Proceedings of 19

th
International Workshop on Rare Earth Permanent Magnets & Their Applications
Effect of Phosphor Incorporation on Magnetic Properties
of Electrodeposited CoPtW Thin Films
WEI Guo-ying, GE Hong-liang, WU Qiong, ZHOU Qiao-ying, WANG Xin-yan
(Magnetism Key Laboratory of Zhejiang Province, College of Science, China Jiliang University, Hangzhou, China)
Abstract: The electrochemical behaviors of CoPtW(P) electrodeposition have been analyzed by means of cyclic
voltarnrnetry. Effect of hypophosphite concentration in the electrolyte on the alloy composition, crystalline structure and
magnetic properties has been investigated. It is turned out that the intensity of [00.1] P.D in the XRD pattern ofCoPtW(P)
has been strengthened when the concentration of hypophosphite increased from 0 to 0.1 M. Parallel and perpendicular
coercivity of electrodeposited CoPtW(P) reached a maximum when the hypophosphite concentration was 0.06 M, but the
perpendicular magnetic anisotropy increased gradually with the increase of hypophosphite concentration. Moreover,
saturation magnetization of the electrodeposited CoPtW(P) with more P content decreased when the films were exposed to
the air. This can be explained by the fact that the hydrogen evolution would be favored thanks to an increase of
hypophosphite concentration, which led to the acceleration of corruption speed.
Key words: CoPtW(P) thin film; magnetic property; electrodeposition
1 Introduction
Fabrication of cobalt and its alloys has been
widely used in the production of new magnetic
materials utilized as microactuators, sensors, and
magnetic recording heads, etc[I-41. Electrodeposition
processes possess several advantages over conven-
tional casting techniques, enabling very close tailoring
of the microstructure and magnetic properties of the
films by better control of the growth. At the same time,
this technique entails a purely additive step into the
microfabrication process, thus limiting the generation
of defects due to etching prccesses'i",
In recent years particular interest is growing
towards the electrodeposited CoPt alloys with perpen-
dicular anisotropy, a very interesting material not only
for perpendicular high-density magnetic recording
media, but also as magnet for small electronic devices.
Recent discoveries have shown that by adding a third
alloying element, W, the magnetic properties of the
CoPt alloys at high thickness can be increased, and
another advantage is the decreasing Pt content to less
than half while maintaining high coercivity [7-9].
Co-deposition of phosphor compounds (phosphor was
added in the electrolyte as NaH
2P02)
can increase the
coercivity as a result of decoupling the magnetic grains.
This work discusses the effect of hypophosphite con-
centration in the electrolyte on the alloy composition,
crystalline structure and magnetic properties.
2 Experiments
2.1 Preparation of electrodeposited CoPt.W(P)
thin films
The alloy was prepared in a three-electrode cell by
means of electrodeposition. A copper plate was used as
the working electrode with the surface area of 0.5 em".
The surface was polished to a mirror finish with
different alumina grades down to 0.05 urn, and cleaned
ultrasonically before the experiments. The platinum
plate anode was about 10 times larger.
All chemicals were of analytical grade and
prepared by ultra-pure millipore water. The electrolyte
had the following composition: 0.1 M CO(NH
2S03h,
0.01 M (NHthPtCI
4,
0.27 M Na2W042H20, 0.2 M
and x(x=O-O.1) M NaH
2P022H20.The
solutions were adjusted to pH 8.50.1 with suitable
additions of H
2S04
or NaOH solutions. All investiga-
tions were conducted at a temperature of 60 'C and the
current of 12 rnA.
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Proceedings of 19
th
International Workshop on Rare Earth Permanent Magnets & Their Applications
3 Results and Discussion
Cyclic voltammetry has been used to determine
the electrochemical details of CoPtW(P) electrodeposi-
tion. Fig.l shows typical cyclic voltammograms for
deposition of CoPtW and CoPtWP at 5 mV SI.
It can be seen that CoPtWP alloy deposition
appeared in the more negative potential than CoPtW
alloy deposition and the cathode current of electro-
deposited CoPtW was larger than that of electro-
deposited CoPtWP, which implied that the electro-
2.2 Characterization
The cyclic voltammetry study was performed in a
conventional three-electrode system. GC electrode
was used as the working electrode. Cyclic voltam-
metry sweeps were recorded as a function of scan rate
(5 mV/s).
X-ray diffraction (XRD) patterns of the samples
were recorded on an X-ray diffractometry (X' Pert
MPD Philips PW 1830) with Cu Ka radiation. The
magnetic properties of CoPtW(P) thin films were
measured by vibrating sample magnetometer (VSM)
(LakeShore 7407) in magnetic field both perpendicular
and parallel to the substrate. The surface morphology
was assessed by SEM (Cambridge Stereoscan 360).
0,02
0.Q1
0,00
-0,01

