JOM

https://doi.org/10.1007/s11837-019-03739-7
 2019 The Minerals, Metals & Materials Society

ADVANCES IN SURFACE ENGINEERING

Parametric Characterization of Copper Metal Coatings

Produced by Supercritical Argon Electroplating

HO-CHIAO CHUANG1 and JORGE SANCHEZ 2,3

1.—Department of Mechanical Engineering, National Taipei University of Technology, Taipei

10608, Taiwan. 2.—Graduate Institute of Manufacturing Technology, National Taipei University
of Technology, Taipei 10608, Taiwan. 3.—e-mail: t103569010@ntut.edu.tw

An electroplating process under supercritical argon applied to a copper sulfate

bath with no additives is presented in this work. Adjusting electroplating
parameters such as temperature, pressure and current density changed the
deposition behavior, thus changing the coating properties. The finest grains
( 20.91 nm) were obtained at 2500 psi and 35C, which were relatively
higher pressure and lower temperature than those found for SC-CO2 pro-
cesses, respectively, 2000 psi and 50C. Mechanical, electrical and corrosion
analyses revealed the coating properties were enhanced compared with those
produced by the conventional process. Finally, the results point to optimal
fabrication parameters of 35C, 5 A/dm2 and 2500 psi, achieving the relatively
best coating properties and highest current efficiency ( 93%).

environmentally friendly and relatively cheap noble

INTRODUCTION
Supercritical fluids (SCF) have received extensive
study in recent decades, mostly focused on CO2 as
the solvent for various applications such as clean-
ing, chemical extraction, and electroless- and elec-
tro-plating.1–6 Advantages of supercritical (SC)
electroplating include a substantial reduction of
the surface tension of the electrolyte, grain refine-
ment, higher coating hardness, shorter fabrication
times, better coverage, etc.7–11 Electrolyte mixed
with SCF can easily penetrate into very small holes,
which is an important technology for high-aspect-
ratio interconnection schemes in the electronics
industry.12–16 In the case of CO2, benefits arise
because of emulsification between the electrolyte
and SCF, enhancing reactions over the substrate
surface from effects similar to pulse plating.16
Although the SC-CO2 method displays many advan-
tages, there is one major issue resulting from its
use, namely, the relatively higher internal stress
developed in the structure because of the extremely
refined grain sizes, which has been reported
previously.17–19
To solve this issue, noble gases are interesting
because they are unreactive with electrolyte chem-
istry under normal conditions, resulting in little to
no emulsification, while avoiding undesired byprod-
ucts, such as carbonic acid.10 Argon is a common,
gas. Moreover, many reports in recent years have
focused on the previously unknown reactive prop-
erties of pressurized Ar.20–23 To our knowledge,
there is little literature on this subject, so we believe
more work is warranted. Chung and Tsai16 reported
successful electroplating under pressurized Ar envi-
ronment. Chuang et al.18 reported that under the
same experimental parameters, supercritical argon
(SC-Ar) electroplating achieved  3 9 lower inter-
nal stress in the coating structure than the SC-CO2
method.
In this work we aim to find the optimal fabrica-
tion parameters for coatings produced by SC-Ar
electroplating by adjusting various temperatures,
pressures and current densities. Cu was chosen
because of its popularity in the electronics industry.
Mechanical, electrical and corrosion analyses were
performed to compare the results of each parameter
combination.
EXPERIMENTAL DETAILS
Materials and Methods
A piece of Cu (99.99% purity) trimmed to
30 mm 9 20 mm 9 5 mm served as anode. Circular
pieces of brass (ø: 2 cm, thickness: 0.03 cm) served
as cathode substrate; circular substrates were used
for most analyses, except for internal stress

