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Magneto-optical properties and magnetic anisotropy of Nd_05Bi_25Fe_5-

yGa_yO_12 thin films on glass substrates

Article  in  Optical Materials Express · July 2017

DOI: 10.1364/OME.7.002248

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 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2248

Magneto-optical properties and magnetic

anisotropy of Nd0.5Bi 2.5Fe 5-yGa yO 12 thin films
on glass substrates
GENGJIAN LOU,1 TAKESHI KATO,2 SATOSHI IWATA,3 AND TAKAYUKI ISHIBASHI1,*
1
Department of Materials Science and Technology, Nagaoka University of Technology, Nagaoka,
Niigata 940-2188, Japan
2
Department of Electronics, Nagoya University, Nagoya 464-8603, Japan
3
Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8603, Japan
*t_bashi@mst.nagaokaut.ac.jp

Abstract: Thin films of the highly bismuth-substituted neodymium iron garnet Nd0.5Bi2.5Fe5-
yGayO12 (Bi2.5Ga:NIG) were prepared on Nd2BiFe4GaO12 (Bi1Ga1:NIG) buffer layers on
glass substrates. These thin films exhibited a large magneto-optical (MO) effect,
demonstrating that the magnetic anisotropy of this material can be varied by substituting
gallium for iron. As gallium content was increased from 0 to 1, the Bi2.5Ga:NIG thin films
showed Faraday rotation angles varying from 21.9 to 14.9°/μm, and effective magnetic
anisotropy energy values varying from −3.3 × 104 to 1.3 × 104 erg/cm3. The variation of the
effective magnetic anisotropy is discussed in terms of the shape anisotropy depending on the
saturation magnetization and the induced magnetic anisotropy caused by the different thermal
expansion coefficients for the thin films and the glass substrate. The significant decrease in
saturation magnetization upon gallium substitution is believed to result from 85% of the
gallium being preferentially substituted at tetrahedral sites in the garnet, which is consistent
with changes observed in the Faraday rotation spectra of the thin films.
© 2017 Optical Society of America
OCIS codes: (160.3820) Magneto-optical materials; (160.1190) Anisotropic optical materials; (310.6860) Thin
films, optical properties; (230.2240) Faraday effect.

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 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2249

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1. Introduction
Magneto-optical (MO) devices such as indicators [1–3], spatial light modulators for three
dimensional holographic displays [4, 5] and waveguide-type isolators [6, 7] have attracted
much attention. Bismuth-substituted rare-earth iron garnets having the general formula R3-
xBixFe5O12 show particular promise with regard to these applications, since they exhibit the
largest MO figure of merit in the visible light region [8–14]. This MO effect is enhanced by
increasing the extent to which bismuth is substituted for the rare-earth elements at
dodecahedral sites, as a result of the significant spin-orbit interaction between the 6p orbitals
of bismuth and the 2p orbitals of oxygen [15–19]. Various thin film preparation techniques
such as a pulsed laser deposition method [12, 13], a thermal decomposition method [20–23],
an ion beam sputtering [10, 11], a radio frequency (RF) magnetron sputtering [24], etc., were
studied to obtain highly bismuth-substituted iron garnet thin films, while liquid phase epitaxy
(LPE) method [8] was already established for single crystalline bismuth-substituted iron
garnet with bismuth content of 1. As a result, the fully bismuth-substituted iron garnet
Bi3Fe5O12 (BIG) exhibiting an extremely large Faraday rotation of 24 – 30°/μm at
approximately 520 nm were obtained [11, 25–31]. However, considering the significant light
absorption of BIG thin films and the difficulty in controlling the magnetic anisotropy of these
materials [26, 27], it is preferable to employ bismuth content of less than 3. Our own group
previously reported that Y0.5Bi2.5Fe5O12 (Bi2.5:YIG) thin films prepared on Gd3Ga5O12
(GGG) single crystal substrates by MOD method [31], has better crystallinity and a larger
MO figure of merit than BIG thin films. Moreover, we found that bismuth and gallium-
substituted neodymium iron garnets, Nd0.5Bi2.5Fe5-yGayO12 (Bi2.5Ga:NIG), prepared on GGG
substrates had a larger figure of merit than that for Bi2.5:YIG, and that the magnetic
anisotropy of these new materials could be readily controlled [32].
Moreover, we have developed a technique to grow polycrystalline highly bismuth-
substituted iron garnet thin films on glass substrate, in which they can be grown on a buffer
layer, bismuth-substituted iron garnet films with bismuth content of 1 [33–35]. We consider
that this technique could be applied not only for glass substrates, but also other materials such
as silicon, if bismuth-substituted iron garnet films with bismuth content 1 could be grown as
reported in Ref. 31. When considering MO applications that require low production costs and
 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2251

