In Situ Scanning Tunneling Microscopy Study of 3-Mercaptopropanesulfonate Adsorbed on Pt(111) and Electrodeposition of Copper in 0.1 M KClO<sub>4</sub> + 1 mM HCl (pH 3)

Yen, Po-Yu; Tu, Hsinling; Wu, Heng‐Liang; Chen, Sihzih; Vogel, Walter; Yau, Shuehlin; Dow, Wei Ping

doi:10.1021/jp111568z

Cited by 8 publications

(12 citation statements)

References 40 publications

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“…7,29,30,[50][51][52] Neither SPS nor MPS can facilitate copper electrodeposition in the absence of chloride ions. However, several groups 37,45 have explored the effect of electrolyte pH on the acceleration of an accelerator for copper electrodeposition. Figure 8A demonstrates that the accelerating effect of TBPS on copper electrodeposition depends strongly on the H 2 SO 4 concentration in the copper plating solution.…”

Section: Resultsmentioning

confidence: 99%

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Use of 3,3-Thiobis(1-propanesulfonate) to Accelerate Microvia Filling by Copper Electroplating

Chan

Chiu

Dow

et al. 2013

J. Electrochem. Soc.

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The most widely used accelerators for microvia filling by copper electroplating are 3-mercapto-1-propanesulfonate (MPS) and bis(3-sulfopropyl) disulfide (SPS). In this study, a new accelerator, 3,3-thiobis(1-propanesulfonate) (TBPS), which has neither a thiol group (e.g., MPS) nor a disulfide group (e.g., SPS) but rather contains a thioether group and two sulfonic acid groups, was investigated and formulated to perform microvia filling by copper electroplating. The accelerating effect of TBPS on copper electrodeposition and its chemical interaction with chloride ions and H 2 SO 4 were characterized by galvanostatic measurements. Electrochemical analyzes showed that the acceleration of TBPS on copper electrodeposition strongly depended on the chloride ion and H 2 SO 4 concentrations. An optimal copper plating solution composed of CuSO 4 , polyethylene glycol (PEG), TBPS, chloride ions, and H 2 SO 4 was developed and used to perform bottom-up copper filling of microvias. Although TBPS contains a thioether group instead of a thiol group, a trace amount of TBPS can strongly accelerate copper electrodeposition in the presence of proper chloride ion and H 2 SO 4 concentrations.

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Section: Resultsmentioning

confidence: 99%

“…Nevertheless, several papers reported that protons can enhance the surface coverage of SPS and MPS on gold and copper due to easy formation of trans conformations in the presence of protons. 37,45,[54][55][56][57] In addition, numerous researchers have reported that protons facilitate discharge …”

Section: Resultsmentioning

confidence: 99%

Use of 3,3-Thiobis(1-propanesulfonate) to Accelerate Microvia Filling by Copper Electroplating

Chan

Chiu

Dow

et al. 2013

J. Electrochem. Soc.

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“…Accelerators are usually small molecular compounds with sulfonic acid group (─SO 3 − ), disulfide bond and sulfhydryl (─SH) groups, [1,[17][18][19] adsorbed on the crystal surface of copper through ─SH group, and ─SO 3 − group, which can rapidly capture and reduce Cu 2+ to Cu under the action of chloride ions, thereby accelerate the deposition of copper. [20][21][22][23][24][25] Simultaneously, the adsorption mode of accelerators will change with the bath temperature. For example, with the increase of temperature, the adsorption of MPS (sodium 3-sulfhydryl 1-propane sulfonate) on the crystal surface of copper (111) will change from parallel adsorption to vertical adsorption, which affects the acceleration effect and the preferred orientation of grains.…”

Section: Introductionmentioning

confidence: 99%

Effects of DPS on Surface Roughness and Mechanical Properties of Electrodeposited Copper Foils

Zhang,

Yang,

Qin

et al. 2023

Cryst. Res. Technol.

