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Electrochimica Acta 53 (2007) 934943

Electrodeposition of CoWP lm
III. Effect of pH and temperature
S.M.S.I. Dulal

, Hyeong Jin Yun, Chee Burm Shin, Chang-Koo Kim

Department of Chemical Engineering and Division of Energy Systems Research, Ajou University, Suwon 443-749, South Korea
Received 12 June 2007; received in revised form 31 July 2007; accepted 1 August 2007
Available online 7 August 2007
Abstract
Polarisationbehaviour andnucleationmechanismof inducedco-depositionof cobalt, tungstenandphosphorus fromcitrate electrolytes containing
cobalt sulphate, sodium tungstate and sodium hypophosphite on copper disc electrode at various electrolyte pH values were studied using cyclic
voltammetry and chronoamperometry, respectively. It was found that the onset potentials for reduction and oxidation gradually shifted towards
more cathodic direction with increase in pH. Co-deposition of cobalt, tungsten and phosphorus occurred under diffusion control and followed
instantaneous type of nucleation mechanism. The highest current efciency (>70%) was found when the CoWP lms were deposited from neutral
or slightly acidic solution. Larger variation of lm composition, cobalt from 48 to 74 at.%, tungsten from 13 to 38 at.% and phosphorus from 8 to
33 at.%, could be made by changing the pH of the electrolyte between 3 and 8. The lms deposited from very acidic solutions contained larger
amounts of tungsten and phosphorus and were amorphous; while the lms deposited fromnear neutral solutions were polycrystalline and contained
hexagonal cobalt. The surfaces of the amorphous lms were smoother than those of the polycrystalline lms. Needle-like dendritic crystallites
were obtained when the lms were deposited from basic solution or at elevated temperature.
2007 Elsevier Ltd. All rights reserved.
Keywords: CoWP lm; Electrodeposition; Nucleation mechanism; Barrier layer; Coating
1. Introduction
There is a signicant research interest in copper interconnec-
tions in microelectronic devices. A major drawback for copper
metallization, however, is its oxidation and diffusion into SiO
2
layers, which degrade the performance of the microelectronic
devices [13]. To prevent copper from oxidation and diffusion,
barrier/capping layers with dielectric or metallic materials have
been introduced [411]. Among them, CoWP layer has been
found very promising because of its better barrier capability and
performance at higher temperature [10,1214]. There are some
reports on the fabrication of CoWP barrier/capping layers by
electroless deposition [1522].

Corresponding author at: Department of Materials Science and Technology,


University of Rajshahi, Rajshahi 6205, Bangladesh.
Tel.: +880 721 750041x4156; fax: +880 721 750064.

Corresponding author. Tel.: +82 31 219 2389; fax: +82 31 219 1612.
E-mail addresses: dulal smsi@yahoo.com (S.M.S.I. Dulal),
changkoo@ajou.ac.kr (C.-K. Kim).
CoWP lms can also be useful for other technological appli-
cations. CoP is known to have good magnetic property and
it has recently been used in integrated sensors and inductors
[23,24]. CoWlms showsome promising physical and mechan-
ical properties such as hardness, wear and corrosion resistances
[25,26]. Therefore, it is envisaged that with appropriate compo-
sition, CoWP lms may exhibit superior and unique properties,
which can be utilized in sophisticated electronic and automobile
industries and space technology.
Electroless deposition technique, however, is very much
selective and requires higher processing temperature. Some-
times, the copper substrate needs to be activated by a catalyst
to initiate the deposition process. It has been found that phos-
phorus in the CoWP layers plays a very important role against
the diffusion of copper by stufng the grain boundaries of the
barrier/capping layers, but layers containing more than 12 at.%
phosphorus cannot be plated by electroless deposition [12]. On
the other hand, electrochemical deposition offers lower process-
ing temperature, better control over the deposition technique and
thus, a wide range of compositions. It is well known that tung-
sten and phosphorus cannot be electroplated individually from
0013-4686/$ see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.08.006
S.M.S.I. Dulal et al. / Electrochimica Acta 53 (2007) 934943 935
aqueous electrolyte. However, they can be co-deposited from an
electrolyte containing iron group metals (Fe, Co, Ni), which is
called induced co-deposition [25]. There are also some reports
in the literature on the electrodeposition of CoP [2732], NiCoP
[27,33] and CoW [34,35] lms.
The electrochemical aspects for the deposition of CoWP lm
have recently been reported by Dulal et al. [36] and a bath for its
electrodeposition has been developed. It is well known that pH
and temperature of the electrolyte play very important roles in
electrodeposition process. This paper reports the effects of pH
and temperature on current efciency, composition, microstruc-
ture and surface morphology of the electrodeposited CoWP
lms.
2. Experimental
CoWP lms were electrodeposited on copper-coated silicon
wafers from an electrolyte containing 0.13 M CoSO
4
7H
2
O,
0.005 M Na
2
WO
4
2H
2
O, 0.003 M NaH
2
PO
2
H
2
O and 0.3 M
tri-sodium citrate (TSC) by a potentiostatic method. Tri-sodium
citrate was chosen as a complexing agent because it was
non-toxic and had brightening, levelling and buffering actions
[37,38]. Moreover, citrate electrolyte has recently been used
for precision electrodeposition [39]. The electrolytes were pre-
pared by dissolving appropriate amounts of the chemicals in
de-ionised water. The pH of the electrolyte was 7. For pH-
dependent experiments, the pH was adjusted by the addition
of either NaOH or H
2
SO
4
and the deposition was carried out
at room temperature (23 3

C). For temperature-dependent


experiments, an electrolyte without pHadjustment was used (i.e.
pH 7). Before electrodeposition of CoWP lms, the electrolytes
were de-aerated using nitrogen gas for ve minutes. In all cases,
the deposition was carried out for 5 min. After deposition, the
samples were washed with jets of water and dried by blowing
with nitrogen gas. The chemicals used were of the highest purity
supplied by SigmaAldrich.
Electrodeposition was performed using a standard three-
electrode cell where a platinumcoated titaniummesh of 2.5 cm
2
was used as a counter electrode. The substrate was copper
deposited by sputtering on silicon wafer. The wafer was cut
into 1 cm3 cm sized pieces with a diamond saw and lac-
quered to expose 1 cm
2
for plating CoWP lms. The substrate
was cleaned by blowing with nitrogen gas before deposition.
A saturated Ag/AgCl electrode was used as a reference elec-
trode. The electrochemical measurements were conducted using
a computer-controlled potentiostat (VSP-Princeton Applied
Research). The thickness of the lm was measured by a sur-
face proler (Alpha Step). Surface compositional analysis was
carried out by X-ray photoelectron spectroscopy (XPS). The X-
ray source of 1486.6 eV was generated using a moveable Al
anode (monochromated) at 15 kV. Microstructural analysis of
the deposited CoWP lms was carried out using a high power
X-ray diffractometer (D/max-2500V/PC Rigaku), which used
a CuK

