The prospect of application of the multiferroics in devices and spintronics devices is shown. A comparative analysis of magnetic and dielectric properties of nanostructures based on bismuth ferrite which were synthesized by various ways was made. The results of studies of the structure and properties of the nanostructured bismuth ferrite powder, synthesized by combustion of nitrate - organic precursors, are presented

Alikhanov, N.M.-R.

Murlieva, Zh.Kh.

Sarnatsky, V.M.

Vinokurov, N.A.

English

SocioEconomic Challenges Journal (Sumy State University)

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ 
Vol. 8 No 3, 03008(4pp) (2016) Том 8 № 3, 03008(4cc) (2016) 
 
 
2077-6772/2016/8(3)03008(4) 03008-1  2016 Sumy State University 
Magnetic and Electrical Characteristics of Bismuth Ferrite, Depending on the Impurities, 
Method of Preparation and Size of the Nanoparticles 
 
V.M. Sarnatsky1, N.A. Vinokurov1, Zh.Kh. Murlieva2, N.M.-R. Alikhanov2 
 
1 St. Peterburg State University, 7/9, Universitetskaya nab., 199034 St. Petersburg, Russia 
2 Dagestan State University, 43, Gadzhiyev st., 367000 Makhachkala, Russia  
 
(Received 25 April 2016; published online 03 October 2016) 
 
The prospect of application of the multiferroics in devices and spintronics devices is shown.  A compar-
ative analysis of magnetic and dielectric properties of nanostructures based on bismuth ferrite which were 
synthesized by various ways was made. The results of studies of the structure and properties of the 
nanostructured bismuth ferrite powder, synthesized by combustion of nitrate - organic precursors, are pre-
sented. 
 
Keywords: Bismuth ferrite nanoparticles, Dielectric properties, Curie temperature, X-ray, magnetic prop-
erties, The Neel temperature 
 
DOI: 10.21272/jnep.8(3).03008 
 
PACS numbers: 61.46. + w, 77.22.Ch 
 
 
1. INTRODUCTION 
 
Creating the substances - multiferroics, having both 
magnetic and electrical properties [1], opens up new 
opportunities and prospects for their use in spintronics 
- the science   engaged in the processing problems, 
storage and transmission of information using the 
magnetic moment of the electron. The main task of 
spintronics - the transformation of the information pro-
vided in the form of the magnetization in the electric 
voltage and vice versa. The transformation of the mag-
netization in the electric voltage can naturally be at the 
expense of a linear magnetoelectric effect, which can be 
written as two relations M   E and P   H, where M 
– magnetization, E – electric field, P – polarization, H – 
intensity of the magnetic field,  – coefficient charac-
terizing the magneto-electric effect. For the first time 
the interaction of the electronic and magnetic subsys-
tems was observed Astrov DN [2] in the compound 
Cr2O3, and a little later in the GA Smolensky lab was 
created  a whole class of multiferroics with magnetoe-
lectric properties [3]. The value of α in of Cr2O3, as de-
fined in the system CGSM units, was 20 mV/(cm Oe). It 
should be noted that in the bismuth ferrite films thick-
ness 50 nm at room temperature was opened giant 
magnetoelectric effect [4] with the  value equal to 
3B/(cm Oe). It should be noted that the linear  magne-
toelectric effect in BiFeO3 can only occur when the anti-
ferromagnetic spin cycloid (with a period of 62 nm) is 
suppressed. One way to achieve this effect is production 
BiFeO3 (BFO) in nanoscale form (film, nanopowders, 
nanostructured ceramics). Doping with ions of rare 
earths leads to structural transformation of BFO, 
whereby there is a change of magnetoelectric properties 
of the material. In [5] it is shown that the simultaneous 
doping BFO nanocrystalline yttrium and manganese 
increases the magnetic and electrical properties, as 
well as magnetoelectric coefficient compared to pure 
BFO. At the same time, the doping leads to increasing 
of conductivity even at room temperature, which reduc-
es the effect of the spontaneous polarization and dielec-
tric properties. Epitaxial thin films can, in principle, 
may be weak  ferromagnetic, but epitaxial stresses can 
influence on the crystal structure, polarization and 
magnetization. 
 
2. METHODS FOR THE PREPRATION OF BIS-
MUTH FERRITE NANOPOWDERS 
 
High values of , the temperature of the antiferro-
magnetic (TN  370 С) and ferroelectric (the 
TC  827 С) transitions in bismuth ferrite predeter-
mined his prospects of wide application in spintronics, 
sensory and microwave technology, devices for convert-
ing, recording, reading and storing information [6] and 
other. Analysis of the literature shows a certain spread 
of values of the dielectric and magnetic properties, Cu-
rie and Neel temperatures  in nanostructures based on 
bismuth ferrite, what may be due to size effects, differ-
ent regimes of annealing (temperature - time, the sur-
rounding atmosphere), the influence of impurities. 
Among the many ways to obtain bismuth ferrite na-
nopowders can be identified the following methods. 
The sol-gel method [6] with using bismuth nitrate and 
iron nitrate, followed by annealing at a temperature of 
600 oC for 30 minutes. The method does not provide a mo-
nophasic composition and requires additional procedures 
for the purification of the resulting material from 
Bi2Fe4O9, Bi36Fe24O57 and Bi2O3 impurities. The authors 
reported about method of production the nanopowders 
bismuth ferrite with a particle size of 200 nm and the val-
ue of the real part of the permittivity at room temperature 
equal 15 at the frequency 10 kHz. 
Single phase BiFeO3 nanoparticles (nanoparticles 
size - 47 nm) have been prepared [8] by a combustion 
method using metal nitrates and citric acid without any 
solvent. Dielectric constant at room temperature at a 
frequency of 10 kHz equal ε'  60. The magnetization of 
nanoparticles is small, but the dependence not saturat-
ed at H  17,500 Oe, Mössbauer effect indicates the 
presence only of ferric (Fe3+).  
 Method of combustion of organic nitrate precursors 
with the addition of ethylene glycol and simultaneous 
doping In and Mn is given in [5]. Such doping reduces 
the average grain size of 15 nm, and thus affects on 
their magnetic and electrical properties. For example, 
 V.M. SARNATSKY, N.A. VINOKUROV, ZH.KH. MURLIEVA, ET AL. J. NANO- ELECTRON. PHYS. 8, 03008 (2016) 
 
 
03008-2 
the saturation magnetization increased significantly 
from 0,20 emu / g for the BFO to 3,50 emu /g for In and 
Mn co-doped sample. The disadvantage of the method 
can be considered the use of toxic ethylene glycol. 
Solid phase synthesis of samples Bi1 – xBaxFeO3 c 
x  0,15; 0.25, 0.35 it was used in [9]. Received a signifi-
cant increase of the saturation magnetization of the 
samples M  6.0 emu/g, the value of ε' is equal to 380 at 
10 kHz at room temperature. For the first time, in the 
doped bismuth ferrite it was measured magnetic field 
effect on the value of ε'. The effect is to increase the ε' 
by 1.7 % in the field of 8 kOe. 
In [10-12] is described the role of size effects, de-
termining the effect of the size of the bismuth ferrite 
nanoparticles on the saturation magnetization and 
Neel temperature. In particular, in [14] reported the 
Neel temperature shift to 60 at changing nanoparticle 
size in the range 23-54 nm. 
 
3. EXPERIMENTAL MEASUREMENTS OF  
MGNETIC AND DIELECTRIC PROPERTIES 
OF BISMUTH FERRITE NANOPOWDERS 
 
BiFeO3 nanopowder was synthesized [13] by method 
of burning equimolar precursors from aqueous solu-
tions of nitrates iron Fe(NO3)3 and bismuth Bi(NO3)3 
with the addition of nitric acid and glycine. The result-
ing solution evaporated with stirring to the density 
1,14-1,16 g/cm, the heating rate up to the flash point 
was 10-30 K /min. On the X-ray source of nanopowder 
(diffractometer PANalytical Empyrean-2) are not ob-
served crystals of other stoichiometry, except the 
BiFeO3 (1a). The average particle size of the powder 
determined from the Debye-Scherrer formula was 50 
nm. After heat treatment for 1 hour at 600, 700 and 
800 °C (Fig. 1b, 1c, 1d) in the nanopowder appear and 
recrystallized sillenite Bi25FeO39 and mullite Bi2Fe4O9 
phases.  
The magnetization of nanopowders [14] was studied 
at room temperature under field 15 kOe. Already since 
4 kOe dependence M-H reaches saturation. 
The maximum value of the initial powder magnetiza-
tion at 15 kOe (6 emu /g) significantly exceeds the val-
ue of M, presented in [5,10], and after calcination, 
starting with the 700 °C, the magnetization approaches 
to characteristic for BiFeO3 values. High values of the 
initial magnetization nanopowder may be associated 
with the presence there of amorphous incidental phase, 
such as, for example, maghemite (-Fe2O3). For ma-
ghemite above 400 °C is observed [15] transition  
-Fe2O3 → -Fe2O3 (hematite-antiferromagnetic), which 
completes at 600 °C [15]. The samples heat treated  at 
600 °C and above, practically not contained maghemite. 
The magnetization of nanopowders, after heat treat-
ment at 700 °C and 800 °C corresponds to the values 
characteristic of the BiFeO3, as part of the nanopowder 
retains the dimensions below 62 nm. 
 
 
 
Fig. 1 – Diffraction patterns of the initial and the heat-treated nanopowders 
 
 
 
Fig. 2 – The dependence χ (T) of nanopowder bismuth ferrite: Δ – not heat-treated; Ο – after heat treatment at 600 °C 
 MAGNETIC AND ELECTRICAL CHARACTERISTICS OF BISMUTH FERRITE… J. NANO- ELECTRON. PHYS. 8, 03008 (2016) 
 
 
03008-3 
Measurements of the magnetic susceptibility χ per-
formed using complex to study the physical properties 
of materials in a wide range of temperatures and mag-
netic fields of PPMS-9 + EverCool-II in the temperature 
range 4-350 K in  the alternating magnetic field with 
frequencies from 10 Hz to 10 kHz and intensities of 
0.01 Oe-10 Oe. 
The dispersion of χ vaiue in the specified frequency 
range is not detected, and nonlinear effects when 
changing the intensity of the alternating magnetic field 
H is not manifested, so we present the results of meas-
urements χ obtained at a frequency of 1 kHz and in a 
field H  1Oe. Figure 2 shows the temperature depend-
ence of the magnetic susceptibility χ (T) of two samples 
of the nanocrystalline powder of bismuth ferrite:  not 
heat treated and after heat treatment at 600 С for 
2 hours. 
It should be noted the following. In – the first, at 
350 K, the magnetic susceptibility of the calcined sam-
ple is at 30 % lower compare to the non-calcined  sam-
ple [8]. The difference in the magnetic susceptibility of 
these samples decreases with decreasing temperature, 
and at 4K they are the same. It is known that the mag-
netic susceptibility (χ) of antiferromagnetics near 0 K is 
small, because the strong exchange interaction pre-
vents the spin orientation by an external magnetic 
field. With increasing temperature, spin ordering is 
disturbed and magnetic susceptibility of AF, in contrast 
to the paramagnetic materials, increases to the Neel 
temperature TN.  
Second, for the non heat-treated sample near the 
temperature 120 K there is a bend in the behavior of 
χ(T). This behavior χ(T) can be explained by the pres-
ence in the sample a small amount of magnetite, for 
which at this temperature is intense recharging of fer-
rous ions and ferric iron, and the corresponding change 
in the magnetization, which is confirmed by Mossbauer 
spectroscopy [16]. The technical capabilities of the ex-
perimental setup does not allow to reach the Neel tem-
perature of the bismuth ferrite (TN  643 K), however, 
the linear extrapolation of the χ (T) dependence for the 
heat-treated sample to the value TN shows that the 
value of χ at TN nearly twice higher than χ at 4 K, 
which agrees well with earlier measurements by Smo-
lenskiy and other [17] for polycrystalline bismuth fer-
rite samples. 
Dielectric properties of cold pressed (pressure 
 1 GPa) and the heat treated powders were measured 
using the dielectric NOVOCONTROL BDS spectrome-
ter in the temperature range from 123 to 723 K in the 
frequency range from 10 Hz to 40 MHz. Contacts to the 
samples with a diameter of 4 mm, 2 mm thick were 
made using silver paste brand SP-40 + Water Based 
Silver Ink. Fig. 3 in a semi-logarithmic scale shows the  
 