calculations where brass strips (purchased as
10 cm 9 15 cm sheets, cut to shape; thick-
ness:  0.022 cm) were used for convenience of
measurements. The SCF used was argon (99.99%
purity), purchased from C.C. Gaseous Corp. (Tai-
wan). The electrolyte used was a copper sulfate
solution, purchased from Blue Giant Inc. (Taiwan).
An electrolyte bath was used as is, with no further
refinement; components as described by the sup-
plier are listed in Table I. Other commonly encoun-
tered copper electrolytes are the copper nitrate and
copper chloride solutions; they will be the focus of
future works.
Yan et al.24 reported that the CO2 concentration
in solution should not exceed 50% of the total
volume to maintain a stable emulsion. To uphold
this requirement, 330 mL of electrolyte was used,
with a fixed concentration of SCF at 46%. Previous
works reported that the optimal electroplating
temperature and pressure parameters for SC-CO2
are 50C and 15 MPa, respectively.9,12 These
parameters were tested in Ref. 18; however, we
cannot confidently claim these parameters were
optimal for production under SC-Ar. Moreover,
although it is possible that the optimal concentra-
tion for SC-Ar might be different from that of SC-
CO2, the same parameter was used here for sim-
plicity of experiments. Increasing gas concentration
(thus decreasing electrolyte content) might result in
insufficient immersion of the substrate in our setup;
this requires redesigning of experiments. Thus,
adjusting the gas concentration will be the focus of
future works. Electroplating parameters considered
in this work are shown in Table I.
Equipment and Preparation
The electroplating equipment was described in
Ref. 18. The reaction chamber was made of 316L
stainless steel with a usable inner volume of
 606 mL. After trimming and before electroplat-
ing, substrates were cleaned with NaOH (10 wt.%)
solution for 30 s and activated in HCl (35 wt.%)
solution for 30 s at STP. Substrates were then
Table I. Electroplating bath and parameters
applied in this work
Parameter Quantity
CuSO4Æ5H2O 200 g/L
H2SO4 50 g/L
Cl 38.5 ppm
pH £2
Gas concentration (vol.%) 46
Temperature (C) 35, 45, 55
Pressure (psi)a 1100, 1500, 2000, 2500
Current density (A/dm2) 1, 3, 5, 7
a
145.04 psi = 1 MPa.
Chuang and Sanchez
blown dry with N2 gas and weighed; the weighing
step was important for current efficiency (CE)
calculations, detailed in ‘‘Analysis Methods’’ sec-
tion. Insulating tape was attached to the substrate
backside, after which the substrate was fixed to the
holder in the reaction chamber. Next, the anode was
scrapped with an iron-bristled brush to remove
surface oxidations and then soaked in deionized
water, blown dry with N2 gas and finally fixed to its
holder inside the reaction chamber. The distance
between electrodes was 10 mm. Then, the elec-
trolyte and gas were loaded into the reaction
chamber. After appropriate mixing steps, experi-
ments were performed. Adequate mixing was
extremely important to maintain a uniform metal
ion distribution, which in turn affected electroplat-
ing quality. Other effective mixing methods such as
ultrasonic agitation have been reported recently.25
Electroplating is dependent on parameters such
as pressure, temperature and current density. In
this work, parameters were systematically adjusted
to yield optimal coating characteristics produced by
SC-Ar electroplating. Once electroplating was com-
pleted, pressure was released; then, the plated
substrate was retrieved from the chamber, soaked
in deionized water and blown dry with N2 gas. The
insulating tape was carefully peeled off and the
substrate weighed again. Finally, substrates were
stored until analyses were performed. Electrolyte
pH was measured before and after experiments
with a pH meter (model GBS-EC500, Extech Instru-
ments, Nashua, NH, USA).
Analysis Methods
Surface morphology observations were performed
by SEM (model SIGMA Essential, Zeiss Microscopy,
Germany); grain sizes were estimated from SEM
images, analyzed with ImageJ software (version
1.50i, NIH, Bethesda, MD, USA). Surface roughness
was measured by a surface profilometer (model
SEF-3500DK31, Kosaka Instruments, Japan) with
a scrapping speed of 0.1 mm/s. Microhardness was
measured from coating surfaces with a microhard-
ness tester (model HM-113, Mitutoyo, Japan); a load
of 50 g force was applied for 10 s. Grain size and
crystal structure were analyzed by x-ray diffrac-
tometer (model X’Pert Pro, PANalytical, The
Netherlands) at STP with a scan speed of 2/min
and a Cu-Ka x-ray source. Crystal phases were
identified comparing 2h values and intensities
against a reference Cu pattern (ICDD# 01-085-
1326). Average grain size (D) was calculated by the
Scherrer equation:26,27
K k
D¼ ð1Þ
b  cos h
where K is the dimensionless shape factor (0.9 for
unknown shapes), k is the incident x-ray wave-
length (1.5418 Å), b is the FWHM in radians, and h
Parametric Characterization of Copper Metal Coatings Produced by Supercritical Argon
Electroplating
is the diffraction angle studied. Dimensionless
microstrain (e) can also be calculated from the
XRD data,28 according to:
b  cos h
e¼ ð2Þ
4 nology (Taiwan). A geometrical correction factor
Finally, the preferred orientation can also be
determined from the XRD data. Preferred orienta-
tion of coatings can be influenced by certain fabri-
cation parameters and directly affects properties
such as hardness, elastic modulus, tribology, chem-
ical reactivity, etc. The preferred orientation was
calculated by the relative texture coefficient
(RTC),29,30 defined as:
 0
Ihkl Ihkl
RTC ¼ P P 0 ð3Þ
Ihkl Ihkl
where Ihkl is the measured peak intensity of the
0
diffracted x-ray, and Ihkl is the reference peak
intensity obtained from the ICDD reference. The
h, k, l, quantities refer to the Miller indices of the
crystallographic planes. The summations in the
denominator are taken for the three peaks visible
in the XRD data over the analyzed range (20–80),
i.e., [111] (at  43.32), [200] (at  50.45) and [220]
(at  74.13). If the calculated RTC £ 1, it suggests
preferred growth in that plane and vice versa. It is
important to note that no impurity analyses such as
electron probe microanalyzer (EPMA), secondary
ion mass spectroscopy (SIMS) or energy dispersive
spectroscopy (EDS) were considered in this work.
As metal coatings are electroplated over the
substrate surface, the substrate experiences bend-
ing. For thick substrates this bending can be
ignored, but for thinner substrates, the bending
becomes increasingly evident. The bending can be
measured by optical techniques, which can then be
correlated to the coating’s internal stress (r). A
popular method for internal stress calculations in
this way is by the Stoney equation,31 as:
ESubs  t2Subs
r¼ ð4Þ
6Rð1  tSubs ÞtCoat
where ESubs and mSubs are the Young’s modulus and
Poisson’s ratio of the substrate, respectively; R is
the substrate’s calculated curvature; tSubs and tCoat
are the thicknesses of the substrate and coating (in
lm), respectively. For the Stoney equation to apply,
the coating thickness must not exceed 1/10th of the
substrate thickness; therefore, the thickness was
fixed at  20 lm. The thin-strip substrates were
heat-treated to release any pre-existent stress and
were then cleaned by the process described in
‘‘Equipment and Preparation’’ section. After elec-
troplating, the substrate bending was measured
with an optical diffractometer; the substrates were
placed on a XY table, and a single point was
measured at a time. The individual coordinates of
each point were curve-fitted with a circular arc
function in SigmaPlot software (version 11.0,
Systat Software, San Jose, CA, USA) to obtain
curvature of the substrate.
Resistivity of coatings was measured by a four-
point (4P) setup purchased from KeithLink Tech-
was applied according to the shape of the 4P array;
distance between the electrodes was 1.6 mm
arranged in a single line. From the V/I relationship,
the sheet resistance can be calculated by Eq. 5:
 