radiation (wavelength =0.154 nm) as an incident beam


and worked at 40 kV and 150 mA. Surface morphology was
examined using scanning electron microscopy (SEM).
3. Results and discussion
3.1. Effect of pH
pH effect on the polarisation behaviour of citrate elec-
trolyte containing cobalt sulphate, sodiumtungstate and sodium
hypophosphite has been studied using cyclic voltammetry tech-
nique. In this case, a copper disc of geometrical area of 0.95 cm
2
and of 99.9999% purity was used as a working electrode. Then
CoWP samples were deposited on copper-coated silicon wafers
for compositional and structural studies.
3.1.1. Polarisation behaviour
Fig. 1 shows cyclic voltammograms of electrolytes contain-
ing cobalt, tungstate, hypophosphite and citrate ions of various
pH values at a copper disc electrode. The potential was scanned
from 0.05 V to the cathodic direction up to 1.2 V and ended
at 0.05 V. The scan rate was 50 mVs
1
in all cases. The voltam-
mograms suggest that co-deposition of cobalt, tungsten and
phosphorus occurs on limiting current at around 1.0 V. The
limiting current peaks are more obvious in the cases of pH val-
ues 4 and 5. A gradual shift of onset potential for the reduction
of ions towards more negative direction is also observed. The
onset potentials for deposition from electrolytes of various pH
values are also given in Table 1. An increased cathodic current
is found at 0.55 V during potential scan toward more negative
direction in the case of pH 3 electrolyte, whereas the reduction
of the electroactive species initiates at a potential more negative
than 0.90 V in an electrolyte of pH 8. The shifting of onset
potential for reduction at various pH values is inuenced by
protons in the case of low pH values and by hydroxide ions in
the case of higher pH values. Moreover, depending on pH, the
citrate ions form a variety of complexes with cobalt [40]. A spe-
Table 1
Onset potentials for the reduction and oxidation, cathodic and anodic charges and calculated current efciencies at various pH values for the deposition of CoWP
lm
Electrolyte pH Onset potential for reduction (V) Onset potential for oxidation (V) Cathodic charge (mC) Anodic charge (mC) Current efciency (%)
3 0.53 0.30 335.65 8.87 2.64
4 0.60 0.56 152.65 31.07 20.35
5 0.74 0.61 77.21 30.05 38.93
6 0.86 0.72 52.29 24.63 47.13
7 0.88 0.74 51.51 24.90 48.35
8 0.94 0.80 22.91 7.39 32.29
936 S.M.S.I. Dulal et al. / Electrochimica Acta 53 (2007) 934943
Fig. 1. Cyclic voltammograms of electrolytes of various pH values on copper
disc electrode. The potential was swept between 0.05 and 1.2 V at the rate
of 50 mVs
1
.
ciation analysis shows that Co
2+
is the dominant species in a
citrate electrolyte of pH less than 4. At pH values between 5 and
7, the dominant species is CoCit

and the reduction of cobalt


occurs from this species in this pH range [40]. Fig. 1 also shows
that, on the reverse scan, the stripping potential shifts towards
cathodic direction with increasing the pH of the electrolyte. In
the case of pH 3 electrolyte, stripping current (anodic current) is
observed at 0.30 V on the reverse scan. On the other hand, the
dissolution of the deposit starts at much higher negative potential
(0.80 V) in the pH 8 electrolyte.
All the voltammograms show a gradual increase in the
anodic current which results in the formation of humps on
the anodic peaks. These humps are considered as the results
of the oxidation of Co(OH)
2
, which forms on the surface of the
deposit during cathodic scan [4143]. With increasing pH, more
Co(OH)
2
is formed on the surface which is stripped more easily
onthe reverse scan. Todetermine the relative amounts of elemen-
tal cobalt andcobalt hydroxide onthe surfaces of the CoWPlms
deposited from electrolytes of various pH values, the surfaces
have been analysed using XPS. Fig. 2 shows Co-2p electron
spectra of CoWP lms. In these spectra, the peaks at binding
energy of 778 eV correspond to elemental cobalt, while peaks
