196 Thin Solid Films, 227 (1993) 196-199

Magnetic and magneto-optical properties of Cu-doped Bi, Al:

DyIG films prepared by the pyrolysis method

Yong Zhou”, De Fang Shenb and Fu Xi Gana

“Shanghai Institute of Optics and Fine Mechanics, Chinese Academy Sciences, Shanghai 201800 (People’s Republic of China)
bShanghai Institute of Metallurgy. Chinese Academy Sciences, Shanghai 200050 (People’s Republic of China)
(Received October 7, 1992; accepted December 23, 1992)

Abstract

Bi, Al: DyIG and Cu-doped Bi, Al: DyIG films on glass substrates have been prepared by the pyrolysis method.
Magnetic and magneto-optical properties were investigated. Films were annealed at 650 “C for 30 min, then
quenched to room temperature within about 60 s. For Cu-doped Bi, Al: DyIG films, the coercive force (H,) was
increased with the Cu content increasing. The H, value of 557.2 kA m-’ was obtained in Cu-doped Bi, Al: DyIG
films, and the Faraday rotation angle was about 7” pm-’ at a wavelength of 500 nm. The increased H, was
attributed to Cu entering lattice sites.

1. Introduction dissolved in nitric acid. This concentrated solution

Bismuth-substituted garnet films on glass substrates
have attracted much attention as the next generation of
magneto-optical recording materials because of their
high corrosion resistance and large Faraday rotation at
short wavelength. To obtain a well-defined written pat-
tern, garnet films with high coercivity at room tempera-
ture must be prepared. It has been reported previously
by the authors [l-4] that doping with W, MO, Ba and
Cu are effective in increasing H,. A possible reason for
the increase in H, in those films was considered to be
that the doped elements may have acted as a pinning
site for the magnetic domain wall.
This paper describes a new explanation for the in-
crease in H, for Bismuth-substituted garnet films with
Cu doping.
2. Experimental details
Films were prepared on glass substrates by the pyrol-
ysis [5-81 method. The pyrolysis method is simple, and
it is easy to control the chemical compositions of the
films. In these films, the uniaxial perpendicular mag-
netic anisotropy of garnet films on glass substrates
results from the inverse magnetostriction effects [l-9];
thus DyIG, having a large negative magnetostriction
coefficient, was incorporated in order to produce high
perpendicular anisotropy. Certain amounts of nitrates
and oxides such as Bi(N03)3. 5H,O, Al(NO,), .9H,O,
Fe(NO,)J. 9H,O, Dy,O, and CuO were used and
was fixed to 0.1 mol/l-‘, based on the garnet. A small
quantity of the solution was dropped onto a well-
cleared glass substrate. Spin coating was performed
with a practical spin coater. During spinning, the
solution was distributed into a uniform film, and then
dried by an infrared lamp and an electric furnace in
the range of 250440 “C. This process was repeated
until a desired film thickness was obtained. The amor-
phous films were crystallized at 650 “C for 30 min,
then quenched to room temperature within about 60 s.
According to refs. 5-7, the film compositions were
estimated to be the same as those obtained from the
concentrated nitrates solutions. The film thickness was
about 0.2 urn.
The coercive force (H,) and the Faraday rotation
angle were measured by an effective Faraday rotation
hysteresis loop [lo] and a magneto-optical spectrome-
ter respectively. The compensation temperature ( Tcomp)
values were measured by the vibrating sample magne-
tometer (VSM) through the magnetic moment us. tem-
perature.
3. Results and discussion
Figure 1 shows the H, of Bi,.,Dy,.,Fe,_,Al,Cu,~O,,
films us. Cu content. H, was increased with Cu content
increasing, up to 557.2 kA m-’ for Cu content at 0.8
per formula unit. It is about 7 times as large as that in
non-Cu-doped garnet films. The high H, values cannot

0040-6090/93/%6.00 0 1993 - Elsevier Sequoia. All rights reserved

 2. Yong et al. 1 Magnetic and Magneto-optical Properties of Cu-doped Bi, AI: Dy1G~Vm.s 197

600.0

4oo.o
/
300.0 -

400.0 5z
2
a
c300.0 r200.0
b - 1
s
100.0
200.0

100.0 t I I
0.0 ’
0.0 0.5 1.0 1.5
Al content
0.0
0.0 0.2 :I” corl?&t 0.6 1.0 Fig. 3. Calculated Tcomp vs. Al content in Bi,.,Dy,.,Fe,_,Al,O,,
films.

