Journal of Applied Electrochemistry (2021) 51:219–233

https://doi.org/10.1007/s10800-020-01485-2

RESEARCH ARTICLE

Stainless steel substrate pretreatment effects on copper nucleation

and stripping during copper electrowinning
Florian Verbruggen1,2 · Erika Fiset1,2,5 · Luiza Bonin1,2 · Antonin Prévoteau1,2 · Michael S. Moats4 ·
Tom Hennebel1,2,3 · Korneel Rabaey1,2

Received: 29 June 2020 / Revised: 11 September 2020 / Accepted: 14 September 2020 / Published online: 1 October 2020
© Springer Nature B.V. 2020

Abstract
The effects of surface pretreatment of 304 stainless steel (SS) substrates on copper film formation, adhesion, and purity
obtained by galvanostatic electrodeposition at a current density of – 30 mA ­cm−2 are presented. The polished substrate
produced more copper nuclei, resulting in an increase of the adhesion as compared to chemically oxidized SS substrate. The
adhesion of the copper deposits was characterized by a Nano-scratch tester (NST). The nucleation behavior is associated with
the flatband potential of the SS surface, which was derived from capacitance measurements. The grain size of copper deposits
was characterized by field emission scanning electron microscopy (FESEM). Copper grains were smaller on the polished SS
with a size of less than 1 µm after 5 min of electrodeposition. High-purity copper deposits with < 1 ppm S (detection limit)
were obtained on the oxidized SS substrate compared to 2.5 ppm for the polished SS substrate. Atomic force microscopy
(AFM) measurements showed that the copper deposits were 25% less rough on the polished SS as compared to the oxidized
SS. The results indicate that the obtained purity of the copper deposit relates to the grain size of the deposit, rather than the
initial surface roughness. In the context of industrial electrowinning, high adherence to the polished substrate could increase
the operation time of the copper cathode stripping. Hence for electrowinning from copper sulfate electrolytes, oxidizing the
SS surface prior to deposition could lead to higher purity along with enhanced stripping.

Electronic supplementary material The online version of this

article (https​://doi.org/10.1007/s1080​0-020-01485​-2) contains
supplementary material, which is available to authorized users.

* Korneel Rabaey
Korneel.Rabaey@ugent.be
1
Center for Microbial Ecology and Technology (CMET),
Ghent University, Coupure Links 653, 9000 Ghent, Belgium
2
CAPTURE, Ghent, Belgium
3
Umicore, Group Research & Development, Competence Area
Recycling and Extraction Technologies, Watertorenstraat 33,
2250 Olen, Belgium
4
Materials Research Center, Missouri S&T, Rolla, MO 65401,
USA
5
Present Address: BOSAQ, Technologiepark 82 POB 7,
9052 Zwijnaarde, Belgium

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220 Journal of Applied Electrochemistry (2021) 51:219–233

Graphic abstract

Keywords Electrodeposition · Electroplating · Blank maintenance · Surface roughness · Adhesion

1 Introduction 4–9]. Less work has been done on the chemical purity of
electrowon copper. Instead, the surface roughness and mor-
Annually, 4.5 million tons of metallic copper are produced phology of copper deposits are generally regarded as the
by electrowinning operations from acidic sulfate electro- determining factor for obtaining high-purity copper. This has
lytes, which account for roughly 20% of the world’s refined been previously rationalized by the postulation that uneven
copper [1]. In the copper electrowinning process, metal is copper growth results in the occlusion of electrolyte in the
usually electrodeposited on SS cathodes for 6–7 days after growing deposit and the entrapment of anode scale, which
which the copper is harvested [1, 2]. After harvesting, the SS results in high sulfur and lead content, respectively [3, 7,
cathodes are visually inspected, washed with process water, 8, 10]. Since surface roughness increases with electrolysis
and returned to the production cells. time, it seems essential to produce an initial copper deposit
If the visual inspection detects a problem (broken edge morphology with a low surface roughness [11–13]. A rela-
strip, too much bending, and/or residual copper), then before tively high nucleation rate on the substrate is then preferable
inserting the SS substrates in the electrowinning baths, cor- to develop a smooth and fine grained copper deposit with
rective actions are taken. One of these actions is an abrasive a complete coverage at low film thickness [14, 7]. Indeed,
pretreatment step to remove residual copper from previous several studies were concerned with the initial phases of
electrodeposition and to smooth the SS surface [3]. During copper nucleation and growth and the fundamental ques-
this abrasive pretreatment, the passive oxide film protecting tions regarding the copper morphology development [3, 6,
the steel against corrosion is removed. The SS is usually 8, 15–23]. Delplancke et al. [24–26] and Zhou and O’Keefe
allowed to stand in the air to re-grow the protective oxide. [27] studied the copper nucleation and growth on oxidized
As a mature technology, the quality of electrowon cop- substrates. The altered nucleation behavior on the oxidized
per has been widely investigated, usually in terms of copper substrates was explained in terms of the physical properties
morphology and current efficiency with the main param- of the surface film. Delplancke et al. [24] postulated that
eters being current density, mass transfer (i.e., electrolyte micropores in the anodized T ­ iOx surfaces served as nuclea-
agitation, and temperature), and electrolyte additives [2, tion sites for copper. Zhou and O’Keefe [27] suggested that

