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Electrochemical Deposition of Silver and Copper from a Deep Eutectic Solvent Studied Using Time-Resolved Neutron Reflectivity.

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journal contribution
posted on 2018-01-17, 12:19 authored by Andrew D. Ballantyne, Robert Barker, Robert M. Dalgliesh, Virginia C. Ferreira, A. Robert Hillman, Emma J. R. Palin, Rachel Sapstead, Emma L. Smith, Nina-Juliane Steinke, Karl S. Ryder
Here, we describe new developments in the study of electrodeposition processes with timeresolved 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 of the here has increased from 1-2 hours per data set (in our previous studies) to approximately 8 minutes. 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 5-10% 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.


The authors gratefully acknowledge the STFC for provision of beam time at ISIS (Rutherford Appleton Lab. Oxford; experiment No’s: RB1320411 and RB1510528) on OFFSPEC . The raw data for these experiments are made available at DOI: 10.5286/ISIS.E.47624376 and DOI: 23 10.5286/ISIS.E.59115258 for experiment RB1320411 and at DOI: 10.5286/ISIS.E.58449398 for experiment RB1510528. KSR also thanks Innovate UK (Manufacturing Electronic Systems of the Future) for funding under the MACFEST project (Project No: 102020).



Journal of Electroanalytical Chemistry, 2018

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/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry


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Journal of Electroanalytical Chemistry


Elsevier, International Society of Electrochemistry (ISE)





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