Applied Surface Science 307 (2014) 731735

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsus

Controlled electropolishing ofcopperfoilsatelevatedtemperature

Gi Duk Kwona, Young Woo Kima, Eric Moyena, Dong Hoon Keuma, Young Hee Leea,c,d,

Seunghyun Baika,b,c, Didier Pribata,

a
Department of Energy Science, Sungkyunkwan University, Suwon 440-746, Republic of Korea b School of Mechanical Engineering, Sungkyunkwan University, Suwon 440-
746,Republic of Korea c IBSCenter for Integrated Nanostructure Physics (CINAP), Institute of Basic Science (IBS), Daejeon, Republic of Korea d Department of Physics,
Sungkyunkwan Advanced Institute of Nano-technology (SAINT), Sungkyunkwan University, Suwon 440-746, Republic of Korea

ar ti cl e in fo a bs tr ac t

Article history: We have studied the electrochemical polishing of copper foils at elevated temperature, in H3PO4 electrolytes of various concentrations.
Received 2 March 2014 Atomic force microscopy, surface reflectance measurements as well as optical microscopy and scanning electron microscopy
Received in revised form 17 April 2014 (including electron backscattering diffraction) have been used throughout this study to characterize the surface of the electropolished
Accepted 18 April 2014 Available
foils. We have found that copper foils electropolished at 65C in 2.17M H3PO4, exhibited a lower surface roughness and a higher percent
online 9 May 2014
specular reflection, comparing with values obtained after classical electropolishing in concentrated H3PO4 at room temperature or
comparing with values obtained after chemical-mechanical polishing. This work could open up new prospects for the preparation of
Keywords: copper foils before the growth ofhigh quality graphene layers.
Electropolishing 2014 Elsevier B.V. All rights reserved.
Elevated temperature
Rolled copper foils rms
roughness
Surface reflectance

1. Introduction
Electrochemical polishing, or electropolishing, is a widely
used process in industry, applied to a large number of metals and
alloys for deburring as well as surface finishing and removal of
tarnishing. Electropolishing, which is performed by controlled
anodic dissolution of the metal surface in an appropriate
electrolyte, can yield a significant decrease in surface roughness,
usually characterized by anincrease in the gloss ofthe metal [1].
The electropolishing (EP) of copper, which has been studied
for more than 80 years [2,3], has been recently considered for the
replacement/improvement of the chemical-mechanical
planarization (CMP) of Cu interconnects in ultra-large-scale-
integrated (ULSI) circuits [46]. More recently, EP of Cu has been
used for the surface preparation of rolled foils on which graphene
layers of good crystalline quality can be grown by chemical vapor
deposition [711]. As with any epitaxial or thin film deposition
process, some kind of surface preparation must be performed
before graphene growth on Cu foils, in order to remove the rolling
marks or other machining defects which are usually preferred and
uncontrollable nucleation sites [12]. Although mechanical or
chemical-mechanical polishing can be employed [12], electro-
polishing is a much
Corresponding author.Tel.: +82 31 299 6271.
E-mail address: didier53@skku.edu (D. Pribat).
http://dx.doi.org/10.1016/j.apsusc.2014.04.144 0169-
4332/ 2014 Elsevier B.V. All rights reserved.
simpler process which can be performed on large surface areas, with
elementary foil handling and manipulation operations. In particular,
when using EP, there is no need for a complex polishing machine,
highly incompatible with a roll-to-roll graphene synthesis process
[13]. Also, there is no need for several abrasives, clothes and colloidal
suspensions as with chemical-mechanical polishing and there is no
risk of surface contamination by residues from the polishing slurry
[14].
In most studies so far [221], even if various additives have been
employed, Cu EP has been performed in electrolytes based on highly
concentrated H3PO4 and at room temperature. Moreover, in order to
avoid preferential crystallographic etching of the Cu surface (leading
to an increase in roughness), all authors have been working in the
kinetic regime of mass transfer limitation, corresponding to a current
plateau in the anodic polarization curves [22]. In this kinetic regime,
two mechanisms have essentially been proposed to explain the current
limitation, namely (i) the formation of a salt film on the Cu surface or (ii)
the formation of a viscous boundary layer in which metal ions must be
complexed by water molecules or other electrolyte species before
they can diffuse away from the Cu surface (the so-called acceptor
mechanism) [16,22]. The formation of a surface oxide has also been
invoked in the literature [21,23]. When the anode voltage is increased,
a concurrent oxygen evolution (corresponding to water
decomposition) drives
the current above the plateau value, even though mass transfer still
732 G.D. Kwon et al./ Applied Surface Science 307 (2014) 731735
limits the Cu etching reaction. In this regime of higher anode voltage,
pitting of the Cu surface also starts to occur and this has been explained
by the local breakdown of the salt film or viscous layer [22]. Fig. S1 of
the Supplementary Data, which shows polarization curves of Cu foil
anodes in 7.59 M and 14 M H3PO4 recorded in our laboratory at room
temperature, summarizes the 3 regions of interest briefly described
above.
Cu foils, the typical polishing and CMP conditions are summarized in
Table 1 below.
3. Results and discussion
In the present work, we have explored the EP of Cu foils in H3PO4
electrolytes of different concentrations and at various temperatures.
The EP experiments were performed on high purity (99.99%)
NILACO [24] and WACOPA [25] Cu foils which were originally 100
m thick; the results are essentially the same for both types of foils. We
have used a constant current mode (see Section 2), and when the H3PO4
concentration is low, most of the

