Simulation of Shape Evolution during Electrodeposition of Copper in the Presence of Additive

Γεωργιαδου, Μαρια; Veyret, D.; Sani, R. L.; Alkire, Richard C.

doi:10.1149/1.1344540

Cited by 85 publications

(82 citation statements)

References 23 publications

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“…In the presence of 1.0 M sodium sulfate, as described previously, pH had no effect; thus all pH data fell close to one straight line (closed symbols). The diffusion coefficient calculated in the absence of background electrolyte was 0.8 )/10 (5 cm 2 s (1 , compared with the values of 0.57 Á/0.61 )/10 (5 published elsewhere [3,14,15], while in the presence of background electrolyte, the diffusion coefficient was 0.43 )/10 (5 .…”

Section: Diffusion Coefficients Calculationsupporting

confidence: 49%

Electrodeposition of copper: the nucleation mechanisms

Grujicic

Pešić

2002

Electrochimica Acta

609

444

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The nucleation mechanisms of copper during electrodeposition of thin films from sulfate solutions were studied by utilizing the electrochemical techniques (cyclic voltammetry and chronoamperometry) and atomic force microscopy (AFM). Near atomically smooth glassy carbon was used as the deposition substrate (electrode). The copper nucleation mechanisms were examined as a function of solution pH, copper concentration, deposition potential, temperature, and background electrolyte. It was found that with pH and copper concentration increase, the nuclei size increased, while the nuclei population density decreased. An increase of deposition potential produced smaller nuclei and higher nuclei population density. Temperature affected the morphology of deposited copper. The presence of background electrolyte also influenced the morphology and population density of copper nuclei. The nucleation mechanisms were examined by fitting the experimental data (chronoamperometry) into the Scharifker Á/Hills nucleation models. It was found that at pH 1, in the absence of background electrolyte, copper nucleation was instantaneous. At pH 2 and 3, the mechanism was inconclusive. In the presence of background electrolyte, the mechanism at pH 1 and 2 was mixed, while at pH 3, the mechanism was progressive nucleation. #

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Section: Diffusion Coefficients Calculationsupporting

confidence: 49%

Electrodeposition of copper: the nucleation mechanisms

Grujicic

Pešić

2002

Electrochimica Acta

609

444

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“…The electroplating cell as used in the experimental set-up of reference [3,24] is given in figure 3 The electrochemical problem is approached with the PM which is characterized by the Laplace equation (1) with non-linear boundary conditions (6). The following phenomena will be taken into account:…”

Section: Model Definitionmentioning

confidence: 99%

“…tional domain in figure 6 is found from the equations (1)(2)(3)(4)(5)(6) and represented in figure 7 by zero LS for the initial position of the insulating shield (top) and for the optimal position of the insulating shield (bottom). The initial standard deviation of current density at the cathode (17) is 70%.…”

Section: Optimizationmentioning

confidence: 99%

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Optimization of the current density distribution in electrochemical cells based on the level set method and genetic algorithm

Purcar

Ţopa

Munteanu

et al. 2011

Eur. Phys. J. Appl. Phys.

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Abstract. This paper proposes a general applicable algorithm for the optimization of the current density distribution in the electrochemical cells using the insulating shields during the electroplating process. The innovative aspect is that the position of the insulating shield is displaced over a number of predefined time steps convecting its surface proportional with and in the direction of a well chosen rate provided by a genetic algorithm. The aim of this method is to develop a systematic modification of the insulating shield position in order to get a more uniform distribution of the current density, hence a more uniform deposited layer at the cathode. As the displacement of the insulating shield is performed with the Level Set Method, the re-meshing of the computational domain with finite elements is not required anymore. Finally an example related to the optimization of the current density distribution in the vicinity of a singularity (incident angle between the electrode and insulator = 180 o ), using an insulating shield will be presented.

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“…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.…”

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confidence: 99%

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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Simulation of Shape Evolution during Electrodeposition of Copper in the Presence of Additive

Cited by 85 publications

References 23 publications

Electrodeposition of copper: the nucleation mechanisms

Electrodeposition of copper: the nucleation mechanisms

Optimization of the current density distribution in electrochemical cells based on the level set method and genetic algorithm

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

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