V
Rs ¼ Kp  ð5Þ
I
where Rs is the calculated sheet resistance, Kp is the
correction factor (4.5324 for linear geometry), I is
the input current, and V is the detected voltage.
From Faraday’s laws of electrolysis, we know that
by measuring the quantity of electricity passing
through the system, the amount of chemical change
produced by that system can be calculated; through
these principles, the CE of the fabrication processes
was calculated. Weight of the substrates before and
after electroplating was measured by a digital scale
(model AB204, Mettler Toledo, Switzerland) with a
resolution of 0.1 mg and recorded. The initial
weight was subtracted from the final weight to find
the actual coating weight, and this value was
compared with the theoretical weight calculated
beforehand.
Finally, to understand the corrosion behavior of
metal coatings, potentiodynamic polarization scan-
ning (PPS) was performed. A potentiostat (model
ECW-5000, Jiehan Technology, Taiwan) was used.
The produced coating, a piece of graphite and a
saturated calomel electrode served as the working
electrode (WE), counter electrode (CE) and refer-
ence electrode (RE) of the analysis cell, respectively.
A 1 cm2 exposed area of the WE was submerged into
a 3.5% NaCl solution until a steady open circuit
potential (OCP) signal was reached (about 1800 s).
Scanning speed was set to 1 mV/s. OCP was taken
as the corrosion potential (Ecorr). After equilibra-
tion, a range of ± 250 mV for PPS was set according
to Ecorr. All experiments were performed at
20 ± 2C. Through PPS, a graph containing both
cathodic and anodic polarization curves was
obtained. Corrosion current density (Icorr) was cal-
culated by Tafel extrapolation through Cview soft-
ware (version 2.6b, Scribner Associates, Southern
Pines, NC, USA). Finally, from the Icorr we can
estimate the material corrosion rate.
RESULTS AND DISCUSSION
Effects of Temperature
Before experiments, electrolyte pH was measured
at  0.81 (at STP). Electrolyte pH (at atmospheric
pressure) for 35C, 45C and 55C was 0.83, 0.90
and 0.96, respectively. Temperature actively affects
electrolyte pH, viscosity and diffusion layer

