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Title: Electrodeposition of copper using additive-containing low metal ion concentration electrolytes for EnFACE applications
Author: Dela Pena, Eden May B.
ISNI:       0000 0004 6061 4151
Awarding Body: University of Strathclyde
Current Institution: University of Strathclyde
Date of Award: 2017
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In the past decade a new electrodeposition process called Electrochemical nano and micro Fabrication by flow and Chemistry (EnFACE) was developed which enabled mask-less pattern transfers onto a metallic substrate. EnFACE uses a novel acid-free, additive-free plating electrolyte containing low concentrations of metal salts (0.1 MCuSO4), as the process requires electroplating under conditions of fast kinetics and low electrolyte conductivity. However, for electronic applications,industry requires the use of additives, which improve deposit properties such as thickness uniformity, strength, ductility, and conductivity. The use of pulsed current is also known to improve deposit properties such as grain structure, mechanical strength and throwing power. Therefore, in order to use EnFACE for fabrication of industrially useful products, the effect of additives on the electrochemical behaviour and deposit properties of this process needs to be assessed. In addition, the influence of current modulation; i.e. direct current vs pulsed current, on deposit properties also warrants investigation. Potentiodynamic polarisation experiments were performed on additive-free and additive-containing EnFACE electrolyte (0.1 M CuSO₄). The additives tested were Copper Gleam A, Copper Gleam B, and chloride ions (Cl⁻). The effect of two parameters: (i) additive type and (ii) additive concentration, on cathode polarisation were studied. Copper films were electroplated on stainless steel substrates from electrolytes containing different concentrations of plating additives (0%, 17%, 33%, 50%, 100%,200% of the industry recommended additive concentration). Both direct current (DC)ABSTRACT|ii and pulsed current (PC) plating were used. The deposit was characterised using scanning electron microscope (SEM), electron back scattered diffraction (EBSD),tensile test machine (UTM), four-point probe and X-ray diffraction (XRD). Cathode polarisation occurred when the additives were used individually. Thecombination of Copper Gleam B and Cl- suggested synergistic inhibition, particularly in the diffusion-limited region. The addition of Copper Gleam A to the CopperGleam B-Cl⁻ mix increased the limiting current and suggested plating acceleration. These effects are interpreted in terms of the adsorption-desorption behavior of the additives on the cathode surface. SEM and EBSD images indicated that additives caused a concentration dependent decrease in the grain size of the deposit in both the DC and PC plated deposit. This grain refinement resulted in an increase in yield and tensile strength,but reduced the ductility and resistivity of deposits. The PC-plated copper from theEnFACE electrolytes generally possessed better mechanical properties than its DC-plated counterparts, though both plating modes created copper films that can meet industry standards. The optimum additive concentration for the EnFACE electrolyte was 50% of the recommended value when using DC plating; while the optimum was only 33% when using PC plating.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral