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