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Journal of Applied Electrochemistry (2021) 51:219–233 221

the copper nucleation behavior was related to the chemical is more suitable for microscopic imaging of copper nuclea-
composition of the near surface film that was obtained after tion and fundamental studies of copper electrodeposition
thermal oxidation. Both studies indicate that those physi- [12, 35].
cal surface properties of the substrate influence the cop- Some of the polished electrodes were chemically oxi-
per nucleation behavior, but an overall explanation is still dized. The oxidation procedure of the SS electrodes con-
lacking. sisted of two consecutive steps: (1) the electrodes were
In parallel, corrosion studies have shown that the oxide immersed for 20 min in ~ 3 mL of 0.15 M ­H2SO4 solution,
layer on stainless steel and titanium exhibit semiconductive (2) an equal volume of 9.8 M ­H2O2 was added to the H ­ 2SO4
properties that can be related to corrosion rates [28–34]. solution, and the electrodes were immersed for 20 more min.
We sought to expand this pathway to copper electrodeposi- No external means were applied to provide convection in
tion and elucidate the causes of copper nucleation by iden- the solution.
tifying the semiconductive properties of the pretreated SS The SS current feeder and the unpolished backside of
substrates. the electrode were covered with chemically resistant non-
For that, we selected a polishing and chemical oxidation conductive tape (RS components, Great Britain) to assure a
pretreatment to obtain a comparison between a stainless flat deposition area of 1 c­ m2 available for electrodeposition.
steel substrate with a stable oxide layer and its counterpart The counter electrode (CE) was a 2 cm × 2 cm anode made
[29]. A mechanism for the copper nucleation behavior on from titanium covered with an iridium mixed metal oxide
the pretreated stainless steel substrates is described for the coating (Magneto Special Anodes (an Evoqua brand), The
first time. The initial copper nucleation and growth phases Netherlands).
on the different pretreated SS substrates were studied by the Materials were purchased in the grade indicated and used
measured potential transients during the galvanostatic elec- as received. Sulphuric acid ­(H2SO4, 98%, Rotipuran, Carl
trodeposition and FESEM images. Additionally, we aimed Roth), hydrogen peroxide (­ H2O2, 30 wt%, Ph. Eur., Sigma
to evaluate the effect of the stainless steel pretreatment on Aldrich), nitric acid ­(HNO3, 65 wt%, EMSURE, VWR,
critical properties (adhesion and copper purity). Finally, Merck), hydrochloric acid (HCl, 32 wt%, EMSURE, Merck),
we discuss the impact of our findings on industrial copper Copper(II) sulfate pentahydrate ­(CuSO4·5H2O, ≥ 99.5%,
electrowinning. ACS, Carl Roth), and sodium sulfate anhydrous (­ Na2SO4,
99.5%, ACS, Fisher Scientific).

2 Material and methods 2.2 Electrochemical measurements

2.1 Stainless steel pretreatment and electrode All electrochemical measurements were performed in a 6 cm
preparation diameter three-electrode cell setup with a working volume of
150 mL. The cell was closed with a Perspex lid which con-
Annealed AISI 304 stainless steel sheets with a thickness of tained two slots and one circular hole to position the WE and
0.2 mm were purchased from Goodfellow (Cambridge Ltd, CE holders and the reference electrode (RE), respectively.
England). The composition of the stainless steel material as The WE and the CE were supported in the electrode holders
provided by the supplier was added to the supplementary with their adjacent faces positioned in parallel with a fixed
information (Table S1). The sheet was cut into 1 cm × 1 cm distance of 2 cm. The distance between the midpoint of the
pieces (projected surface area of 1 cm2) and used as work- WE and the RE was 1 cm. A scheme of the setup was added
ing electrodes (WE). All pretreatments were performed in the supplementary information (Fig. S1). All reported
at room temperature (~ 25 °C). One side of each WE was potentials refer to the Ag/AgCl RE (3 M KCl, ALS, Japan,
polished in different steps with SiC papers up to grit 4000 + 0.208 V vs. standard hydrogen electrode at 28 °C). The
(Struers GmbH, The Netherlands). Subsequently, the WE electrochemical data were recorded with a VSP-300 (Bio-
were successively polished to a mirror finish on a felt cloth logic SAS, France) potentiostat, except for the capacitance
using alpha alumina suspensions with a grain size of 0.3 and measurements that were recorded with a Reference 3000
0.1 µm (Struers GmbH, The Netherlands). The surface was potentiostat (Gamry Instruments, USA).
thoroughly rinsed with distilled water after each polishing All experiments were performed at a constant temper-
step. ature of 28 °C without stirring of the electrolyte. Fresh
The pretreated SS substrates in our study are smoother electrolyte was used for each experiment. An immersion
than the cathode substrates obtained after the typical abra- corrosion test was performed with a 180 g L ­ −1 ­H 2SO 4
−1 −
sive pretreatment that is applied in industrial electrowinning. and 20 mg L ­ ­C l solution to indicate a difference in
Our pretreatment was used to obtain a uniform SS surface the protective behavior of the passive layer obtained on
with a geometric area of 1 cm2. This smooth surface finish the polished and oxidized SS. The polished and oxidized

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222 Journal of Applied Electrochemistry (2021) 51:219–233

