Working mechanism of iodide ions and its application to Cu microstructure control in through silicon via filling

Sung, Minjae; Kim, Sang‐Hyeok; Lee, Hyojong; Lim, Taeho; Kim, Jae Jeong

doi:10.1016/j.electacta.2018.10.141

Cited by 16 publications

(26 citation statements)

References 26 publications

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“…However, at 3500 s, the inhibitory effect of the leveler suddenly failed, and the cathodic potential increased rapidly (Δη = 62 mv). Unlike PTZ-8, PTZ-6 showed stable quenching at 1000 rpm and failed at 100 rpm, so it could achieve a strong CDA behavior that had not been observed in our previous work …”

Section: Resultsmentioning

confidence: 54%

“…Unlike PTZ-8, PTZ-6 showed stable quenching at 1000 rpm and failed at 100 rpm, so it could achieve a strong CDA behavior that had not been observed in our previous work. 38 To confirm that PTZ-6 did not lose its effect under conditions of strong convection, a stability test was performed to record the potential (Figure 3c) of PTZ-6 for 2000 s after it was added. It could be seen that the potential of the electrode was very smooth until 4200 s when a small oscillation of the potential occurred.…”

Section: Galvanostatic Measurementsmentioning

confidence: 99%

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Strong Convection-Dependent Adsorption of Phenothiazine Skeleton Levelers and Their Application in Copper Electroplating

et al. 2023

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The design and synthesis of high-performance levelers remain a major challenge to date. Herein, a series of phenothiazine (PTZ) derivatives were designed and synthesized, and they had a butterfly conformation, and their adsorption capacities were easier to modulate. To check out the inhibition capabilities among these eight PTZ derivatives, electrochemical measurements and theoretical calculations were carried out, and PTZ-8 indicated the strongest inhibition capabilities among these PTZ derivatives. Besides, galvanostatic measurements were also carried out to evaluate the overall performance of the levelers. The results showed that PTZ-8 had a potential oscillation, but PTZ-6 had strong convection-dependent adsorption. Due to the potential oscillation of PTZ-8, PTZ-6 as the representative leveler was selected for through-hole electrodeposition. In addition, field-emission scanning electron microscope images and X-ray diffraction results displayed the surface morphology, which indicated that the addition of PTZ-6 could lead to a fine copper deposit and cause the preferential orientations of copper deposits to change from [220] to [111]. This study might lay the foundation for the design of high-performance levelers.

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Section: Resultsmentioning

confidence: 54%

Section: Galvanostatic Measurementsmentioning

confidence: 99%

Strong Convection-Dependent Adsorption of Phenothiazine Skeleton Levelers and Their Application in Copper Electroplating

et al. 2023

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“…Many studies have been conducted on the behavior of additives and their growth mechanisms; however, various additives are still being developed for copper electrodeposition. [19][20][21][22][23][24] In the case of nickel, one of the iron group metals, there have also been many studies on additives for superconformal filling. Polyethyleneimine (PEI) and benzimidazole derivatives, such as 2-mercaptobenzimidazole (MBI) and 2-mercapto-5-benzimidazolesulfonic acid (MBIS), were shown to yield void-free feature filling.…”

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confidence: 99%

Superconformal Cobalt Electrodeposition with a Hydrogen Evolution Reaction Suppressing Additive

Kang

Sung

Byun

et al. 2020

J. Electrochem. Soc.

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In this study, superconformal cobalt filling of submicron trenches by electrodeposition is investigated in the presence of 2-mercaptobenzimidazole (MBI), which suppresses both cobalt deposition and the hydrogen evolution reaction (HER). The mechanism through which this single additive enables superconformal cobalt filling is investigated. The formation and breakdown of the suppression layer are characterized by linear sweep voltammetry and chronoamperometry. The convection-driven local concentration of MBI exerts different suppressing effects on cobalt reduction and the HER, leading to a change in the deposition rate and the current efficiency of cobalt. These phenomena induce a deposition rate differential between the top and bottom of the submicron trench, enabling bottom-up cobalt filling with a V-shape profile.

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“…For the Damascene features, a combination of an accelerator and a suppressor is sufficient to achieve defect-free filling, whereas an additional organic leveler is necessary for microvias and through-holes. [5][6][7][8][13][14][15][16][17][18] The leveler additionally inhibits Cu deposition near the opening of filling features, facilitating the bottom-up filling of Cu. The previous achievements in Cu electrodeposition and the development of organic additives have contributed to the continuous development of the semiconductor industry.…”

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confidence: 99%

Bromide Ion as a Leveler for High-Speed TSV Filling

Sung

Yoon

Hong

et al. 2019

J. Electrochem. Soc.

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Organic levelers have been essential additives for Cu electrodeposition to achieve defect-free filling of through-silicon vias (TSVs). They selectively inhibit Cu deposition on top of TSVs, avoiding the occlusion of TSV openings and concentrating Cu deposition inside the TSVs. We recently reported that iodide ions (I − ) can act as an inorganic leveler to induce defect-free TSV filling. However, it was found that I − considerably decreased the efficiency of Cu electrodeposition because of the formation of an unstable CuI suppression layer on top of the wafer. The CuI layer easily detached from the wafer, and additional electrons were consumed to reestablish the suppression layer during gap-filling. This study introduces a TSV filling process with bromide ions (Br − ) as an alternative to I − . Although the suppression strength of Br − to Cu electrodeposition is weaker than that of I − , Br − forms a more stable suppression layer that does not reduce the efficiency of Cu electrodeposition, enabling high-speed TSVs filling. As a result, the filling rate with Br − was twice as fast as that with I − at the same applied current density; thereby TSVs 60 μm deep and 5 μm in diameter were completely filled in 500 s.

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Working mechanism of iodide ions and its application to Cu microstructure control in through silicon via filling

Cited by 16 publications

References 26 publications

Strong Convection-Dependent Adsorption of Phenothiazine Skeleton Levelers and Their Application in Copper Electroplating

Strong Convection-Dependent Adsorption of Phenothiazine Skeleton Levelers and Their Application in Copper Electroplating

Superconformal Cobalt Electrodeposition with a Hydrogen Evolution Reaction Suppressing Additive

Bromide Ion as a Leveler for High-Speed TSV Filling

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