-0,02
- O,06MNaH,PO,
- without NaH,PO,

deposition of CoPtWP was more difficult than that of

CoPtW. Moreover, a crossover of the cathodic and
anodic branches in the CVs was observed, which
means that electrodeposition of both CoPtW and
CoPtWP involved the formation of a new phase; during
the positive scan, one can see the potential of CoPtW
alloy oxidation peak was less positive than that of
CoPtWP alloy oxidation peak. From the CVs' results.
we can conclude that the incorporation of P can
increase the corruption resistance of alloys.
Fig.2 indicates the XRD patterns detected in
electrodeposited CoPtW(P) alloys that resulted from
changes of the concentration of hypophosphite. XRD
analysis showed that Co-Pt-W(P) films exhibited a
strong dependence on the phosphor content of the
deposited alloy. At a high hypophosphite concentration
of 0.1 M, CoPtWP developed a microstructure
consisting of hexagonal-closed-packed (hcp) matrix
with [00.1] preferential orientation. This means that
CoPtWP films have the c-axis oriented perpendicular
to the film plane. At a relative low phosphor content of
1.41 a1.% and 3.96 a1.%, however, CoPtWP films
exhibited two mixed phases (fcc-hcp) and the PO of
[00.1] became weaker. From the above results, it im-
plies that as the hypophosphite concentration increases
the growth direction of CoPtWP films changes from
parallel to perpendicular orientation with respect to the
c-axis of the hexagonal structure.
The transition of PO in electrodeposited CoPtWP
films is closely related to magnetic properties. Fig.3
shows the variation of both parallel coercivity and per-
-0,03
-0,04
-1,4 -1.2 -1.0 -0,8 -0,6 -0.4 -0,2 0,0 0,2 0.4
EN
Potential scan started at 01 V toward negative direction and then
reversed at -1.15 V. at a rate of 5 mV!s; Experiments were made
under stirring condition
Fig.l Typical CV curve obtained in solutions: (1) CoS0
4
0.1 M, Na2W040.27 M, 0.2 M and
(NH..)2C611ti07 0.2 M (pH=8.0); (2) CoS0
4
0.1 M,
Na2W0
4
0.27 M, (NH..hPtCI
4
0.2 M, (NH..hC6I1ti07
0.2 M and NaH2P02 0.06 M (pH=8.0)
ilrp(001)
.
.e
.
.
.
fnnr
A

,
If-----f-t-
b


'-'------
--
e
---
a-O.02 M; b-0.04 M; c-O.l M; s- Substrate
Fig. 2 XRD patterns of CoPtWP thin films electro-
deposited from different hypophosphite
concentrations
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Proceedings of 19
th
International Workshop on Rare Earth Permanent Magnets & Their Applications
Table 1 Saturation magnetization (M
s
) of CoPtWP thin
films exposed to air for different days
M,ofCoPtWP M,ofCoPtWP M,ofCoPtWP
Concentration of
explosed for 0 explosed for 30 explosed for 60
hypophosphiteIM
day/temu-g") days/temu-g") days/(emu'g-
l
)
0 6.8384 6.68 6.46
0.02 9.9347 9.699 9.323
0.04 13.858 13.422 13
0.06 22.1695 21.685 21.126
0.08 16.164 15.15 13.894
0.1 9.6598 8.2127 7.1235
0.10 0.08 0.06 0.04 0.02
Concentration ofNaH,PO, in the solutionlM
/ " O , ~
, ,
, ,
, ,
, '
_-0
i'/\
f-- ~
0.00
2000
2200
1800
1600
o
1
1400
~ 1200
U 1000
800
600
400
200 + - - , - ~ - - r - ~ - - , - ~ - , - ~ - - r - ~ - - , -
Fig. 3 Variation of parallel and perpendicular coercivity
of electrodeposited CoPtWP
pendicular coercivity with increasing the hypo-
phosphite concentration. It can be seen that the coer-
civities of CoPtWP films reached the maximum in the
parallel and perpendicular direction when the concen-
tration of H
2P02
- was 0.06 M. Moreover, the perpen-
dicular magnetic anisotropy has been strengthened
with the concentration of H2P02- (Fig.3), which can be
explained by the fact that the high perpendicular
magnetic anisotropy (PMA) originates from the high
magnetocrystalline anisotropy of the hcp phase of
CoPtWP with c-axis perpendicular to the film[71.
The saturation magnetization (M
s
) of the CoPtWP
thin films exposed to the air for different days has been
tested. It was observed that M, of the electrodeposited
CoPtW(P) with more P content decreased with
exposing days in the airs (Table 1). This could be
attributed to the fact that the hydrogen evolution would
be favored thanks to an increase of hypophosphite
concentration (FigA), which led to the acceleration of
corruption speed.
(a) 0.38at%; (b) 0.49at%
Fig. 4 Surface morphology of eIectrodeposited CoPtWP
thin films with different phosphor atomic percentage
4 Conclusions
CoPtWP thin films have been prepared by
electrodeposition. The electrochemical essential of
CoPtW(P) electrodeposition was discussed by means
of cyclic voltammetry method. It was found out that the
electrodeposition of CoPtWP was more difficult than
that of CoPtW. And the incorporation of an appropriate
amount of P can increase the corruption resistance of
alloys. XRD results shows that the intensity of [00.1]
P.O of CoPtW(P) has been strengthened when the con-
centration of hypophosphite increased from 0 to 0.1 M.
Parallel and perpendicular coercivity of electrode-
posited CoPtW(P) reached a . maximum when the
hypophosphite concentration was 0.06 M, but the
perpendicular magnetic anisotropy increased gradually
with the increase of hypophosphite concentration.
Moreover, saturation magnetization of the electrode-
posited CoPtW(P) with more P content decreased when
the films were exposed to the air.
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Proceedings of 19
th
International Workshop on Rare Earth Permanent M a g l l ~ t s &: '11Jeir Appncanons
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