BiFeO3 - BaTiO3

David Silva S.
07/11/2018
Universidad de Antioquia
Medellín
1
 1

Why is its study important?

Environment-friendly Properties
Since it doesn’t have any lead, it is
This material has multiferroics and
more environment-friendly than
piezoelectrics properties.
others piezoelectrics.

Theoretical interest Practical interest

Double excitation source sensors and
¿Why are this type of materials so scarce?
actuators [1]
 2

Importance
Why is this compound’s
multifunctionality important?

Since it has magnetic and electrical properties,

it can be used in the development of double
excitation source sensors for memory devices
without a huge energy loss [2]. The
piezoelectric gives huge possibilities for
actuators.

Also, since its characteristics are so unique, it’s

really interesting theoricaly, for it can help in
the understanding of multiferroics’ origins.

Maecenas tempus massa
Lorem ipsum dolor sit amet, consectetur adipiscing elit. Integer non
est in enim placerat varius. Maecenas tempus massa eget ex
consequat, ut rhoncus urna dignissim. Nulla et velit vel nulla suscipit
ultricies id vitae est. In felis arcu, pellentesque eget pulvinar iaculis,
posuere in est. Etiam gravida sed nisi sed pellentesque. Donec placerat
sem nisi, eget tempus arcu iaculis quis. Nulla facilisi. Cras felis turpis,
malesuada vitae purus quis, tempus scelerisque nibh. Nulla
fermentum turpis et dui elementum ullamcorper. Morbi dapibus velit
metus.
3
Before synthesis
What is the material’s behaviour at
different concentrations?
First of all, we’d like to have a concentration that
gives a material near the MPB so we can have
maximal electromechanical properties [3].
Here we also have the SEM for (1-x)BF - xBT
ceramics, where we can see the reduction of
porosity when x grows.
Coppa, B. J., Fulton, C. C., Kiesel, S. M., Davis, R. F.,
Pandarinath, C., Burnette, J. E., ... & Smith, D. J. (2005).
Structural, microstructural, and electrical properties of gold films
and Schottky contacts on remote plasma-cleaned, n-type ZnO
{0001} surfaces. Journal of applied physics, 97(10), 103517.
 4

XDR pattern

Curabitur ante libero

Lorem ipsum dolor sit amet, consectetur adipiscing elit. Aliquam
libero tortor, viverra eu rhoncus quis, vehicula

Curabitur ante libero

Lorem ipsum dolor sit amet, consectetur adipiscing elit. Aliquam
libero tortor, viverra eu rhoncus quis, vehicula

Coppa, B. J., Fulton, C. C., Kiesel, S. M., Davis, R. F., Pandarinath, C., Burnette, J. E., ... & Smith, D.
J. (2005). Structural, microstructural, and electrical properties of gold films and Schottky contacts on
1
remote plasma-cleaned, n-type ZnO {0001} surfaces. Journal of applied physics, 97(10), 103517.
 5

Phase diagram
Which concentrations are best suited
for our material?

Since we want our material to be in

the MPB, we can, by seeing the phase
diagram, conclude that the best
concentrations for our study are in
Maecenas tempus massa the x = 0.28 neighbourhood
Lorem ipsum dolor sit amet, consectetur adipiscing elit. Integer non
est in enim placerat varius. Maecenas tempus massa eget ex
consequat, ut rhoncus urna dignissim. Nulla et velit vel nulla suscipit
ultricies id vitae est. In felis arcu, pellentesque eget pulvinar iaculis,
posuere
Coppa, B. in est. Etiam gravida
J., Fulton, C. C., sed nisi sed
Kiesel, pellentesque.
S. M., Davis, R. Donec placerat C., Burnette,
F., Pandarinath,
sem nisi, eget tempus arcu iaculis quis. Nulla facilisi.
J. E., ... & Smith, D. J. (2005). Structural, microstructural, Cras felis turpis, and electrical
malesuada vitae purus quis, tempus scelerisque nibh.
properties of gold films and Schottky contacts on remote plasma-cleaned, Nulla n-type
fermentum turpis et dui elementum ullamcorper. Morbi
ZnO {0001} surfaces. Journal of applied physics, 97(10), 103517. dapibus velit
metus.
 6

Synthesis process: BFO and BTO

Milling and drying

The compounds will be milled for 24h

in a plastic jar with ZrO2 balls in air
atmosphere. Then they’ll be dried for
48h.

