects in Electroplated-Copper Solder Joints

Impurity Effects in Electroplated-Copper Solder Joints

Interpretation of Negative Resistance Observed in Electrochemical Impedance during Copper Electrodeposition Containing Thiourea

Electrodeposition of Copper

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