Investigation of orbital magnetization in inverse spinel cobalt ferrite using

magnetic Compton scattering

H. S. Mund, Shailja Tiwari, Jagrati Sahariya, M. Itou, Y. Sakurai et al.

Citation: J. Appl. Phys. 110, 073914 (2011); doi: 10.1063/1.3650251

View online: http://dx.doi.org/10.1063/1.3650251
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Published by the American Institute of Physics.

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 JOURNAL OF APPLIED PHYSICS 110, 073914 (2011)

Investigation of orbital magnetization in inverse spinel cobalt ferrite

using magnetic Compton scattering
H. S. Mund,1 Shailja Tiwari,1 Jagrati Sahariya,1 M. Itou,2 Y. Sakurai,2 and B. L. Ahuja1,a)
1
Department of Physics, University College of Science, M. L. Sukhadia University, Udaipur 313001, India
2
Experimental Research Division, Japan Synchrotron Radiation Research Institute, Spring-8, Mikazuki,
Hyogo 679-5198, Japan
(Received 15 June 2011; accepted 27 August 2011; published online 13 October 2011)
We present the spin momentum densities of CoFe2O4 measured at 8 and 300 K using magnetic
Compton scattering. The magnetic Compton profiles were decomposed into component profiles of
constituents namely Fe and Co, to determine their role in the formation of total spin moment. It is
seen that the major contribution (about 80%) in the spin moment is from Co, whereas the itinerant
electrons show a small reverse polarization. Moreover, it is clearly visualized that the spin moment
at Co reduces from 2.55 ! 2.35 lB/f.u. while going from 8 ! 300 K. The magnetic Compton
profiles, when compared with the magnetization data, show about 17% contribution of orbital
moment to the total magnetic moment at both temperatures. The origin of the orbital moment is
explained on the basis of rotation of hole on t2g orbital of Coþ2 ion. VC 2011 American Institute of

Physics. [doi:10.1063/1.3650251]

I. INTRODUCTION tion (GGA). Dielectric and magnetic properties of ZnO

doped cobalt ferrites have been measured by Zhou et al.13
Ferrites have a wide range of applications because of
Recently, Hou et al.14 have presented structural, electronic,
their magnetic and electrical properties. Particularly, cobalt
and magnetic properties of CoFe2O4 using GGA approach.
ferrites are important materials in the microwave industry
The authors show that the magnetic moment of CoFe2O4
because of their low cost and remarkable electrical and mag-
decreases while changing the structure from normal to
netic properties. The inverse spinel cobalt ferrites
 (CFO) are inverse spinel.
represented by the formula ðFeþ3 Þp Coþ2 Feþ3 q O2 4 , where It is known that magnetic Compton scattering (MCS) is
p and q correspond to tetrahedral and octahedral sites as a powerful probe to study the spin momentum densities. The
shown in Fig. 1. The unit cell of CFO contains eight formula MCS, which is sensitive to unpaired (magnetic) electrons,