Reactives to be used:

BiO3: Sigma Aldrich 99% purity Calcination Sintering

TiO2: Sigma Aldrich -- purity
Fe2O3: Alfa Aesar 98% purity BF: 800 - 880 °C / 4h BF: ??
BaCO3: Merck -- purity
BT : 1000 - 1225 °C / 7 - 12 h BT: 1350°C / 6h
 7

BTO Calcination
Change of symmetry with calcination temperature

Majumder et al [4] show that for

calcination temperatures below 1000 °C the
cubic symmetry dominates. Whereas, for
higher calcination temperature tetragonal
symmetry dominates.
B1: 1000°C /12h
B2: 1000°C / 4h - grinding - 1200 °C / 3h
B12: 1000°C / 12h - grinding - 1225 °C / 12h
 8

BFO Calcination
Change of secondary phases amount with calcination temperature

U Nuraini and S Suasmoro [5] show that

with varying temperature comes a
change in the number of phases. The XRD
pattern shows that for increasing
calcination temperature, the number of
secondary phases also increases.
 9

Synthesis process: xBTO-(1-x)BFO

Silawongsawat, C., Chandarak, S.,
Sareein, T., Ngamjarurojana, A.,
Milling and drying Maensiri, S., Laoratanakul, P., ... &
Yimnirun, R. (2008). Effect of calcination
conditions on phase formation and
characterization of BiFeO3 powders
As before, the compounds will be synthesized by a solid-state reaction. In
milled for 24h in a plastic jar with ZrO2 Advanced Materials Research (Vol. 55,
pp. 237-240). Trans Tech Publications.
balls in air atmosphere. Then they’ll be
dried for 48h.

Concentrations to be used for xBTO-(1-

x)BFO:
Calcination Sintering
x1 = 0.44
Results from DTA/TG shows that for Sintering temperature is shown to be
x2 = 0.48 0.5 >x > 0.2 concentrations , the best in the range of 960-1020°C [1]
calcination temperatures are in the
range of 900-950°C [8]
 10

Known results
Best piezoelectric BF-BT composite

Positive Negative
➢ Large small-field piezoelectric ➢ Bad DC resistivity
constant:
○ d33 = 116pC/N ➢ Oxygen atmosphere sintering
needed for improving DC
➢ High Curie temperature: resistivity
○ Tc = 619°C
➢ Almost inevitable BF secondary
phases
 11

Proposed solution
Rare-Earth doping

Improves ferroelectric properties Secondary phases reduction

Re-doping causes reduction in the density of Jie Wei et al. showed that Re-doping greatly
the freely moving charges, therefore reduces the emergence of secondary phases
improving ferroelectric properties [6] [7]
 12

Re-doping XDR

ICDD FIle Card No. 86-1518 shows how a

XDR pattern for a rhombohedral distortion
perovskite structure with a space group of
R3c should look. Comparing with the
experimental data, one can assure the non-
existence of secondary phases in RE-doped
BFO ceramics.
 13

Conclusions
➢ Exploiting the uniqueness of BFO together with BTO’s piezoelectricity, could lead
to the study of BFO-BTO system in a new way, since it’ll more of a multiferroic
with piezoelectric properties than a piezoelectric with multiferroic properties.

➢ Rare-Earth doping in BFO-BTO system offers a new possibility in its study, since
there is almost no literature about it.
 14

References
[1] Coppa, B. J., Fulton, C. C., Kiesel, S. M., Davis, R. F., Pandarinath, C., Burnette, J. E., ... & Smith, D. J. (2005). Structural, microstructural,
and electrical properties of gold films and Schottky contacts on remote plasma-cleaned, n-type ZnO {0001} surfaces. Journal of applied
physics, 97(10), 103517.

[2] Fiebig, M., Lottermoser, T., Meier, D., & Trassin, M. (2016). The evolution of multiferroics. Nature Reviews Materials, 1(8), 16046.

[3] Ahart, M., Somayazulu, M., Cohen, R. E., Ganesh, P., Dera, P., Mao, H. K., ... & Wu, Z. (2008). Origin of morphotropic phase boundaries
in ferroelectrics. Nature, 451(7178), 545.

[4] Majumder, S., Choudhary, R. J., Tripathi, M., & Phase, D. M. (2018, May). Effect of calcination routes on phase formation of BaTiO3 and
their electronic and magnetic properties. In AIP Conference Proceedings (Vol. 1953, No. 1, p. 110020). AIP Publishing.

[5] Nuraini, U., & Suasmoro, S. (2017). Crystal structure and phase transformation of BiFeO3 multiferroics on the temperature variation. In
Journal of Physics: Conference Series (Vol. 817, No. 1, p. 012059). IOP Publishing.

[6] Cheng, Z., Wang, X., Dou, S., Kimura, H., & Ozawa, K. (2008). Improved ferroelectric properties in multiferroic Bi Fe O 3 thin films through
La and Nb codoping. Physical Review B, 77(9), 092101.

[7] Wei, J., Wu, C., Liu, Y., Guo, Y., Yang, T., Wang, D., ... & Haumont, R. (2017). Structural Distortion, Spin-Phonon Coupling, Interband
Electronic Transition, and Enhanced Magnetization in Rare-Earth-Substituted Bismuth Ferrite. Inorganic chemistry, 56(15), 8964-8974.

[8] Silawongsawat, C., Chandarak, S., Sareein, T., Ngamjarurojana, A., Maensiri, S., Laoratanakul, P., ... & Yimnirun, R. (2008). Effect of
calcination conditions on phase formation and characterization of BiFeO3 powders synthesized by a solid-state reaction. In Advanced
Materials Research (Vol. 55, pp. 237-240). Trans Tech Publications.