International Journal of Inorganic Materials 3 (2001) 503507

Vibrational spectra of lithium ferrites: infrared spectroscopic studies of

Mn-substituted LiFe 5 O 8 q
E. Wolska*, P. Piszora, W. Nowicki, J. Darul
Laboratory of Magnetochemistry, Adam Mickiewicz University, Faculty of Chemistry, Poznan Grunwaldzka 6, PL.-60780 Poznan , Poland

Abstract
Investigations on the series of manganese-substituted lithium ferrites reveal the destructive effect of manganese ions on the ordering of
Li 1 cations in the spinel-type crystal lattice. A spectacular orderdisorder transition with increasing substitution of Mn 31 ions has been
observed with infrared spectroscopy, in the region of lattice vibrations. The preference of manganese ions for the octahedral coordination,
appears to be associated with the migration of Li 1 from octahedral to tetrahedral positions. Results for the LiFe 52y Mny O 8 solid solution
have been confronted with an orderdisorder transition in the pure lithium ferrite. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Lithium ferrites; Substitutional solid solutions; Orderdisorder transition; Infrared spectra; Factor group analysis

1. Introduction
The infrared spectrum may be of great importance in
resolving the orderdisorder problem in the spinel structure. Vibrational spectroscopy is sensitive to the shortrange environment of oxygen coordination around the
cations in both tetrahedral and octahedral crystal sites.
Contrary to the diffraction data, which give an average of
similar interplanar spacing, the vibration spectrum is a
superposition of the spectra of all local structures. The
bands in IR and Raman spectra are sensitive to coordination geometry and oxidation states, and remain relatively
unaffected by crystalline size or the degree of long-range
order [1].
Cubic ferrites, such as LiFe 5 O 8 are soft magnetics, with
the high Curie temperature, a square hysteresis loop, and
high magnetization, that are of interest as low cost
materials for memory core and microwave applications.
The magnetic properties of lithium ferrite may be improved by the addition of small amounts of other cations,
e.g. nickel, manganese, chromium or cobalt ions [26].
The preparation of LiFe 5 O 8 using the conventional high
temperature ceramic methods often results in a low quality
material, the volatility of lithium above 10008C affecting

This paper was presented at Solid State Chemistry 2000 in Prague,

Czech Republic.
*Corresponding author. Tel.: 148-61-829-1236; fax: 148-61-8658008.
E-mail address: emilia@main.amu.edu.pl (E. Wolska).

the magnetic properties and resistivity. A number of wet

chemical methods was therefore used to prepare LiFe 5 O 8
at low temperature. They include the hydrothermal transformation of hydroxide precursors [7], freeze-drying of
Li,Fe-formates [8] and the citrate precursors method [9].
This contribution refers to the comprehensive studies on
the modelling of structures and cation distribution in the
spinel oxide solid solutions. We present new results,
obtained by the infrared spectroscopic and X-ray powder
diffraction studies, on the orderdisorder effect and on the
distribution of lithium ions in the spinel structure, in a
series of the Mn-substituted lithium ferrites, prepared by
thermal treatment, from the MnFe oxide precursors.

2. Experimental details
A series of the ironmanganese oxide precursors were
prepared by coprecipitation of amorphous MnFehydroxides from the mixed Mn 21 / Fe 31 nitrate solutions of
the mole ratio of Mn:(Fe1Mn)50.00.3, with sodium
hydroxide. Washed and dried at room temperature, they
were then dehydrated at 4008C. Crystalline single-phase
products, displaying the hematite structure, were mixed
with Li 2 CO 3 in the Li:M 2 O 3 ratios (M5Mn1Fe) corresponding to a LiFe 52y Mn y O 8 stoichiometry (0#y#1.5),
underwent the thermal treatment in air, successively at 700
and 7508C, for 6 h. The disordered form of lithium ferrite
was obtained by heating the LiFe 5 O 8 sample up to 10008C
and quenching it in solid CO 2 .

1466-6049 / 01 / $ see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S1466-6049( 01 )00069-1

E. Wolska et al. / International Journal of Inorganic Materials 3 (2001) 503 507

504

X-ray diffraction patterns were recorded with a computerized TUR-61 (HZG-3) diffractometer, employing the
Fe-filtered Co Ka radiation.
Infrared absorption spectra were registered on the FT-IR
spectrometer NICOLET model MAGNA 760 (4000225
cm 21 , resolution 2 cm 21 ), using CsI pellets.