at 781 eV indicate the presence of cobalt hydroxide [44,45].
As can be seen, the intensity of peak corresponding to elemen-
tal cobalt decreases with increasing the pH of the electrolyte,
whereas the intensity of the cobalt hydroxide peak increases with
pH. This result conrms the fact that more hydroxide species
have been formed on the surface during cathodic scan (in Fig. 1)
withincreasingthe pHof the electrolyte. Details analyses of XPS
spectra of a CoWP sample deposited from an electrolyte of pH
7 reveal that the surface of the lm contains elemental cobalt,
tungsten, phosphorus, and hydroxide of cobalt and oxides of
cobalt and tungsten [36].
3.1.2. Current efciency
Determination of current efciency for the deposition of
ternary deposit like CoWP from a rather complex electrolyte by
gravimetry method is very complicated. Therefore, two simple
electrochemical techniques (cyclic voltammetry and chronoam-
perometry) have been applied to estimate the current efciency
(CE) for the deposition of CoWP lm using the following equa-
tion.
CE =
Q
a
Q
c
100 (1)
where Q
a
and Q
c
are total (integrated) anodic and cathodic
charges, respectively. In the cyclic voltammetry technique, the
charges were calculated from the voltammograms given in
Fig. 1. In chronoamperometry technique, CoWPlms were elec-
trodeposited on copper disc electrode by the application of a
constant potential of 1 V for 1 min. The transient currents at
various pHvalues are shown in Fig. 3. The total cathodic charges
were calculated from these curves. The deposited CoWP lms
were then stripped in the same solution by holding the electrode
at a constant potential of 0.1 Vuntil the anodic current reached
to zero. The stripping current transients are shown in Fig. 4. The
anodic charges were calculated from these stripping currents.
S.M.S.I. Dulal et al. / Electrochimica Acta 53 (2007) 934943 937
Fig. 2. Co-2p electron spectra (XPS) of CoWP lms deposited fromelectrolytes
of various pH values.
Fig. 3. Current transients of electrolytes of various pH values on copper disc
electrode at an applied potential of 1 V vs. Ag/AgCl. The numbers on the
curves correspond to the pH of the electrolytes.
Fig. 5 shows the current efciencies, determined by both
cyclic voltammetry and chronoamperometry techniques, for the
electrodeposition of CoWP lms fromcitrate electrolytes of var-
ious pH values. Both curves show similar behaviours. At pH 3,
the current efciency is very low. Dulal et al. also reported a
very low current efciency of cobalt during pulse plating of
magnetic multilayers from citrate electrolytes of lower pH val-
ues [46,47], which was due to the evolution of large amount of
hydrogen fromthe bulk of the electrolyte. The current efciency,
however, increases with pH up to near neutral values. A further
increase in pH results in the decrease in current efciency due
to the formation of hydroxide in the solution. When the pH of
the electrolyte was tried to adjust at 9, precipitation of cobalt
hydroxide occurred. Fig. 5 also shows that, except pH 3, current
efciencies determined by amperometric technique are higher
than those calculated fromcyclic voltammograms. As the cyclic
Fig. 4. Stripping currents of CoWP lms at an applied potential of 0.1 V after
60 s of deposition at 1 V from electrolytes of various pH values. The numbers
on the curves correspond to the pH of the electrolytes.
938 S.M.S.I. Dulal et al. / Electrochimica Acta 53 (2007) 934943
Fig. 5. Current efciencies for the deposition of CoWP lms from electrolytes
of various pHvalues, determined by () cyclic voltammetry and () chronoam-
perometry (stripping) techniques.
voltammetry is a dynamic process, a lower current efciency can
be resulted. Comparingthese twotechniques, it canbe concluded
that calculating current efciency by chronoamperometry is
more appropriate than dynamic cyclic voltammetry. The highest
current efciency (73%) has been found when CoWP is plated
from an electrolyte of pH 6. Notably, the amount of CoCit