 
 
Fig. 3 – The dependence of ε'(f) (T  30 °C, Δ – not heat-treated; Ο – after heat treatment at 600 °C 
 
 
Fig. 4 – The ε-T dependence at different frequencies (sample calcined at 600 C) 
 
 V.M. SARNATSKY, N.A. VINOKUROV, ZH.KH. MURLIEVA, ET AL. J. NANO- ELECTRON. PHYS. 8, 03008 (2016) 
 
 
03008-4 
dependence of the real part of the dielectric constant ε' 
on the frequency f at temperature T  300 °C both for 
the unannealed sample and heat treated sample (an-
nealing temperature of 600 oC).  
The Figure 3 shows significant variance of ε', espe-
cially for the initial sample and that as a result of an-
nealing, character of dependence ε' changes considera-
bly, especially at low frequencies. 
Figure 4 shows the temperature-frequency depend-
ence of ε at high temperatures (100-450 C for a sample 
annealed at 600 C. Near Neel temperature (370 °C) on 
the ε'(T) curves is clearly observed anomalies associat-
ed with an antiferromagnetic phase transition. 
The results of studies of the magnetic and dielectric 
properties of nanocrystalline bismuth ferrite obtained 
by different methods, are summarized in Table 1, 
which gives the values of ε'at 300 C at the frequency of 
10 kHz; the nanocrystals size d; the magnitude of satu-
ration magnetization Ms (emu/g) and values saturation 
fields Hs. 
 
Table 1 – Results of studies of the magnetic and dielectric characteristics BiFeO3 powder 
 
Method Annealingre
nealingre-
gime 
d, nm 𝜀 Ms Hs 
Sol-gel [7] 600 С, N2 200 15 – – 
Citrate combus-
tion method [8] 
600 С, 2 h 47 60 0,2 15 kOe 
Citrate combus-
tion method [5] 
600 С, 1 h 15  In    +Мn – 3,5 2 kOe 
Solid phase syn-
thesis doped with 
Ba [10] 
– – 380 6.0 15kOe 
Combustonofprecu
rsor [11] 
600 С-
800 С 
50 180-120 6.0-0,15 4 kOe 
 
4. CONCLUSION 
 
A review of the experimental measurements and 
own researches by the authors of this article clearly 
demonstrate the presence of magnetoelectric coupling 
and significant dependence of magnetic and dielectric 
properties of bismuth ferrite from the frequency of the 
alternating electric field, temperature, conditions for 
synthesis and heat treatment, the magnitude of the 
magnetic field, the nanocrystal size and the degree of 
doping by impurity ions. 
Scientific research were performed at the Center for 
Diagnostics of Functional Materials for Medicine, 
Pharmacology and Nanoelectronics of Research park of 
St.Petersburg State University; this work was finan-
cially supported by the Russian Department of Science 
and Education, Projects Numbers 2560 and 
16.1103.2014/K, using equipment SEC "Nanotechnolo-
gy" DSU. 
 
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Magnetic and Electrical Characteristics of Bismuth Ferrite, Depending on the Impurities, Method of Preparation and Size of the Nanoparticles

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Magnetic and Electrical Characteristics of Bismuth Ferrite, Depending on the Impurities, Method of Preparation and Size of the Nanoparticles

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