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Bismuth Ferrite

The potential of future electronic memory devices are at its twilight of


booming into a new set of generation of memory chips. Instead of having the
memory devices of which are as big as tens of nanometer, which is what our
today technologys advanced system offers, comes a memory device
shrinking to one or two nanometer. If only one can synthesize a way to gasp
into his hands the controls of how to separate those regions that have
different electric, magnetic and other properties this would be possible.
Bismuth ferrite is a compound of bismuth, iron and oxygenBiFeO 3.
This compound was discovered to have domain walls never been seen by
scientists of the department of energy at Lawrence Berkeley National
Laboratory of the University of California. Even though Bismuth ferrite was
originally know as an insulator, this compound was discovered to have
different electrical polarity that conducts electricity at room temperature. In
this review, I will focus primarily on the synthesis, physical and chemical
properties, industry use and its effect upon disposal to the environment of
Bismuth Ferrite.

Chemical and physical properties

Bismuth ferrite, being an inorganic chemical compound, has perovskite


structure ( in which planes of heavy atoms, bismuth for this compound, and
oxygen alternates with planes of lighter atoms, Iron for this compound, and
oxygen atoms) and is said to be one of the most promising multiferroic
materials that exhibits multiferroic properties at room temperature. At room
temperature, BiFeO3 is classified as rhombohedral that belongs to group R3c.
It is synthesize in thin film and in bulk and it temperaturesantiferrmagnetic
Neel and ferroelectric Curieare well above room temperature (653 K nd
1100 K, respectively). Its polarization occurs with a magnitude of 90-95
C/cm2 along the pseudocubic 111 direction. Its walls are oriented along two
different crystallographic planes, meaning it can be separated with 109degree, 71-degree, or 180-degree differences in the direction of the
polarization. Bismuth ferrite films contains ferroelectric sphere that is
between 5 to 10 micrometers. It exhibits week magnetism at room
temperature because of the spiral magnetic spin cycloid with a periodicity of
62 nm.

Synthesis/preparation of Bismuth ferrite

In synthesizing this promising alloy, many ways were developed. The


following are just some of the ways on how to produce Bismuth ferrite:
SOL-GEL TECHNIQUE
A 2:1 ratio of bismuth and iron was prepared from the starting
materials bismuth nitrate and ferric chloride. The excess bismuth is used to
compensate the bismuth evaporated during high temperature annealing.
Bismuth nitrate and ferric chloride were dissolved in acetic acid and was
added with ethylene glycol that served as a drying control agent to restrict
cracking of the thin films before coat spinning. The solution was them
refluxed for 5 hour.
Figure 1. Flow chart of the synthesis
of BiFeO3 .
The precursor was coated on copper
substrate at 3000 rpm for 30 seconds
while spinning after it was cooled down to
room temperature. For thicker film, the
process was repeated. After the process,

Figure 1

the film was kept exposed for 1 hour for gel film to form via hydrolysis and
polymerization. The film was dried via heat treatment at a temperature of
300o C for 2 hours. The Crystallization, densification and microstructure of
the films were then examined.

SUPERFACTANT ASSISTED AUTOCOMBUSTION SYNTHESIS


Bismuth
synthesized

by

ferrite
a

powder

solution

route. A 0.25 M Bi(NO3)3

was

evaporation

and a 0.25 M

Fe(NO3)3 was prepared by dissolving it in


dilute nitric acid. The two solutions were
mixed in a beaker. A 0.1 mole ratio of
glycine was added to the solution above
with respect to nitrate. The supernatants
Triton

X,

and

ALS

(ammonium

lauryl

sulfate) were added to the solution with a


mole ratio of 0.05 with respect to the
Figure 2

metals. The solution was then

heated on a hot plate with continuous stirring until it reaches its boiling
temperature such time that all liquid have already evaporated. A brown fume
that evolves during the process was obtained at the bottom of the beaker.
The powder was than calcined at 500oC and 550oC. the crystalline size of the
powder was then computed using the Scherrer formula.
Figure 2. Flow chart of supernatant assisted autocombustion synthesis.
SUPER CRITICAL HYDROTHERMAL SYNTHESIS
The

equal

mole

amount

(0.003

mol)

of

Bi(NO3)35H2O

and

Fe(NO3)3.9H2O was weighted. Then, Bi(NO3)3.5H2O and Fe(NO3)3.9H2O

was dissolved in 250 ml deionized water and was heated until homogenized.
It was than transferred to a reactor vessel. A stainless steel 316 with 180 mL
volume bath type reactor was used and was heated using an electrical
heater.
The hydrothermal reaction was performed in the reactor vessel at 500 o
C for 2 hours. After then, the reactor vessel was reduced to stop the reaction
with cold water so that the product will be collected through washing the
reactor with deionized water and cetrifugate to remove the reagent that
didnt reacted. Then the BiFeO nanoparticles were dreid at 40 o C for 24
hours.
The identity of the synthesized nanoparticled was then X-rayed for
diffraction measurements. The size and the shape of the obtained
nanoparticled was then studied using transmission electron microscopy.

CO-PRECIPITATE/ HYDROTHERMAL SYNTHESIS


The starting materials were 0.227 g of FeCl3* 6H2O and 0.407 g
Bi(NO3)3* 5H2O. These were dissolved in ethandiol of 20 mL of with stirring for
2 hrs. for fine precipitation, Fe/Bi solution was dissolved slowly and was
dripped into diluted ammonia solution (0.3 mol/L) with stirring for 30
minutes. A precipitate will then be observed. This precipitate was then
washed with de-ionized water for 5-6 times, and underwent a hydrothermal

reaction using NaOH as mineralizer. The hydrothermal was performed with


various reaction temperatures ranging from 140o-220o and with varied NaOH
concentrations of 0.05-0.25 mol/L for 12 hrs. The autoclave was then cooled
naturally to room temperature after the hydrothermal reaction. The products
were then washed with de-ionized water until it was neutral.
The phase structure of as-prepared BiFeO 3 powders then subjected to
characterization by X-ray diffraction (XRD), Rigaku D/max220PC) with
graphite monochromatozed CuK

radiation, the scan rate was 10 o/min.

