Thin Solid Films 636 (2017) 425–430

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Thin Solid Films

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Electroless deposition of CoBW coatings using morpholine borane as a

reducing agent
Z. Sukackienė ⁎, L. Tamašauskaitė-Tamašiūnaitė, V. Jasulaitienė, A. Balčiūnaitė, A. Naujokaitis, E. Norkus
Department of Catalysis, Center for Physical Sciences and Technology, Saulėtekio av. 3, LT 10257, Vilnius, Lithuania

a r t i c l e i n f o a b s t r a c t

Article history: Electroless cobalt-tungsten-boron (CoWB) coatings have been obtained on the copper surface from glycine con-
Received 21 November 2016 taining solutions, using morpholine borane as a reducing agent. The effects of concentration of the reactants, so-
Received in revised form 17 May 2017 lution pH and temperature on the deposition rate were investigated. The morphology and composition of CoBW
Accepted 17 June 2017
coatings were characterized by means of Field-Emission Scanning Electron Microscopy and X-ray Photoelectron
Available online 19 June 2017
Spectroscopy.
Keywords:
It has been determined, that the rate of electroless deposition of the CoBW coatings and their composition de-
Electroless deposition pends on the concentration of disodium tungstate and reducing agent, as well as on pH and temperature of
Cobalt the plating solution. Electroless deposition of the CoBW coatings can be performed in a wide temperature
Boron range from 30 to 70 °C. Changing conditions of the electroless deposition of CoBW the coatings containing 5.5
Tungsten to 16 at.% of boron and 5 to 14 at.% of tungsten can be obtained.
Morpholine borane © 2017 Elsevier B.V. All rights reserved.

1. Introduction (aminoboranes) R3N·BH3, where R3 is hydrogen, alkyl, aril, or amine;

“Electroless plating” of nickel or cobalt alloys was described for the
first time by Brenner and G. Riddell in 1947 [1,2]. Compared to other de-
position methods, electroless deposition is a relatively simple and low
cost with low processing temperature. Electroless deposition allows
obtaining high quality coatings with the desired properties and is an ef-
fective method for micro- and nanosystem technologies. Cobalt coatings
have unique magnetic and mechanical properties having potential ap-
plications as high wear-resistant coatings or in electronic devices.
Therefore, lately, Co coatings have attracted a lot of attention [3–6].
Renewed interest in the electroless deposition process of cobalt is due
to the application of CoP [7,8] or CoB [9,10] films as barrier and cladding
layers for the protection of Cu layer in microelectronic systems. It is
known that the inclusion of tungsten [7,11–14] or molybdenum [15,
16] in the cobalt coatings can improve the barrier efficiency of the CoP
or CoB coatings. An application of ternary Co-based films as diffusion
barriers and capping layers for Cu improves interconnection perfor-
mance and solves some problems preventing contamination by copper
[7,13]. Boron, phosphorus, tungsten or molybdenum are considered to
be elements capable of blocking the diffusion of Cu at the grain bound-
ary of cobalt thereby playing a vital role as a diffusion barrier.
Traditionally, in electroless cobalt baths were typically used
hypophosphite ions [7,8,17–20] or boron-containing compounds as re-
ducing agents, such as borohydrides (NaBH4, KBH4) [21–27], borazanes
⁎ Corresponding author.
E-mail address: zita.sukackiene@ftmc.lt (Z. Sukackienė).
borazenes (aminoboranes) R2N·BH3; borazines RN·BH and borazoles
(RH·BH)3 [28]. Concerning boron-containing reducing agents used for
electroless deposition of Co bi-component (CoB, CoW), or
polycomponent alloys (CoBW, CoWPB) are sodium borohydride and
dimethylamineborane (DMAB, (CH3)2 NH·BH3) [12,13,21–31]. Boron
containing compounds are stronger reducing agents compared to
hypophosphites, because they give 6 or 8 electrons for reduction of
metals, therefore cobalt coatings with boron have higher hardness, bet-
ter corrosion resistance, and a higher melting point compared to those
of cobalt coatings with phosphorus. Sodium borohydride is the most
popular reducing agent, however, the main disadvantage of electroless
plating solutions with NaBH4 as a reducing agent is that high deposition
rates are obtained only at elevated temperatures (90–95 °C) and in
strong alkaline media (pH 12–14) [28]. Application of boron-nitrogen
compounds – borazanes, e.g. dimethylamineborane, as reducing agents
allows the deposition process to be carried out in a wide pH and tem-
perature range [28]. Recently, morpholine borane (MB, C4H8ONH·BH3)
was proposed for electroless metal deposition as a reducing agent and a
source for boron [32–37]. Morpholine borane compared to
dimethylamineborane is less volatile and toxic due to its structure
[31]. The main advantage of MB as a reducing agent is the possibility
to regulate and predict the composition (content of Co and B) of obtain-
ed CoB alloys. Deposition of high quality coatings containing different
predicted amounts of boron and cobalt is documented in Ref. [32,35].
Since, no investigations of such systems using morpholine borane as a
reducing agent for co-deposition of tungsten with CoB alloys have
been reported, the aim of our study was to investigate the conditions

