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Electrochemical deposition of silver and copper from a deep eutectic solvent studied using time-resolved neutron reflectivity

Ballantyne, Andrew D., Barker, Robert, Dalgliesh, Robert M., Ferreira, Virginia C., Hillman, A. Robert, Palin, Emma J.R., Sapstead, Rachel, Smith, Emma L., Steinke, Nina-Juliane, Ryder, Karl S. and others. (2018) Electrochemical deposition of silver and copper from a deep eutectic solvent studied using time-resolved neutron reflectivity. Journal of Electroanalytical Chemistry, 819 . pp. 511-523. ISSN 1572-6657. (doi:10.1016/j.jelechem.2018.01.032)

Abstract

Here, we describe new developments in the study of electrodeposition processes with time-resolved dynamic neutron reflectivity (NR) methods to achieve insights into the differences between growth of metal films using a range of electrochemical control functions. We show that the temporal resolution has increased from 1 to 2?h per data set (in our previous studies) to approximately 8?min. We have studied the electrochemical deposition of copper and silver as thin-film metals onto a gold electrode substrate from a deep eutectic solvent using potentiodynamic (PD), potentiostatic (PS) and galvanostatic (GS) electrochemical control functions. In particular, we have utilised novel developments in neutron reflectivity methods to acquire real-time data for the growing metal films. Event mode capture of neutron scattering events, as a function of momentum transfer vector, Q, during electrochemical growth has enabled time-resolved measurement of the neutron reflectivity, R(Q), profiles of the growing metal films. Subsequent fitting and iterative optimisation of the R(Q,t) data reveals the thickness, roughness and relative density (spatially resolved solvent content) of the metal film during growth. These data show that the different electrochemical growth methodologies exhibit different trends in thickness, roughness and solvation. Silver films show an increasing roughness trend with time but these trends are largely independent of growth method. In contrast, the roughness of copper films, grown under similar conditions, shows a strong dependency on growth method with PS methods producing smoothest films. These conclusions are confirmed by ex-situ AFM measurements. The fitted NR data show that the Cu and Ag films contain between 5 and 10% volume fraction solvent. Furthermore, we have explored different NR data fitting methodologies in order to process the large numbers of data sets produced. Gratifyingly, the different methodologies and starting conditions yield a very consistent picture of metal film growth.

Item Type: Article
DOI/Identification number: 10.1016/j.jelechem.2018.01.032
Uncontrolled keywords: Neutron reflectivity; Event mode; Electrodeposition; Deep eutectic solvents; Copper; Silver; Thin-film; Cyclic voltammetry; Atomic force microscopy
Subjects: Q Science > QD Chemistry
Divisions: Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Robert Barker
Date Deposited: 14 Feb 2018 15:19 UTC
Last Modified: 23 Jan 2020 04:14 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/66025 (The current URI for this page, for reference purposes)
Barker, Robert: https://orcid.org/0000-0002-8645-5385
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