2. Experimental

2.1. Cu foil preparation andelectropolishing conditions

Before any operation, the 100 m-thick copper foils used in this
work were thoroughly degreased by dipping in acetone, followed by
rising with isopropylic alcohol and ethanol. They were then annealed
at 1050C in forming gas (10% H2 in Ar) for 30 min. After this
annealing step, we have observed a large increase in grain size (up to
several millimeters). A large grain size is usually preferred for
graphene growth. We note however that this thermal treatment has no
incidence on the EP process, since we work in the masscontrolled
kinetic regime, which is not dependent on the surface
structure/orientation of the Cu foils.
The electrochemical cell was a simple 2 electrodes arrangement,
the working electrode being the electropolished foil and a large Cu
plate being used as counter electrode. The electrolytes were: 0.63;
2.17; 3.72; 4.85; 7.59 and 14 Molar (M) H3PO4 (Sigma Aldrich).
Ethylene glycol (Sigma Aldrich) was added in all electrolytes [20],
typically to a concentration of 0.6 g/ml. Anodic polarization curves
were recorded using a BioLogic potentiostat/galvanostat. All EP
experiments were performed in the constant current mode, using an
Agilent E3645A DC power supply. After EP, the copper samples were H PO Concentration (M)
thoroughly rinsed with DI water and ethanol. Unless otherwise stated, 3
4