http://dx.doi.org/10.1016/j.tsf.2017.06.034
0040-6090/© 2017 Elsevier B.V. All rights reserved.
426 Z. Sukackienė et al. / Thin Solid Films 636 (2017) 425–430

of deposition of the CoWB films using the cobalt-glycine plating bath

with morpholine borane. A generally accepted model of the electroless
cobalt-boron deposition process using morpholine borane as a reducing
agent was described earlier [32]. The electroless deposition of the CoWB
films can be divided into two processes: anodic and cathodic. The anodic
reaction is the oxidation of reducing agent - morpholine borane. The ca-
thodic reactions are reduction of cobalt ions, hydrogen, boron and tung-
sten (in our case). It is well known that pure tungsten cannot be
deposited electrolessly or electrochemically, but it can be deposited
with some metals of the iron group. The reduction of the main metal
(Co) and refractory metal (W) run simultaneously. The mechanism of
tungsten incorporation into cobalt coatings as yet remains unclear.
Interpreted, that the tungsten ion WO2− 4 can be transformed into the
tungstile ion, WO2+2 in an alkaline solution, because of the presence of
a complexing agent (in this case – glycine) or a negative charge of the
surface [33]. In this study, the influence of concentration of disodium
tungstate and reducing agent, solution pH and temperature on the
rate of electroless deposition of the CoBW coatings has been
investigated.

