Journal of Molecular Structure 1035 (2013) 2730

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

Nd:YAG laser irradiation effects on the structural and magnetic properties

of polycrystalline cobalt ferrite
Maheshkumar L. Mane a,, V.N. Dhage a, Sagar E. Shirsath a, R. Sundar b, K. Ranganathan b, S.M. Oak b,
K.M. Jadhav a
a
b

Department of Physics, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad (M.S.) 431 004, India
Solid State Laser Division, Raja Ramanna Centre for Advanced Technology, Indore (M.P.), India

h i g h l i g h t s
" Standard double sintering ceramic method.
" Structural and magnetic properties of spinel ferrite.
" Role of laser irradiation.

a r t i c l e

i n f o

Article history:
Received 24 May 2012
Received in revised form 3 August 2012
Accepted 5 September 2012
Available online 15 September 2012
Keywords:
Ferrite
Irradiation
Structural
Magnetization
Defects

a b s t r a c t
Nd:YAG laser irradiation effect on the structural and magnetic properties of CobaltIron oxides were
studied in the CoFe2O4 ferrite composition. CoFe2O4 spinel ferrite was prepared by conventional double
sintering ceramic method. X-ray diffraction analysis reveals single phase cubic spinel structure before
irradiation and defects appears along with the spinel phase after irradiation. It was inferred that the irradiation with laser causes decrease in crystallite size. The physical densities are about 90% to their respective X-ray densities. The results of these characterizations are different for irradiated samples than that of
unirradiated sample. A compressive strain is generated by the irradiation as observed by the X-ray diffraction studies, which have modied the magnetic properties of these materials. On irradiation by
Nd:YAG laser beam, signicant changes in the hysteresis loop features are observed, which may be attributed to formation of defects in the samples due to irradiation.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The magnetic properties of ferrites are dependent on the type of
cations involved and their distribution amongst the tetrahedral (A)
and octahedral [B] sites. The occupancy of cations over available
sites in spinel ferrite matrix can be inuenced by incorporation
of transition metal ions or by any processing technique. Ferrites
are a group of technologically important materials that are used
in the fabrication of magnetic, electronic and microwave devices
[1,2]. Super paramagnetism, spin canting, core/shell structure,
metastable cation distribution, etc. are some of the phenomena,
which have been observed in ferrites. These phenomena depend
on number of factors such as composition, grain size, surface morphology, anisotropy and inter-particle interactions [3]. CoFe2O4
ferrite has received renewed attention for its potential use for

Corresponding author. Tel.: +91 0240 240 3384.

E-mail address: mane.maheshkumar@hotmail.com (M.L. Mane).
0022-2860/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.09.019

high-density recording media. This is due to the remarkable properties observed for bulk CoFe2O4: strong anisotropy, high saturation magnetisation and coercivity along with good mechanical
hardness and chemical stability [46]. The intrinsic properties of
magnetic materials such as saturation magnetization, magnetic
permeability, anisotropy, Curie temperature, magnetic resonance
and electrical resistivity and extrinsic properties of material includes hysteresis loop properties, such as remanence and coercive
force are affected by processing methods.
Recently, a considerable attention was focused on the irradiation effect on metal oxides and has opened new era for scientist
and technologist [79]. Interaction of photon energy with matter
is an extremely important problem from the viewpoint theory
and practice. When energy acts on the materials, their structural
and magnetic properties may change and new phenomenon may
develop. In the last few years, a broad development of nuclear
engineering, use of radioactive isotopes, accelerators of elementary
particles put forward more often the problem of action of various
kinds of ionizing radiations on the materials [10].

M.L. Mane et al. / Journal of Molecular Structure 1035 (2013) 2730

3. Results and discussion

3.1. Structural analysis
The typical variation of X-ray diffraction patterns with laser
irradiation at room temperature are shown in Fig. 1. The most signicant lines in unirradiated CoFe2O4 spinel ferrite sample were
successfully indexed to single phase cubic spinel structure prepared via conventional double sintering ceramic technique. Laser
irradiation generates the disorder in the lattice structure (the
broadening of peaks and the reduction in peak intensity). The similar results were previously reported in gamma irradiated Ni-Zn
ferrite by Karim et al. [11]. The broadening of the peaks indicates
reduction in grain size with laser irradiation doses. The XRD pattern shows disordered cubic spinel structure after laser irradiation.
The distorted cubic structure is assigned to the disappearance of
peak at 2h = 53. The similar behavior was observed in Co ferrite
irradiated with laser [12,5].
The lattice constant a was calculated using inter-planar spacing (d) values and Miller indices (hkl) values. The true lattice
parameter a0 may be obtained by calculating the average of the
a values for each sample. The extrapolation function F(h), i.e.,
the NelsonRiley function for each reection of the studied sample
was calculated [13]:

Before

(440)

(333)

400 mJ
800 mJ
1200 mJ

20

30

40

50

60

70

2
Fig. 1. X-ray diffraction patterns for unirradiated and irradiated samples of
CoFe2O4.

Fh

 2   2 
cos h
cos h

sin h
h

The average values of the lattice parameter a were plotted as

a function of F(h) straight lines (not shown) were obtained. From
extrapolation of those straight lines to h = 90, the variation of
a0 with laser dose is shown in Fig. 3. It is observed from Fig. 3
that the lattice constant increases after irradiation as a result of
the formation of ferrous ions (Fe2+) which have a large radius
(0.74 ) than that of ferric ions (Fe3+) (0.64 ) [9,14].
The effective crystallite size (D) and the degree of microstrain
(e) of the studied cobalt ferrites were determined from XRD line
width using Scherrer formula modied by WilliamsonHall equation [15]:

b cos h

0:9k
4e sin h
D

where b is the full width at half maximum (FWHM) of the XRD

peaks, h is the Bragg angle, k is the X-ray wavelength, D is the effective crystallite size, and e is the value of internal strain. By plotting
the value of b cos h as a function of 4sin h (Fig. 2) the microstrain e
may be estimated from the slope of the curve, whereas the crystallite size D can be obtained from the intersection with the vertical
axis (=0.9k/D). The effective crystallite size and the lattice microstrain obtained from the WilliamsonHall plot are listed in Table 1.
It is clear from Table 1 that the irradiation greatly affects the effective crystallite size and the lattice strain inside the samples.
The physical density was calculated from the mass and pellet
dimensions and has the value of 4.2462 gm/cm3. The X-ray density

0.040
Before
400 mJ
800 mJ
1200 mJ

0.035
0.030

cos

The powders for IronCobalt spinel oxide having the generic

formula CoFe2O4 was synthesized by conventional double sintering
ceramic technique. The pure oxides (CoO and Fe2O3) of 99.9% purity were used. The powders were mixed in stoichiometric proportion and ground in an agate mortar pestle to obtain a very ne
powder. The powder was then sintered at 900 C for 12 h and
cooled to room temperature. The sintered powder is again ground
and then product powders were pressed in pellet form of 10 mm
diameter and 3 mm thickness. These pellets are nely sintered to
1100 C for 24 h and then cooled to room temperature. Finally
the samples were polished to obtain disc with two uniform parallel
surfaces. These discs were then treated as precursor for laser irradiation. The mechanism involved in the present investigation can
be written as Co2+ + Fe3+ M Fe2+ + Co3+.
The discs of CoFe2O4 spinel ferrite samples were irradiated with
ash lamp pumped Nd:YAG laser operated in the free-running
mode with the pulse width of 200 ls and a spot diameter of
8 mm (1/e2 points). Spatial prole of the laser output is super
Gaussian. Samples were irradiated at a repetition rate of 5 Hz for
15 min at three different output energies between 400, 800 and
1200 mJ.
The crystallographic structure were studied with X-ray diffractometry (XRD) (Cu Ka radiation with wavelength of k = 1.54056 ).
The chemical composition of the CoFe2O4 was studied using energy
dispersive analysis (EDAX) on various regions by using JEOL-JSM
6360A. The EDAX study conrmed the expected stoichiometric
proportion of Co and Fe ions in present investigated sample. Physical density was determined from mass and bulk volume of sample
pellets. Magnetic measurements of irradiated and unirradiated
samples of CoFe2O4 ferrite samples were carried out on pulse eld
hysteresis loop tracer at room temperature with applied eld of
5 kOe.

(400)

2. Experimental

(422)

Intensity (Arb. Units)

(311)

The present investigation was carried out in an attempt to

throw light on the effect of laser irradiation on the structural and
magnetic properties of polycrystalline CoFe2O4 spinel ferrite with
different laser output energies.

