Surface Review and Letters, Vol. 21, No.

1 (2014) 1450009 (7 pages)

°c World Scienti¯c Publishing Company
DOI: 10.1142/S0218625X14500097

COPPER PLATING FROM NON-CYANIDE

ALKALINE BATHS

MINGGANG LI*, GUOYING WEI*,‡, JIANFANG WANG*, MENG LI*,

XIXI ZHAO* and YUZE BAI†
*College of Materials Science and Engineering,
China Jiliang University, Hang Zhou 310018, P. R. China
†Environmental Monitoring Station of Yangquan
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Shanxi Province
‡guoyingwei@sina.com

Received 9 September 2013

Revised 24 October 2013
Accepted 24 October 2013
Published 6 December 2013

Non-cyanide alkaline bath was used to prepare copper thin ¯lms. In°uences of various temperatures
on deposition rates, surface morphologies and microstructures of ¯lms were investigated. Copper
thin ¯lms prepared from non-cyanide alkaline bath show typical nodular structures. Copper ¯lms
fabricated at higher temperature possess rough surface due to hydrolysis of complexing agents.
According to the XRD patterns, all deposited ¯lms were crystalline and showed Cu (111), Cu (200)
and Cu (220) peaks. The intensity of peak (200) increases gradually with the rise on bath tem-
peratures. Films with maximum thickness (7:5
m) could be obtained at the temperature of 40
C.
From the cyclic voltammetry curve, it was found that the cathodic polarization decreased slightly
with increase of bath temperatures. In addition, when the bath temperature was equal to 50
C,
current e±ciency could reach to 96.95%.

Keywords: Bath temperature; ¯lms; electrodeposition.

1. Introduction system has become one of the main research hotspots.

Copper electrodeposition is used extensively in a vari-
ety of industrial applications including electroform-
ing, electrore¯ning, soldering, lubricity, rotogravure,
printing rolls and decorative plating of zinc die cast-
ings.1–3 Many kinds of Cu electrodeposition with ex-
cellent properties have been reported. These methods
mainly focused on single-complexing system, such as
pyrophosphate,4,5 citrates,6,7 EDTA8–10 and HEDP
series, which still have many disadvantages compared
to cyanide alkaline technology. Single-complexing
copper plating system is di±cult to replace cyanide
copper plating because of the low current e±ciency and
weak adhesion. Therefore, mixed complexing agent
Pyrophosphate and HEDP is good complexing agent
for Cu electrodeposition and will form stable mixed
complex in alkaline solution. Moreover, pyrophosphate
and HEDP has the strong adsorption and activation on
the electrode surface. When pyrophosphate and HEDP
are used together, the e®ect is more obvious. In addi-
tion, pyrophosphate and HEDP can be used for direct
copper plating on steel matrix with high brightness,
excellent adhesion and low porosity copper deposition.
In the system of pyrophosphate-HEDP copper plating,
pyrophosphate combines with copper ions to form
½CuðP2 O7 Þ2  2 complex. When pH value is equal to
8.8, ½CuL2  6 complex ions could be obtained with the

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 M. Li et al.

complexation of HEDP and copper ions. Chemical and the surface area is 2 cm2. At ¯rst, an alkaline
reactions equations of deposition mechanism are shown solution (12 g/L NaOH, 60 g/L Na2CO3 and 60 g/L
below11,12: Na3PO4) was utilized to get rid of the oils from the
iron surface. Then, the substrate was dissolved in
½CuðP2 O7 Þ2  6 () ½CuðP2 O7 Þ 2 þ P2 O 4
7 ; ð1Þ dilute hydrochloric acid for several seconds. Finally,
½CuðP2 O7 Þ2  2
þ 2e ! Cu þ P2 O 4
7 ; ð2Þ the substrate was immerged in the 250 ml electrolyte
CuL 6 () CuL 2 þ L 4 ; ð3Þ to perform electrodeposition reaction for 20 min.
2
After the deposition, the Cu ¯lm was washed with a
CuL 2
þ 2e ! Cu þ L 4 : ð4Þ
jet of deionized water and dried by a blower.
Our work investigated the e®ects of di®erent tem- The microstructural analysis of the deposited
peratures by using pyrophosphate and HEDP as Cu ¯lms was carried out using an X-ray di®racto-
mixed complexing agents on the composition and meter (DX-2700), which used a Cu K radiation as
microstructure of Cu thin ¯lms. an incident beam and worked at 40 kV and 150 mA.
Surface morphology was examined using scanning
electron microscopy (Hitachi Limited TM3000).
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Thickness of ¯lms was measured by ¯lm thick-