3. Results and discussion

Spinel-type lithium ferrite, LiFe 5 O 8 , is known to occur
in two crystalline forms. In the ordered form (space
group P4 1 32 /P4 3 32) the Fe 31 ions are at octahedral 12d
and tetrahedral 8c sites, and Li 1 ions occupy only the
octahedral 4b positions in the cubic primitive unit cell. The
disordered LiFe 5 O 8 has an inverse spinel structure (space
group Fd3m), with Fe 31 at tetrahedral 8a positions and
Li 1 and Fe 31 randomly distributed over the 16d octahedral
sites. The orderdisorder transition in the lithium ferrite
structure may be recorded by the X-ray powder diffraction
and by infrared and Raman spectroscopy. Relations between the Fd3m and P4 3 32 Wyckoffs positions are as
follows [10]:

P4 3 32

8a (8 Fe )
16d (12 Fe 31 1 4 Li 1 )

8c (8 Fe 31 )
12d (12 Fe 31 ) 1 4b (4 Li 1 )

32e (32 O 22)

24e (24 O 22) 1 8c (8 O 22)

Fd3m
31

quenched from 10008C (Fig. 1B). A similar effect of the

orderdisorder transition may be obtained by the substitution of manganese ions in the lattice of lithium ferrite
[3,4,7,11,12].
The substitution of manganese ions in the solid solution
series, prepared with an assumed stoichiometry
LiFe 52y Mn y O 8 , affects the 1:3 cation ordering of the
octahedral spinel sublattice, bringing about the transformation of the ordered (P4 3 32) to disordered (Fd3m) spinel
type structure. Fig. 2 illustrates the gradual Li 1 randomness increasing with the manganese content. It may be seen
that the intensity of the superstructure reflections, e.g.
110, 210, 211, 310, 320, decreases and that they vanish in
the sample with n Mn 50.30. The X-ray pattern of the latter
sample, LiFe 3.5 Mn 1.5 O 8 , does not differ from the pattern
of the pure, quenched (disordered) lithium ferrite (Fig.
1D).
Infrared spectroscopy may be used to determine the
local symmetry in the crystalline solids, and also the
ordering phenomenon in spinels [1,13,14]. Group theory
predicts, based on the factor group (or unit cell) approximation, that in the cubic spinel, with the space group
Fd3m (O h ), should appear four infrared active vibrations.
In terms of factor group analysis, the observed frequencies
in the vibrational spectra of solids are presumed to result
from the motions of all atoms in the primitive unit cell, and
not from the isolated motions of individual molecules. The
reduced (primitive) unit cell of spinel, equivalent to the

The X-ray powder diffraction patterns of the ordered and

disordered lithium ferrite, presented in Fig. 1, show the
additional superstructure reflections characteristic for the
cubic primitive P4 1 32 /P4 3 32 symmetry of the ordered
LiFe 5 O 8 (Fig. 1A), compared to the cubic spinel (Fd3m)
reflections in the pattern of a disordered LiFe 5 O 8 ,

Fig. 1. X-ray diffraction patterns of the ordered (A) and disordered (D)
form of lithium ferrite, LiFe 5 O 8 .

Fig. 2. X-ray powder diffraction patterns of a series of solid solutions

LiFe 52y Mn y O 8 , with y50.0 (A), y50.75 (B) and y51.50 (C).

E. Wolska et al. / International Journal of Inorganic Materials 3 (2001) 503 507

rhombohedral smallest Bravais cell, contains only 14

atoms, i.e. 1 / 4 of the cubic cell with 56 atoms (Fig. 3b).
The normal and inverse spinels are expected to show the
same number of infrared bands, since no change occurs in
the space group. The 1:3 ordering on the octahedral sites
reduces the space group from O 7h to O 7 . The unit cell of
the ordered spinel is primitive cubic, with the same number
of atoms as the cubic spinel cell (Fig. 3a). The enlargement
of the smallest Bravais cell results in great increase in the
number of allowed modes. Thus for the ordered spinel,
such as LiFe 5 O 8 or LiAl 5 O 8 , the theory predicts 21
infrared active bands [13,15]. The symmetries and selection rules for the normal modes of the disordered cubic
spinel and for the 1:3 ordering, are given in Table 1 [13].
When the substitution with different ions occurs, four
parameters may change simultaneously: the mass of cation,
the metaloxygen bond strength, the metaloxygen bond
length, and the dimensions of the unit cell. All these
parameters affect the infrared spectrum. Our previous IR
spectroscopic studies on the series of LiMnferrite solid
solutions with variable lithium content, revealed the complexity of the mechanism of incorporation of manganese,

Fig. 3. The smallest (primitive) unit cell of an ordered (a) and disordered
(b) lithium ferrite, considered in the assignment of vibrational spectra
with the factor group analysis.

