IEEE TRANSACTIONS ON MAGNETICS, VOL. 36, NO.
5, SEPTEMBER 2000
Effect of Light on the Magnetic Properties of Cobalt
Ferrite Nanoparticles
Anit K. Giri, Kelly Pellerin, Wanida Pongsaksawad, Monica Sorescu, and Sara A. Majetich
Abstract—We report variations in the coercivity of CoFe2 O4
nanoparticles as a function of particle size, temperature and light
intensity. For 30 nm particles, this change in was 2300 Oe at 10K,
120 Oe at 170K, for a light intensity of under 2 milliwatts. The
remanent magnetization was nearly unchanged by illumination. A
simple model of optical absorption followed by electron transfer
between Co2+ and Fe3+ ions is proposed.
Index Terms—Cobalt ferrite, coercivity, photomagnetic effect,
remanent magnetization.
I. INTRODUCTION
T HE PHOTOMAGNETIC effect is a change in the
magnetic properties when a material is illuminated.
Photomagnetic materials include Y Fe O with various
dopants, Ga-doped CdCr Se , Co-doped Ni–Zn ferrite, Li and
Mg–ferrites, Ru-doped Li–ferrite, FeBO [1], and the molec-
ular magnet K Co [Fe(CN) ].6.9H O [2]. The magnetic
ions can assume different valence states so that optical absorp-
tion leads to electronic transfer. For example, light induced
increases in the coercivity of K Co [Fe(CN) ].6.9H O
have been attributed to electron transfer between the Fe and
Co ions following light absorption [2]. Sensing and optical
recording require a photomagnetic effect at room temperature.
To better understand the mechanism, we have investigated the
effect of light on the coercivity and magnetization cobalt ferrite
nanoparticles between 10 and 300K. To stabilize the optically
induced effect at higher temperature, CoFe O ( 520 C
[3]) was selected. Since Co has a greater single ion anisotropy
[4], [5] than other transition metals, charge transfer involving
this ion should cause the largest changes in coercivity. More-
over, cobalt ferrite nanoparticles have a large surface anisotropy
[6].
Manuscript received February 14, 2000. This work was supported in part by
the NSF under Grant CTS-9800127 and ACS Petroleum Research Fund Grant
33866-AC5. The work of W. Pongsaksawad was supported by the Carnegie
Mellon Data Storage Systems Center REU program, funded by NSF Grant
ECD-8907068. The work of M. Sorescu was supported in part by the National
Science Foundation under Grant DMR-990550, and by the Air Force Office of
Scientific Research under Grant F49620-96-1-0454.
A. K. Giri and S. A. Majetich are with the Physics Department, Carnegie
Mellon University, Pittsburgh, PA 15213-3890 USA (e-mail: {giri; sm70}@an-
drew.cmu.edu).
K. Pellerin was with the Physics Department, Carnegie Mellon University,
Pittsburgh, PA 15213-3890 USA. She is now with NEC, Princeton, NJ USA.
W. Pongsaksawad was a REU student with the Carnegie Mellon Data Storage
Systems Center.
M. Sorescu is with the Physics Department, Duquesne University, Pittsburgh,
PA 15282 USA (e-mail: sorescu@duq.edu).
Publisher Item Identifier S 0018-9464(00)10999-9.
0018–9464/00$10.00 © 2000 IEEE
3029
II. EXPERIMENTAL
Standard co-precipitation techniques [7] were used to pre-
pare cobalt ferrite nanoparticles. Aqueous solutions of iron and
cobalt chlorides in a 2 : 1 molar ratio were made and mixed
with an aqueous sodium hydroxide solution, and then heated
for 90 minutes at 100 C. We prepared samples with different
particle sizes by changing the molar ratio of metals to hydroxyl
ions. The resulting powder was then annealed at 250 C for
24 h. Transmission Electron Microscopy (TEM) was used to
determine the average particle size. The phase was verified
using X-ray diffraction. A Mössbauer Spectrometer with a
Co source was used to determine the site occupancies of the
iron ions, and the superparamagnetic fraction.
Dilute samples were prepared by dispersing 0.1 wt.% of
cobalt ferrite nanoparticles in an optical epoxy, so that the
samples could be uniformly illuminated inside the SQUID by
an optical fiber. The cross sectional area of the sample was
0.23 cm , and the length was 1.5 cm.
The magnetic properties were measured using a SQUID
magnetometer between 10 and 300K, with a maximum field of
50 kOe. Broad band visible light from a tungsten halogen lamp
was collimated and focused into the optical fiber. The unifor-
mity of illumination and the power incident on the sample were
calibrated outside. The magnetization at a given temperature
was stabilized prior to data collection. The light intensity
was varied to saturate the change in coercivity. Temperature
dependent measurements used an incident light intensity of
1.95 mW, sufficient for saturation.
III. RESULTS
X-ray diffraction indicated a single phase of cobalt ferrite.
From TEM the average particle sizes of the two samples were
17 4 nm and 30 5 nm. Cobalt ferrite has an inverse spinel
structure which at equilibrium has half of the Fe ions on tetra-
hedral (A) sites and half on octahedral (B) sites. The Co ions
are also on B sites. Mössbauer spectroscopy revealed that for
both samples 49.2% of the Fe atoms exist as Fe ions at A
sites, 33.3% are Fe ions at B-sites, and 7.9% are Fe ions at
B sites. Fits to the Mössbauer spectra also indicated that 9.6%
of total iron particles were superparamagnetic at room temper-
ature for both samples.
Fig. 1 shows the remanent magnetization, , as a function
of light intensity. is almost independent of the intensity up
to the highest value studied, but the coercivity decreased and
then leveled off at approximately 2 mW (Fig. 1). Fig. 2 shows
3030 IEEE TRANSACTIONS ON MAGNETICS, VOL. 36, NO. 5, SEPTEMBER 2000

Fig. 1. Remanent magnetiation and coercivity as a function of incident light

intensity at 80K.
Fig. 3. Coercivity as a function of temperature with and without illumination.
The incident light intensity was 1.95 mW.

