Physics Letters A 359 (2006) 66–69

[Link]/locate/pla

Magnetic properties of tin-doped magnetite nanoparticles

Yan-Wu Lu a , Qin-Sheng Zhu b , Fang-Xin Liu c,∗
a Department of Physics, Beijing Jiaotong University, Beijing 100044, China
b Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083, China
c University of Science & Technology of China, Hefei 230026, China

Received 16 May 2006; accepted 29 May 2006

Available online 9 June 2006
Communicated by V.M. Agranovich

Abstract
Structural and magnetic characteristics of Fe3−x Snx O4 (x < 0.3) nanoparticles synthesized using the precipitation exchange method have been
investigated by X-ray diffraction, transmission electron microscope, Mössbauer spectra, X-ray photoelectron spectroscopy and magnetization
measurement. The mean particle dimension decreases from 8 to 6 nm, the lattice parameters enlarge, the saturation magnetization decreases,
as well as the magnetization and the coercive field increase, with increasing tin-content. The paramagnetic property of the specimens indicates
that the replacement of Fe3+ by Sn4+ on the octahedral sites of Fe3 O4 causes a progressive lowering of the Curie temperature and the Curie
temperatures of the materials are all lower than that of crystallite tin-doped magnetite. This striking debasing is due to the lessening of the grain
size. This is the smallest size reported thus far for paramagnetic tin-doped magnetite particles.
© 2006 Elsevier B.V. All rights reserved.

PACS: 75.50.-y; 61.46.+w; 75.75.+a

Keywords: Tin-doped magnetite; Composition and particle-size effect; Paramagnetic properties

1. Introduction of tin-doped magnetite Fe3−x Snx O4 . Berry et al. [7] presented

the high temperature properties of tin-doped magnetite crys-
The design, synthesis and characteristic of nanophase mate- tal. Previous methods of preparing tin-doped magnetite were
rials are the subject of intense current research [1]. This activity mainly solid phase reactions, in which process reaction temper-
has been inspired in part by the realization that the physical ature was high to 1300 ◦ C; reaction time was long (ten hours);
and chemical properties of nanophase materials are sometimes and the average grain size was large (∼ µm). Here we report
dramatically different from those of the bulk counterparts and preparation of Fe3−x Snx O4 nanoparticles by precipitation ex-
that nanophase materials often exhibit new or crossover phe- change (solid phase reaction in solution) method and investigate
nomena [2]. In addition, small magnetic nanoparticles exhibit the quantum size and composition effects as well as magnetic
unique phenomena [3,4]. The doping of tetravalent tin into properties of the samples.
Fe3 O4 with the inverse spinel-related structure has attracted
attention because of the possible use of the materials in trans- 2. Experiments
former cores, magnetic memories, heterogeneous catalysts and
electrochemistry, biomedicine and biotechnology [5]. Drokin et The starting materials, the aqueous iron(III) chloride hexahy-
al. [6] presented results of the spectral temperature investigation drate and tin(II) chloride were added in aqueous ammonia,
of photoconductivity in synthesized polycrystalline specimens respectively. Then the two solutions were mixed together at
properly conditions so as to the coprecipitated doped-magnetite
* Corresponding author. containing the required concentration of the metal ions is pro-
E-mail addresses: ywlu@[Link] (Y.-W. Lu), fxliu@[Link] duced. The resulting product was filtered, washed with deion-
(F.-X. Liu). ized water until Cl−1 was not being detected by AgNO3 , and
0375-9601/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/[Link].2006.05.080
 Y.-W. Lu et al. / Physics Letters A 359 (2006) 66–69 67

Fig. 2. TEM micrograph (a) and SEAD patterns (b) of Fe2.8 Sn0.2 O4 nanopar-
ticles.