thickness,32 all of which directly affect deposition
phenomena. Usually, electrolyte surface tension is
expected to decrease with increasing temperature,
lowering viscosity and decreasing overall coating
grain size. However, grain sizes actually increased
with increasing temperature in this work. Wu
et al.32 reported similar results; grains in the
produced coatings became larger and coarser as
the electrolyte temperature increased. Figure 1
displays coating surfaces and cross-sections fabri-
cated at 2500 psi, 7 A/dm2 and various electrolyte
temperatures. Cross-sectional views were analyzed
by software to estimate grain sizes. The most
obvious grain refinement was observed from the
35C process. For the sake of simplicity, subsequent
analysis will focus mostly on results of the 35C
process.
The coarsening effect was attributed to higher pH
by increasing electrolyte temperature. Karahan33
reported that grain sizes increase by increasing the
bath pH; additionally, the microstrain decreases as
grain size increases. To verify these assumptions,
the coatings shown in Fig. 1 were analyzed by
software to estimate grain sizes: coatings produced
by 35C, 45C and 55C processes were on average
 20.91 nm,  30.54 nm and  55.78 nm, respec-
tively. Grain sizes calculated from XRD data for
35C, 45C and 55C were on average 22.28 nm,
25.46 nm and 50.92 nm, respectively. Finally,
accompanying microstrains from XRD data were
also calculated for 35C, 45C and 55C processes
and were 8.8159 e2, 8.2963 e2 and 1.7087 e2,
respectively.
Gas densities decrease as temperature increases;
moreover, for a fixed given temperature, gas densi-
ties increase with increasing pressure. On the other
Fig. 1. SEM images of coatings produced by SC-Ar electroplating at 2500 psi, 7 A/dm2. Surfaces produced at: (a) 35C, (b) 45C and (c) 55C;
cross sections produced at (d) 35C, (e) 45C and (f) 55C.
Chuang and Sanchez
hand, the density of SC-CO2 was always much
higher than that of SC-Ar. Gas densities were
calculated by ideal gas law and are shown in
Table S1. The lower densities of SC-Ar allow for
more flow of dissolved species and particularly H+
(incoming from hydrolysis of water in aqueous
electrolyte). H+ actively reduces to H2 on contact
with the cathode surface; all of these phenomena
affect the electrolyte pH. Furthermore, SC-CO2
actively dissolves into electrolyte (resulting in the
formation of carbonic acid16), but at the same time
effectively dissolves H2 microbubbles.34 The
removal of excess hydrogen in the solution can help
balance and stabilize the electrolyte pH (usually a
pH of  3).12,16,17 On the other hand, SC-Ar is not
able to remove excess hydrogen effectively; thus, the
pH under SC-Ar was lower than that of the
electrolyte under SC-CO2.
Effects of Supercritical Pressure
Generally, applied pressure is very important to
all supercritical processes because small changes in
pressure result in large changes in the supercritical
solvent density. For supercritical electroplating
processes in particular, pressure can influence
emulsification, flow of species in the electrolyte,
deposition phenomena, etc. In this work, adjusting
the pressure resulted in changes in the plating
characteristics. Furthermore, for convenient com-
parison to previous reports, a pressure range from
1100–2500 psi was considered. As presented in
‘‘Effects of Temperature’’ section, the pH changed
according to temperature, but we believe the pH
also changed by coming into contact with pressur-
ized SC-Ar. After each pressurized experiment, the
Parametric Characterization of Copper Metal Coatings Produced by Supercritical Argon
Electroplating