those samples were then immediately transferred in a vacuum

desiccator to protect themagainst further oxidation in air.
2.2. Surface analysis
Surface roughness measurements (rms) were performed with an
atomic force microscope AFM SPA400, from Seiko Instruments. The
surface reflectance was measured with a UV-VIS-NIR
spectrophotometer (UV3600, Shimadzu).
An ESCA 2000 instrument from VG MICROTECH was used for
X-ray photoelectron spectroscopy analysis. Various electron
microscopy observations were made inside a JEOL JSM-7600F field
emission gun scanning electron microscope (SEM). Electron
backscattering diffraction (EBSD) images and spectra were recorded
in a JEOL JSM 7000-F SEM equipped with an EDAX-TSL EBSD
detector.
2.3. Chemical-mechanical polishing (CMP)
The CMP control experiments were performed using a MetPrep
3TM/PH-3 polisher (ALLIED HIGH TECH, USA). Starting with raw
Fig. 1. Average specular reflection (600800 nm wavelength range) and surface
roughness (rms values over a 15 m 15 m surface area) of electropolished
NILACO Cu foils as a function of H3PO4 concentration. (a) Electropolishing
experiments performed at 25C. (b) Electropolishing experiments performed at
55C. Note the low roughness and corresponding high specular reflection values
for the 2 M H3P04 concentration at 55C.
potential drop between the working electrode (Cu foil) and counter
electrode occurs due to the high resistance of the electrolyte. So,
even when the voltage is high, the local electric field at the anode
surface is sufficiently low to prevent pitting. The surface quality of
the Cu foils after electro-polishing has been qualitatively assessed
by optical microscopy first. Quantitative surface properties were
then obtained, using atomic force microscopy (AFM) and
reflectance measurements. By varying the electrolyte
temperature, we find that, for low concentration H3PO4, there is a
small temperature window around 65C where the Cu surface
roughness can be significantly decreased. This occurs
concomitantly with a sharp increase in surface specular reflection.
Fig. 1 shows the surface roughness variations (rms values
measured on 15 m 15 m surface areas) as well as the percent
average surface specular reflection as a function of the H3PO4
concentration for EP experiments performed on NILACO Cu foils
at 2 distinct temperatures, namely 25C and 55C (see Fig. S2 for
some qualitative optical characterizations). We first measured the
diffuse reflection values of the samples using an integrating sphere
(see Fig. S3) and then deduced the specular reflection having in
mind that the total reflection at each wavelength is 100%. Also,
since the reflectance of Cu decreases for wavelengths below 600
nm (2 eV), due to the onset of interband transitions [26], the
surface specular reflection values were averaged over the 600800
nm range, where there is no absorption. For all the above
experiments, the EP time was kept constant at 5 min and the EP
current density was held at 380mA/cm2 (i.e., 190mA/cm2 per
face of the Cu
reflectance measurements of the surface of Cu foils
electropolished in low concentration H3PO4, for temperatures
ranging between 25 and 75C. Fig. 2 shows such measurements
performed on WACOPA Cu foils electropolished in 2.17 M
H3PO4. Here again, the average specular reflection was averaged
between 600 and 800 nm. The diffuse reflectance curves recorded
over the whole 300800 nm spectrum are shown in Fig. S4. As
before, the EP experiments have been performed during 5 min and
using a current density of
380mA/cm2.Thesurfaceroughnessandpercentspecularreflectio
n
values show considerable variations over the investigated
temperature range. A minimum roughness value of 8 nm is

foil, assuming a uniform distribution of the current), so that the
total amount of charge passed through the electropolished samples
was 114C/cm2. A quick calculation indicates that this charge
corresponds to an etched thickness of 42m/cm2; cross section
obtained at 65C, which corresponds to a 92% surface specular
reflection.
In comparison, the best rms roughness value that we have
obtained for samples electropolished in 14 M H3PO4 at room
temperature was 12 nm and the corresponding average surface
specular reflection was 91%.

measurements made under anoptical microscope show thatthe

G.D. Kwon et al. / Applied Surface Science 307 (2014) 731735 733

Table 1
CMP procedure for control copper substrates.
Step 1 2 3 4 5

Abrasive 600Grit 1200Grit 3m 1m 0.04 m

Type SiC SiC Da Da Sb
Coolant Water Water Purple Lube Purple Lube Water
Platen Speed (RPM) 300 300 150c 150c 150
Sample Speed (RPM) 150 150 150 150 150
Force(N) 4 4 5 5 4
Time (min) 5 5 5 10 60
a
Diamond. b SiO2
colloidal
c
suspension.
Counter rotation.

etched thickness is around 40m for samples with a 1cm2 sur-

face area.