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The roughness and mechanical properties of ultra‐low profile electrolytic copper foil seriously affect and restrict its application in high‐frequency/high‐speed printed circuit boards and Li‐ion batteries. herein, the electrochemical behavior and mechanism of 3‐N,N‐dimethylaminodithiocarbamoyl‐1‐propanesulfonic acid (DPS), alcohol sulfur propane sulfonate (HP), and hydrolisis animal protein (HAP) as composite additive for electrodeposition of copper foil is reported. Meanwhile, the effect of DPS on the roughness and mechanical properties of electrolytic copper foils is also investigated. The results show that addition of DPS further reduces the surface roughness of copper foil, due to the enhanced competitive adsorption of DPS with HAP, arising from the synergistic interaction between DPS and HP. additionally, the DPS can also reduce the grain size of copper foil and change the preferred orientation of the crystal plane, thereby improving the tensile strength of copper foil. The surface roughness of copper foil is as below as 1.02 µm. The tensile strength and the elongation of copper foil reach 386.5 MPa and 3.7%, respectively. Furthermore, the as‐obtained copper foil has high corrosion resistance and low resistivity. Therefore, the novel composite additive can pave the way for improving the quality of electrodeposited copper foil and realizing the possibility of widespread application.

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“…[8][9][10] The real-time and real-space imaging capability of scanning tunneling microscopy (STM) has been used to examine Cu deposition on Au and Pt single crystal electrodes. [11][12][13][14][15] Molecular-resolution STM imaging of the interface of the Cu deposit on these electrodes has revealed the spatial structures of adspecies, giving insights into the segregation of thiol molecules pre-deposited on the substrates. The MPA modifier to Au(111) results in marked differences in Cu deposition, although it is not imaged by in situ STM.…”

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confidence: 99%

Contrasts in Copper Deposition on Pt(111) Modified by 1-Mercaptopropionic and 1-Mercaptoacetic Acids as Probed by Voltammetry and STM

Yau

Huang

Dow

et al. 2018

J. Electrochem. Soc.

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Copper deposition on metal electrodes modified by organosulfur compounds has been extensively studied, from which some fundamental insights of this indispensable process used for semiconductor packaging have been obtained. This study employs voltammetry and scanning tunneling microscopy (STM) to examine Cu deposition on Pt(111) electrode modified with mercaptoacetic (MAA) and mercaptopropionic acids (MPA) in 0.1 M sulfuric acid containing 10 −5 M CuSO 4 . The slight difference in the molecular structures of these organic surfactants leads to stark differences in Cu deposition. Both electrochemical and STM results show that Cu deposition proceeds much faster at the MAA-than MPA-modified Pt(111) electrode. Bulk Cu deposit grows in layers and 3D crystallites on the MAA-and MPA-modified Pt(111) electrodes, respectively. STM imaging shows that MAA and MPA modifiers segregate from the Pt(111) electrode to the Cu deposit, arranging in ( √ 3 × √ 3)R30 • like structures after Cu UPD, and transforming to Moire and striped patterns for bulk Cu deposition. Although MAA and MPA adsorbed on Pt(111) are both hydrogen-bonded to their neighbors, the latter has a higher degree of freedom to orient on the electrode for more intermolecular hydrogen bonds, which decreases the interaction between -COOH and Cu 2+ and finally causes slower Cu deposition.

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In Situ Scanning Tunneling Microscopy Study of 3-Mercaptopropanesulfonate Adsorbed on Pt(111) and Electrodeposition of Copper in 0.1 M KClO₄ + 1 mM HCl (pH 3)

Cited by 8 publications

References 40 publications

Use of 3,3-Thiobis(1-propanesulfonate) to Accelerate Microvia Filling by Copper Electroplating

Use of 3,3-Thiobis(1-propanesulfonate) to Accelerate Microvia Filling by Copper Electroplating

Effects of DPS on Surface Roughness and Mechanical Properties of Electrodeposited Copper Foils

Contrasts in Copper Deposition on Pt(111) Modified by 1-Mercaptopropionic and 1-Mercaptoacetic Acids as Probed by Voltammetry and STM

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In Situ Scanning Tunneling Microscopy Study of 3-Mercaptopropanesulfonate Adsorbed on Pt(111) and Electrodeposition of Copper in 0.1 M KClO4 + 1 mM HCl (pH 3)

Cited by 8 publications

References 40 publications

Use of 3,3-Thiobis(1-propanesulfonate) to Accelerate Microvia Filling by Copper Electroplating

Use of 3,3-Thiobis(1-propanesulfonate) to Accelerate Microvia Filling by Copper Electroplating

Effects of DPS on Surface Roughness and Mechanical Properties of Electrodeposited Copper Foils

Contrasts in Copper Deposition on Pt(111) Modified by 1-Mercaptopropionic and 1-Mercaptoacetic Acids as Probed by Voltammetry and STM

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In Situ Scanning Tunneling Microscopy Study of 3-Mercaptopropanesulfonate Adsorbed on Pt(111) and Electrodeposition of Copper in 0.1 M KClO₄ + 1 mM HCl (pH 3)