Fig. 2. SEM images of surface morphologies produced by SC-Ar electroplating at 35C, 5 A/dm2 and (a) 1100 psi, (b) 1500 psi, (c) 2000 psi and
(d) 2500 psi.

pH was measured again; on average, electrolyte pH neutral Ar atoms can form van der Waals molecules
treated at 35C, 45C and 55C became  0.71, with one another; a van der Waals radius of Ar is
 0.869 and  0.875, respectively. The combination  180 pm and for CO2 is  151 pm;35 because the
of temperature and pressure lowered the electrolyte Ar molecule size is relatively larger than that of
pH even further compared with temperature alone; CO2, it required higher pressure to approximate CD.
therefore, even smaller grains were achieved.
The critical point of Ar ( 122C,  712 psi) is Effects of Current Density
lower than that of CO2 (31C,  1070 psi). Addi-
To understand the effects of current density on
tionally, notable density changes occur at different
the formation of metal coatings, the temperature
pressures for each solvent. For example, to achieve
and pressure were fixed. As the current density
a density of 150 kg/m3 at 55C, the Ar pressure
increases, more positively charged metal ions were
required is  1490 psi, but only  960 psi for CO2
attracted toward the negatively charged substrate,
(as calculated by ideal gas law); the varying solvent
which then proceeded to reduce over the substrate
densities affect emulsification, achieving different
surface, resulting in more grains forming simulta-
deposition characteristics.
neously. The larger numbers of grains growing
An evident example of changes related to applied
simultaneously will restrict one another, leaving
pressure is presented in Fig. 2. Surface morpholo-
less space to grow freely, compelling grain refine-
gies of coatings produced by SC-Ar electroplating at
ment. Surface SEM images of coatings produced by
35C, 5 A/dm2 and various supercritical pressures
SC-Ar electroplating at 35C, 1100 psi and various
are compared. A high magnification (5000 9) was
current densities are illustrated in Fig. 3. Larger
chosen to clearly show the microstructure changes
nodules gradually smoothed as the current density
induced by pressure.
increased. Additionally, structural microstrains
Chang reported that when the physical size of the
increased with decreasing grain size.
dispersed phase approached the thickness of the
diffusion layer (CD), i.e., the size of supercritical
Analysis of Structural and Mechanical Prop-
microbubbles  CD, the finest morphologies were
erties
achieved; for the SC-CO2 process, it was found at a
pressure of  15 MPa ( 2100 psi).12 However, as Figure 4a shows the measured microhardness
seen from Fig. 2, pressure of 2500 psi (Fig. 3d) values of the produced coatings. Substrates were
actually yields the smoothest morphology for the measured at five different positions to construct
SC-Ar process. At higher pressures, the usually error bars. According to the Hall–Petch relation,
 Chuang and Sanchez