large dimensions, the use of glass substrates becomes important. However, precise control of
the magnetic anisotropy of Bi2.5Ga:NIG on glass substrates has not yet been studied.
In the present work, we investigated the magnetic anisotropy of Bi2.5Ga:NIG thin films
with increasing gallium content from 0 to 1 prepared on Bi1Ga1:NIG buffer layers on glass
substrates by MOD method. To control the magnetic anisotropy of these thin films, the
saturation magnetization was changed by varying the amount of gallium substituted for iron
ions. The magnetic anisotropy and MO properties of these Bi2.5Ga:NIG thin films are
discussed herein.
2. Experimental
Bi2.5Ga:NIG thin films and Bi1Ga1:NIG buffer layers were prepared using the MOD
method. The MOD solutions employed in this study were made with Nd, Bi, Fe and Ga
carboxylates, at a total carboxylate concentration of 4% by mass. MOD solutions having
Nd:Bi:Fe:Ga ratios of 2:1:4:1, 0.5:2.5:5:0 and 0.5:2.5:4:1 (Kojundo Chemical Laboratory Co.,
Ltd.) were used to produce the Bi1:NIGG buffer layer and the Bi2.5Ga:NIG layers. The
solutions were mixed to obtain the appropriate compositions for gallium contents of 0.25, 0.5
and 0.75.
The above MOD solutions were spin-coated onto glass substrates (Eagle XG, Corning
Inc.) at 3000 rpm for 60 s, followed by drying on a hot-plate at 100 °C for 10 min and pre-
annealing to decompose the organic materials at 450 °C for 10 min. These procedures were
repeated three times for each substrate to obtain a Bi1Ga1:NIG buffer layer thickness of
approximately 90 nm, after which each sample was annealed in a furnace at 700 °C for 3 h to
promote crystallization. The spin-coating, drying and pre-annealing processes were then
repeated five times for each buffer layer to obtain a Bi2.5Ga:NIG thin film with a thickness of
approximately 150 nm, after which the samples were annealed at 700 °C for 3 h. The layer
thicknesses of these specimens were measured by ellipsometry (MM-16, Horiba, Ltd.).
X-ray diffraction (XRD) measurements, comprising out-of-plane 2θ/ω scans and in-plane
2 θχ/φ scans, were carried out using a high-resolution XRD instrument (SmartLab, Rigaku
Co., Ltd.) with Cu-Kα radiation. Faraday spectra and Faraday hysteresis curves were acquired
with an MO spectrometer (BH-M800, Neoark Co., Ltd.). Magnetization curves in the out-of-
plane and in-plane directions were acquired using a vibrating sample magnetometer (VSM-5-
19, Toei Industry Co., Ltd.) and magnetic anisotropy energies were measured at 2 kOe with a
torque magnetometer (TRT-2, Toei Kogyo Co., Ltd.). Transmission spectra were measured
with a spectrometer (V-570, JASCO Co., Ltd.). The surface of the thin films was observed
with a field emission scanning electron microscopy (FE-SEM) (SU8230, Hitachi High-Tech.
Co., Ltd.) and the compositions of the thin films were analyzed using an energy dispersive X-
ray spectrometer (EDX) (X-Max SDD, Oxford instruments Co., Ltd.).
3. Results and discussion
Figure 1 and 2 show the XRD patterns obtained from Bi2.5Ga:NIG thin films with increasing
gallium content from 0 to 1 in the out-of-plane and in-plane directions, respectively. For each
sample, the diffraction pattern indicates a polycrystalline garnet structure. The in-plane data
also demonstrate the presence of an unidentified secondary phase for samples with gallium
content of 0.25 and 0.5, as indicated by the asterisks in Fig. 2, while no additional phases are
evident in the out-of-plane XRD patterns. This result indicates that small amounts of a
secondary phase segregated on the surface can be detected via the in-plane measurements,
which are more sensitive to the surface structure.
 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2252