Inspection of Fig. 1 indicates that at 25C, the rms roughness

values of the electropolished Cu surface are smaller at high H3PO4
concentrations (in agreement with previous work, see refs 221),
whereas the opposite is observed for EP experiments performed at
55C. Moreover, the minimum roughness value obtained at 55C
in low concentration H3PO4 is close to the minimum roughness
value obtained at 25C for high concentration H3PO4. The percent Temperature
average specular reflection data, also displayed in Fig. 1, are (oC)
totally consistent with the roughness measurements, since high
Fig. 2. Average specular reflection (600800 nm) and rms surface roughness
values (90%) are observed at 25C for high concentration H3PO4,
values of samples electropolished in 2.17 M H3PO4 for temperatures between 25
whereas at 55C, the highest specular reflections are obtained for and 77C.
lowconcentration H3PO4.
Also, controlled chemical-mechanical polishing (CMP)
In order to get more insights into the high temperature EP
process, we have performed more systematic roughness and experiments performed on WACOPA Cu foils (see Section 2 for the
734 G.D. Kwon et al. / Applied Surface Science 307 (2014) 731735

Fig. 4. Characterization of the surface of a Cu foil electropolished at 65C in 2.17 M H3PO4 electrolyte. (a) Scanning electron microscope picture of the region across a grain boundary. (b) The corresponding EBSD
map showing a (1 1 3)-oriented grain on the left-hand side (pink) and a (1 0 1)-oriented one on the right-hand side (green). The contrast on the SEM picture is only due to the difference in secondary electron emission of
the Cu (1 1 3) and (1 0 1) crystal faces. (For interpretation of the references to color in this

CMP conditions) yielded a rms surface roughness of 14 nm (still on

a 15 m 15 m area) and an average specular reflection value of 90%
over the 600800 nm wavelength range (see Fig. S5 of for optical and
AFM characterizations of a CMP sample). Taken together, those
values indicate a slightly lower Cu surface quality than after EP in 2.17
M H3PO4 at65C.
Fig. 3 shows the variation of the average specular reflection and
rms surface roughness of samples electropolished in 2.17 M H3PO4 at
65C, during various times. Again here, the EP current was
380mA/cm2. Clearly, a minimum surface roughness value of

8 nm, corresponding to a surface specular reflection value of 92%

is obtainedafter 5 min EP.

