Hydroquinone oriented growth control to achieve high-quality copper coating at high rate for electronics interconnection

Li, Zheng; Wang, Chong; Cai, Deng’an; Huang, Yunzhong; Adi, Kegu; Yan, Hong; Chen, Yuanming; Zhou, Guoyun; Armini, Silvia; Gendt, Stefan De; Wang, Shouxu; He, Wei

doi:10.1016/j.jtice.2020.07.004

Cited by 13 publications

(4 citation statements)

References 31 publications

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“…Finally, after the introduction of the ABT additive (solution IV), the surface morphology of the sample almost does not change, but there are no defects in the copper coating, and the surface is the smoothest (Figure 4e). These observations correlate with the data on the smoothing and leveling effects of PEG and ABT [4,11,18,20,21] and confirm that this effect remains in the presence of the DBDA additive as an accelerator.…”

Section: Resultssupporting

confidence: 85%

“…This is of particular importance when filling the through-silicon vias (TSVs) with a high aspect ratio [3], and in particular, a superfilling process [4][5][6] should be implemented because it is significantly important to realize an effective deposition mechanism in microvia metallization for PCBs so as to interconnect those electronic components [7]. Therefore, various organic additives are introduced into the copper plating electrolyte [8][9][10][11][12][13][14][15][16][17][18][19], which, depending on the specific function performed during deposition, are divided into inhibitors, accelerators, and levelers.…”

Section: Introductionmentioning

confidence: 99%

“…Inhibitors are high-molecular compounds, for example, polyethylene glycol (PEG) [4,11,18,20,21]. Acting together with chloride ions, PEG forms a blocking layer on the copper surface, thereby increasing the overpotential of the deposition process [21] and decreasing its rate.…”

Section: Introductionmentioning

confidence: 99%

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Electrocrystallization and Morphology of Copper Coatings in the Presence of Organic Additives

Kozaderov,

Sotskaya,

Yudenkova

et al. 2023

Coatings

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Copper coatings with refined grains and smooth surface morphology were electrodeposited from electrolytes comprising a novel accelerator, the disodium salt of 4,4-dithiobenzene disulfonic acid (DBDA), with sodium chloride and polyethylene glycol (PEG) as inhibitors and 2-aminobenzothiazole (ABT) as a leveler. It was found that the morphology of the coatings strongly depends on the presence and type of additives. In the presence of only DBDA and NaCl, large crystallites are formed, whereas the addition of PEG and ABT significantly decreases their size, and the most fine-grained, smooth, and defect-free copper coating is formed with the combined use of all additives. To establish the correlation between the observed morphology and the kinetics of the additive-assisted copper electrocrystallization in the proposed electrolytes, the nucleation mechanism and its parameters were determined by transient electrochemical characterization. The extended nucleation model, which takes into account not only the copper deposition but also the electric double-layer charging and hydrogen reduction process, was used to establish the electrocrystallization kinetics in the presence of the additives. The results of such kinetic analyses can help to explain the morphological effect. By using the chronopotentiometry method, it was found that the addition of the disodium salt of 4,4-dithiobenzene disulfonic acid with chloride ions gives a catalytic effect, while the sequential introduction of polyethylene glycol and 2-aminobenzothiazole provides an increasing inhibitory effect. Voltamperometry and chronoamperometry tests showed that the process is controlled by the diffusion of ions to the growing three-dimensional cluster of a new phase. The introduction of additives into the electrolyte slows down the copper electroplating process at comparatively negative potentials and increases the probability of transition from instantaneous to progressive nucleation. Moreover, the rate of the process and the density of nucleation active sites increase (up to 2–3 times) with the addition of DBDA but decrease significantly (up to 5–8 times) in the presence of PEG and ABT, which additionally confirms their catalytic and inhibitory effects, respectively, and explains the significant smoothing effect on the morphology of the Cu-coatings.

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Section: Resultssupporting

confidence: 85%

Section: Introductionmentioning

confidence: 99%

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Electrocrystallization and Morphology of Copper Coatings in the Presence of Organic Additives

Kozaderov,

Sotskaya,

Yudenkova

et al. 2023

Coatings

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“…The R a and R q values are further decreased to 85 and 106 nm when the BB1 concentration is increased up to 200 mg/L. The relatively low surface roughness is beneficial for lowering the transmission signal losses …”

Section: Resultsmentioning

confidence: 97%

Experimental and Theoretical Study of the New Leveler Basic Blue 1 during Copper Superconformal Growth

Li,

et al. 2023

ACS Appl. Mater. Interfaces

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A novel chlorinated functional group-modified triphenylmethane derivative leveler BB1 is used to achieve superconformal electrodeposition in microvias. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are performed to study the suppressing effect of BB1, while the convection-dependent adsorption of BB1 on the copper surface is analyzed by galvanostatic measurement, and a BB1 concentration window between 100 and 200 mg/L is beneficial for superfilling. The interactions among BB1, bis-(sodium sulfopropyl) disulfide (SPS), and poly(ethylene glycol) (PEG) are also investigated. Density functional theory (DFT) calculation and in situ Raman spectroscopy are coupled to study the suppression mechanism and synergistic suppression mechanism, namely, the adsorption effect between BB1 and copper substrate, as well as the coordination effect between the modified chlorinated functional group and Cu 2+ , is proposed. The copper layer becomes smoother and more compact with an increase in BB1 concentration, according to scanning electron microscopy (SEM) and atomic force microscopy (AFM), while X-ray diffraction (XRD) analysis shows that the introduction of BB1 is conducive to the formation of the copper (220) plane. Besides, the solution wettability is boosted by BB1. A copper interconnecting layer with high quality is achieved with 150 mg/L BB1, while the surface deposition thickness (SDT) is about 34 μm and filling percentages (FPs) for microvias with diameters of 100, 125, and 150 μm are 81. 34, 82.72, and 81.39%, respectively.

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Periodic pulse reverse plating achieve high throwing power of high aspect ratio electronic interconnection: simulation and experiments

Zhang

You

Liu

et al. 2022

Ionics

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Hydroquinone oriented growth control to achieve high-quality copper coating at high rate for electronics interconnection

Cited by 13 publications

References 31 publications

Electrocrystallization and Morphology of Copper Coatings in the Presence of Organic Additives

Electrocrystallization and Morphology of Copper Coatings in the Presence of Organic Additives

Experimental and Theoretical Study of the New Leveler Basic Blue 1 during Copper Superconformal Growth

Periodic pulse reverse plating achieve high throwing power of high aspect ratio electronic interconnection: simulation and experiments

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