units and cubic symmetry with space group Fd3m. Regard- requires circularly polarized photons to enable interference
ing earlier studies on cobalt ferrite systems, electronic band between charge and magnetic scattering terms.15 The spin-
structures, magnetic high field and neutron diffraction meas- dependent component, the so-called magnetic Compton pro-
urements, magneto-optical transitions, micro-Raman scatter- file (MCP), is deduced from the difference between two
ing, and magneto-crystalline anisotropy have been studied spectra measured with a magnetic field parallel or anti-
by different workers.1–5 Structural and morphological prop- parallel to the scattering vector. The MCP, Jmag (pz), which
erties of FeCo2O4 and CoFe2O4 have been investigated by is the one-dimensional projection of spin-polarized electron
Ferreira et al.6 Antonov et al.7 have studied the electronic momentum density along the scattering vector, is given by
structure and the x-ray magnetic circular dichroism in Ni-
substituted Fe3O4 using ab initio fully relativistic spin- J mag ðpz Þ ¼ J " ðpz Þ  J # ðpz Þ
ðð
polarized linear muffin-tin orbital (LMTO) method. The  " 
authors have also calculated orbital and spin magnetic ¼ n ðpÞn# ðpÞ dpx dpy ; (1)
moments of the compound. X-ray resonant scattering in few
ferrites including CoFe2O4 has been measured by Subias where pz is component of linear momentum of electron
et al.8 Szotek et al.9 have studied the electronic and magnetic along scattering vector and it is a function of energy of scat-
properties of normal and inverse spinel ferrites using self- tered x-rays. The n:(p) and n;(p) are electron momentum
interaction-corrected local spin density approximation densities of the majority and minority spins, respectively.
(LSDA). Bhame and Joy10 have investigated magnetic and Therefore, the area under Jmag(pz) is equal to a spin mag-
magnetostrictive properties of Mn substituted cobalt ferrite. netic moment per formula unit (f.u.). The purpose of pres-
Using x-ray photoelectron spectroscopy, Zhou et al.11 have ent study is manyfold, namely: (i) to measure spin
studied the electronic structure of CoFe2O4. Fritsch and momentum densities at the lowest possible (8 K) and room
Ederer12 have calculated the effect of epitaxial strain on the temperatures, (ii) to examine contribution of different con-
structural and magneto-structural properties of CoFe2O4 and stituents namely Co and Fe in the formation of total spin
NiFe2O4 using LSDA and generalized gradient approxima- moment, (iii) to delineate the contribution of itinerant elec-
trons in the system, and (iv) to compare MCS data with
a)
Author to whom correspondence should be addressed. Electronic mail: magnetization data to find the quantitative contribution of
[email protected]. orbital moment. We have also measured the magnetic effect