(220)

28

0.025
0.020
0.015
0.010
0.005
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8

4 sin
Fig. 2. WilliamsonHall plots for unirradiated and irradiated samples of CoFe2O4.

29

M.L. Mane et al. / Journal of Molecular Structure 1035 (2013) 2730

8.4714

Lattice constant ()

8.4711
8.4708

ath

8.4705

8.388

8.376

ao

8.364
0

400

800

1200

Laser dose (mJ)

Fig. 3. Variation of rA, rB and u with laser dose for unirradiated and irradiated
samples of CoFe2O4.

Table 1
Crystallite size (D), micro-strain (e), jump length (L), polaron radius (rP), X-ray density
(dX), porosity (P%).
D (lm)
Before
400 mJ
800 mJ
1200 mJ

1.13
0.55
0.45
0.36

e (a.u.)
3

5.13  10
9.65  103
11.41  103
16.28  103

1
0:96rCo2 1:04r Fe3 
2

rP ()

dX (gm/cm3)

P (%)

rB

2.957
2.962
2.965
2.968

0.736
0.737
0.738
0.739

5.326
5.298
5.286
5.267

20.274
19.858
19.667
19.385

The oxygen positional parameter or anion parameter (u) for

each sample was calculated using the formula [19].


1
1 p 3
0
2 6N

where N0 number of sites per unit volume = 96/a3. Also we have calculated jump length (L) using relation [17].

La

rA 0:04rCo2 0:96r Fe3

L ()

was calculated by using equation dX = 8M/NaV where M is molecular weight, Na is Avogadros number (6.023  1023) and V is volume of unit cell (a3). The values of X-ray density was given in
Table 1. The porosity of the irradiated and unirradiated cobalt ferrite was calculated from physical density and X-ray density and
values are tabulated in Table 1. It was observed from Table 1 that
the porosity decreases after laser irradiation.
In ferrites, the charge carriers are not completely free but are
strongly localized in the d-shell; this localization may be due to
the formation of polarons. A small polaron defect is created when
an electronic carrier gets trapped at given sites as a consequence of
the displacement of adjacent atoms or ions. An attempt has been
made to calculate the polaron radius (rp) for the irradiated and
unirradiated samples studied by the relation [16].

rp

The cation distribution was calculated by analyzing intensity

ratios of X-ray diffraction data. In this method, the observed intensity ratios were compared with the calculated intensity ratios. The
detail of estimation of cation distribution was briey discussed in
our previous reports [4,5]. The estimated cation distribution for
unirradiated and irradiated cobalt ferrite from XRD data is given
in Table 2. From Table 2 it is observed that the cation distribution
was modied after irradiation with laser dose. Cation distribution
changes when the particle size is reduced. This results into disordered oxides that have properties which are drastically different
from their bulk counterparts. As Co atoms which are known to
have preference for B-sites in bulk compounds were found to migrate to A-sites with reduction in grain size of CoFe2O4 oxide. This
led to the enhancement of magnetic ordering. The mean ionic radius of the tetrahedral A-site (rA) and octahedral B-site (rB) can
be calculated by using the relations based on the cation distribution [18]. The radius of tetrahedral and octahedral sites is given
for the sample irradiated at 800 mJ from the following equations

p
2
4



1 p
a 3  Ro
rA u 
4

where Ro is the radius of the oxygen ion (1.32 ). The variation of

ionic radii (rA, rB) and oxygen positional parameter (u) with laser
doses is shown in Fig. 3. The theoretical lattice parameter ath
was calculated using the values of tetrahedral and octahedral ionic
radii (rA and rB) and is given by the following relation [20]:

p
8
ath p rA Ro 3r B Ro 
3 3

where rA and rB are radii of tetrahedral (A) site and octahedral [B]
site, Ro is the radius of oxygen. It is noticed that ath is higher than
the lattice constant a0 , this deviation may be due to the formation
of Fe2+ ions, which have an ionic radius greater than Fe3+ after irradiation. The variation of lattice constant (a, ao and ath) with laser
dose rate is shown in Fig. 4.
Using the experimental values of lattice constant a, oxygen
positional parameter u and substituting it into equations discussed elsewhere [18] tetrahedral and octahedral bond length
(dAx and dBx), tetrahedral edge, shared and unshared octahedral
edge (dAE, dBEshaired and dBEunshaired) were calculated and the variation of all these parameters with laser dose is depicted in Fig. 5.