SS electrodes were immediately immersed in the solution measurements [31, 32]. The Mott–Schottky equation for a
after the surface pretreatment. The concentration of the n-type semiconductor is as follows [29–31, 33, 39]:
sulfuric acid was chosen to replicate the acidity of the ( )(
electrodeposition electrolyte and chlorides were added to 1 2 kT
)
= E − E FB −
induce corrosion. C2 eND 𝜀𝜀0 e
The electrodeposition experiments were conducted in an
in which e (1.602 × 10−23 C) is the elementary charge (nega-
electrolyte with typical electrowinning concentrations of
tive for electrons), ND the donor density (­ cm−3), ε the die-
40 g ­L−1 Cu and 180 g ­L−1 ­H2SO4 [1]. Copper electrodepo-
lectric constant of the passive layer (dimensionless), ε0 the
sition was performed for various durations − 2 s, 5 s, 10 s,
vacuum permittivity (8.85 × 10−14 F c­ m−1 ), E the applied
30 s, 5 min, 30 min, 2 h, and 24 h using chronopotentiometry
potential, EFB the flatband potential, k the Boltzmann con-
at a constant current density of – 30 mA c­ m−2. The current
stant (1.38 × 10−23 J K­ −1), and T the absolute temperature
density was set to be similar to standard industrial practice
(K). The Mott–Schottky plot is obtained by plotting C−2
[36].
against the working electrode potential E. According to
Linear sweep voltammetry (LSV) was conducted to
the equation, the flatband potential of the semiconductor
compare the polarization behavior of the two pretreated SS
is determined from the intercept with the potential axis.
substrates and determine the onset deposition potentials of
Herein, the linear region in the plot is extrapolated to the
copper. Electrode potential was started at + 0.10 V vs. Ag/
potential axis to obtain the intercept. The donor density in
AgCl and ended at − 0.4 V vs. Ag/AgCl with a scan rate
the passive layer can be calculated from the slope of the lin-
of 25 mV ­s−1. For the accurate determination of the onset
ear region. The value of the dielectric constant of the passive
potential for the nucleation during copper electrodeposition,
film is required for the calculation of the donor density and
in situ characterization techniques are required. However, for
was assumed to be 12 for AISI 304 SS based on previous
the purpose of comparing the two electrode pretreatments,
research [29, 39].
an estimation was made by picking the potential value at
which a current density of − 1 mA ­cm−2 was measured [11,
37, 38]. The current density of – 1 mA c­ m−2 is achieved
2.3 Surface characterization
early in the potential sweep and was therefore selected to
characterize the cathode potential during the initial phases
A JEOL JSM-7600F FESEM was used to evaluate corrosion
of copper electrodeposition on the SS substrate.
damage on the SS substrates and to examine copper nuclea-
The electrodeposition experiments on the polished SS
tion and growth. The FESEM micrographs were acquired in
substrate started after 3 s of immersion in the electrolyte to
secondary electron mode at an accelerating voltage of 15 kV
minimize changes of the original surface film of the polished
with an 8.0 mm effective working distance. On each sample,
SS. During the 3 s of immersion, the open-circuit potential
five different locations were imaged, and for every experi-
(OCP) was measured. The OCP prior to the electrodepo-
mental condition, a triplicate of samples was examined to
sition on oxidized SS substrates was measured for 10 s.
assure reproducibility.
The average OCP value throughout the measurement was
The copper surface coverage, nuclei density, and nuclei
reported ± the standard deviation.
size (average and standard deviation) were determined
After electrodeposition, the WE were immediately
for the deposits on the oxidized SS substrate by analyzing
removed from the electrolyte, thoroughly rinsed with dis-
FESEM images at a magnification of × 200 with Matlab
tilled water, and dried at 28 °C. The equilibrium potential
software and code. The Matlab files are added as supple-
(Eeq) of the ­Cu2+/Cu couple in the experimental conditions
mentary data. In the Matlab procedure, 256 level grayscale
was experimentally measured with the OCP of a copper wire
FESEM images were converted to 8-bit black and white
in the copper electrolyte for 1 h, after which the value was
images in which only the copper nuclei appeared white.
fully stabilized.
The threshold selection for the segmentation of the images
Capacitance (C) measurements were conducted to ana-
was determined using Otsu’s method [40] on the images
lyze the semiconductive properties of the pretreated SS
from 2 to 10 s of electrodeposition. This method involves
substrate according to the Mott–Schottky equation [29–33].
the iteration of all possible threshold values and calculation
The capacitance versus potential was measured stepwise at
of the intra-class variance. Herein, the threshold value that
a fixed frequency (f) of 13 Hz and step size of 0.025 V. The
minimizes the intra-class variance is automatically chosen.
potential was changed stepwise from + 0.648 to − 0.153 V
Analysis of images of electrodepositions performed dur-
vs. Ag/AgCl in a solution of 0.01 M H ­ 2SO4 and 0.09 M
ing 30 s required an additional operation of dilation and a
­Na2SO4. The electrolyte, potential window, and direction
standard deviation filter to improve the edge detection at the
of the potential scan were selected to avoid a faradic cur-
copper nuclei.
rent that would otherwise greatly influence the capacitance

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Journal of Applied Electrochemistry (2021) 51:219–233 223