0021-8979/2011/110(7)/073914/4/$30.00 110, 073914-1 C 2011 American Institute of Physics

V

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073914-2 Mund et al. J. Appl. Phys. 110, 073914 (2011)

were corrected for the beam instability, detector efficiency,

absorption and cross-section corrections, etc. It may be noted
that in such experiments, the multiple scattering correction is
neglected because of its very small contribution in the spin-
dependent scattering.17,18 To determine the total spin
moment using MCS, measurement on the Fe calibrator was
carried out at room temperature. The total magnetic moment
of the sample was determined using the relation
 
ACFO RCFO
lCFO ¼ lFe : (2)
AFe RFe

Here ACFO ( ¼ 105.38 e-) and AFe ( ¼ 24.32 e) are the num-
ber of electrons, which participate in Compton scattering
phenomena between the momentum range 10 to þ 10 a.u.
in the CFO and Fe, respectively. The RCFO and RFe are the
ratio of magnetic to charge signal for CoFe2O4 and Fe,
respectively, as defined earlier. Magnetic properties were
measured using vibrating sample magnetometer (VSM) in
the temperature range 8 to 300 K at 2.5 T.
FIG. 1. (Color online) Inverse spinel structure showing the location of con-
stituents, namely, Fe3þ and Co2þ/Fe3þ at tetrahedral (p) and octahedral (q)
sites. III. RESULTS AND DISCUSSION
The MCPs of CFO at 8 and 300 K under 2.5 T magnetic
R (which is equal to ratio of I "  I# and I" þ I # , where I" field are shown in Fig. 2. The areas of MCPs have been nor-
and I# are the integrated Compton intensities for the major- malized to the value of spin moments calculated using
ity and minority spins) at the temperatures 100 and 200 K, Eq. (2). MCPs were decomposed into individual components
to check the trend of magnetic properties at the intermedi- corresponding to Co, Fe, and diffuse (itinerant electrons)
ate temperatures. parts to find their actual contribution in total spin moment.
Because the Compton profiles of 3d electrons of Fe and Co
II. EXPERIMENT in free atom environment have almost identical shapes at the
present experimental resolution (0.4 a.u.), we have used the
A polycrystalline sample of CoFe2O4 was prepared by theoretical MCP of Co reported by Matsumoto et al.19 using
solid-state reaction method using appropriate amounts of augmented plane wave method. To account for the contribu-
high purity oxides, namely, CoO (99.99%) and Fe2O3 tion of Fe 3d electrons, the free atom Compton profile from
(99.98%). The mixture was calcined at 900  C for 24 h. The the table of Biggs et al.20 was used. From Fig. 2, it is clear
calcined powder was thoroughly ground in an agate mortar that the central dip (volcanic structure) cannot be explained
and palletized under the high pressure. The pellet was sin-
tered at 1100  C for 5 h. Both the calcination and sintering
were performed at ambient atmosphere. The metallic compo-
sition and homogeneity were confirmed using extended
energy dispersive analysis of x-rays (EDAX). The crystal
structure was confirmed by powder x-ray diffraction using a
Cu–Ka line.
The MCS measurements were carried out on the poly-
crystalline sample using circularly polarized x-rays at the
High Energy Inelastic Scattering Beam Line (BL08 W),
SPring-8, Hyogo, Japan.16,17 The energy of incident circularly
polarized x-rays, emitted from an elliptical multipole wiggler,
was kept as 182.65 keV. To avoid magnetic contamination,
the sample was sandwiched in a high purity Cu holder. The
size of x-ray beam at the sample position was 0.6 mm
(width)  0.5 mm (height). The scattering angle was set to
178 , whereas the scattered x-rays were detected by a multi-
segmented (ten) Ge solid-state detector (Canberra, USA). The
resolution (Gaussian full width at half maximum) of the spec-
trometer was 0.40 a.u. (1 a.u. ¼ 1.993  1024 kg m/s).
FIG. 2. (Color online) Experimental magnetic Compton profile (MCP) of
The magnetization of the sample was reversed with a CoFe2O4 at 8 and 300 K and fixed 2.5 T. Also shown here is the fitted (solid
3-T superconducting magnet. The sequence of sample mag- line) profile along with the contributions of the constituent profiles. Experi-
netization is mentioned in our earlier work.17 The MCP data mental error in the MCP of CFO is within the size of the symbol used.

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073914-3 Mund et al. J. Appl. Phys. 110, 073914 (2011)

