Structure of barium titanate particles obtained by peroxide method was studied by SEM, X-ray phase analysis, IR spectroscopy and Raman scattering. Found, that particles have preferably a spherical shape with a diameter of 20-200 nm and contain both cubic and tetragonal phases.
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Emelianov, N.

Kuzmenko, A.

Sizov, A.

Yacovlev, O.

SocioEconomic Challenges Journal (Sumy State University)

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ 
Vol. 5 No 4, 04024(2pp) (2013) Том 5 № 4, 04024(2cc) (2013) 
 
 
The article was reported at the International Conference «Physics and Technology of Nanomaterials and Structures», Kursk, 21-22 November, 2013 
 
2077-6772/2013/5(4)04024(2) 04024-1  2013 Sumy State University 
Short Communication 
 
Formation of Spherical Nanoparticles BaTiO3 by Peroxide Method 
 
A. Kuzmenko1, A. Sizov1, O. Yacovlev1, N. Emelianov2 
 
1 Southwest State University, 94, 50 Let Octyabtya Str, 305040 Kursk, Russia 
2 Kursk State University, 33, Radishchev Str. 305000 Kursk, Russia 
 
(Received 15 October 2013; published online 10 December 2013) 
 
Structure of barium titanate particles obtained by peroxide method was studied by SEM, X-ray phase 
analysis, IR spectroscopy and Raman scattering. Found, that particles have preferably a spherical shape 
with a diameter of 20-200 nm and contain both cubic and tetragonal phases. 
 
Keywords: Barium titanate, Peroxide method, Cubic and tetragonal phases. 
 
 PACS number: 61.46. – w 
 
 
1. INTRODUCTION 
 
Barium titanate is a well-used material for the produc-
tion of components of microwave technology, such as phase 
shifters, delay lines, parametric amplifiers and harmonic 
generators. Improvement of the parameters of devices is 
possible with increasing purity requirements, the number 
of defects and the dielectric properties of this material. 
Well known that the structure and dielectric properties of 
the ferroelectric, including barium titanate, essentially 
depend on the particle size [1]. Miniaturization particle 
size leads to improved electrical and mechanical properties 
of ceramics based on the compound. Analysis of the meth-
ods of obtaining BaTiO3 shows that the most promising is 
its preparation by the thermal decomposition of the inor-
ganic precursor. 
 
2. EXPERIMENTAL SECTION 
 
BaTiO3 precursor was synthesized according to reac-
tion: 
 
TiCl4 + BaCl2 + 2H2O2 + 6NH4OH →  
BaO2O2TiO∙2H2O↓ + 6NH4Cl + 3H2O  
 
The resulting precipitate was filtered off, washed out 
and dried. Thermal treatment of the precursor was per-
formed in air during one hour at temperatures of 700, 800 
and 900 C. Method of the scanning electron microscopy 
(Quanta 650 FEG) shows that the obtained particles have 
a spherical shape with a diameter of 50 to 200 nm and 
agglomerated into clusters of up to several micrometers 
(Fig. 1a). 
Microprobe analysis shows a uniform distribution of 
barium, titanium and oxygen on the surface of particles 
with an aspect ratio typical of BaTiO3, which follows 
from the data element mapping. Particles produced in 
the decomposition of the precursor at a temperature of 
700 °C, a peak is observed and the peak of carbon, chlo-
rine indicative of partial decomposition of the precursor. 
Further reduction of the precursor products is achieved 
by annealing at 800 °C (Fig. 1b). 
This fact is also confirmed by X-ray diffraction data 
(GBC EMMA, CuKα), as seen in X-rays (Fig. 2a), on 
which there are reflexes typical of the cubic phase of 
BaTiO3 (Fig. 2a). Reflexes had broadening, indicating  
 
 
 
 
Fig. 1 – SEM-images of nanoparticles BaTiO3 (a), spectrum of 
X-ray microanalysis (b)  
 
incomplete decomposition of the precursor. For the par-
ticles annealed at 700 °C there is a splitting of the re-
flex (200/002), characteristic of the tetragonal phase 
(Fig. 2b). 
During the heat treatment, peroxide synthesis and 
also noted the formation of BaTiO3 in the cubic struc-
ture distortion, for example, in the form of inclusions 
BaTi2O5 at angles 2  26° and 70°. The ratio of the 
a 
b 
 A. KUZMENKO, A. SIZOV, O. YAKOVLEV, N.EMELIANOV J. NANO- ELECTRON. PHYS. 5, 04024 (2013) 
 
 
04024-2 
intensities for reflections I101 / I002 also marks the for-
mation of the cubic phase. 
 