2. Experimental Methods
Cu thin ¯lms were obtained on an iron substrate by
electrodeposition method. The electrolyte composi-
tion and process conditions were given in detail in
Table 1. Potassium pyrophosphate (K4P2O7) and
HEDP were utilized as complexing agent to form
strong copper complexes. Copper pyrophosphate
(Cu2P2O7  4H2O) was chosen as the source of Cu
ions. Ammoniumcitratedibasic (C6H14 N2O7) and
potassium citrate (C6H5K3O7) were added as assis-
tant complexing agent and conducting salt, respec-
tively. Potassium hydroxide (KOH) was served as a
bu®ering additive to e®ectively adjust the pH values.
Working pH was adjusted to 8.8 while the electro-
deposition current density was kept up to 71.5 Am 2
during the experiment process. The working tem-
peratures were controlled from 30
C to 60
C to in-
vestigate the temperature in°uences on the
composition, electrochemical behaviors and micro-
structure of Cu thin ¯lms.
Pure copper and iron were used as the anode and
working electrode for every experiment. The surface
of working electrode was polished to a mirror ¯nish
Table 1. Bath composition for
preparing Cu thin ¯lms.
Chemical Concentration
Cu2 P2 O7  4H2 O 70 g/L
K4 P 2 O7 300 g/L
HEDP 40 g/L
C6 H14 N2 O7 10 g/L
C 6 H 5 K3 O7 10 g/L
ness detector (Kla Tencor P-6). The quartz crystal
microbalance (QCM25) and chronoamperometric
method (solartron modulab PARSTAT2273) were
used to study the relationship between the mass
change and the time. According to Sauerbrey's
equation,13 quartz crystal frequency changes (
f)
was proportional to the mass change (
m) that
occurred on the crystal, expressed as the following
equation:

f ¼ Cf 
m; ð5Þ
where
f was the observed frequency change in
Hz,
m was the change in mass per unit area
(
gcm 2 ), Cf was the sensitivity factor of crystal
(56.6 Hzcm 2
g 1 ) and the area of gold disk coated on
the crystal was 1.37 cm2.
3. Results and Discussion
Figure 1 shows the SEM micrograph for the ¯lms
deposited at various bath temperatures. It could be
found that surface morphology of Cu thin ¯lm is
densely covered with typical nodular aggregates. The
surface morphology of the samples deposited at bath
temperature of 30
C shown in Fig. 1(a1) was similar
to that of 40
C shown in Fig. 1(b1). The SEM images
of Figs. 1(a1)–(c1) displayed that the surface of the
¯lms looked compact covered and very smooth.
Compared to Fig. 1(a1), the size of grains was a little
larger in Figs. 1(b1) and 1(c1). When the bath tem-
perature was controlled to 60
C, more porosities and
micro-cracks appeared in copper surface due to the
acceleration of hydrogen evolution with the decrease

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Fig. 1. SEM of electrodeposited Cu ¯lms under di®erent bath temperatures, (a1) 30
C (b1) 40
C (c1) 50
C and (d1) 60
C.
The other electroplating conditions were referred to Table 1.

