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

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

Research output: Contribution to JournalArticle

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.
Original languageEnglish
Pages (from-to)511-523
Number of pages13
JournalJournal of Electroanalytical Chemistry
Volume819
DOIs
Publication statusPublished - 15 Jun 2018

Fingerprint

eutectics
silver
metal films
reflectance
neutrons
copper
roughness
methodology
trends
temporal resolution
electrodeposition
momentum transfer
solvation
neutron scattering
time measurement
atomic force microscopy
gold
optimization
electrodes
thin films

Keywords

  • Atomic force microscopy
  • Copper
  • Cyclic voltammetry
  • Deep eutectic solvents
  • Electrodeposition
  • Event mode
  • Neutron reflectivity
  • Silver
  • Thin-film

Cite this

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. / Electrochemical deposition of silver and copper from a deep eutectic solvent studied using time-resolved neutron reflectivity. In: Journal of Electroanalytical Chemistry. 2018 ; Vol. 819. pp. 511-523.
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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.",
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Ballantyne, AD, Barker, R, Dalgliesh, RM, Ferreira, VC, Hillman, AR, Palin, EJR, Sapstead, R, Smith, EL, Steinke, N-J & Ryder, KS 2018, 'Electrochemical deposition of silver and copper from a deep eutectic solvent studied using time-resolved neutron reflectivity', Journal of Electroanalytical Chemistry, vol. 819, pp. 511-523. https://doi.org/10.1016/j.jelechem.2018.01.032

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.

In: Journal of Electroanalytical Chemistry, Vol. 819, 15.06.2018, p. 511-523.

Research output: Contribution to JournalArticle

TY - JOUR

T1 - Electrochemical deposition of silver and copper from a deep eutectic solvent studied using time-resolved neutron reflectivity

AU - Ballantyne, Andrew D

AU - Barker, Robert

AU - Dalgliesh, Robert M

AU - Ferreira, Virginia C

AU - Hillman, A Robert

AU - Palin, Emma J R

AU - Sapstead, Rachel

AU - Smith, Emma L

AU - Steinke, Nina-Juliane

AU - Ryder, Karl S

PY - 2018/6/15

Y1 - 2018/6/15

N2 - 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.

AB - 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.

KW - Atomic force microscopy

KW - Copper

KW - Cyclic voltammetry

KW - Deep eutectic solvents

KW - Electrodeposition

KW - Event mode

KW - Neutron reflectivity

KW - Silver

KW - Thin-film

UR - http://www.mendeley.com/research/electrochemical-deposition-silver-copper-deep-eutectic-solvent-studied-using-timeresolved-neutron-re

U2 - 10.1016/j.jelechem.2018.01.032

DO - 10.1016/j.jelechem.2018.01.032

M3 - Article

VL - 819

SP - 511

EP - 523

JO - Journal of Electroanalytical Chemistry

JF - Journal of Electroanalytical Chemistry

SN - 1572-6657

ER -