Fig. 1. Out-of-plane XRD patterns for Bi2.5Ga:NIG thin films.

Fig. 2. In-plane XRD patterns for Bi2.5Ga:NIG thin films.

The in-plane and out-of-plane lattice parameters of Bi2.5Ga:NIG thin films with
increasing gallium content from 0 to 1 were determined using the Nelson-Riley function [36]
and are plotted against the gallium content in Fig. 3. The calculated equivalent lattice
parameter a, assuming a cubic unit cell is also plotted. It can be seen that all the lattice
parameters decreased slightly with increasing gallium content, and that the in-plane parameter
was always larger than the out-of-plane parameter. This dependence on the gallium content
suggests that gallium ions, having a smaller ionic radius (62 pm) [37], substituted for iron
ions (67 pm) in the lattice [38]. In addition, for gallium content of 0, the a value of 1.261 nm
is consistent with the value of 1.262 nm calculated from Vegard’s law using literature data for
BIG [12] and Nd3Fe5O12 (NIG) [39].
The lattice distortion, (aip - a)/a, was determined to be 0.071, 0.069, 0.058, 0.058 and
0.048% for gallium contents of 0, 0.25, 0.5, 0.75 and 1.0, respectively, as shown in Fig. 4.
Here, aip is the in-plane lattice parameter. We attribute this distortion to the different thermal
expansion coefficients for Bi2.5Ga:NIG and the glass substrate. Although the thermal
expansion coefficient for Bi2.5Ga:NIG is not known, it is likely similar to that reported for
BIG thin films (12.9 × 10−6 K−1) [40]. Comparing this value to that for the glass substrate,
3.17 × 10−6 K−1, we would expect that the thin films would experience tensile stress as the
temperature decreased from the annealing temperature of 700 °C to ambient.
 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2253

Fig. 3. Relationship between lattice parameters and gallium content.

Fig. 4. Relationship between lattice distortion and gallium content.

The Faraday rotation spectra of Bi2.5Ga:NIG thin films with increasing gallium content
from 0 to 1 are shown in Fig. 5. All spectra exhibit characteristics of a garnet structure,
having a peak around 520 nm [30–35, 41, 42]. As gallium content increases from 0 to 1, the
Faraday rotation angle decreases and the peak becomes less sharp. This change is caused by
the imbalance in contributions from the tetrahedral and octahedral sites in the garnet, as
discussed in detail below.
Faraday hysteresis loops for Bi2.5Ga:NIG thin films with increasing gallium content from
0 to 1 obtained at the wavelengths corresponding to the maximum Faraday rotation around
520 nm are shown in Fig. 6. As the gallium content increases from 0 to 1, the hysteresis loops
are seen to become more square while the rotation angle slightly decreases.
 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2254

Fig. 5. Faraday spectra forBi2.5Ga:NIG thin films.

Fig. 6. Faraday hysteresis loops for Bi2.5Ga:NIG thin films acquired at 520 nm.