The Matlab image analysis was not performed for the Student t-test was applied to the surface roughness and sul-
deposits on the polished SS substrates. It was not possible fur content data to calculate the statistical significance of
to distinguish individual (unsegregated) nuclei after 2 s of the differences. The calculated probability (p-values) were
electrodeposition at – 30 mA ­cm−2 ,and hence nuclei size reported.
and density could not be determined. The copper grain size
was derived from FESEM images of deposits on the polished
and oxidized SS after 5 min and 24 h of electrodeposition 3 Results and discussion
at – 30 mA ­cm−2.
The average roughness (Ra) of the SS substrates after 3.1 Stainless steel surface pretreatment
pretreatment and of copper deposits after 2 h of electro-
deposition at – 30 mA ­cm−2 were characterized by AFM The average surface roughness of the polished and oxidized
(Nanowizard ® 4, JPK instruments, Germany) in quantita- SS substrate measured with an AFM were 21.7 ± 15.5 nm
tive imaging (QI®) mode in air. The images were obtained and 22.7 ± 13.8 nm, respectively. Similar average surface
with an All-In-One probe, (Budget sensors, Bulgaria), using roughness were expected since both substrates received the
the cantilever, which had a nominal frequency of 150 kHz same abrasive pretreatment and potential shape perturba-
and a force constant of 7.4 N/m (calibrated in contact free tions in a stable passive film are expected not to exceed the
mode). On every sample, three images were acquired from typical film thickness of 1–3 nm [41, 42]. Therefore, the
random locations on the surface, and a triplicate of samples average surface roughness of the SS obtained by the pre-
for every experimental condition was measured to ensure treatments in our study is a controlled variable and expected
reproducibility. The images were collected at 4 ms per pixel, to have no significant impact on the copper nucleation and
with Z length of 0.8 µm and a tip speed of 200 µm ­s−1. growth [3].
All AFM images were obtained with 256 × 256 pixels and The OCP was measured before the electrodeposition
100 µm × 100 µm in size, giving a resolution of 0.391 µm experiments in a solution with 40 g ­L−1 Cu and 180 g ­L−1
per pixel. The equation for the calculation of the surface ­H2SO4. The average OCP values throughout the measure-
roughness is added in the supplementary information (Equa- ment were + 0.093 ± 0.004 V vs. Ag/AgCl for the polished
tion S1). SS and + 0.477 ± 0.002 V vs. Ag/AgCl for the oxidized
Adhesion properties of the copper deposits on the oxi- SS. The higher OCP of the oxidized substrate indicates the
dized and polished SS substrates were assessed with a NST formation of a protective surface film during the chemical
(NST³, Anton Paar GmbH, Germany). All copper depos- oxidation.
its were obtained through galvanostatic electrodeposition The corrosion damage on the polished and oxidzed SS
for 30 min to achieve a thickness of approximately 20 µm. substrate was measured with FESEM images (Fig. S2) after
Scratches were implemented by a Rockwell diamond stylus 15 h immersion of the SS in a solution with 180 g ­L−1 ­H2SO4
indenter along the surface to delaminate the copper deposits. and 20 mg ­L−1 chlorides ions. Preliminary immersion corro-
A 2 mm scratching track was performed three times to a trip- sion experiments in the electrodeposition electrolyte (i.e., no
licate of samples. The normal load of indenter was linearly chlorides) indicated that no corrosion nor copper cementa-
ramped from the minimum to the maximum load of 130 mN tion occurred on the pretreated SS in this environment.
during the scratch. The resulting scratches and morphologi- The surface of the oxidized SS (Fig. S2a) remained
cal features related to the critical load and spallation were smooth, except for local pits. The pitting is typically caused
observed using a Hirox KH-8700 3D optical microscope. by the local breakdown of the passive layer in the presence
The purity of the copper deposits after 24 h of electro- of chlorides [43]. The surface of the polished SS substrate
deposition at – 30 mA c­ m−2 was evaluated by analysis of (Fig. S2b) after immersion became rough, indicating a com-
the sulfur content (present as sulfate from the electrolyte) plete breakdown of the initial surface and corrosion of the
with an ICP-OES (Spectro Acros, Spectro Analytical Instru- SS. The SS substrate obtained after the chemical oxidation
ments GmbH, Germany). The copper deposits on the SS pretreatment was more corrosion resistant in the sulfuric
substrates were first sonicated in distilled water for 30 min acid electrolyte containing chlorides. The oxidation proto-
to remove the remaining electrolyte on the surface before the col for the SS was based on the work of Yue et al. [29]
analysis. The copper deposits were then stripped from the that examined the passivity of SS under chemical oxida-
SS, weighted, and dissolved in 65 wt% H ­ NO3 solution with tion with a H
­ 2SO4–H2O2 solution. The oxidation of SS in
−1
a volume of 4 mL ­g copper. The solution was diluted with ­H2SO4–H2O2 solution was found to result in the formation
32 wt% HCl to a concentration of 50, 20 or 10 g Cu ­L−1 to of a passive layer with improved corrosion resistance as
match the matrix concentration. opposed to the passive film formed spontaneously in the air
Mean values on the text and figures (error bars) are pro- after polishing. The results of our immersion corrosion test
vided ± the standard deviation of the mean. A two-tailed highlight the difference in electrochemical behavior between

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224 Journal of Applied Electrochemistry (2021) 51:219–233