species in the solution is also the highest at this pH [40].


3.1.3. Nucleation mechanism
Current transient experiment in which the potential is stepped
from the open-circuit potential to a potential at which reduc-
tion of electroactive species occurs under diffusion control is
considered as a suitable way to study nucleation and growth
mechanisms during electrodeposition process. There are two
extreme cases for nucleation, namely, instantaneous and pro-
gressive [48]. In instantaneous nucleation all nuclei form at the
same time and growcomparatively slowly. In progressive nucle-
ation new nuclei form during the course of deposition process
and grow relatively faster. The models for instantaneous and
progressive nucleation which are proposed by Scharifker and
Hills [48] are given by Eqs. (2) and (3), respectively.
_
I
I
m
_
2
= 1.9542
_
t
t
m
_
1
_
1 exp
_
1.2564
_
t
t
m
___
2
(2)
_
I
I
m
_
2
= 1.2254
_
t
t
m
_
1
_
1 exp
_
2.3367
_
t
t
m
_
2
__
2
(3)
where I
m
and t
m
are current and time coordinates, respectively, at
the peak maximumin the current transients. Study of nucleation
involves comparison of experimental data with these models.
Nucleation of cobalt on a variety of substrates in several exper-
imental conditions was studied using these models [43,4951].
However, these models can also be applied to elucidate nucle-
ation mechanisms of multi-components system as Eqs. (2) and
(3) include only time and current components. Therefore, effort
has been made to study nucleation during electrodeposition of
CoWP at different pH values using these models.
Fig. 3 showed transient currents of electrolytes containing
CoSO
4
, Na
2
WO
4
, NaH
2
PO
2
, and TSC and of various pH val-
ues on a copper disc electrode at an applied potential of 1 V.
(I/I
m
)
2
versus t/t
m
plots of experimental data derived fromFig. 3
Fig. 6. Comparison of the theoretical non-dimension plots for instantaneous and progressive nucleation and experimental data (circles) derived from Fig. 3.
S.M.S.I. Dulal et al. / Electrochimica Acta 53 (2007) 934943 939
and of theoretical data generated from Eqs. (2) and (3) are given
in Fig. 6. In these plots the theoretical instantaneous and pro-
gressive curves are shown in solid lines and the experimental
data are shown in circles. The gures suggest that the electrode-
position of CoWP from citrate electrolytes containing cobalt,
tungstate and hypophosphite ions follows theoretical curve of
instantaneous nucleation mechanism in all pH values, which is
in good agreement with a recent nding reported by Grujicic
and Pesic [43]. They have shown that even if the chronoamper-
ometry experiments (current transient experiments) suggest a
progressive nucleation of cobalt in ammoniacal solutions, AFM
studies, however, reveal that cobalt nucleation is always instan-
taneous. Fig. 6 also shows that the experimentally determined
reduced current versus time plot in the case of pH 4 (and in the
case of pH 3, as well) deviates signicantly from the theoretical
instantaneous and progressive nucleation models. Deviations of
experimentally constructed curves from the theoretical models
for the nucleation of cobalt have also been observed by other
researchers and it has been concluded that this type of devia-
tion occurs due to the evolution of hydrogen [43,51]. However,
deviations also occur at higher pH values when t/t
m
>1.5, even
though no hydrogen evolution was observed on copper elec-
Fig. 7. Effect of electrolyte pH on (a) deposition current density and lm thick-
ness and (b) composition of CoWP lms. The lms were deposited by an applied
potential of 1 V for 5 min at room temperature.
trode at 1 V in neutral or basic aqueous solution containing
tri-sodium citrate. This can also be explained in term of hydro-
gen reduction. At the beginning of the deposition process, no
hydrogen reduction occurs on the bare copper surface. After few
seconds, nuclei of cobalt form and hydrogen reduction starts on
the nuclei of the deposited cobalt. Therefore, with the progress
of electrodeposition, the cobalt nuclei get larger and more
hydrogenevolutionoccurs, whichcauses the deviations of exper-
imental data from theoretical ones when t/t
m
becomes greater
than 1.5.
Fig. 8. XRD spectra of CoWP lms deposited from electrolytes of various pH
values.
940 S.M.S.I. Dulal et al. / Electrochimica Acta 53 (2007) 934943
Fig. 9. SEM images of CoWP lms deposited from electrolytes of various pH values.
3.1.4. Film thickness and composition
Fig. 7 shows the effect of electrolyte pHon the deposition cur-
rent density, thickness and composition of the electrodeposited
CoWP lms. At lower pH values, the deposition current is very
high, which is due to the reduction of proton from the bulk of
the electrolyte. As discussed previously, the current efciency
is very low in lower pH values. Therefore, most of the charges
at low pH electrolytes are consumed for reduction of protons.
The deposition current density decreases with the increase in
electrolyte pH, i.e. with the decrease in hydrogen ions in the
electrolyte.
Fig. 7a also shows that the thickness of the lms decrease
when they are plated from very acidic or basic electrolytes,
which is because of the lower current efciencies in these media
(Fig. 5) due to hydrogen evolution at lower pHvalues and forma-
tion of hydroxide in basic solution. The thickest lm has been
obtained when it was deposited from an electrolyte of pH 5,
even though the current efciency at this pH is much lower than
that at pH values of 6 and 7. This is because more deposition
occurs along with larger amount of hydrogen evolution. Table 1
shows that the stripping charge was higher in the case of pH 5
electrolyte than in the cases of pH values 6 and 7. Thus, there
is a good agreement between the cyclic voltammetry and the
thickness results.
The dependence of composition of the electrodeposited
CoWP lms has been depicted in Fig. 7b. Cobalt content in
the lm increases from 48 to 71 at.% when the pH of the elec-
trolyte is raised from 3 to 5, then remains almost constant with
further increase in pHup to 7. Cobalt content decreases when the
lm is deposited from pH 8 electrolyte, which is mainly due to
the formation of cobalt hydroxide in the solution. As discussed
Fig. 10. Effect of electrolyte temperature on (a) deposition current density and
lm thickness and (b) composition of CoWP lms. The pH of the electrolytes
was 7. The lms were deposited by an applied potential of 1 V for 5 min.
S.M.S.I. Dulal et al. / Electrochimica Acta 53 (2007) 934943 941
previously, cobalt deposition is facilitated by the formation of
CoCit