Fig. 2. Remanent magnetization as a function of temperature, with and without

Fig. 4. The change in coercivity, 1H between I = 0 mW and I = 1.95 mW,
as a function of temperature.
1.95 mW illumination from a tungsten–halogen lamp. Measurements were made
after saturating the samples in 50 kOe field.
even at room temperature. drops off to roughly the same
the remanent magnetization as a function of temperature. value at 170K for both samples. If this is a blocking temperature
depends strongly on temperature but is unchanged by op- for the smaller particles in each sample, the particle size can be
tical illumination. The smaller remanence for the 17 nm sample estimated from the relation ) where is
is attributed to larger surface area and hence greater surface spin the magnetocrystalline anisotropy, is the particle volume,
canting [6]. is the Boltzmann constant, is the blocking temperature, is
If the change in remanence upon illumination is entirely the typical measurement time and is the thermal attempt
due to heating, then frequency, here taken to be the Larmor frequency (10 Hz).
Using ergs/cc at the room temperature [3],
(1) 10 s and 170K, the average diameter is calculated to be
roughly 9 nm. This is consistent with a bimodal size distribution
For consistency the change in coercivity should be given by a
with the small size peak at 9 nm for both samples, and agrees
related formula,
with the Mössbauer results. However, the remanent magnetiza-
(2) tions show no kink at this temperature and we cannot prove this
is the reason for the change in . If cobalt ferrite has
with the same value of . For our data at 80K and a a metal-insulator transition analogous to Verwey transition in
light intensity of 1.95 mW, 0.12% and 0.6K. How- magnetite, with rapid charge exchange above 170K and local-
ever from Fig. 3, (80.6K, 0 mW) 10 400 Oe, while ized charges below, then the sample could relax to its original
(80K, 1.95 mW) 9265 Oe, so the effect cannot be explained state within the measurement time and should drop off.
by heating. Similar inconsistencies are found at different tem- The microscopic mechanism responsible for optically
peratures and light intensities for both samples. induced changes in is interpreted in terms of published
Fig. 4 shows that the coercivity decreases with temperature spectroscopic data for bulk CoFe O and Co Fe O thin
whether or not the sample is illuminated. The change in coer- films. In cobalt ferrite the magnetic moments of tetrahedral
civity with and without 1.95 mW illumination, , drops off (A) and octahedral (B) site ions are antiparallel. From the data
nearly linearly up to 170K, and then decreases more slowly up of polar Kerr rotation angle as a function of photon energy
to room temperature. In comparison, the largest for other and Mössbauer spectroscopy [8], [9], two peaks with energies
ferrite systems was approximately 5 Oe at 77K, and for yttrium of approximately 2 eV were assigned. One was a crystal
iron silicate was 21 Oe at 66K [1]. A small change, field transition of Co ( A T (P)) at the tetrahedral
15 2 Oe, persisted to room temperature for both samples. By site. Overlapping it was a broad peak associated with charge
similar arguments, heating was ruled out as a cause of this effect transfer between Co and Fe ions, both at octahedral (B)
GIRI et al.: EFFECT OF LIGHT ON THE MAGNETIC PROPERTIES OF COBALT FERRITE NANOPARTICLES
sites. With tetrahedral site symmetry Co absorbs strongly,
but the same transition is much weaker for crystals where it
has octahedral site symmetry. It is strictly forbidden with a
center of inversion, but disorder in the second nearest neighbor
arrangement reduces the symmetry [10], since B sites may be
occupied by either Fe or Co . Higher energy transitions at
roughly 3–3.5 eV were assigned to crystal field absorption of
Fe [9] and there is another crystal field transition of Co at
0.86 eV [8]. Because the energy difference between Co and
Co and between Fe and Fe is approximately the same
[11], electron transfer between these ions is highly efficient
[12]. In CoFe O this energy difference is also nearly resonant
with the Co absorption energy, so that absorption at this site
leads to electron transfer [13]. Electron transfer between the
B and A sites is presumed to be much less efficient because it
requires a spin flip.
A simple model is proposed to explain the experimental re-
sults. After illumination, the photon is absorbed by Co at the
B site and an electron is then transferred to a nearby Fe ion,
leaving Co and Fe . The magnetic moment of CoFe O per
formula unit is the sum of moment on Fe (A) and the an-
tiparallel moments on Co (B) and Fe (B). Here the total
moment in dark , 394–397, 1996.
and immediately following optically induced charge transfer,
and overall magnetic
moment is unchanged. This agrees with the experimental results
and with previous work showing that charge transfer occurs be-
tween B site ions [13]. In the dark, the coercivity is dominated
by the Co ions. Following the charge transfer the coercivity
decreases due to lower single ion anisotropy of Co and Fe
ions.
IV. CONCLUSION
Light induced changes in the coercivity of cobalt ferrite
nanoparticles have been observed in samples with different
average particle sizes. Though other ferrites have been
studied previously, to our knowledge this is the first report of
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photomagnetism in CoFe O . Sample heating following light
absorption cannot explain the results. A significant decrease in
coercivity under illumination is observed up to 170K, above
which diminishes, though a small effect persists to room
temperature. The temperature 170K may be associated with a
ferromagnetic–superparamagnetic phase transition or it may
be related to a metal-insulator transition. Further experiments
are needed to determine which mechanism dominates, and
therefore to focus attempts to find materials with a usable
( Oe) photomagnetic effect at room temperature.
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