Self-Diffusion of Oligo- and Poly(ethylene glycol)s in Poly(vinyl alcohol) Aqueous Solutions As Studied by Pulsed-Gradient NMR Spectroscopy

Masaro, L.; Zhu, X. X.; Macdonald, Peter M.

doi:10.1021/ma9710242

Cited by 52 publications

(113 citation statements)

References 29 publications

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“…37,44 Considered that the diffusive coefficient of accelerator (SPS) is two orders of magnitude bigger than that of suppressor (PEG), 3,25,45 the difference in diffusion rate of SPS and PEG was first taken into model to explain the inhibited via-top and accelerated via-bottom in via. Diffusion of additives in electrolyte is described by Fick's law…”

Section: 43mentioning

confidence: 99%

RETRACTED: Copper Electrodeposition in Through-Silicon Via under Galvanostatic Condition

Luo

Chen

Zhang

et al. 2016

J. Electrochem. Soc.

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We present a tertiary current-distribution model for copper electrodeposition under galvanostatic conditions, with detailed surface chemistry kinetics for the model system of copper electrodeposition. The values of the kinetic parameters are extracted from results of statistical chronoamperometry and linear sweep voltammetry experiments using a potential-dependent, diffusion-adsorptiondesorption model of the experimental system. The resulting surface chemistry description is combined with fundamental conservation laws, including mass transport, potential distribution, and competitive adsorption, to form the tertiary current distribution model. Two-dimensional finite element simulations of this model provide information about the causes of the thickness of the copper electrodeposition layer, including potential variations of the cathodic surface, fluctuations in the cupric ion concentration and coverage of the accelerator. The model is used to predict the filling process with different current densities and SPS concentrations and is verified by copper electrodeposition experiments. The "optimal zone" was determined for the SPS concentration and the inward current density to achieve good TSV filling. Sample points in the outer zone were selected and the failure mechanism was studied to help to infer the right direction toward the "optimal zone" in copper electrodeposition. The models are potentially useful tools for measuring the properties of electrolyte solutions and for the optimization of copper electrodeposition processes. Through-Silicon via (TSV) is one of key techniques for 3D integration with many advantages. The electroplated copper is a major interconnect material in TSV due to its high electrical conductivity, lower cost than alternative deposition methods.1,2 Copper electrodeposition as an efficient method of metallization is widely accepted, and it has been proposed by many researchers. [3][4][5] According to the feature of TSV on chip, some special additives such as accelerator (Bis-(3-sulfopropyl) disulfide, or SPS), suppressor (Polyethylene glycol, or PEG), leveler (Janus Green B) and Cl − , are usually applied in electrolyte solution to assist copper filling with void-free.6-8 An appropriate distribution of additives provides a fast growth at the bottom and the growth rate at via opening is suppressed, as improper distribution of additives result in unfilled feature.9 Hence, behaviors of additives on the cathode surface are very important for TSV filling process. However, there are still some challenges for establishing the optimal process for copper filling because the influence of feature of TSV, complicated mechanisms of additives behaviors and complicated fabricated process.2 A predictive numerical model of the copper electrodeposition process is a very helpful tool to investigate the optimal process with some advantages, such as low cost and efficiency. A typical numerical model should have the ability to predict feature evolution of copper electrodeposition under different operating conditi...

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Section: 43mentioning

confidence: 99%

RETRACTED: Copper Electrodeposition in Through-Silicon Via under Galvanostatic Condition

Luo

Chen

Zhang

et al. 2016

J. Electrochem. Soc.

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“…34 Clearly, the previously reported values 11,12,33,34 provide too little polarization at all rotation rates tested.…”

Section: Results and Discussion Of The Co-injection Model And Experimmentioning

confidence: 67%

Additives Co-Injection: A Test for Determining the Efficacy and Process Parameters of Bottom-up Plating