The MO figures of merit of Bi2.5Ga:NIG thin films with gallium contents of 0, 0.5 and 1
are shown in Fig. 7. We used MO figure of merit defined with an equation Q = 2|θF|/α =
2|θF|t/ln(1/T) [28, 43, 44], where θF (deg/μm) is the measured Faraday rotation angle, α =
t/ln(1/T) is the absorption coefficient, t is the thickness of thin films, and T is the
transmittance. In Fig. 7, the maximum value of MO figure of merit was larger than 8.5 for the
gallium content of 0. This value was higher than those reported for Y0.5Bi2.5Fe5O12
(Bi2.5:YIG) thin films [30], Bi2.5Ga:NIG thin films on GGG [32] and BIG films [28], and
was the highest values for a single layer, as far as we know.
Figure 8 shows SEM images for Bi2.5Ga:NIG thin films with gallium contents of 0, 0.5
and 1. In the images, no cracks were observed, although precipitates of impurity phases with
 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2255

diameters of approximately 0.1 μm found, while severe cracks were observed on the surface
of BIG films prepared reported in Ref. 29.

Fig. 7. MO figures of merit for Bi2.5Ga:NIG thin films.

Fig. 8. SEM images for Bi2.5Ga:NIG thin films with gallium content of (a) 0, (b) 0.5 and (c) 1.

The composition ratios for Bi2.5Ga:NIG thin films measured by EDX are summarized in
Table 1. We should note that these values included signals from both Bi2.5Ga:NIG layers and
Bi1Ga1:NIG buffer layers, since the EDX measurement detected X-ray signals from the
depth of larger than 1 μm. Figure 9 shows measured gallium content for iron plotted as a
function of the nominal compositions in the MOD solutions, where averaged nominal
compositions of Bi2.5Ga:NIG layers and Bi1Ga1:NIG buffer layers were shown as a green
solid line. We consider that measured gallium contents agree with those in MOD solutions,
and the difference could be within the error.
Table 1. The composition ratios for Bi2.5Ga:NIG thin films
Ga content in MOD solutions Nd Bi Fe Ga
0 1 1.55 4.15 0.25
0.25 1 2.18 5 0.5
0.5 1 2.5 5.36 0.64
0.75 1 1.64 3.8 0.84
1 1 1.63 3.74 1.05
 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2256

Fig. 9. Gallium content for iron of Bi2.5Ga:NIG thin films.

The magnetization curves obtained from Bi2.5Ga:NIG thin films with increasing gallium
content from 0 to 1 are presented in Fig. 10. The red and blue lines represent hysteresis loops
acquired in the out-of-plane and in-plane directions, respectively. These data show that the
saturation magnetization, Ms, for the samples decrease from 137.2 to 46.3 emu/cm3 as the
gallium content is increased. In addition, the shapes of the hysteresis loops acquired in the
out-of-plane direction match those of the out-of-plane Faraday hysteresis loops shown in Fig.
6.
The saturation magnetization and maximum Faraday rotation angle in the vicinity of 520
nm are plotted as functions of the gallium content in Fig. 11. The saturation magnetization
decreases by 67% as gallium content increases from 0 to 1, while the Faraday rotation angle
decreases by 35%. We believe that this can be attributed to an imbalance in the site
occupation of gallium ions. The saturation magnetization for Bi2.5Ga:NIG results from the
magnetic moments of neodymium ions as well as iron ions in tetrahedral and octahedral sites.
If the gallium ions preferentially substitute for iron ions at tetrahedral sites, the saturation
magnetization for the Bi2.5Ga:NIG would rapidly decrease, since the direction of the
magnetic moments at the tetrahedral sites is opposite that at the octahedral sites.
The magnetic moment of Bi2.5Ga:NIG with gallium content of 0 (Bi2.5:NIG) at room
temperature, nB (Bi2.5:NIG), was estimated using the equation

nB ( Bi2.5 : NIG ) = 1/ 6nB ( Nd 3+ ) + nB ( Fe3+ ) . (1)