 
 
 
 
Fig. 2 – X-ray patterns of BaTiO3 after annealing at 800 °C (a), 
splitting reflex (200 / 002) after annealing at 700 °C (b) 
 
The sizes of BaTiO3, can be evaluated (the coherent 
scattering areas (L) of X-ray radiation) from the Scherer 
equation: L  k/(Bcos). The reflection width was con-
sidered by the level 0.5 (B), θ is the Bragg angle, 
  0.154178 nm for CuK, k is a constant equal to 0.9. 
Considering the arising during synthesis microstrain 
and instrument broadening their sizes are about 20 nm. 
Raman scattering spectra samples BaTiO3 annealed 
at temperatures 700 and 800 °C lines marked appear-
ance as an amorphous halo in the range of 170-320 cm –
 1, ~ 520 and 720 cm – 1, characteristic of the cubic struc-
ture [2]. Comparison of the Raman spectra with in-
creasing annealing temperature is characterized by 
both a decrease in the intensity of all the lines, so they 
shifted to lower frequencies, indicating a decrease in 
the size of nanoparticles and the increase in the cubic 
phase. 
IR spectra and peroxide precursor powders after 
heat treatment similar to the spectra of the powders 
obtained by mechanochemical synthesis of oxalate pre-
cursor [2]. Peaks of absorption 1356 and 1415 cm – 1 for 
the untreated and ~ 1344 and 1413 cm – 1 for the treated 
precursor at 700 °C of impurities caused by the pres-
ence of carbonates. 
 
 
 
Fig. 3 – Raman scattering spectra samples BaTiO3 annealed 
at temperatures 700 and 800 °C 
 
3. RESULTS AND DISCUSSION 
 
The difference between the SEM and X-ray analysis 
relative to the size of the particles may be explained by 
the significant variation in shape and size of the syn-
thesis products. In the SEM images at different magni-
fications indicated forming cubic, whiskers, cluster 
structures of different phase composition. 
 
4. CONCLUSIONS 
 
Thus, the peroxide synthesis by the of barium titan-
ate powder according to SEM are nanosized particles of 
50 to 200 nm by XRD are cubic and tetragonal phases 
with sizes of about 20 nm nanoparticles. With increas-
ing annealing temperature of the precursor from 700 to 
800 C promotes structural perfection of the lattice, and 
the reduction of the content of the tetragonal phase. 
 
 
REFERENCES 
 
1. T. Ohno, D. Suzuki, H. Suzuki, T. Ida, J. Soc. Powder 
Technol. 41, 86 (2004). 
2. B.M. Gorelov, E.V. Kotenok, S.N. Makhno, V.V. Sydorchuk, 
S.V. Khalameida, V.A. Zazhigalov Tech. Phys. 56, 83 
(2011). 
 