Fig. 3. SEM images of surface morphologies produced by SC-Ar electroplating at 35C, 1100 psi and (a) 1 A/dm2, (b) 3 A/dm2, (c) 5 A/dm2 and
(d) 7 A/dm2.

Fig. 4. Average (a) microhardness and (b) Ra of coatings produced at 35C.

microhardness should increase with decreasing
grain size, and the results comply with the expected
trend. Microhardness increased with increasing
pressure and current density for all cases. Grain
refinement leads to more grain boundaries in the
structure, acting as dislocation barriers; this is
known as grain boundary strengthening.10 Addi-
tionally, the metal coatings plated under SC-Ar at
35C displayed relatively higher hardnesses com-
pared with the other electroplating process.
Measured surface roughness of coatings is shown
in Fig. 4b. Substrates were measured at four differ-
ent positions to construct error bars. Comparing
results revealed that the combination of 2500 psi,
7 A/dm2 produced the lowest surface roughness for
each individual process. Additionally, the lowest
overall surface roughness ( 0.38 lm) was observed
at the 35C process.
Crystalline structures of the produced coatings as
measured by XRD are shown in Fig. 5a. The effects
of instrumentation broadening, twins, stacking
faults, etc., were not considered in this work;
measurements were considered as an observational
tool rather than for precise numbers. A slight peak
broadening was observed by decreasing the elec-
trolyte temperature, suggesting grain refinement by
Parametric Characterization of Copper Metal Coatings Produced by Supercritical Argon
Electroplating

Fig. 5. (a) XRD spectra, (b) grain sizes, (c) microstrains and (d) internal stresses obtained from all coatings fabricated at 35C. Spectra in each
figure are listed as: (A) 1100 psi, 1 A/dm2; (B) 1100 psi, 3 A/dm2; (C) 1100 psi, 5 A/dm2; (D) 1100 psi, 7 A/dm2; (E) 1500 psi, 1 A/dm2; (F)
1500 psi, 3 A/dm2; (G) 1500 psi, 5 A/dm2; (H) 1500 psi, 7 A/dm2; (I) 2000 psi, 1 A/dm2; (J) 2000 psi, 3 A/dm2; (K) 2000 psi, 5 A/dm2; (L)
2000 psi, 7 A/dm2; (M) 2500 psi, 1 A/dm2; (N) 2500 psi, 3 A/dm2; (O) 2500 psi, 5 A/dm2; (P) 2500 psi, 7 A/dm2.