Fig. 1. X-ray diffraction patterns obtained from Fe3−x Snx O4 samples a

(x = 0), b (x = 0.1) and c (x = 0.2). Table 1
The tin content x, lattice constant a, coercive field Hc , and saturation magneti-
zation Ms for Fe3−x Snx O4 nanoparticles
dried. After processing, the desired Sn and Fe wt% values of the
powders were verified by inductively coupled plasma–atomic Sample x a (Å) Hc (kA/m) Ms (kA m2 /kg)
emission spectroscopy (ICP–AES); these values agreed within A 0.0 8.39 6.0 21.0
B 0.1 8.41 1.0 14.0
1% with the values anticipated from the starting solutions.
C 0.2 8.44 2.0 13.0
X-ray diffraction (XRD) was taken on a Rigaku DMAX -
γ A X-ray diffractometor. A Hitachi model H-800 transmission
electron microscopy (TEM) was used to obtain the morphology served. In addition, from the bright spots it also can be deduced
and selected area electron diffraction (SAED). The magnetic that the sample is composed of fine grains with different crystal
behavior of iron in the specimens was studied using an Ox- orientations. These results are also in agreement with the XRD
ford MS-500 Mössbauer Spectrometer with a source of 57 Co. measurement.
The magnetization measurement was performed using a vibrat- The refinement of XRD spectra indicates an increase of the
ing sample magnetometer (BHV-55) at magnetic fields ranging lattice parameters a of the Fe3 O4 structure (see Table 1). The
from 0.5 to 896 kA/m. X-ray photoelectron spectra (XPS) were unit cells of tin-doping magnetite are significantly larger than
recorded with an ESCALAB MK II system using A1 Kα radia- that of Fe3 O4 (a = 8.396 Å) [8] and the lattice parameter in-
tion (hν = 1486.6 eV) under an operating vacuum 1 × 10−9 Pa. creases with incrementing tin content, these are consistent with
All binding energies were corrected to the C 1s signal, which the large octahedral ionic radii of Fe2+ (0.78 Å) and Sn4+
was set at 284.6 eV. The XPS peak decomposition was deter- (0.69 Å) compared with Fe3+ ions (0.65 Å) [9]. Considering the
mined using Gaussian–Lorentzian curve fitting software pro- dimensions of the tetrahedral A- or the octahedral B-sites and
vided by this XPS system. the sizes of the ionic radii: Sn4+ ion has a larger ionic radius
than the Fe3+ ion, thus the B-site which is more voluminous
3. Results and discussion than the A-site is occupied by the larger Sn4+ ion. As a con-
sequence, Fe2+ ions enter tetrahedral sites. Higher-voluminous
XRD patterns collected at same temperature and under the “extra Fe2+ ions” are entering the A-sites on increasing Sn-
same pH conditions show a set of broadened peaks (see Fig. 1) doping.
of a similar inverse spinel-related structure, having a lattice con- Two 57 Fe Mössbauer spectra (MS) recorded in situ from the
stant nearly equal to that of bulk Fe3 O4 [9]. No evidence for a nanoparticles of composition Fe2.9 Sn0.1 O4 following heating at
discrete tin(IV) oxide phase was observed. The observed in- 340 K in vacuo (pressure ca. 0.2 Pa) are collected in Fig. 3.
crease in the peak broadening is due to decreasing long-range The spectrum at 300 K (Fig. 3(a)) showed doublet structure of
order and decreasing grain size of the modified Fe3−x Snx O4 paramagnetic Fe3+ species, and the magnetic hyperfine fields
particles, may also result from a lattice distortion due to the in- of the sextets to be very smaller. The doublet indicates all the
troduction of tin elements. The mean crystallite sizes calculated tin-doped nano-magnetites had being in the paramagnetic state
according to the Scherrer formula from the broadening peaks, and the materials being within a few degrees of the Curie tem-
decrease from 8 to 6 nm with increasing tin-content, were con- perature. MS recorded at 340 K (Fig. 3(b)) showed the material
firmed by TEM. to be completely paramagnetic, and the material being within a
Representative TEM image [see Fig. 2(a)] shows that the few degrees of the Curie temperature. The results demonstrate
particles are very small and uniform. The clear diffraction rings that the magnetic transition takes place over an interval of 40 K.
in the SAED pattern [see Fig. 2(b)] confirm that the sample By fitting the magnetic fields at different temperature to the re-
has a spinel polycrystalline structure. These diffraction rings lationship B(T ) = Bo (1 − T /Tc )β [7], we can calculate, for the
can be indexed as Fe3 O4 (111), (220), (311), (400), (511) and compound Fe2.9 Sn0.1 O4 , Tc is 300 ± 5 K, 370 K lower than the
(440). No evidence for a discrete tin(IV) oxide phase was ob- Curie temperature of crystallite tin-doped magnetite [7], and
68 Y.-W. Lu et al. / Physics Letters A 359 (2006) 66–69

Fig. 3. Room-temperature MS of Fe2.9 Sn0.1 O4 nanoparticles.