2. Experiment

Electroless deposition of CoBW layers was performed on the copper

(1 × 1 cm) surface. The composition of solutions and deposition param-
eters of electroless deposition of the CoBW alloys are given in Table 1.
Prior to the electroless deposition of CoBW, copper sheets were cleaned
and activated with Pd(II) ions by immersion of copper sheets in a 1 g l−1
PdCl2 solution for 15 s, rinsed with deionized water and placed into an
electroless cobalt plating solution. The deposition of films was per-
formed in a freshly prepared solution at temperatures of 30–70 °C.
The solution pH value of 6–8 was adjusted with a solution of NaOH.
All the chemicals used were of analytical purity grade.
The thickness of deposited films was determined gravimetrically
and the average deposition rate in μm h−1 was calculated from the re-
sults of film deposition during 60 min (in some cases the deposition
time was varied with the aim to obtain the same film thickness). The
composition of the CoBW films obtained was determined by means of
X-ray photoelectron spectroscopy (XPS) using an “ESCALAB MKII” spec-
trometer (VG Scientific, UK) equipped with an Al Kα X-ray radiation
source (1486.6 eV) operated at a fixed pass energy of 20 eV. To obtain
depth profiles, the samples were etched in the preparation chamber
by ionized argon at a vacuum of 5·10− 4 Pa. XPS analysis data are
given for coatings at a depth of 24 nm. The quantities of Co, B, W and
O in the coatings were expressed in at.%. The standard deviation for
the method was estimated to be 0.1–0.5 at.%. The morphology of the
CoBW coatings was characterized using a SEM/FIB Workstation Helios
Nanolab 650 with an energy dispersive X-ray (EDX) spectrometer Fig. 1. Influence of tungsten concentration on the Co alloy plating rate and coating
INCA Energy 350 X‐Max 20. composition. Solution composition (mol l−1): CoSO4 - 0.1, glycine - 0.2, MB - 0.2, citric
acid - 0.175, pH 7, 60 °C.
3. Results and discussion
increase in concentration of disodium tungstate in the solution, whereas
Fig. 1 shows the influence of tungsten concentration on the Co alloy the tungsten and oxygen incorporation increases (Fig. 1. c). When the
plating rate (a) and coating composition (b,c). As evident, the deposi- disodium tungstate concentration is increased up to 20 mmol l−1, the
tion rate, cobalt and boron content in the coatings decreases with deposition rate of cobalt coatings slows down dramatically (Fig. 1a),
showing, that the reduction of tungsten ions competes with the reduc-
Table 1
tion of cobalt and boron ions. It follows, that the tungsten does not cat-
Composition of electroless plating solution and deposition parameters of CoBW alloys. alyze the reaction of morpholine borane oxidation. In all cases the
addition of disodium tungstate to the electroless plating solutions di-
Chemical Formula Concentration/mol Temperature/°C pH
minishes the overall process rate. According to the XPS spectral analysis
l−1
of the CoBW coatings, at a depth of 24 nm the cobalt content varies from
Cobalt sulphate CoSO4·7H2O 0.1 30–70 6–8
66 to 76.5 at.%, that of boron varies from 6 to 9.3 at.%, that of tungsten
heptahydrate
Borane morpholine C4H8ONH·BH3 0.05–0.4 varies from 5.5 to 13.7 at.%, and the oxygen content varies from 6 to
complex 15 at.% (Fig. 1a-c).
Glycine NH2CH2COOH 0.2 It has been found that the structure of cobalt coatings depends on
Disodium tungstate Na2WO4 0.001–0.02 the boron content [12]. Films with a low B content (about 2 or less
Citric acid C6H8O7 0.175
at.% of boron) are polycrystalline, whereas the films containing up to
 Z. Sukackienė et al. / Thin Solid Films 636 (2017) 425–430 427

5 at.% of boron have an amorphous or nanocrystalline structure. As
shown in Fig. 1, the deposition rate of the CoBW coatings is strongly in-
fluenced by the amount of W. Since the structure (morphology) of the
coatings depends on the thickness of coatings we chose to deposit coat-
ings of the same thickness to elucidate the influence of W. The deposi-
tion time was longer if we increased the amount of W in solution to
get the thickness of 1 μm. Fig. 2 presents the SEM images of the CoBW
coatings deposited in the cobalt-glycine plating bath with different con-
centrations of Na2WO4. The growth of active Co centers is suspended
when W is interposed into the cobalt coating (Fig. 2a,b). The coating is
formed from crystallites of similar size when the concentration of
Na2WO4 in the plating solution is 3 mmol l−1 (Fig. 2b). The growth of
crystalline surface markedly slows down and the crystallites size dimin-
ishes with further increase in the concentration of W (Fig. 2c,d). The
amorphous structure dominates when the concentration of Na2WO4
in the plating solutions is 5 mmol l−1 or more. The corresponding EDX
spectra of the as-prepared CoBW coatings using 0.003 mol l−1 (f) and
0.020 mol l−1 (g) of Na2WO.4confirm the presence of Co, B and W.
Fig. 3 shows the dependence of the CoBW coatings deposition rate
and their composition on the concentration of morpholine borane in
the plating solution. A rise in the concentration of morpholine borane
in the range of 0.05–0.3 mol l−1 in glycine solutions leads to an increase
in cobalt alloy deposition rate, whereas a subsequent increase in the
concentration of morpholine borane above 0.3 mol l−1 slightly dimin-
ishes the deposition rate of films (Fig. 3a). The content of cobalt slightly
diminishes in the coatings from ca. 75 at.% to 68 at.% (Fig. 3b). The con-
tent of boron slightly increases while the content of tungsten decreases
(Fig. 3c). An increase in the concentration of reducing agent in the elec-
troless cobalt solutions increases the content of oxygen in the coatings.
It is considered that the oxidation of reducing agent proceeds via five co-
ordinate oxygen containing intermediates [30], that is why oxygen may
be included in the coatings.