of cathode current e±ciency. Surface became coarser
as shown in Fig. 1(d1). The roughness of Cu ¯lms is
also shown in Fig. 1. With the temperature increases
from 30
C to 60
C, roughness of Cu ¯lms range from
95.4 nm to 416.8 nm (see Figs. (a2)–(d2)), which is
coincident with the conclusion of SEM images. This is
because when temperature was too high, the hydro-
lysis of complexing agent could be caused and the
volatilization of plating solution could be accelerated
which resulted in rough surface.
E®ects of the di®erent of temperatures, (a) 30
C
(b) 40
C (c) 50
C and (d) 60
C on Cu ¯lms' thickness
in Fig. 2. With the increase of temperature, the ¯lm
thickness ¯rst increased then decreased and the
maximum ¯lm thickness was achieved at 40
C. When
the temperature is below 40
C, with the increase of
temperature, the solubility and electric conductivity
of the solution increases and the di®usion rate of
copper ion increases, which results in the increase of
deposition rate and Cu ¯lm thickness. When the
temperature is beyond 40
C, higher temperature
resulted in the hydrolysis of complexing agent.
Figure 3 shows the XRD patterns for the ¯lms
deposited at various bath temperatures. Three main

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 M. Li et al.
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Fig. 2. E®ects of the di®erent of temperatures, (a) 30
C (b) 40
C (c) 50
C and (d) 60
C on Cu ¯lms' thickness.

di®raction peaks were observed at 43:297
, 50:433
the Debye–Scherrer equation

and 74:130
approximately, referring to the major
orientation (111) and minor orientation (200)
and (220) with the Cu peaks stored in JCPDS
(pdf#85-1326). With the increase of bath tempera-
ture, the intensity of the peak (200) was increased.
Therefore, the increase of the temperature improved
the crystallinity of the deposit. The average grain
sizes of the crystalline ¯lms can be calculated using
D ¼ k=ð cos Þ; ð6Þ
where D is the grain size, k is the Scherrer constant, 
is the wave length of X-ray,  is the full width at half
maximum (FWHM) and  is the di®raction angle.
Based on the Debye–Scherrer equation, the range of
grain size could be calculated from 30 nm to 50 nm.

Fig. 3. XRD pattern of electrodeposited Cu ¯lms under di®erent bath temperatures, (a) 30
C (b) 40
C (c) 50
C and (d)
60
C. The other electroplating conditions were referred to Table 1.

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 Copper Plating from Non-Cyanide Alkaline Baths
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Fig. 4. E®ect of di®erent bath temperatures, (a) 30
C (b) 40
C (c) 50
C and (d) 60
C on cyclic voltammetry process with
10 mV/s scan rate. The other electroplating conditions were referred to Table 1.

Figure 4 shows the voltammograms of Cu elec-
trodeposition from di®erent bath temperature. It was
very obvious that the voltammograms curves of (a),
(b), (c) and (d) showed the same overall shape. It
could be seen from Figs. 4(a)–4(d) that there was a
single reduction peak (m) and a coupled oxidation
peak (n) on the voltammograms. The cathodic wave
appeared at 0:5 V and the peak potential was
1:25 V. The cathodic peak (m) could represent the
reduction reactions of Cu (II) to Cu and anodic peak
(n) represented the stripping of Cu. It was also found
that the cathodic polarization decreased slightly with
increasing the bath temperature. This fact could be
explained that higher bath temperature promoted the
hydrolysis of complexing agent.
Figure 5 demonstrated the typical chronoampero-
metric curves and the in situ associated mass change
measurement during copper electrodeposition from

Fig. 5. E®ect of di®erent bath temperatures on chronoamperometric curves, (a) 30
C (b) 40
C (c) 50
C and (d) 60
C.
Potential applied: 1:1 V. The other electroplating conditions were referred to Table 1.