a 
b 


English

Formation of Spherical Nanoparticles BaTiO3 by Peroxide Method

Electronic Sumy State University Institutional Repository

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ Vol. 5 No 4, 04024(2pp) (2013) Том 5 № 4, 04024(2cc) (2013)   The article was reported at the International Conference «Physics and Technology of Nanomaterials and Structures», Kursk, 21-22 November, 2013  2077-6772/2013/5(4)04024(2) 04024-1  2013 Sumy State University Short Communication  Formation of Spherical Nanoparticles BaTiO3 by Peroxide Method  A. Kuzmenko1, A. Sizov1, O. Yacovlev1, N. Emelianov2  1 Southwest State University, 94, 50 Let Octyabtya Str, 305040 Kursk, Russia 2 Kursk State University, 33, Radishchev Str. 305000 Kursk, Russia  (Received 15 October 2013; published online 10 December 2013)  Structure of barium titanate particles obtained by peroxide method was studied by SEM, X-ray phase analysis, IR spectroscopy and Raman scattering. Found, that particles have preferably a spherical shape with a diameter of 20-200 nm and contain both cubic and tetragonal phases.  Keywords: Barium titanate, Peroxide method, Cubic and tetragonal phases.   PACS number: 61.46. – w   1. INTRODUCTION  Barium titanate is a well-used material for the produc-tion of components of microwave technology, such as phase shifters, delay lines, parametric amplifiers and harmonic generators. Improvement of the parameters of devices is possible with increasing purity requirements, the number of defects and the dielectric properties of this material. Well known that the structure and dielectric properties of the ferroelectric, including barium titanate, essentially depend on the particle size [1]. Miniaturization particle size leads to improved electrical and mechanical properties of ceramics based on the compound. Analysis of the meth-ods of obtaining BaTiO3 shows that the most promising is its preparation by the thermal decomposition of the inor-ganic precursor.  2. EXPERIMENTAL SECTION  BaTiO3 precursor was synthesized according to reac-tion:  TiCl4 + BaCl2 + 2H2O2 + 6NH4OH →  BaO2O2TiO∙2H2O↓ + 6NH4Cl + 3H2O   The resulting precipitate was filtered off, washed out and dried. Thermal treatment of the precursor was per-formed in air during one hour at temperatures of 700, 800 and 900 C. Method of the scanning electron microscopy (Quanta 650 FEG) shows that the obtained particles have a spherical shape with a diameter of 50 to 200 nm and agglomerated into clusters of up to several micrometers (Fig. 1a). Microprobe analysis shows a uniform distribution of barium, titanium and oxygen on the surface of particles with an aspect ratio typical of BaTiO3, which follows from the data element mapping. Particles produced in the decomposition of the precursor at a temperature of 700 °C, a peak is observed and the peak of carbon, chlo-rine indicative of partial decomposition of the precursor. Further reduction of the precursor products is achieved by annealing at 800 °C (Fig. 1b). This fact is also confirmed by X-ray diffraction data (GBC EMMA, CuKα), as seen in X-rays (Fig. 2a), on which there are reflexes typical of the cubic phase of BaTiO3 (Fig. 2a). Reflexes had broadening, indicating      Fig. 1 – SEM-images of nanoparticles BaTiO3 (a), spectrum of X-ray microanalysis (b)   incomplete decomposition of the precursor. For the par-ticles annealed at 700 °C there is a splitting of the re-flex (200/002), characteristic of the tetragonal phase (Fig. 2b). During the heat treatment, peroxide synthesis and also noted the formation of BaTiO3 in the cubic struc-ture distortion, for example, in the form of inclusions BaTi2O5 at angles 2  26° and 70°. The ratio of the a b  A. KUZMENKO, A. SIZOV, O. YAKOVLEV, N.EMELIANOV J. NANO- ELECTRON. PHYS. 5, 04024 (2013)   04024-2 intensities for reflections I101 / I002 also marks the for-mation of the cubic phase.      Fig. 2 – X-ray patterns of BaTiO3 after annealing at 800 °C (a), splitting reflex (200 / 002) after annealing at 700 °C (b)  The sizes of BaTiO3, can be evaluated (the coherent scattering areas (L) of X-ray radiation) from the Scherer equation: L  k/(Bcos). The reflection width was con-sidered by the level 0.5 (B), θ is the Bragg angle,   0.154178 nm for CuK, k is a constant equal to 0.9. Considering the arising during synthesis microstrain and instrument broadening their sizes are about 20 nm. Raman scattering spectra samples BaTiO3 annealed at temperatures 700 and 800 °C lines marked appear-ance as an amorphous halo in the range of 170-320 cm – 1, ~ 520 and 720 cm – 1, characteristic of the cubic struc-ture [2]. Comparison of the Raman spectra with in-creasing annealing temperature is characterized by both a decrease in the intensity of all the lines, so they shifted to lower frequencies, indicating a decrease in the size of nanoparticles and the increase in the cubic phase. IR spectra and peroxide precursor powders after heat treatment similar to the spectra of the powders obtained by mechanochemical synthesis of oxalate pre-cursor [2]. Peaks of absorption 1356 and 1415 cm – 1 for the untreated and ~ 1344 and 1413 cm – 1 for the treated precursor at 700 °C of impurities caused by the pres-ence of carbonates.    Fig. 3 – Raman scattering spectra samples BaTiO3 annealed at temperatures 700 and 800 °C  3. RESULTS AND DISCUSSION  The difference between the SEM and X-ray analysis relative to the size of the particles may be explained by the significant variation in shape and size of the syn-thesis products. In the SEM images at different magni-fications indicated forming cubic, whiskers, cluster structures of different phase composition.  4. CONCLUSIONS  Thus, the peroxide synthesis by the of barium titan-ate powder according to SEM are nanosized particles of 50 to 200 nm by XRD are cubic and tetragonal phases with sizes of about 20 nm nanoparticles. With increas-ing annealing temperature of the precursor from 700 to 800 C promotes structural perfection of the lattice, and the reduction of the content of the tetragonal phase.   REFERENCES  1. T. Ohno, D. Suzuki, H. Suzuki, T. Ida, J. Soc. Powder Technol. 41, 86 (2004). 2. B.M. Gorelov, E.V. Kotenok, S.N. Makhno, V.V. Sydorchuk, S.V. Khalameida, V.A. Zazhigalov Tech. Phys. 56, 83 (2011).  a b 

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Formation of Spherical Nanoparticles BaTiO3 by Peroxide Method

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