both studied surfaces. The passivity of 304 stainless steel oxidation of SS enriched the Cr in the surface film relative
is driven by the formation of a ­Cr2O3 surface film and the to the polished SS.
proportion of Cr oxide phases with respect to other possible The semiconductive properties and the electrochemical
oxides (Fe or Ni based) determines the overall corrosion behavior of the polished and oxidized SS with respect to the
resistance [44–46]. As opposed to the air grown film on the polarization and copper nucleation will be discussed in the
polished SS, the passive film on the oxidized SS is enriched next section.
in chromium by the preferential dissolution of iron during
the pretreatment in the sulfuric acid media [44, 45, 47, 48]. 3.2 Copper nucleation
From this, it can be assumed that the pretreatments in our
study had a marked difference in chromium content in the Representative LSV plots of copper electrodeposition in
surface film, with the highest chromium content in the sur- 40 g ­L−1 Cu and 180 g L ­ −1 ­H2SO4 for the polished and
face film of the oxidized SS. oxidized substrates are shown in Fig. 2. The onset poten-
Figure 1 shows the Mott-Schottky plot for the oxidized tials for the nucleation on the polished and oxidized sub-
and polished SS substrates measured in a solution with strates were estimated at – 0.059 ± 0.008 V vs. Ag/AgCl
0.01 M ­H2SO4 and 0.09 M ­Na2SO4. The measured capac- and – 0.118 ± 0.008 V vs. Ag/AgCl, respectively. For both
itance is assumed to be associated with the space charge substrates, the onset potential for nucleation was substan-
layer formed in the passive layer of the SS substrates. The tially lower than the equilibrium potential for the C ­ u2+/
plot followed a linear relationship with a positive slope in Cu couple, (0.107 V vs. Ag/AgCl). This indicates that the
the potential region of 0.372–0.248 V and 0.323–0.198 V electrodeposition of copper was more favorable on freshly
vs. Ag/AgCl for the polished and oxidized SS substrates, deposited copper nuclei compared to the bare SS substrates.
respectively. The positive slope indicates that the passive Furthermore, the energy barrier for nucleation was higher
layers exhibited n-type semiconducting properties. The (lower onset potential) for the oxidized substrate compared
donor density was calculated as 4.19 × 1021 ± 7.87 × 1020 to the polished one. The constant shift (~ 0.060 V) between
and 5.01 × 1021 ± 1.03 × 1021 ­cm−3 for the polished and the two curves for the range of current densities measured
oxidized SS substrates, respectively. The flatband potential suggests that the presence of the oxide layer had no substan-
was 0.084 ± 0.007 V and 0.037 ± 0.016 vs. Ag/AgCl for the tial contribution to the electrical resistance of the electro-
polished and oxidized SS, respectively. Ohtsuka et al. [31] chemical system (similar uncompensated ohmic drops for
examined stainless steels with different chromium content. both pretreatments) [49].
The donor density in the oxide film was found to not vary The initial phases of copper nucleation and growth
significantly in this work. However, the flatband potential of during the galvanostatic electrodeposition at − 30 mA
stainless steel was found to decrease with increasing chro- ­c m −2 were investigated with FESEM images. Figure 3
mium content. Likewise, our results indicate that the donor shows the copper nucleation and growth on the chemi-
density did not vary significantly among the pretreated SS, cally oxidized (a) and polished (b) SS substrate after 2, 5,
but the flatband potential shifted due to the oxidation of 10, and 30 s of electrodeposition at 200 times magnifica-
the SS. Interestingly, this matches the assumption that the tion and after 10 s at 1000 times magnification. For the

Fig. 1  Mott-Schottky plots of

capacitance for a polished and
oxidized SS substrate

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Journal of Applied Electrochemistry (2021) 51:219–233 225

The similar donor densities of the polished and oxidized

SS substrates could not clarify the difference observed in
copper nucleation rates with the assumption that the elec-
tron donors are homogenously distributed over the surface.
When the flatband potential of the semiconductive substrate
is below the equilibrium potential of the metal redox cou-
ple, the energy barrier for nucleation arises from the rela-
tive position of the potential values [52]. Accordingly, the
decrease of 59 mV in the onset potential of copper electro-
deposition on the oxidized SS can be associated with the
decrease of the flatband potential by 46 mV.
The smooth copper layer covering the polished substrate
at early stage validates the copper was reduced on a rela-
tively large number of surface sites (high nuclei density).
The high energy barrier for nucleation on the oxidized sub-
strate made growth on the existing Cu nuclei more localized.
The size distribution of copper nuclei on the oxidized sub-
strate indicates favorable deposition on existing nuclei and
absence of energy sufficient sites for nucleation.
Fig. 2  Representative linear sweep voltammetries of copper elec-
The surface chemistry of austenitic stainless steel is
trodeposition on polished and chemically oxidized SS substrates known to impact the semiconductive properties of the sur-
recorded at 25 mV s­ −1 in 0.63 M C
­ uSO4 and 1.8 M ­H2SO4 face [31, 33]. Hence, a difference in surface chemistry and
associated semiconductive properties of the SS pretreat-
ments could explain the change in copper nucleation rates.
oxidized substrate, a clear dispersion in nuclei size was The copper surface coverage (a), average nuclei size (b),
observed, which suggests progressive nucleation. The cop- nuclei density (c), and average standard deviation on the
per initially appeared as white spots on the darker back- nuclei size (d) for the deposits on the oxidized SS substrate
ground of the oxidized SS substrate. The hemispherical at different electrodeposition times were extracted from
nuclei were randomly distributed over the surface and still FESEM images (Fig. 4). This analysis was not performed
mostly segregated during the first 10 s of electrodeposi- for the polished SS. The surface was almost completely
tion, except in the scratches produced by polishing, which covered with copper after 2 s of electrodeposition, and it
acted as preferred nucleation sites. Considerable aggrega- was not possible to distinguish individual (unsegregated)
tion of the growing nuclei was observed on the images nuclei and hence nuclei size and density could not be deter-
after 30 s of electrodeposition (Fig. 3a). In contrast, a rela- mined. The copper coverage increased almost proportionally
tively smooth layer of copper was observed on the polished with the electrodeposition time from 2.6 ± 0.7% after 2 s to
substrate after only 2 s of electrodeposition. The dark areas 44.4 ± 14.9% after 30 s. The average nuclei size remained
on the images represent bare polished SS in the otherwise approximately constant (0.81 ̶ 0.99 µm2), while the nuclei
continuous white appearing copper deposit. The copper density increased with time during the first 10 s of elec-
coverage was not continuously flat or completed over the trodeposition ( 0.03–0.14 µm−2). This can be explained by
surface as interruptions of the coverage appeared along the simultaneous growth of the existing nuclei and the progres-
scratches from the polishing pretreatment. The interrup- sive formation of new nuclei within the same time frame.
tions disappeared with time as the thickness of the copper The nuclei size dispersion increases between 2 and 10 s of
layer further exceeded the depth of the polishing scratches electrodeposition as illustrated by the average standard devi-
and continued copper growth over the surface. ation on the nuclei size. Between 10 and 30 s of electrodepo-
The nucleation rate on the SS substrate depends on the sition, the average nuclei size increased from 0.81 ± 0.18 µm
number of active sites (e.g., localized defects on the pas- to 73 ± 49 µm, while the nuclei density decreased from
sive layer) that are available at a specific electrode potential 0.14 ± 0.036 µm−2 to 0.0066 ± 0.0057 µm−2 due to the sub-
[3, 50, 51]. Copper nucleation requires a specific surface stantial nuclei coalescence.
concentration of electrons (overpotential) to cause enough The evolution of the cathode potential during the first
interaction with the copper ions [52]. The surface concen- 30 s of a galvanostatic electrodeposition at − 30 mA
tration of electrons depends on the electrode potential and ­cm−2 is shown in Fig. 5. The potential after 10 ms was
the semiconductive properties of the SS surface (flatband − 0.15 ± 0.02 V and − 0.41 ± 0.10 V for the polished and
potential and the donor density) [52]. oxidized SS substrate, respectively. The cathode potentials