1450009-5
 M. Li et al.
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Fig. 6. E®ect of di®erent bath temperatures, (a) 30
C (b) 40
C (c) 50
C and (d) 60
C on mass change recorded simul-
taneously on platinum substrate. Potential applied: 1:1 V. The other electroplating conditions were referred to Table 1.
di®erent bath temperatures, (a) 30
C (b) 40
C
(c) 50
C and (d) 60
C. The potential applied while
recording the chronoamperometric curves was 1:1 V.
In Fig. 5, the chronoamperometric curves showed
the same overall shape and possessed various steady
current values. For example, current was about
0:0099 A, 0:0117 A, 0:0141 A and 0:0151 A
(t ¼ 100 s), respectively at (a) 30
C (b) 40
C (c) 50
C
and (d) 60
C.
The QCM measurements are shown in Fig. 6. It
can be found that the Cu mass increased linearly with
the electrodeposition time. Suppose that the current
was stable during the process of electrodeposition
from 100 s to 200 s and the current e±ciency could be
calculated from the following equation:

m
¼  100%;
kIt
where,
m was the change in mass (g), k is the
electrochemical equivalent of Cu (1.186 gðA  hÞ 1 Þ, I
was the current of electrodeposition (A), t was the
time of electrodeposition (h). The current e±ciency of
(a), (b), (c) and (d) was 89.65%, 93.52%, 96.95% and
49.25%, respectively. When bath temperature is
30
C, 40
C and 50
C, the current e±ciency was very
close to the current e±ciency of cyanide copper
plating. When the bath temperature is 60
C, the
current e±ciency is the lowest which could be due to
the hydrolysis of complexing agent.
4. Conclusion
In this study, e®ects of bath temperature on copper
electrodeposition in alkaline solutions by using pyro-
phosphate and HEDP as mixed complexing agents
were investigated. Morphology of copper thin ¯lms
obtained with the bath temperature of 30
C, 40
C
and 50
C resulted in smooth and compact deposit.
With the bath temperature increased, the intensity of
the peak (200) was further increased. It was also
found that the cathodic polarization decreased
slightly with increasing the bath temperature from
the cyclic voltammetry curve. When bath tempera-
ð7Þ ture was 40
C, the thickness of Cu thin ¯lms was
7.5
m. The current e±ciency of baths under di®erent
temperatures (30
C, 40
C, 50
C and 60
C) was
89.65%, 93.52%, 96.95% and 49.25%, respectively.
Acknowledgments
This research was supported by the National Natural
Science Foundation (No. 21171155), International
Science and Technology Cooperation Program of
China (No. 2011DFA52400), Important Science and
1450009-6

Technology Innovation Team of Zhejiang China
(No. 2010R50016) and the Natural Science Founda-
tion of Zhejiang Province (No. LQ12E01005).
References
1. M. Schlesinger and M. Paunovic, Modern Electro-
plating, 4th edn. (Wiley, New York), p. 63.
2. J. Horner, Plating Surf. Finish. 74 (1987) 34.
3. H. F. Guo et al., Surf. Rev. Lett. 19 (2012) 1250049.
4. A. C. Hamilton Jr., Plating Surf. Finish. 85 (1998) 30.
5. A. Radisic, G. J. Long, M. P. Ho®mam and C. P.
Searson, J. Electrochem. 148 (2001) C41.
6. V. Alvarez, S. Gonzalez and A. Arevalo, Electrochim.
Acta. 29 (1984) 1187.
by STONY BROOK UNIVERSITY on 10/17/14. For personal use only.
Surf. Rev. Lett. 2014.21. Downloaded from www.worldscientific.com
1450009-7
Copper Plating from Non-Cyanide Alkaline Baths
7. E. Chassaing and K. V. Quang, J. Appl. Electrochem.
22 (1986) 591.
8. R. Y. Ying, R. Moy, L. C. Fraser, S. O'Bannion and
F. M. Donahue, J. Electrochem. 135 (1988) 654.
9. R. M. Krishnan, M. Kanagasabapathy, S. Jayakrish-
nan, S. Sriveeraraghavan, R. Anantharam and S. R.
Natarajan, Plating Surf. Finish. 7 (1995) 56.
10. I. A. Carlos and M. M. Oizume, Inter¯nish Latino–
Americano EBRATS-97, Sao Paulo-SP Brazil,
CDROM, (1997).
11. R. Chu, C. Guan and C. Chu, Mater. Prot. 39 (2006)
58–66.
12. Q. Wen and J. Chen, Mater. Prot. 4 (2005) 35–37.
13. G. Sauerbrey, Z. Phys. 155 (1959) 206.