presents the temperature-dependent total spin moment along

with the individual atom specific contributions. Table I
shows that the total spin moment at 8 K obtained from the
MCP data (3.10 6 0.03 lB/f.u.) is in good agreement with
local-spin-density functional calculations (3.00 lB/f.u.).1
The spin moment at Co atom (2.55 lB/f.u.) derived from
MCP agrees well with the result (2.53 6 0.03 lB/f.u.) of Pen-
icaud et al.1 It is interesting to note that the spin moment for
Coþ2 ion is close to Hund’s value of 3 lB, which can be
derived from its 3d7 states (S ¼ 3/2). Figure 3 shows the
magnetic moments of CFO calculated from present VSM
(spin þ orbital) and MCP (spin) measurements. Both the
VSM and MCP data show a slight enhancement in magnetic
moment near the temperature 200 K; thereafter, if one moves
toward room temperature, the magnetic moment decreases
and becomes slightly smaller than that at 8 K. It is observed
that while going from 8 K to 300 K, the spin moment from
FIG. 3. (Color online) Temperature-dependent magnetization (M–T) for the Co atom decreases from 2.55 to 2.35 lB/f.u., which is in con-
Co-ferrite measured at a field of 2.5 T along with spin moments at few data
points deduced from MCS. The lines through MCP data points are drawn to
trast to Fe atoms. Surprisingly, the role of itinerant electrons
guide the eyes only. In the inset, variation in total magnetization (M–H data that contribute negatively in the formation of total spin
from VSM) and also the spin moment (MCP data) with external magnetic moment almost remains the same.
field (at 8 K) are depicted. It is noteworthy that in the inset, the total spin To separate the orbital moment, we have combined
moment in MCP data is calculated using the flipping ratio (R) with low statis-
tics (one cycle consisting of four times reversal of field). The errors in MCP
M–T (spin þ orbital) and MCP data. The total moment
data at 8 and 300 K (12–15 cycles) are within the size of the symbols used. observed from M–T measurement is higher than the MCP-
based spin moment. Figure 3 shows that the deviations
only on the basis of the Compton profiles of Co and Fe, between the M–T data and the limited MCP data at different
although magnetic Compton profile of Co at few pz values temperatures remain almost the same, which rules out the
shows a similar structure as those from the MCP profile of possibility of major change in the orbital moment at 2.5 T.
CFO. This volcanic shape in MCP may be because of the At 8 (300) K temperature, M–T measurement shows total
delocalized (itinerant) electrons of Fe and O, which may be moment of 3.72 (3.58) lB/f.u., whereas the spin moment
polarized negatively with respect to total spin moment. Our from MCP is 3.10 (2.97) 6 0.03 lB/f.u. Therefore, in CFO,
earlier experience in the field of MCS tells us that the shape the orbital contribution in total moment is found to be about
of diffuse electrons can be well characterized by a Gaussian 0.60 6 0.03 lB/f.u. From our MCP data, the ratio of orbital
profile corresponding to itinerant electrons.21,22 In the pres- moment to total spin moment comes out to be 0.20, which is
ent case, the FWHM of Compton profile for diffuse electrons in good agreement with the spin-orbit-based LSDA calcula-
is taken to be 1.6 a.u., which corresponds to the FWHM of tions (0.19) reported by Szotek et al.9 The orbital magnetic
free electrons Compton profile responsible for diffuse moment in CFO can be explained on the basis of subtle inter-
components (remaining Fe 4s and O 2sp electrons). All the play between spin-orbit coupling and crystal-field interac-
individual Compton profiles were convoluted with the exper- tion. The octahedral crystal field lifts the fivefold degeneracy
imental resolution (0.4 a.u.) to incorporate the experimental of d electrons present in Coþ2 ions by splitting the energy
smearing. From Fig. 3, it is seen that Co has the largest levels and forming low lying triply degenerate t2g (dxy, dxz,
contribution in the formation of total spin moment. A small and dyz) states and a higher doublet of eg (dx2 y2 and dz2 )
contribution of Fe, in the total spin moment, is because of states. For the Coþ2 ions, the ground state of the 3d7 configu-
anti-parallel alignment of Feþ3 at p and q sites. Diffuse con- ration (eg2 t2g5) in octahedral symmetry has a hole state on
tribution is found to be anti-ferromagnetically coupled to the t2g orbital. The hole on t2g orbital rotates about an axis,
spin moments resulting from the Co and Fe atoms. Table I which may generate the orbital moment.

TABLE I. Temperature-dependent magnetic moments by the line shape analysis of MCPs of cobalt ferrite. The magnetization (M–T) data measured using the
VSM is also included. The error involved in the MCP and its components is within 60.03 lB/f.u.

Magnetic moment in lB/f.u.

Temperature (K) Co (spin) Fe (spin) Diffuse Fitted total (spin) Direct from MCP data M–T (VSM) Spin-theoretical Orbital- theoretical
a–c
8 2.55 0.69 0.21 3.03 3.10 3.72 3.00 0.58c
300 2.35 0.80 0.23 2.92 2.97 3.58

a
Reference 1.
b
Reference 5.
c
Reference 9.