440 K than pure magnetite [10]. The sharpness of the transi-

tion is consistent with the high degree of homogeneity of the
sample as indicated by XRD. MS recorded from the compound
Fe2.8 Sn0.2 O4 showed the Curie temperature to be far under the
room temperature. The lowering of the Curie temperature with
increasing tin content can be attributed to the substitution by tin
on the octahedral sites of Fe3 O4 .
The notable lowering of the Curie temperature of the Fig. 4. XPS recorded from Fe3−x Snx O4 nanoparticles.
Fe3−x Snx O4 nanoparticles than that of the Fe3−x Snx O4 crys-
talline originates the effect of particle size. The magnetic orders Shown in Fig. 4 is the XPS of Fe (2p) for the as-prepared
in the nanoparticles are well preserved above the transition tem- samples. The binding energies recorded from Fe3 O4 for the
perature. However, the magnetic anisotropy is overcome by the main peaks maximum 2p3/2 and 2p1/2 corresponding to the
thermal activation and an external magnetic field, and the mag- tetrahedral Fe3+ components are 710.6 and 724.3 eV, respec-
netization direction follows the direction of applied magnetic tively, these are similar to data reported in the literature [13].
field as a paramagnetic material does. As the temperature de- The peaks in the Fe (2p) XPS recorded from Fe2.9 Sn0.1 O4 and
creases, the thermal activation energy is reduced. When the Fe2.8 Sn0.2 O4 were broader than those observed in the spectrum
temperature drops below the transition temperature, the mag- recorded from Fe3 O4 and the maxima of the Fe 2p3/2 envelopes
netic anisotropy is no longer overcome and the magnetization were shifted to the lower energies of 710.3 eV and 710.0 eV
direction within each nanoparticles aligns along the easy axis respectively. A peak at 715.4 eV, which corresponds to the bind-
of the nanoparticles. When a stronger external magnetic field ing energy of the Sn 2p3/2 core level. The Fe (2p) spectrum
is applied, the magnetic anisotropy of the nanoparticles is over- recorded from Fe2.8 Sn0.2 O4 suggested an additional structure at
come at a relatively lower temperature, and hence, the transition 714.0 eV, which we associate with the presence of a Fe2+ satel-
temperature shifts to a lower value. In the present system, lite. The shifts to lower binding energy of the Fe 2p3/2 level,
particles of Fe3−x Snx O4 with an average size of 8–6 nm are the increase in broadening of the Fe (2p) peaks and the devel-
surrounded with air. In such an assembly of single magnetic opment of satellite structure are all indicative [14] of increas-
domain particle held at blocking temperature T and consisting ing Fe2+ content as increasing amounts of tin are incorporated
of a distribution of volumes, we can define the critical particle within the Fe3 O4 structure. This is more clearly demonstrated
volume Vc [11], from the deconvolution of the Fe 2p3/2 peak. The single compo-
nent in the Fe 2p3/2 peak of Fe3 O4 at 710.9 eV is characteristic
Vc = 25kB T /K, (1) of Fe3+ and, although Fe3 O4 contains both Fe2+ and Fe3+ , the
surface is usually oxidized such that only the Fe3+ contribution
where K is the anisotropy constant of the particle, kB , Boltz- is observed in the XPS [15]. In contrast the Fe 2p3/2 peak in the
mann constant. Particles with volume larger than Vc have block- spectra recorded from Fe2.9 Sn0.1 O4 and Fe2.8 Sn0.2 O4 were de-
ing temperatures higher than T and are, therefore, magnetically convoluted to four peaks. The peaks at 710.8 eV and 715.5 eV
frozen. Only particles with volume smaller than Vc , can respond correspond to Fe3+ and the Sn 2p3/2 level respectively. In addi-
paramagnetically to an external field at temperature T . We can tion, the peak at 709.1 eV, together with the satellite at 714.1 eV,
estimate the anisotropy constant K of the nanoparticles using are characteristic [13] of Fe2+ . Taken together the results show
Eq. (1) from the nanoparticle volume of 2.16 × 10−25 m3 cor- that the replacement of Fe3+ by Sn4+ in Fe3 O4 is achieved by
responds to a diameter of 6 nm, and the temperature of 300 K. substitution on the octahedral sites of the inverse spinel struc-
The estimated K of 4.79 × 105 J/m3 is qualitatively consistent ture and is accompanied by the partial reduction of Fe3 O4 to
with those (∼ 105 J/m3 ) given by Ref. [12]. Fe2+ .
 Y.-W. Lu et al. / Physics Letters A 359 (2006) 66–69 69

4. Conclusions

Nanometer Fe3−x Snx O4 (x < 0.3) with a narrow particle

size distribution (6–8 nm) have been synthesized by the precipi-
tation exchange method at relatively lower temperature, shorter
reaction time for relatively large-scale preparation of nanopar-
ticles. XRD, TEM, MS, XPS and magnetization data results
clearly indicate that the low concentrations of tin in compo-
sition Fe3−x Snx O4 (x < 0.3) adopt the octahedral, as opposed
to tetrahedral, sites of the inverse spinel structure. The satura-
tion magnetization decreases, whereas the magnetization and
the coercive field increase, with increasing tin-content, thus
indicating a change of cation substitution. Substitution by tin
on the octahedral sites of Fe3 O4 causes a progressive lower-
ing of the Curie temperature, and the Curie temperature are all
Fig. 5. Magnetization curves for the Fe3−x Snx O4 nanoparticles at room tem-
lower than room temperature, the lessening of the grain size
perature: (a) (x = 0), (b) (x = 0.1), (c) (x = 0.2). The maximum applied mag- brings another remarkable debasing of the Curie temperature.
netic field is 60 kA/m. The magnetic behavior of the tin magnetite particles changed
from ferromagnetic, as normal for magnetite, to paramagnetic
when decreasing the particle size to nanometer scale at room
Fig. 5 shows the magnetization loops obtained at room tem- temperature. This is the smallest size reported thus far for para-
perature of Fe3−x Snx O4 nanoparticles under the maximum ap- magnetic tin-doped Fe3 O4 nanoparticles.
plied magnetic field of 896 kA/m, and the variations of coer-
civity Hc , and saturation magnetization Ms , as a function of the Acknowledgements
Sn4+ composition parameter x. From Figs. 3 and 5, we can see
that for pure Fe3 O4 specimen, a larger hysteresis appears, and This work is supported by National Natural Scientific Foun-
for tin-doped magnetite the hysteresis becomes smaller. This dation of China under Grant No. 60376014.
can be explained by the presence of anisotropy of Fe spins in-
side nanoparticles as well as in their local environments. The References
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