species in the pH range from 5 to 7. Therefore, the


highest amount of cobalt in the lm in this pH range is quite
expectable. Depending on the pH of the electrolyte, tungsten
content in the lm varies from 13 to 38 at.%. Higher tungsten
content has been obtained when the lm is plated from an elec-
trolyte of higher pH values (>7). The amount of phosphorus,
however, decreases with the increase in pHof the solution. Phos-
phorus content varies from 8 to 33 at.%, depending on the pH
of the electrolyte. The gure suggests that lms with higher
amount of phosphorus can be deposited using a highly acidic
bath.
3.1.5. Microstructure and surface morphology
Fig. 8 shows XRDspectra of the CoWP lms deposited from
electrolytes of various pHvalues. The XRDspectrumof the lm
deposited from pH 4 electrolyte gives a peak with high intensity
at 2 around 43.33

, which is due to the substrate copper with


preferred crystallographic orientation of [1 1 1]. A small peak at
2 =38.2

is related to titanium adhesion layer. The absence of


any other peak related to cobalt, tungsten or phosphorus suggests
that the CoWP lm deposited at pH 4 is amorphous. The lms
deposited from electrolytes of pH values of 3 and 5 give sim-
ilar X-ray diffraction pattern, which leads to a conclusion that
CoWP lms deposited from an electrolyte of pH 5 or less are
amorphous. However, the XRD spectrum of the lm deposited
at an electrolyte pH of 6 gives three peaks at 2 =41.7, 44.5 and
47.3

, which correspond to hexagonal cobalt with [1 0 0], [0 0 2]


and [1 0 1] directions, respectively. The CoWP lm deposited at
pH 7 also gives similar diffractogram. Therefore, it can be said
that lms deposited fromelectrolytes of pHvalues of 6 and 7 are
polycrystalline with no strong preferred orientation. The XRD
spectrum of the lm deposited at pH 8 shows a small and wide
-Co [1 0 1] peak. The shoulder on the Cu [1 1 1] peak suggests
that the -Co [0 0 2] peak gets convoluted with the Cu [1 1 1]
peak. Therefore, this lm can also be called crystalline.
The crystallinity of CoWP deposit mainly depends on its
composition. Amorphous structures of electrolessly deposited
CoWP lms were obtained when the phosphorus content in the
lm exceeded 11 at.%, keeping the tungsten content less than
5 at.% [18,52]. However, phosphorus and tungsten have syner-
gistic effect on the crystallinity of CoWP lms. As discussed
previously, the CoWP lms electrodeposited from electrolytes
of low pH values contains higher amounts of phosphorus and
tungsten, and hence they are amorphous. On the other hand,
lms deposited at pH values 6, 7 and 8 have less phosphorus in
them, which makes these lms crystalline.
SEM images of CoWP lms deposited from electrolytes of
various pH values are shown in Fig. 9. The lms deposited
from electrolytes of pH values of 3 and 5 have spherical nodu-
lar structures and their surfaces look densely covered and very
smooth. Relatively larger and irregular shaped crystallites are
observed when the lms have been plated fromelectrolyte of pH
7. However, the surface is quite different when plated frombasic
solution (pH 8). As can be seen in Fig. 9, needle-like dendritic
crystallites form when CoWP lms are deposited from an elec-
trolyte of pH 9. Although the roughness has not been measured
for the present study, a visual observation of the SEM images
Fig. 11. SEM images of CoWP lms deposited from electrolytes of various temperatures. The pH of the electrolytes was 7. The lms were deposited by an applied
potential of 1 V for 5 min.
942 S.M.S.I. Dulal et al. / Electrochimica Acta 53 (2007) 934943
suggests that the amorphous lms have smoother surfaces than
the crystalline lms.
3.2. Effect of temperature
Fig. 10a illustrates the effect of bath temperature on the depo-
sitioncurrent densityandthickness of the CoWPlms, deposited
by an applied potential of 1 V. The pH of the electrolytes was
7. The current density increases almost linearly with increase
in bath temperature. The thickness also increases very sharply
from 142 to 1303 nm when the bath temperature is raised from
25 to 65