Fig. 2. SEM images of as-prepared CoBW films deposited on the Cu surface. CoBW was deposited from the solution containing (mol l−1): CoSO4 - 0.1, glycine - 0.2, MB - 0.2, citric acid -
0.175, Na2WO4: 0.001 (a), 0.003 (b), 0.005 (c), 0.01 (d), 0.02 (e), pH 7, 60 °C. Thickness of the films - 1 μm. The typical EDX spectra of the as-prepared CoBW coatings were deposited using
0.003 mol l−1 (f) and 0.020 mol l−1 (g) of Na2WO4.
428 Z. Sukackienė et al. / Thin Solid Films 636 (2017) 425–430
Fig. 3. Influence of morpholine borane concentration on the Co alloy plating rate and
coating composition. Solution composition (mol l−1): CoSO4 - 0.1, glycine - 0.2, Na2WO4
- 0.003, citric acid - 0.175, pH 7, 60 °C.
The deposition rate of the CoBW coatings increases with increase in
pH of the plating solution from 6 to 8 and reaches ca. 4.3 μg cm−2 h−1 at
pH 8 (Fig. 4a). This can be explained by the fact that OH– ions accelerate
the anodic oxidation of morpholine borane as the first stage of overall
process deposition. The composition of the coatings obtained changes
with solution pH. A slightly acidic medium is favourable for boron incor-
poration into the cobalt coatings (Fig. 4c). The increase in solution pH
diminishes the content of boron incorporated into the coatings. The
content of tungsten remains almost unchanged with increase in solu-
tion pH up to 7, whereas when pH of solution is higher than 7, the con-
tent of tungsten markedly diminishes (Fig. 4c). The content of oxygen in
the coatings decreases with increase in solution pH. In this case, the con-
tent of cobalt increases (Fig. 4b). It is evident, that the reduction of co-
balt is competitive with the reduction of boron, tungsten and their
incorporation into the films.
Fig. 4. Influence of pH on the Co alloy plating rate and coating composition. Solution
composition (mol l−1): CoSO4 ‐ 0.1, glycine - 0.2, MB - 0.2, Na2WO4 - 0.003, citric acid -
0.175, 60 °C.
The effect of temperature on the Co alloy plating rate and coating
composition is shown in Fig. 5. As evident from Fig. 5a, the deposition
rate of cobalt coatings only slightly increases with increase in tempera-
ture of the plating solution from 30 up to 50 °C, while it increases mark-
edly with increase in temperature up to 70 °C. Therefore, the increase in
temperature leads to a considerable increase in the overall plating rate
of the CoBW coatings. The content of cobalt increases (Fig. 5b), whereas
the content of boron markedly decreases, meantime, the dependence of
the content of tungsten and oxygen on temperature is not clearly de-
fined (Fig. 5c).
4. Conclusions
High-quality CoBW coatings have been obtained from a cobalt-gly-
cine plating bath using morpholine borane as a reducing agent. It has
 Z. Sukackienė et al. / Thin Solid Films 636 (2017) 425–430
Fig. 5. Influence of temperature on the Co alloy plating rate and coating composition.
Solution composition (mol l−1): CoSO4 ‐ 0.1, glycine - 0.2, MB - 0.2, Na2WO4 ‐ 0.003,
citric acid - 0.175, pH 7.
been determined, that the rate of electroless deposition of the CoBW
coatings and their composition depend on the concentration of
disodium tungstate and the reducing agent morpholine borane, as
well as on pH and temperature of plating solution. Electroless deposi-
tion of the CoBW coatings can be performed in a wide temperature
range from 30 to 70 °C. The CoBW coatings with the boron content
from 5.5 to 16 at.% and the tungsten content from 5 up to 14 at.% have
been obtained.
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