decreasing temperature. Coatings displayed poly-
crystalline structure, with a preference for Cu[111],
because of its significant intensities (verified by
RTC calculations). RTC values are listed in
Table S2. Moreover, Cu[200] and Cu[220] intensi-
ties decreased or even disappeared completely as
the current density increased under similar pres-
sures. Grain growth usually starts at the plane with
lowest surface energy barrier;36–38 moreover, the
plane with the lowest surface energy in FCC metals
such as Cu is found toward the [111] orientation.
Because the Cu[111] phase is a very stable form of
Cu,39 structural change could be attributed to faster
preferential crystallization, which does not allow
the other phases to form as efficiently when adjust-
ing current density. Furthermore, as the pressure
increased the overall intensities decreased; pressure
is known to affect the crystallization dynamics of
metal deposits,12,16,40 and we believe similar prin-
ciples apply to this work.
Grain sizes calculated from XRD data are shown
in Fig. 5b. Increasing pressure and current density
were expected to decrease the grain sizes regardless
of the applied temperature, as discussed in ‘‘Effects
of Supercritical Pressure’’ and ‘‘Effects of Current
Density’’ sections, which also verified the SEM
results obtained. Accompanying microstrains
calculated from XRD data are shown in Fig. 5c;
microstain is expected to increase with decreasing
grain size. The results comply with our
expectations.
Calculated internal stresses of coatings produced
on the rectangular substrates are shown in Fig. 5d.
Internal stress should increase according to
decreasing grain sizes. Chuang et al.18 reported
that the internal stress developed in coatings pro-
duced under SC-CO2 were  3 9 higher than those
produced by SC-Ar. Additionally, higher deposition
rates do not allow enough time for internal stress to
release effectively, so internal stresses are expect to
increase according to increasing current density and
pressure. Internal stress and grain size have an
inverse relationship, and experimental results
showed that the 35C process produced the smallest
grains sizes; therefore, decreasing grain size sug-
gested increased internal stresses.
Electrical Properties and Current Efficiency
Resistivities of coatings measured by the 4P
method are shown in Fig. 6a. The influence of grain
size over resistivity was reported in Refs. 41 and 42;
defects, grain boundaries, dislocations, etc., all
affect the passing of electricity through the
 Chuang and Sanchez

Fig. 6. (a) Resistivities and (b) current efficiencies calculated in this work at 35C.