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226 Journal of Applied Electrochemistry (2021) 51:219–233

Fig. 3  FESEM images of galva-

nostatic electrodeposited copper
at – 30 mA ­cm−2 on a chemi-
cally oxidzed stainless steel and
b polished stainless steel after
different electrodeposition times
of 2, 5, 10, and 30 s. Scale bars
of 100 and 10 µm indicate the
magnification of 200 and 1000
times, respectively

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Journal of Applied Electrochemistry (2021) 51:219–233 227

Fig. 4  Evolution with electro-

deposition time of a the copper
surface coverage, b the average
nuclei size, c the nuclei density,
and d the standard deviation on
the nuclei size on the oxidized
stainless steel ( – 30 mA c­ m−2)

over electrodeposition time are consistent with the observed

shift of the onset potential due to substrate oxidation
(Fig. 2). The potential with the polished substrate initially
increased to a maximum of – 0.05 ± 0.01 V after 2.8 ± 0.9 s,
after which it decreased to – 0.073 ± 0.006 V. In contrast,
a gradual increase of potential to an almost identical value
of – 0.071 ± 0.018 V was observed during the 30 s of elec-
trodeposition on the oxidized substrate.
The comparison of the potential transients with the
FESEM images of the initial phases of nucleation and
growth (Fig. 3) suggests that the increase in potential
(decrease in overpotential) can be related to the evolution of
the copper coverage with electrodeposition time. Moreover,
a sharp increase of potential with electrodeposition time on
the polished substrate was observed. The sharp increase of
potential arrests early as nearly full coverage (Fig. 3b) was
observed on the FESEM images of 2 s of electrodeposition.
A gradual increase of potential during the electrodeposi-
tion on the oxidized SS was accompanied by a proportional
increase of copper coverage with time. The similar poten-
Fig. 5  Representative evolution of the cathodic potential during the
tial after 30 s of electrodeposition on the polished and oxi-
first 30 s of galvanostatic electrodeposition on a polished and oxi-
dized stainless steel substrate (– 30 mA ­cm−2) dized SS substrate suggests that the potential of polarized

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228 Journal of Applied Electrochemistry (2021) 51:219–233

