Assessment of the Nucleation and Growth Mechanism of Copper Electrodeposition Over Graphene Oxide

Gupta, A and Srivastava, C (2021) Assessment of the Nucleation and Growth Mechanism of Copper Electrodeposition Over Graphene Oxide. In: Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science, 52 (6). pp. 2522-2533.

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Abstract

The characteristics of copper electrodeposition over graphene oxide (GO) were studied using cyclic voltammetry (CV), chronoamperometry (CA), and microscopy techniques. CV results established the diffusion-controlled nature of Cu reduction over GO. Mathematical modeling of CA data revealed the simultaneous occurrence of three competing reactions at the electrode-electrolyte interface: adsorption/double-layer charging, 2D instantaneous nucleation, and 3D nucleation and growth of Cu islands. The steady-state nucleation rates (Ist) for Cu island formation increased with an increase in the cathodic voltage from � 0.40 V (Ist = 4.23 � 106 cm�2 s�1) to � 0.60 V (Ist = 14.04 � 106 cm�2 s�1). Application of the classical theory of nucleation revealed that under the overpotential ranges provided in the experiment, the critical Gibb�s free energy required for Cu nucleation over GO substrate is lower than the room-temperature thermal energy. It means that the Cu deposition mechanism is not activation-controlled but rather a kinetically controlled mechanism. Application of Milchev�s atomistic theory reveals that the critical nucleus size is one atom, which implies that every Cu atom depositing over GO is a supercritical nucleus that can grow irreversibly. © 2021, The Minerals, Metals & Materials Society and ASM International.

Item Type:	Journal Article
Publication:	Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science
Publisher:	Springer
Additional Information:	The copyright for this article belongs to Springer
Keywords:	Chronoamperometry; Copper metallography; Crystallization; Cyclic voltammetry; Electrodeposition; Electrodes; Electrolytes; Free energy; Graphene; Nucleation, Copper electrodeposition; Critical nucleus size; Diffusion controlled; Electrode-electrolyte interfaces; Instantaneous nucleations; Kinetically controlled; Nucleation and growth; Steady-state nucleation rate, Copper compounds
Department/Centre:	Division of Mechanical Sciences > Materials Engineering (formerly Metallurgy)
Date Deposited:	15 Jul 2021 10:39
Last Modified:	15 Jul 2021 10:39
URI:	http://eprints.iisc.ac.in/id/eprint/68819

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