4
3.2. Magnetic properties

The values of jump length for irradiated and unirradiated cobalt

ferrite are summarized in Table 1. This shows that jump length (L)
and polaron radius (rp) increases with laser uence. The observed
increase in L and rp with irradiation suggests that charge carriers
require more energy to jump from one cationic site to other.

The magnetic behaviour of irradiated spinel ferrite crystals has

a marked dependence on the decrease in particle size, where the
surface morphological effects start to dominate. The magnetic
properties of the unirradiated and irradiated cobalt ferrite were

Table 2
Cation distribution, Iron distribution parameter (d), saturation magnetization (Ms) and magneton number.
Cation distribution

Before
400 mJ
800 mJ
1200 mJ

(Fe1.0) [Co1.0Fe1.0] O4
(Fe0.98 Co0.02) [Co0.98Fe1.02] O4
(Fe0.96 Co0.04) [Co0.96Fe1.04] O4
(Fe0.95 Co0.05) [Co0.95Fe1.05] O4

1.00
0.961
0.923
0.905

Ms. (emu/g)

68
70
73
77

Magneton number
nCal
B

nObs
B

3
3.08
3.16
3.2

2.857
2.941
3.067
3.235

30

M.L. Mane et al. / Journal of Molecular Structure 1035 (2013) 2730

0.708

0.38590

Ionic radii (Ao)

0.38585

0.706

0.38580

0.674

0.38575

0.673

0.38570

0.672
0.671

0.38565

rA

Oxygen positional parameter (Ao)

rB

0.707

0.670
0.38560
0

400

800

1200

and thus Hc decreases. The decrease in coercivity and increase of

saturation magnetization are difcult to justify considering surface
effects only.
The magnetic order in the cubic system of ferrimagnetic spinels
is due to super-exchange interaction mechanism occurring between the metal ions in the tetrahedral A-sites and octahedral Bsites [21]. The Co2+ ion which has preferential octahedral site occupancy in unirradiated CoFe2O4 and after irradiation it is distributed
in both A- and B-site. This results in the enhancement of super-exchange interaction between A and B-sites. In other meaning, as the
laser dose increases, the magnetization of the B-site (MB) increases
while that of A-site (MA) decreases. As the net magnetization is the
difference between magnetization at A-site and B-site (Ms = MB
MA), therefore, the net magnetization increases.

Laser dose (mJ)

4. Conclusions
Fig. 4. Variation of lattice parameters (a, a0, ath) with laser dose for unirradiated
and irradiated samples of CoFe2O4.

Structural parameters ()

3.6

LA

3.4

dAE

3.2

dBEunshaired

3.0

LB

2.8
2.6
2.04

dBEshaired

2.02

dBX

2.00

dAX

Acknowledgments
The authors wish to express their gratitude to University Grant
Commission (UGC) for providing nancial assistance in the scheme
of Research Fellowship for Science Meritorious Students (RFSMSs).

1.98

References
0

400

800

1200

Laser dose (mJ)

Fig. 5. Variation of LA, LB, dAX, dBX, dAE, dBEshaired, dBEunshaired with laser dose for
unirradiated and irradiated samples of CoFe2O4.

80

Magnetization (emu/g)

The magnetic and physical properties of ferrites are very sensitive to microstructure which in turn critically depends on the irradiation process. The XRD study shows the formation of disordered
cubic spinel structure after laser irradiation. The cation distribution
was modied which causes the enhancement in the magnetization
of the investigated samples. The morphological study reviles the
damage structure after laser irradiation.

Before
400 mJ
800 mJ
1200 mJ

60
40
20
0

-4

-2

-20
-40
-60
-80

Magnetic Field Strength (kOe)

Fig. 6. Magnetization plots for unirradiated and irradiated samples of CoFe2O4.

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as shown in Fig. 6. From magnetization experiments, the magnetic
parameters such as saturation magnetization (Ms), coercivity (Hc)
and magneton number (nB) were obtained. The values of saturation
magnetization (Ms) are given in Table 2. It is observed from Table 2
that saturation magnetization increases as laser dose increases. As
the porosity decreases high eld is needed to push the domain wall

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