copper was reached. This was confirmed by galvanostatic electrodeposition time and the height of surface, features
electrodeposition at − 30 mA ­cm−2 using a polished copper with longer deposition times would far exceed the opera-
substrate (Fig. S3). The potential on the copper substrate tional limit of the measuring tip of the AFM [12, 35]. The
stabilized at – 0.083 ± 0.003 V. The similar potentials indi- electrodeposition of the copper for surface roughness analy-
cate that copper was mainly electrodeposited on fresh copper sis was therefore limited to 2 h.
after 30 s of electrodeposition on SS. Even so, in some images, artifact points can be observed
as white stains and exhibit elevated height values. These
3.3 Surface and deposit characterization artifacts might be related to the surface roughness of the
copper being close to the operational limit of the AFM. The
Top view AFM images of the cathodes after 2 h of elec- impact of these artifacts (deviating height values) on the
trodeposition at − 30 mA c­ m−2 are shown in Fig. 6. More surface roughness is negligible if the distribution of height
top view AFM images are provided in the SI (Fig. S4). The values resemble a normal distribution [53, 54].
AFM 3D view images are added in the SI (Fig. S5) and pro- The details of the control for normality are given in the
vide insight on the height and width of the morphological supplementary information. The correlation coefficients
features of the copper deposit surface. The average surface of the normal probability plots were 0.994 ± 0.003 and
roughness of the copper deposits on the polished and oxi- 0.995 ± 0.003 for the data from the polished and oxidized
dized SS substrates were 1.32 ± 0.25 µm and 1.77 ± 0.17 µm, substrate, respectively. There was no or little deviation on the
respectively. The significance of the difference of means was outer right part (largest height values) of the distributions.
evaluated with a two-tailed Student t-test. The observed This indicates the independency of the surface roughness
means (based on nine observations) were statistically dif- by the artifacts. It also confirms that the surface roughness
ferent (p = 0.00035). The surface roughness of the cop- characterizes the topography of the copper growth features,
per deposits from oxidized substrates were significantly rather than random bumps and holes on the surface [54].
smoother than those from polished substrates. The surface roughness of copper that is grown at indus-
Assuming 100% current efficiency and fully dense pure trial relevant current densities (above 20 mA c­ m−2) increases
copper, the copper deposits had a thickness of 80 µm after 2 with electrodeposition time even when additives are used
h of electrodeposition at – 30 mA c­ m−2. In contrast, indus- [12]. Regardless of additives, the initial difference of the
trial copper electrowinning harvests copper after 7 days of copper surface roughness on the pretreated SS obtained after
electrodeposition or plate thickness of 5–8 mm. From this 2 h of electrodeposition is expected to amplify at longer
perspective, it’s more relevant to produce copper at a longer electrodeposition times. This indicates that the initial
deposition time to examine the effects of substrate pretreat- phases of copper nucleation and growth modes are critical
ments. Since surface roughness, however, increases with to obtain smooth copper deposits. Hence, in our study, the

Fig. 6  AFM top view image of the surface of the copper deposits after 2 h of galvanostatic electrodeposition on a an oxidized and b a polished
SS substrate ( – 30 mA c­ m−2)

13
Journal of Applied Electrochemistry (2021) 51:219–233 229

Table 1  Critical load for the damage features on 20-µm-thick copper substrate can be explained by the high nucleation rates and
deposits with polished and oxidized stainless steel substrates fast copper coverage [55–57]. Furthermore, the presence of
Stainless steel Critical load for the damage features/mN a passive layer, which separates the substrate and the coat-
substrate ing, was reported to decrease the adhesion at the substrate-
Transverse tensile crack Spallation
coating interface [58]. Therefore in this study, it is believed
Polished 97 ± 11 (N = 9) > 130 (N = 0) that the adhesion decreased due to the chemical oxidation
Oxidized 53 ± 24 (N = 9) 94 ± 10 (N = 7) of the SS and contributed to the spallation of the copper in
the scratch test.
N the number out of nine observations in which the damage feature
took place within the assesed load range (max = 130 mN) The S (sulfur) contents of the copper deposits after 24 h
of electrodeposition at – 30 mA c­ m−2 are shown in Fig. 7.
The S (as sulfate) content in the copper deposits on a pol-
high nucleation rates and fast copper coverage on the pol- ished and oxidized substrate are compared and related to the
ished substrate resulted in the smoothest copper deposits standard specification for electrolytic copper cathodes [59].
compared to the oxidized substrate. The S content of the copper deposits was 2.5 ± 0.95 ppm
The adhesion properties of the copper deposits on the oxi- for the polished substrate and ≤ 1 ppm (all samples below
dized and polished substrates were assessed through careful detection limit) for the oxidized substrate, which in both
observation of the damage features and their position along cases is below the standard specification limit of 15 ppm. A
the track (critical load (mN)). The goal of the scratch test two-tailed t-test was performed to calculate the significance
was not to obtain the exact adhesion strength of the copper of the different mean values with 1 ppm (overestimation) as
deposits to the SS substrate. The term adhesion is used in a mean for the oxidized group. The p-value was 0.053.
relative context. The critical load values of adhesion failures The equilibrium solubility of sulfur in copper is nihil at
were used to indicate the general ability to resist the physi- room temperature [60]. Accordingly, sulfur (as sulfate from
cal handling associated with commercial operations such as the electrolyte) reports to the space between copper grains.
automatic stripping in copper electrowinning. Moreover, sulfur-based inclusions have been measured in
The damage features and values of the critical load are grain boundaries in copper electrodeposited from an acidic
given in Table 1, and the microscopy images of the indented copper sulfate electrolyte [61]. Sulfur (as sulfate) is there-
scratches and damage features are provided in Figure S6. fore considered to segregate at the copper grain boundaries,
The scratches in the copper deposits on the polished sub- aside from the pure interior copper grains as illustrated in
strate were smooth and shallow (Figure S6b). This suggests Figure S7.
that the copper deposit showed high elastic recovering prop- Wasekar et al. recently developed a mathematical model
erties at loads below 130 mN. A transverse tensile crack for Ni electrodeposition, which explains the relationship
was observed towards the end of the scratch (97 ± 11 mN), between grain size and insoluble impurity content (e.g., sul-
which represents a cohesive failure in the copper deposit. No fur as sulfate) [62]. The model predicts a grain size that is
adhesion failures were observed in the operated load range. directly proportional to the current efficiency and deposition
The scratches in the copper deposits on the oxidized were rate, but inversely proportional to the current density and the
rough and shallow, which implies reduced cohesiveness and insoluble impurity content of the electrodeposited coating.
high elastic recovery properties at loads below 130 mN. A
transverse tensile crack occurred at a lower load (53 ± 24
mN) comparing with the copper deposits on the polished
substrate. In contrast to the copper deposits on the polished
substrate, adhesion failures were observed in the operated
load range in 7 out of 9 test runs. Due to the compressive
stress, copper was separated from the substrate at an intender
load of 94 ± 10 mN (N = 7). The spallation of the copper
deposit is highlighted on the optical microscope image in
Figure S6a.
Murray et al. investigated the effect of different electrow-
inning parameters on the adherence of copper to SS and
noticed a negative correlation between the resulting grain
size and adherence strength [55]. Small copper grains at the
substrate copper deposit interface were believed to maximize Fig. 7  Sulfur content of copper deposits after 24 h of galvanostatic
electrodeposition ( – 30 mA ­cm−2) on a polished and oxidized stain-
the area of direct attachment and consequently increase the less steel substrate and the Grade A limit as reference for sulfur con-
adherence. The high adherence of copper on the polished tent