Boehme

Landau

2016

J. Electrochem. Soc.

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The additives co-injection test is shown to provide important and unique insight into the bottom-up plating process. The observed transient peak polarization depends on the convective flow and reflects the electrode coverage by both the suppressor and the anti-suppressor species, much like the electrode coverage during the actual bottom-up plating process. A computer implemented analytical model of the co-injection test is presented. This model, which accounts for the additives transport through the flow-induced boundary layer and their adsorption kinetics, characterizes the actual wafer plating process more comprehensively than previous models, linking for the first time the wafer rotation rate to the process effectiveness. Correlating the model to experimental data provides the values of process parameters, including additives adsorption rates and their displacement constants, which heretofore were not accessible. It is found that previously reported values of diffusivities, saturated surface coverages, and the SPS adsorption rate constant are consistent with the presented co-injection model, however, values for the rate constants of PEG adsorption (k PEG ) and PEG displacement by SPS (k SPS,PEG ), which previously have only been inaccurately estimated, are now correctly quantified. The interconnects, which provide the intrinsic electrical wiring network in semiconductor devices, are fabricated by electroplating copper within vias and trenches, from electrolytes containing special additives. The latter control the plating rates such that the plating from the bottom of the features is enhanced, while plating on the sidewalls and the top wafer surface is inhibited.1 The variable plating rate is achieved by the additives distribution on the plated surface: additives which suppress plating, e.g., polyethers, adsorb preferentially on the wafer top surface and the rims of the features, while additives that block the adsorption of the suppressor, the so called 'anti-suppressors', predominantly accumulate at the features bottom, preventing suppressor adsorption at those locations and thus maintaining fast plating from the bottom. The interaction between these additives is imperative for achieving void-free bottom-up fill. Electrolytes containing common additives, polyethylene glycol [PEG] as suppressor and bis(3-sulfopropyl) disulfide [SPS] as anti-suppressor, have been studied extensively 1-28 and models have been developed to explain and characterize the bottom-up fill process. [5][6][7][8][9][10][11][12][13] Modeling and optimization of the interconnect metallization process requires the application of numerous process parameters, including the diffusion coefficients of the suppressor and the anti-suppressor, their surface adsorption rates, and their competitive interaction. The determination of many of these parameters is difficult and consequently their values had often only been estimated.11-13 Electrochemical tests such as the sequential injection technique have been used to provide adsorption constants with li...

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“…25 PVA was dissolved in D 2 O containing 1 wt % of an OEG or PEG solute. The PVA concentration ranged from 0 -0.38 g/mL.…”

Section: Methodsmentioning

confidence: 99%

“…We have used the diffusion model of Petit et al 24 for the treatment of the data in a previous article. 25 The model of Petit et al seems adequate in the description and interpretation of the self-diffusion of diffusants of various sizes over a large range of polymer concentrations. 25 The interpretation of the effect of diffusant size, polymer concentration, and temperature was also successful.…”

Section: Introductionmentioning

confidence: 99%

“…25 The model of Petit et al seems adequate in the description and interpretation of the self-diffusion of diffusants of various sizes over a large range of polymer concentrations. 25 The interpretation of the effect of diffusant size, polymer concentration, and temperature was also successful. However, it seems that interests have mounted and it was requested that some of the other models be used for interpretation of the data.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Study of the self-diffusion of poly(ethylene glycol)s in poly(vinyl alcohol) aqueous systems

Masaro

Zhu

Macdonald

1999

J. Polym. Sci. B Polym. Phys.

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Self-Diffusion of Oligo- and Poly(ethylene glycol)s in Poly(vinyl alcohol) Aqueous Solutions As Studied by Pulsed-Gradient NMR Spectroscopy

Cited by 52 publications

References 29 publications

RETRACTED: Copper Electrodeposition in Through-Silicon Via under Galvanostatic Condition

RETRACTED: Copper Electrodeposition in Through-Silicon Via under Galvanostatic Condition

Additives Co-Injection: A Test for Determining the Efficacy and Process Parameters of Bottom-up Plating

Study of the self-diffusion of poly(ethylene glycol)s in poly(vinyl alcohol) aqueous systems

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