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Studies on the Influence of Mps, PEG and Cl~ˉ Additives on Copper Electrodeposition

Author: ZhongQin
Tutor: GuMin
School: Chongqing University
Course: Environmental Science
Keywords: Copper Additive Electrodeposition Electrocrystallization
CLC: TG174.4
Type: Master's thesis
Year: 2010
Downloads: 101
Quote: 0
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Abstract


Aluminum is a conventional integrated circuit interconnection medium is more desirable than aluminum material, because copper has a lower resistivity than aluminum and higher electromigration resistance. To achieve carved grooves of micron or sub-micron level of copper in the chip isometric electrodeposition filled, must use additives. 3 - mercapto -1 - propane sulfonate (MPS) or poly the Disulfide propane sulfonate (SPS), polyethylene glycol (PEG) and chlorine copper ultra isometric deposition filled bath typically used in additive ion (Cl -). Papers by cyclic voltammetry (CV), linear sweep (LSV), chronoamperometry (CA) and AC impedance (AC impedance) electrochemical method combined with scanning electron microscopy (SEM) CuSO4-H2SO4 system, the additive MPS , PEG, Cl ~ - and its synergy of copper electrodeposition process on the glassy carbon electrode (GCE). CV, LSV and electrochemical impedance spectroscopy (EIS) experimental results consistently show that: MPS alone, the resistance of copper electrodeposition, and as the the MPS concentration increases, the resistance of the enhanced role; electrolyte additives MPS Cl ~ - (MPS-Cl ~ -) when, CV curve on copper deposition peak potential shifted positively the extent rather than contain of Cl ~~ - greater the LSV curve is shift a greater degree, the reaction resistance than just containing Cl ~~ - more These indicate MPS-Cl ~ - for copper electrodeposition process has a strong role in promoting, and stronger than just containing the same concentration of Cl ~ - role in promoting, and as the MPS concentration increases, the role of promoting enhanced; MPS having the electro-deposition of the copper and the synergy of the PEG (MPS-PEG) inhibition, and stronger than the barrier effect under the MPS or PEG alone, when the PEG concentration in the solution was maintained constant, as the concentration of the MPS increase the barrier effect of the copper electrodeposition is also increased; additives the MPS, PEG and Cl ~ - (MPS-PEG-Cl ~ -) exist simultaneously having a promoting effect on the electro-deposition of copper, and with the increase in the MPS concentration promote enhanced role. CA and SEM results show that: MPS can improve a copper crystal nucleation number density of copper electrical performance for the role, and as the number of nuclei increased with increasing MPS concentration did not change significantly, the diffusion coefficient of the copper ions; MPS-Cl ~~ - copper nucleation density and the copper ion diffusion coefficients can be improved, and into the nuclear number density increases with increasing MPS concentration; MPS-PEG under the action will reduce the density of the copper nucleation, into audit density tends to decrease with increasing MPS concentration, no significant effect on the diffusion coefficient of the copper ions; MPS-PEG-Cl ~ - will increase copper nucleation density, and to audit density with MPS concentration increases. CA experimental of copper nucleation mechanism that: CuSO4-H2SO4 electrolyte without additives, copper electrocrystallization on a glassy carbon electrode in line with the three-dimensional instantaneous nucleation mechanism; the additive MPS or MPS-PEG does not change the Cu the electric crystal nucleation mechanism still instantaneous nucleation and three-dimensional growth pattern; the the MPS the-Cl ~~ - or MPS-PEG-Cl ~~ - under, beginning in electrocrystallization 3D instantaneous nucleation mechanism of nucleation meet, but too After some time, the mechanism of nucleation gradually transformed into a continuous nuclear, and Cl to - the nucleation mechanism is basically the same. SEM characterization results can prove MPS or MPS-Cl to - under the action of copper electrocrystallization is still in line with the three-dimensional instantaneous nucleation mechanism. EIS experimental results show that the MPS or MPS-PEG copper electrodeposition resistance decreases with increasing polarization potential, increasing the MPS-Cl ˉ or MPS-PEG-and Cl ˉ copper electrodeposition role. EIS are displayed in the different additive under the action of the arc in the case of increase in polarization potential, the high-frequency end of the capacitive reactance decreases in diameter, the reaction resistance decreases.

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CLC: > Industrial Technology > Metallurgy and Metal Craft > Metallurgy and Heat Treatment > Metal corrosion protection,metal surface treatment > Corrosion control and protection > Metal surface protection technology
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