C, which suggests a steady increase in deposition rate


with temperature.
The compositions of the lms deposited from various tem-
peratures are shown in Fig. 10b. Cobalt content in the lm
increases from 72 to 87 at.% with increase in temperature from
25 to 65

C. Both tungsten and phosphorus contents in the


lms, however, decrease with bath temperature. The relative
amounts of tungsten and phosphorus in the lms decrease from
17 to 10 at.% and 11 to 3 at.%, respectively, when the bath tem-
perature is raised from 25 to 65

C. As discussed earlier, the


co-deposition of cobalt, tungsten and phosphorus occurs under
diffusion control. The composition analysis suggests that the
inuence of temperature onthe diffusivityof cobalt species inthe
solution is dominant than that on tungstate and hypophosphite
ions.
The microstructures of the CoWP lms deposited from elec-
trolytes of various temperatures have been examined using
X-ray diffraction. It has been found that all the lms plated
at the temperature range used in this study are polycrystalline
and contain -Co with crystallographic orientations of [1 0 0],
[0 0 2] and [1 0 1]. The SEM images, as given in Fig. 11,
show the formation of randomly oriented needle-like den-
dritic crystallites, which gets larger with the increase of bath
temperature.
4. Conclusions
The electrochemical characterisations of the deposition of
CoWP lms fromelectrolytes containing 0.13 MCoSO
4
7H
2
O,
0.005 MNa
2
WO
4
2H
2
O, 0.003 MNaH
2
PO
2
H
2
Oand0.3 Mtri-
sodiumcitrate and of various pHvalues on copper disc electrode
were carried out by cyclic voltammetry and chronoamperome-
try techniques. The effects of electrolyte pH and temperature
on the current density, thickness, composition, microstructure
and morphology of potentiostatically deposited CoWP lms
were studied. Based on these experimental results, following
conclusions could be made.
(a) Cyclic voltammetry experiments showed that the onset
potentials for co-deposition and dissolution of cobalt, tung-
sten and phosphorus shifted towards more cathodic direction
with increase in electrolyte pH, which might be due to the
formation of various Co(II) species at different pH values in
the case of deposition on the forward scan and due to the
formation of surface hydroxide in the case of dissolution on
the reverse scan.
(b) Surface compositional analysis by XPS revealed that the rel-
ative amount of hydroxide on the deposit surface increased
with increase in electrolyte pH.
(c) Co-deposition of cobalt, tungsten and phosphorus occurred
under diffusion control and followed instantaneous type of
nucleation mechanism.
(d) The current efciency for the deposition of CoWP lms
determined fromstripping charges was found to be the high-
est (>70%) when they were deposited fromneutral or slightly
acidic solution.
(e) Larger variation of lm composition, cobalt from 48 to
74 at.%, tungsten from 13 to 38 at.% and phosphorus from
8 to 33 at.%, could be made by changing the electrolyte pH
between 3 and 8.
(f) The lms deposited fromvery acidic solutions contained rel-
atively higher amounts of tungsten and phosphorus, which
made them amorphous; while the lms deposited from near
neutral solutions were polycrystalline and contained hexag-
onal cobalt.
(g) The surfaces of the amorphous lms were smoother than
those of the polycrystalline lms.
(h) The deposition current density and lm thickness increased
almost linearly with increasing bath temperature. Cobalt
content in the lms was found to increase with temperature,
while both tungsten and phosphorus contents decreased.
(i) Needle-like dendritic crystallites was obtained when the
lms were deposited from basic solution or at elevated tem-
perature.
Acknowledgements
The authors wouldlike tothankProfessor Soonil Lee, Depart-
ment of Physics, for providing thickness measurement facilities.
This work has been supported by Brain Korea 21 project and the
Basic Research Program of the Korea Science and Engineering
Foundation (Grant Nos. R01-2006-000-11264-0 and R01-2006-
000-10239-0), and Eugene Technology Co., Ltd.
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