conductive coatings. The main contribution to mate- those reported in Refs. 11 and 19. This topic will be
rial resistivity was the increased quantity of grain the focus of future studies.
boundaries due to grain refinement; the results Finally, inclusion of surfactants could be consid-
obtained appear in agreement. The 35C process ered in order to effectively emulsify the SC-Ar and
produced the smallest grains in this work, so the electrolyte. Although argon chemistry under high
measured resistivities were the highest overall. pressure is still not well understood, surfactants
However, overall differences in resistivity for all previously used for SC-CO2 processes could be
processes were actually very small (a few lX cm), considered since both solvents are non-polar. To
which might be negligible in real-world applications better understand the chemical effects and associ-
and indicate that all processes have potential for ated properties, calorimetry analysis43 could be
industrial use. considered. This will be the focus of future studies.
The calculated CEs are shown in Fig. 6b. When
secondary reactions such as hydrolysis of the aque- Corrosion Behavior Analyses
ous electrolyte occurred, pH was affected, in turn
Corrosion behavior of the coatings produced were
directly influencing CE. When inspecting each
analyzed by PPS and Tafel extrapolation; represen-
individual process, 5 A/dm2 appeared optimal,
tative polarization curves are shown in Fig. 7. The
because it steadily yields the highest CE. While
inset in each figure is meant to show Ecorr variations
the 7 A/dm2 resulted in more evident grain refine-
more clearly. Each figure also includes a Tafel plot
ment, the higher current density could also incite
of the Cu coating produced by conventional electro-
faster hydrolysis of water, resulting in more H2 in
plating for reference; Ecorr and Icorr of conventional
the solution, which became too detrimental to the
coatings were about  0.366 V and 2.5 lA/cm2,
process, thus lowering CE; 5 A/dm2 might be a
respectively. The Ecorr and Icorr derived for each
‘‘sweet spot’’ for the balance between grain forma-
coating produced by SC-Ar electroplating are listed
tion and hydrolysis. The best ‘‘quasi-emulsion’’
in Table S3.
effect was encountered at 35C, achieving the
Results suggest that the corrosion resistance of
relatively highest CE of all processes studied (as
coatings produced by SC-Ar was superior to that of
well as the enhanced mechanical properties pre-
coatings produced by conventional electroplating
sented). Lower temperatures seem to change Ar
regardless of the parameters used. Figure 7a com-
chemistry more effectively to produce consistent Ar
pares the relation between polarization curves of
compounds;20,21,23 although the temperatures in
films produced at 35C and 1100 psi; Fig. 7b shows
those reports were much lower than those used in
the relation between 35C and 1500 psi; Fig. 7c
this work, we suspect a similar effect applies.
shows the relation between 35C and 2000 psi;
Moreover, Li et al.21 reported that application of
Fig. 7d shows the relation between 35C and
high-pressure environments can reduce atomic dis-
2500 psi. Previous reports10,44–46 suggest that
tances and emphasize the repulsive part of the
decreasing grain sizes should increase the corrosion
atomic interaction potentials, which can change the
resistance of the material. However, if grain refine-
bonding characteristics of elements and lead to
ment is too intense, the coatings actually become
novel chemical phenomena, inducing Ar to become
prone to intergranular corrosion.47 Fortunately, this
an electron acceptor. It is possible that even without
was not observed here. The corrosion resistance of
surfactants, there are small inclusions of SC-Ar into
coatings produced under a higher current density
the electrolyte (but to a lesser extent than in the SC-
parameter appeared better, hinted at by the rela-
CO2 process). If confirmed, this could be developed
tively higher Ecorr measured and the relatively
into a post-SC electroplating process, similar to
higher Icorr fitted.
Parametric Characterization of Copper Metal Coatings Produced by Supercritical Argon
Electroplating
Fig. 7. Tafel plots measured at 35C and (a) 1100 psi, (b) 1500 psi, (c) 2000 psi and (d) 2500 psi.
Increasing current density should decrease the
grain sizes of the coating, which resulted in a steady
increase of the measured Ecorr values for all cases.
Pressure also affected grain sizes; thus, more
defined passivation regions were observed as the
pressure increased.
Additionally, passivation regions became notice-
able in the Tafel plots as current density increased;
moreover, when comparing each group of curves as
a whole, passivation regions were more apparent in
Tafel plots produced at higher pressures. The
passivation region usually hints at the formation
of barrier layers over the coating, which lowers the
corrosion rate; breakdown of these layers occurred
until a sufficiently high Ecorr was achieved. Wasekar
et al.48 reported that passivation layers forming
over coatings with smaller grains were relatively
more protective.
CONCLUSION
Deposition of copper metal coatings by supercrit-
ical argon under various electrolyte temperatures,
supercritical pressures and applied current densi-
ties was successfully demonstrated in this work.
Surface morphology, roughness, hardness, crystal-
lographic structure, state of internal stresses, resis-
tivity and corrosion behavior of the produced
coatings were investigated. From the results, the
following conclusions were drawn:
1. Regardless of the parameters applied, charac-
teristics of coatings produced by the SC-Ar
process were significantly better than those
produced by the conventional process. Although
less prominent grain refinement was observed
compared with other supercritical processes
reported in the literature, SC-Ar is still advan-
tageous because it yields lower structural inter-
nal stress while keeping the enhanced coating
properties.
2. Although increasing temperature usually re-
sulted in grain refinement, this was not the case
here; we infer this behavior was due to changes
in electrolyte pH caused by interactions between
argon (which becomes slightly reactive when
pressurized) and the electrolyte.
3. Results suggest the best coating characteristics
under consistent current efficiency were pro-
duced by the SC-Ar process at 35C, 2500 psi
and 5 A/dm2.
ACKNOWLEDGEMENTS
The authors express their gratitude to Prof. C.Y.
Lee and his research group at the Department of
Mechanical Engineering, National Taipei Univer-
sity of Technology, for providing invaluable insight
into and discussions on the fabrication processes.
Also, the authors gratefully acknowledge the Min-
istry of Science and Technology of Taiwan for sup-

porting this work under Contract Nos. MOST 105-
2221-E-027-046-MY3 and MOST 107-2622-E-027-
010-CC3.
ELECTRONIC SUPPLEMENTARY
MATERIAL
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10.1007/s11837-019-03739-7) contains supplemen-
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