Fig. 1. Coercivity of Bi,,,Dy,.,Fe,_,Cu,AI,O,, films us. Cu con-

tent.
was about 50 Kin Bi,,~Dy,,,Fe~,2Al,Cu0,80,2 films. This
300 , increase in H, was due to the entering of Cu2+ ions
I
mostly in 24d sites in the garnet films. The calculated
T camp fits the experimental data well and the fraction of
Cu*+ ions in 24d site is 53% of the total Cu content.
It is well known that Al is usually used to replace Fe
in garnet to reduce saturation magnetization. A13+ ions
have 24d site preference and could raise Tcomp in garnet
films. Figure 3 shows the calculated Tcomp us. Al content
:Meamred Tcomp in Al-substituted garnet films. Tcompwas all below room
:Calculated Tcomp
temperature, and was increasing with the Al content
increasing. Figure 4 shows the coercive force VS. Al
content. H, was increased with the Al content increasing
and reached 131.3 kA m-’ for Al content of about 1.0
per formula unit. One can see from Figs. 1 and 4 that

200 1
0.0 1.0
cu z%ltent 150.0

Fig. 2. Tcomp of Bi,,,Dy,,,Fe,_,~Cu,Al,O,, films vs. Cu content.

be explained simply by the pinning effects. One of the

reasons for the increase in H, was associated with
0.1 entering lattice sites. It makes Tcomp increase and
produces additional anisotropy. According to Hansen
and coworkers and Krishnan [ 11, 121, Cu2+ ions could
enter 24c sites in which have contributions to saturation
magnetostriction Is [ 1l] or enter 16a and 24c sites in
which could contribute to perpendicular anisotropy of
Ku through spin-orbit coupling [ 121. Since the Tcompof
Bi-substituted garnet films lies below room temperature,
the Lmp could be increased in Cu-doped garnet films. 0.0 ’ I ,

Figure 2 shows the calculated and the experimental 0.0 0.5 1.0 1.5
d ,

T=_, us. Cu content. The Tcomp was increased with the Al content

Cu content increasing; the amount of increase in Tcomp Fig. 4. Coercive force of Bi,.,Dy,,,Fe,_,Al,O,, films vs. Al content.
198 2. Yong et al. / Magnetic and Magnero-optical Properties of G-doped Bi, AI: DyIG films

the tendency for H, is similar, but the H, values in

Cu-doped garnet films are much higher than those in
Al-substituted garnet films. Thus the high H, cannot
completely be attributed to the increase of Tcomp: there
may be some other factors such as additional anisotropy
caused by I, [ 1l] and the spin-orbit coupling [ 121, local
tetragonal distortion (John-Teller effect) [ 121 and the
pinning effects [4].
The unstoichiometric ratio of Bi,.,Dy,.,Fe,Al,O,, +
0.8 CuO films was also investigated. Tcompmeasurements
show that it has not changed in the films. On the contrary,
H, was raised from 79.6 kA m- ’ (non-Cu-doped film) to
54.7 kA m-l. K. Shimokawa et al. [4] prepared the
Cu-doped Bi, Ga: DyIG films by the sputtering method
0.0 1.0
using metal chips of Cu as additives. The maximum H, cu zltent
value of 429.8 kA m-’ was obtained at the area ratio of
Fig. 6. Faraday rotation of Bi, ,Dy,.,Fe, _ .AI,Cu, O,, films us. Cu
3.4%. In our experiments, Cu*+ ions have similar pinning content
effects in unstoichiometric ratio films. In this case, Cu2+
ions could act as the pinning effects in unstoichiometric
10.0
ratio films; thus H, would be increased. 3 u cu=o.o
Figure 5 shows the typical Faraday rotation hysteresis Q.MLwclGo.4
QcGQo cu=o.e
loops of the Cu-doped films compared with those of 2
non-Cu doped films. The squareness of the loops does $
not change in Cu-doped garnet films and the remanence
ratio of all the loops is unity, which is an important 8
3
factor required for magneto-optical recording media. 4( 5.0 -
Figures 6 and 7 show the Faraday rotation angle and the 2
Faraday rotation spectrum of Cu-doped Bi, Al: DyIG
4
films respectively. The Faraday rotation angle was de- w
pendent on Cu content and has the value of about 7” u-’ 2
d
at a wavelength of 500 nm in Cu-doped garnet films with
an H, value of 557.2 kA m-’ for Cu content at 0.8 I I I
per formula unit. This benefits high-density magneto- 550.0 650.0 750.0
Wavelength (nm)
optical recording. The Faraday rotation spectrum
measured in the wavelength range of 450-700 nm Fig. 7. Faraday rotation spectrum of Bi,.,Dy,.hFe,_, Al, Cu,O,,
showed no remarkable change with the addition of Cu. films.

BV (Deg. ) (8) cu=O. 0 The possible mechanisms for increasing H, are given
d=O. 24 IJ m as follows.
0. 4
(1) Since Cu*+ has a small radius, Cu could enter lat-
tice sites and change Tcompand H, in Bi, Al: DyIG films.
(2) Cu enters lattice sites (24c, 16a, 24d); this will
-160 160 He M/m) produce additional anisotropy and coercivity.
-0. 4 (3) Cu enters lattice sites; this may change the thermal
+ expansion coefficient of the film or local tetragonal
0, (Deg.) (b) Cu=O.8 distortion (John-Teller effect), resulting in additional
d=O. 18 I m
---a. 3
anisotropy and coercivity.
(4) Cu may act as the pinning effect at the grain
1 / ,
boundaries; thus H, could be increased.
,
-1120 1120
Hc (A/m) 4. Conclusions
---0.3

Fig. 5. Typical Faraday hysteresis loops of films at room tempera- Cu-doped Bi, Al: DyIG films have been prepared on
ture. glass substrates by the pyrolysis method. The high H,
 Z. Yong et al. I Magnetic and Magneto-optical Properties of Cu-doped Bi, AI: DyIG films 199

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