Based on the magnetic moments of NIG and Y3Fe5O12 (YIG) (i.e., nB (NIG) and nB
(YIG)) [45–47], we used [nB (NIG) − nB (YIG)] and nB (YIG) to find nB (Nd3+) and nB (Fe3+),
respectively. Consequently, we determined a magnetic moment for Bi2.5:NIG at room
temperature of 3.79 μB, which is consistent with the experimental value of 3.71 μB ( = 137.2
emu/cm3) in Fig. 10. To express the degree of imbalance in gallium substitution, we can write
the chemical formula for Bi2.5Ga:NIG as {Nd3-xBix}[Fe2-zaGaza] × (Fe3-zdGazd)O12. Here { }, [
] and () indicate dodecahedral, octahedral and tetrahedral sites, respectively, and za and zd are
the occupancy ratios of gallium ions substituting for iron ions at octahedral and tetrahedral
sites, respectively.
In the case of Bi2.5Ga:NIG, the magnetic moment of the iron ions should be nB (Fe3+) ×
[(3 − zd) − (2 − za)]. Considering that for Bi2.5Ga:NIG at gallium content of 1 (or za + zd = 1),
the decrease in the saturation magnetization was 67%, zd was determined to be 85%. This
result agrees with the value of approximately 90% reported for liquid phase epitaxial-grown
garnet thin films [48–50].
 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2257

Fig. 10. Magnetization curves for Bi2.5Ga:NIG thin films.

The variations in the Faraday rotation spectral shapes that are evident in Fig. 5 also agree
with an imbalance in gallium substitution. The spectral shape in the vicinity of 520 nm
originates from optical transitions from O 2p to Fe 3d orbitals in the tetrahedral and
octahedral sites, with the deconvoluted tetrahedral spectra being narrower than the octahedral
spectra. The results shown in Fig. 5 demonstrate a broadening of the spectra as gallium
 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2258

content is increased, which is consistent with a diminishing contribution of tetrahedral sites to

the Faraday rotation.

Fig. 11. Saturation magnetization and Faraday rotation angle as functions of gallium content.

Finally, we consider the magnetic anisotropy of the Bi2.5Ga:NIG thin films. The torque
curves obtained from thin films of Bi2.5Ga:NIG with increasing gallium content from 0 to 1
at an applied magnetic field of 2 kOe are presented in Fig. 12. All samples exhibit two-fold
symmetry in these plots, indicating uniaxial magnetic anisotropy, although it should be noted
that small background signals indicating four-fold symmetry could not be subtracted
completely. The effective magnetic anisotropy constants, Keff, and the uniaxial magnetic
anisotropy constants, Ku, are both plotted as functions of gallium content in Fig. 13. Here Ku
was calculated as Ku = Keff + 2πMs2. It is apparent that Keff changed from negative to positive
as the gallium content increased, in good agreement with the change in the hysteresis curve
shapes in Fig. 10. In contrast, the Ku value for each specimen is positive and decreases from
8.5 × 104 to 2.6 × 104 erg/cm3 as gallium content increases from 0 to 1. The positive Ku values
are believed to result from the tensile stress discussed above, and the decrease is attributed to
a reduced magneto-strictive effect as the gallium content is increased [51].

Fig. 12. Torque curves for Bi2.5Ga:NIG thin films.

 Vol. 7, No. 7 | 1 Jul 2017 | OPTICAL MATERIALS EXPRESS 2259

Fig. 13. Relationship between anisotropy energy and gallium content.

4. Conclusions
Bi2.5Ga:NIG thin films with increasing gallium content from 0 to 1 prepared on Bi1Ga1:NIG
buffer layers on glass substrates by the MOD method exhibited large Faraday rotation angles
of 21.9 – 14.9°/μm. The uniaxial magnetization anisotropy constant for all samples was
positive, which was attributed to the induced magnetic anisotropy resulting from lattice
distortion. In addition, the effective magnetic anisotropy constant changed from −3.3 × 104 to
1.3 × 104 erg/cm3 as gallium content increased from 0 to 1. The observed variations in the
saturation magnetization and the Faraday rotation angle were explained by assuming that 85%
of the gallium was preferentially substituted at tetrahedral sites in the garnet. This theory is
consistent with changes in the Faraday rotation spectra shape with gallium content.
Funding
Nanotechnology Platform Program (Molecule and Material Synthesis) of the Ministry of
Education, Culture, Sports, Science and Technology (MEXT), Japan; Nagoya University.

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