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073914-4 Mund et al. J. Appl. Phys. 110, 073914 (2011)

3
IV. CONCLUSIONS K. J. Kim, H. S. Lee, M. H. Lee, and S. H. Lee, J. Appl. Phys. 91, 9974
(2002).
4
We have measured the temperature-dependent MCP of T. Yu, Z. X. Shen, Y. Shi, and J. Ding, J. Phys.: Condens. Matter 14, L613
CoFe2O4 at a 2.5-T field. Our experimental data clearly (2002).
5
H. T. Jeng and G. Y. Guo, J. Magn. Magn. Mater. 239, 88 (2002).
shows that Co has major contributions in the formation of 6
T. A. S. Ferreira, J. C. Waerenborgh, M. H. R. M. Mendonca, M. R.
the total magnetic moment, whereas the spin moments at Co/ Nunes, and F. M. Costa, Solid State Sci. 5, 383 (2003).
7
Fe atoms are antiferromagnetically coupled to the diffuse V. N. Antonov, B. N. Harmon, and A. N. Yaresko, Phys. Rev. B 67,
component arising from itinerant electrons. A first-ever com- 024417 (2003).
8
G. Subias, J. Garcia, M. G. Proietti, J. Blasco, H. Renevier, J. L. Hodeau,
parison between present MCP and magnetization data estab- and M. C. Sanchez, Phys. Scr., T 115, 603 (2005).
lishes, quantitatively, the existence of an orbital magnetic 9
Z. Szotek, W. M. Temmerman, D. Ködderitzsch, A. Svane, L. Petit, and
moment (about 0.60 6 0.03 lB/f.u.) at 8 and 300 K in 10
H. Winter, Phys. Rev. B 74, 174431 (2006).
CoFe2O4. A small change in the orbital moment in the tem- S. D. Bhame and P. A. Joy, J. Phys. D: Appl. Phys. 40, 3263 (2007).
11
Z. Zhou, Y. Zhang, Z. Wang, W. Wei, W. Tang, J. Shi, and R. Xiong,
perature range 8 to 300 K is observed. Appl. Surf. Sci. 254, 6972 (2008).
12
D. Fritsch and C. Ederer, Phys. Rev. B 82, 104117 (2010).
13
ACKNOWLEDGMENTS J.-P. Zhou, L. Lv, and X.-Z. Chen, J. Ceram. Proc. Res. 11, 263 (2010).
14
Y. H. Hou, Y. J. Zhao, Z. W. Liu, H. Y. Yu, X. C. Zhong, W. Q. Qiu, D.
The magnetic Compton scattering measurements were C. Zeng, and L. S. Wen, J. Phys. D: Appl. Phys. 43, 445003 (2010).
15
M. J. Cooper, P. E. Mijnarends, N. Shiotani, N. Sakai, and A. Bansil,
performed with the approval of Japan Synchrotron Radiation X-ray Compton Scattering (Oxford University Press, Oxford, 2004).
Research Institute (JASRI) (Proposal No. 2010B-1394). We 16
Y. Kakutani, Y. Kubo, A. Koizumi, N. Sakai, B. L. Ahuja, and B. K.
are grateful to UGC-DAE-CSR, Indore for providing VSM Sharma, J. Phys. Soc. Jpn. 72, 599 (2003).
17
facilities for M–T data. We are thankful to DST, New Delhi B. L. Ahuja, V. Sharma, and Y. Sakurai, Adv. Mater. Res. 52, 145 (2008).
18
B. L. Ahuja, B. K. Sharma, S. Mathur, N. L. Heda, M. Itou, A. Andrejc-
and Professor A. K. Raychaudhari for travel support to visit zuk, Y. Sakurai, A. Chakrabarti, S. Banik, A. M. Awasthi, and S. R.
SPring-8, Hyogo, Japan. We are also thankful to DRDO, Barman, Phys. Rev. B 75, 134403 (2007).
19
New Delhi for financial assistance. One of us (S.T.) is thank- M. Matsumoto, K. Tomimoto, and S. Wakoh, J. Phys. Soc. Jpn. 62, 2734
ful to UGC, New Delhi for a grant of Dr. D. S. Kothari Post- (1993).
20
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21
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1
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2 22
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