13
230 Journal of Applied Electrochemistry (2021) 51:219–233

Accordingly, the S content in the entire deposit increases crystallographic site and incorporate into the metal lattice
with decreasing grain size (increasing intergranular area) as [63]. The incorporation proceeds through the incorporation
illustrated by Figure S8. into an existing grain (growth) or through the formation of a
Figure 8 shows the copper deposits obtained after 5 min nuclei (nucleation) [63, 64]. The competition between nucle-
(top) and 24 h (bottom) of galvanostatic electrodeposition on ation and growth dictates the resulting grain size and, thus,
(a) an oxidized and a polished (b) SS substrate. The oxidized the intergranular area [64, 65]. The area between grains is
SS was not completely covered with copper after 5 min of regarded as open space and defect structure in which impuri-
electrodeposition with open spots in evidence (Fig. 8a). ties (e.g., sulfur as sulfate) can report [62].
The copper grain size was approximately 5 µm. The copper The higher sulfur content on the polished SS substrate
deposits after 5 min of electrodeposition on the polished SS is, therefore, a consequence of smaller copper grains that
were dense and covered the complete surface (Fig. 8b). The have more intergranular area per unit of deposited metal
copper grain size was much smaller as compared to the oxi- volume in which the electrolyte can accumulate. It could be
dized SS substrate and estimated to be less than 1 µm. After speculated that the extremely small nuclei that were formed
24 h of electrodeposition the copper grain size increased to during the first 2 s of electrodeposition on the polished SS
roughly 50–100 µm on the oxidized and 25–75 µm on the contributed considerably to the contamination of sulfur (as
polished SS substrate. The relative difference in grain size sulfate) into the deposit. Our results are somewhat contra-
of the copper on the oxidized and polished SS decreased dictory with the general assumption that incorporation of
after the initial phases of nucleation and growth as expected. impurities is promoted by the surface roughness of copper
After complete coverage, the electrodeposition and resulting deposits in industrial operations [7, 10]. It should, however,
grain size is no longer subject to the SS substrate, but con- be noted that the surface roughness of copper deposits could
trolled by the plating conditions (i.e., current density, mass contribute to the incorporation of impurities through another
transfer, electrolyte composition) [26]. mechanism when a suspended solid matter is present in the
We briefly review the principles of crystal formation electrolyte or as indication of nodulation with the presence
through electrodeposition (electrocrystallization) in order of voids in the copper deposit that could be filled with elec-
to further rationalize the difference in sulfur content that trolyte. Suspended solid matter occasionally appears in the
were obtained in the copper deposits. During metal elec- industrial electrolyte (e.g., Pb anode scale, ­PbSO4, arsenic-
trodeposition, the discharged metal species find a suitable bismuth-antimony slimes) and can be entrapped into the

Fig. 8  FESEM images of galva-

nostatic electrodeposited copper
at – 30 mA ­cm−2 on a chemi-
cally oxidzed stainless steel and
b polished stainless steel after 5
min (top) and 24 h (bottom) of
electrodeposition times

13
Journal of Applied Electrochemistry (2021) 51:219–233 231

growing copper deposit after collision with the copper sur- PhD fellowship to Florian Verbruggen (HBC.2017.0224) and by the
face [10]. It seems reasonable to assume that the incorpora- Research & Development Umicore Group. EF is supported by the
Fonds voor Wetenschappelijk Onderzoek - Vlaanderen (FWO) PRO-
tion of suspended solid matter is promoted by the roughness JECT G020616N. KR and AP are supported by a Ghent University
of the copper. Further research on the chemical quality of Bijzonder Onderzoeksfonds GOA grant (BOF19/GOA/026). LB is sup-
copper should therefore be concerned with both the influ- ported by the Fonds voor Wetenschappelijk Onderzoek - Vlaanderen
ence of grain size and surface roughness when solid sus- (FWO) PROJECT 3G0I1818W.
pended matter is present in the electrolyte.
Data aavailability The datasets generated during and/or analyzed dur-
ing the current study are available from the corresponding author on
reasonable request.
4 Conclusion
Code availability The custom made software used in the study is avail-
able from the corresponding author on reasonable request.
The pretreatment of the SS substrate significantly impacted
the initial nucleation and growth phases during galvanostatic
Compliance with ethical standards
copper electrodeposition. Polished SS induced higher nucle-
ation rates and faster substrate coverage. On the contrary, the Conflict of interest The authors report no conflicts of interest. The au-
growth of formed copper nuclei was more favored on the thors alone are responsible for the content and writing of this article.
oxidized SS. The decrease of onset potential on the oxidized
SS substrate was attributed to the decrease of the flatband
potential. The copper deposits on the polished SS substrate,
with smaller grains, included more electrolyte. Fast and References
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