To further check the quality of our elevated temperature EP
process, we have performed scanning electron microscope (SEM)
observations of the Cu surface around grain boundaries, after EP at
65C in 2.17 M H3PO4 during 5 min. Fig. 4 shows a SEM picture taken
across a grain boundary and the corresponding electron backscattered
diffraction (EBSD) inverse pole figure map of the same region. The
EBSD map clearly shows the 2 different grain orientations, namely
close to (1 1 3) for the pink region and close to (1 0 1) for the green one.
On the SEM image, the Cu surface exhibits fine striations (probably
surface steps) which are continuous across the grain boundary. Within
the resolution of the SEM, there is no height difference between the 2
grains, as anticipated when the kinetics of the etching reaction is mass-
transfer-controlled. The contrast of the SEM picture originates from
the variation in secondary electron emission between the (1 1 3) and (1
0 1) crystallographic facets of the Cu foil [27]. Note that very different
results are obtainedafter a simple chemical etch of the Cu surface in
Fig. 3. Average specular reflection (600800 nm wavelength range) and surface
roughness values (rms) of samples electropolished in 2.17 M H3PO4 at 65C during
various times.
figure legend, the reader is referred to the web version of the article.)
Fe(NO3)3, where the roughness is increased and etch pits start to
appear [28].
Table 2 below summarizes the best results which we have obtained
in terms of surface roughness and average specular reflection values
for samples polished by CMP and electropolished in various
conditions.
Finally, we have tried to identify some surface oxides layer which
would be formed during EP, other than the native oxides/hydroxyde
that naturally form upon exposure of a fresh Cu surface to air [29,30].
Fig. 5 compares X-ray photo-electron spectroscopy (XPS) data
recorded on a bare Cu foil and on an electropolished sample (WACOPA
foil).
The electropolished sample was loaded in the XPS chamber less
than 2 min after rinsing, while the bare Cu foils were analyzed as
received, without any treatment. The Cu2p3/2 peak corresponds to
binding energies of 932.6 eV, 932.5 eV, 933.7 eV and 935.1 eV the bare Cu foil (black) and the electropolished sample (red dots). (c)
respectively in metallic Cu, Cu2O, CuO and Cu(OH)2 [29]. The O 1s Deconvolution of the O1s peak for the bare Cu and electropolished samples. (For
peak corresponds to binding energies of 529.6 eV, 530.3 eV and 531.2 interpretation of the references to color in this figure legend, the reader is referred
to the web version of the article.)
eV respectively in CuO, Cu2O and Cu(OH)2 [29]. Clearly, the surface
of the bare Cu foil is oxidized and exhibits the characteristic peak of
Cu2O at 932.68 eV (with probably a contribution from Cu, but we
know from literature that the surface of Cu exposed to air is oxidized),
as well as a peak at 934.88 eV which we assign to Cu(OH)2, see Fig. 5a
and b. We do not detect a clear peak at 933.7 eV, which would
correspond to CuO, but there is a large hump between 940 and 947 eV
which is generally ascribed to the presence of CuO (Fig. 5a) [30]. The
small peak at937.08 eV is unidentified. Forthe
O 1s signal (Fig. 5c), the peak at 531.23 eV probably corresponds to
Cu2O (with a contribution from CuO), whereas the one at 532.78 eV
would correspond to Cu(OH)2 although it is shifted by 1.5 eV. Those
observations are consistent with reports from the literature for native
oxides on Cu [29,30]. Now, concerning the electropolished sample,
the Cu 2p3/2 peak at 932.48 eV can be ascribed to Cu and/or Cu2O.
However, the presence of a small hump between 936 and 944 eV
(related to the presence of CuO [30]) makes us think that the surface is
slightly oxidized, in agreement with recent results obtained on
electropolished samples and based only on electrochemical
measurements [21]. Moreover, it is well known that the formation of
CuO at room temperature is very slow [30], so we can assign any CuO
detection on the electropolished sample to the EP process itself and not
to oxidation in air during the small amount of time between rising and
loading in the XPS machine.With this in mind, the Cu 2ppeak at934.08
eV would then represent the Cu binding energy in CuO and the small
one at 935.98eVwould be

Fig. 5. X-ray photoelectron spectroscopy data recorded on a bare Cu foil and on an

electropolished sample. (a) Comparison of the 2 spectra over the 925970 eV
range, evidencing the CuO satellite hump. (b) Deconvolution of the Cu2p 3/2
peak for
 G.D. Kwon et al. / Applied Surface Science 307 (2014) 731735 735

Table 2
The best rms surface roughness and reflectance values of sample (a) without any treatment (raw), (b) CMP, (c) EP in 14 M H3PO4 at room temperature, (d) EP in 7.59 M H3PO4 at room temperature, (e) EP in 2.17 M
H3PO4 at 65C.
a b c d e

RMS value (nm) 72.27 14.36 14.46 29.21 8.444

Specular reflection (%) 25.98 90.03 93.20 88.03 93.11

Table 3
Summary of the copper and oxygen XPS data.
Cu 2p3/2 Cu Cu2O CuO Cu(OH)2

Reference peaks (eV) (Ref. [29]) 932.6 932.5 933.7 + Hump between 940 and 947 (Ref. 30) 935.1
Raw Cu (eV) 932.68 932.68 Large hump between 940 and 947 934.88
EP Cu (eV) 932.48 932.48 934.08 + Small hump between 936 and 944 935.98

O 1s Cu2O CuO Cu(OH)2

Reference peaks (eV) (Ref. [29]) 530.3 529.6 531.2

Raw Cu (eV) 531.23 531.23 532.78
EP Cu (eV) 530.88 530.88 532.58

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Supplementary data associated with this article can be found,

in the online version, at http://dx.doi.org/10.1016/j.apsusc.
2014.04.144.
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