505

Table 1
(a) Normal modes of cubic spinel (site symmetry: O h )

A 1g
A 2g
Eg
T 1g
T 2g
A 1u
A 2u
Eu
T 1u
T 2u

Total
modes

Translations

Vibrations

Selection
rules

1
0
1
1
3
0
2
2
5
2

0
0
0
0
0
0
0
0
1
0

1
0
1
1
3
0
2
2
4
2

Raman

Raman
Inactive
Raman

Inactive
Inactive
IR
Inactive

(b) Allowed modes and selection rules for spinel with

1:3 ordering on the octahedral sites (site symmetry: O):
A1
6
0
6
A2
8
0
8
E
14
0
14
T1
22
1
21
T2
20
0
20

Raman
Inactive
Raman
IR
Raman

After Ref. [13].

its oxidation degree and distribution of Li 1 ions in the

spinel lattice [7,11]. Evidence is given, that both the cation
distribution and ordering depend on the preparation conditions.
In the present experiment we obtained the solid solutions with the invariable lithium content, and the oxidation
degree of manganese ions was (13) for the whole range of
0.0#y#1.5 in LiFe 52y Mn y O 8 . The ionic radii and masses
of Fe 3 and Mn 31 being similar, this resulted in the nearly
constant unit-cell dimensions, hence the infrared spectra
should be only slightly affected by the Mn-substitution.
Nevertheless, we were able to register the displacement of
infrared absorption bands, caused by Mn 31 ions, and the
results are given in Table 2.
Most of the transition metal spinel-type oxides display
four infrared-active bands, appearing in the following
regions of spectra: n1 (630560 cm 21 ), n2 (525390
cm 21 ), n3 (380335 cm 21 ) and n4 (255170 cm 21 ). The
n1 band may be attributed to the vibrations of the MO 6
octahedra, n2 and n3 are assigned to the complex vibrations
involving both octahedral and tetrahedral sites, the n4 band
is assigned to a vibration of tetrahedral sublattice [16]. The
infrared-active modes all belong to the same symmetry,
T 1u , and can interact strongly with one another.
The infrared spectra of the solid solution series
LiFe 52y Mn y O 8 with 0.0#y#1.5, presented in Fig. 4,
illustrate a gradual transition from the ordered to disordered Mn-substituted lithium ferrite. The slight but
distinct displacement of absorption bands with increasing
y, indicates the incorporation of Mn 31 in the octahedral
spinel sublattice. No such displacement occurs during the
orderdisorder transition in the pure lithium ferrite. The IR
spectra, shown in Fig. 5, allowed the comparison of the

E. Wolska et al. / International Journal of Inorganic Materials 3 (2001) 503 507

506

Table 2
The band positions in the infrared absorption spectra of LiFe 52y Mn y O 8 solid solutions, recorded in the range 800300 cm 21
n Mn

Composition

IR bands (cm 21 )

0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.00

LiFe 5 O 8 (ordered)
LiFe 4.75 Mno 25 O 8
LiFe 4.50 Mn 050 0 8
LiFe 4.25 Mn 1.00 O 8
LiFe 4.00 Mn 1.00 O 8
LiFe 3.75 Mn 1.25 O 8
LiFe 3. 50Mn 1.50 O 8
LiFe 5 O 8 (disordered)

708
708
708
708
(708)
(708)

673
670
670
669

582
584
584
586
586
586
586
583

548
549
549
549
550
552
(556)
548

469
470
471
471
471
471
471
470

439
440
440
440
440
440
(440)
440

396
397
395
394
395
395
395

374
374
374
374

375

328
328
328
328
328
328
328
328

Fig. 4. Infrared absorption spectra of a series of solid solutions

LiFe 52y Mn y O 8 , with 0.0#y#1.5 and 0.0#n Mn #0.3, respectively,
(n Mn 5Mn /(Mn1Fe)).
Fig. 5. Infrared absorption spectra of the ordered (A) and disordered (D)
LiFe 5 O 8 , compared to the spectrum of LiFe 3.5 Mn 1.5 O 8 solid solution (C).

ordered lithium ferrite (A) with the disordered Mn-substituted LiFe 3.5 Mn 1.5 O 8 (C), and the disordered pure
LiFe 5 O 8 obtained by quenching a sample from 10008C
(D). A distinction between the last two samples has not
been possible on the basis of X-ray powder diffraction
data.

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