Investigation of novel leveler Rhodamine B on copper superconformal electrodeposition of microvias by theoretical and experimental studies

Li, Yaqiang; Ren, Penghui; Zhang, Yuanhang; Li, Ruopeng; Zhang, Jinqiu; Yang, Peixia; Liu, Anmin; Wang, Guangzhao

doi:10.1016/j.apsusc.2022.156266

Cited by 26 publications

(8 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Cyclic voltammetry (CV) is widely used to determine the suppressing effect of additives Figure a shows that the onset cathodic potential without BB1 is about −0.45 V. In contrast, 20 mg/L BB1 effectively increases cathodic polarization, leading to the onset potential shifting to −0.55 V. When the BB1 concentration is 500 mg/L, the cathodic onset potential is reduced to lower than −0.65 V, illustrating that BB1 has suppressing effects during copper electrodeposition.…”

Section: Resultsmentioning

confidence: 99%

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

Li,

et al. 2023

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 99%

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

Li,

et al. 2023

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

show abstract

“…The role of additive concentration has not been studied in this work. When choosing this parameter for this or that additive, we took into account that the concentration range of the accelerator, inhibitor, and leveler varies quite widely when studying their effect on the process of copper electrodeposition: from 0.001-1 mg/L [6,25,28,38,[44][45][46][47][48][49] to 1-5 g/L [19,29,[50][51][52]. In this study, concentrations close to the average values for the particular type of additive were used.…”

Section: Additives and Their Concentrations Electrolyte Codementioning

confidence: 99%

“…Levelers are used to obtain smooth coatings since they locally decrease the copper electrodeposition rate on the surface protrusions and promote its growth in hollows, as a result of which the surface roughness of the copper deposit decreases. Nitrogen-containing heterocyclic and high-molecular compounds are among the most common levelers [28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

“…This paper considers in more detail one of the most important factors determining the choice of additive-assisted electrolyte composition, namely their influence on the kinetics and mechanism of the electrochemical deposition of copper at the limiting stages of charge transfer and electrocrystallization [6,29,34,39,40]. It is well known that the quality of electrodeposited copper depends on the rate of the early stage of electroplating and especially that of nucleation [41].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Kozaderov,

Sotskaya,

Yudenkova

et al. 2023

Coatings

View full text Add to dashboard Cite

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.

show abstract

“…6 To meet the high-performance requirements of electronic products, the filling of microvias with copper plating is imperative to achieve seamlessness or gap-free structures, referred to as "superfilling" or "bottom-up filling," thereby posing a challenge to the copper plating process. 7,8 Presently, the copper plating process encounters difficulties in actual production due to the edge effect, wherein the local current density at the aperture opening surpasses that of other hole regions, leading to the formation of defective UNCORRECTED PROOF cavities. 9,10 Moreover, there exists a certain lack of copper layer flatness, diminishing the quality and reliability of copper interconnections and impacting the service life of electronic chemicals.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Quinacridone Derivatives and Their Application as High Performance Levelers in Electroplating

ZOU,

XIANG,

et al. 2024

Electrochemistry

View full text Add to dashboard Cite

A series of quaternary ammonium salts base on quinacridone aromatic ring were synthesized using 2,9-quinacridone as the parent material, and their leveling performance were evaluated using constant-current chronoamperometry addition curves. Additionally, the adsorption abilities of the leveler molecules on copper surfaces were investigated through quantum chemical calculations and molecular dynamics simulations, and their specific adsorption sites on the copper surface were investigated by XPS, then the effect of concentration on the leveling performance was probed by through-hole plating, and the copper surface was characterized by XRD and SEM. Among four quinacridone aryl quaternary ammonium salts, DCQA-C 8 -MI exhibits optimal leveling effects, serving as an excellent leveler with outstanding performance. This study expands the application scope of quinacridone aromatic heterocyclic quaternary ammonium salts and offers insights for exploring efficient organic additives for copper electrodeposition.

show abstract

Investigation of novel leveler Rhodamine B on copper superconformal electrodeposition of microvias by theoretical and experimental studies

Cited by 26 publications

References 53 publications

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

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

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

Synthesis of Quinacridone Derivatives and Their Application as High Performance Levelers in Electroplating

Contact Info

Product

Resources

About