SEM (Dutch Quanta 200) was employed to determine particle morphology


and size. Differential scanning calorimetry (DSC, SDT 2960) of BiFeO 3
powders was then carried out from room temperature to 1100 oC in nitrogen
ambient at a scan rate of 10oC/min.
MORPHOLOGY-CONTROLLED HYDROTHERMAL SYNTHESIS USING VARIOUS
ALKALINE MINERALIZERS
The chemical reagents used were bismuth nitrate [Bi(NO3)35H2O],
iron chloride (FeCl36H2O), potassium hydroxide (KOH), sodium hydroxide
(NaOH) and lithium hydroxide (LiOH). The equal molar amount (0.02 M) of
Bi(NO3)35H2O and FeCl36H2O were carefully weighted. To beaker 1,
Bi(NO3)3*5H2O was liquefied in 10 ml ethylene glycol with continuous
stirring and to beaker 2, FeCl36H2O was dissolved in 10 ml distilled water.
Then, the solution in beaker 2 was slowly added into the solution in beaker 1

stirring for 15 min. To adjust its pH to or greater than 10, 13.2 M solution of
ammonia was slowly dropped into the homogenous solution with constant
stirring, and a brown-colored precipitate will be formed. To remove NO3- and
Cl- ions from the precipitate, it was filtered and repeatedly was washed with
distilled water. The suspension was then transferred into a 40 ml Teflon-lined
stainless steel autoclave and to fill the capacity of 70%, mineralizer solutions
was added. Potassium hydroxide (KOH), lithium hydroxide (LiOH) and sodium
hydroxide (NaOH) were utilized for the preparation of mineralizer solutions.
The hydrothermal was performed with a reaction temperature of 180o C with
varied concentratios of the mineralizer (0.02-0.15 M) for 16 hours with
autogeneous pressure. The final products of the autoclave were filtered out
and were washed with distilled water and absolute ethanol several times to
remove residual soluble salts and unreacted ions after the autoclave was
cooled down naturally to room temperature. The obtained powders were
dried at 80C for 5 hours before characterization.
The phase structure of the as-synthesized BiFeO3powders was
characterized by X-ray powder diffraction with monochromated CuK
radiation ( = 1.5406 ) at 40 Kv and 50 Ma. The transmission electron
microscope (TEM), high-resolution transmission electron microscope (HRTEM) and selected area electron diffraction (SAED) images of the final
products were then observed using a JEOL 200 CX TEM with acceleration
voltage of 300 Kv.

Important use in the industry


In the past studies, bismuth ferrite has proven itself for its effective
and applications to the industry. Bismuth ferrite was used as high tech
magnetic tapes, used for its superconductivity, used in environmental
engineering; and finally, is used to enhance spontaneous magnetization. But
for this review, I will focus on the new discovered application of bismuth
ferrite--nanoscale shape-memory oxide.
Bismuth ferrite is a compound of bismuth, iron and oxygen. This
multiferroic compound has been studied thoroughly in recent years by many
scientists. As bismuth ferrite, being a multiferroic alloy, displays both
ferromagnetic and ferroelectric properties, meaning it responds to
applications of magnetic field or external electric. In this latest study by the
scientists of the University of California in Berkley they were able to
introduce an elastic-like phase transition into bismuth ferrite by means of
electric field.
Bismuth ferrite's application to the electric field allowed them to
develop a phase transformation to be achieve that is reversible even without
assistance of an external stress recovery said Ramesh of the University of
California in Berkley.
This new discovery of the shape-memory alloys claimed to be the
champion for elasticity and is primed to take over the shape memory apps to
a whole new level---which is shrinking it to nanoscale. Researchers in Berkley

laboratory have discovered a way to introduce recoverable strain into


bismuth ferrite up to 14%.
This is larger than any shape-memory effect observed in any metals
for now. This discovery opens new door to for the application of many fields
such as that in medical, energy, and specially electronics.
According to Jinxing Zhang this bismuth ferrite they newly developed
displays amazing features including being stable even when reduced to
nanometer compared to other shape-memory alloys. One more feature is
that its responses are fast due the electrical field needed to activate shapememory alloy rather than the primitive way of using thermal fields.
A shape-memory effect is when a solid material grows back to its
original shape after being deformed after stress is applied is an ability of a
metal to be elastic. In the past, this has always been involved with heating.
Nickel-titanium or "nitinol alloy is a shape-memory alloy that has a great
use to those that are in the field of medicine. It is used intents for
angioplasty and in medical joints. This memory effect of alloy has also have a
great impact for non-medical fields. An example is the actuators in smart
materials and in Microelectro-Mechanical Systems (MEMS). But as scientist
try to achieve nano-scale size of this shape-memory alloys, various problems
and instabilities arises such as micro-cracking and oxidation. But with the
new study on bismuth ferrite, scientists of Berkley Lab's materials Sciences
Division of the University of California in Berkley were able to eliminate

surface issues and were able to integrate it with microelectronics by


achieving shape-memory effect to an oxide material rather than in alloy
metals. According to Zhang, this bismuth ferrite they developed has "ultrahigh work function density during actuation that is almost two orders of
magnitude higher than what a metal alloy can generate." Ramesh also added
that even though aspects like hysteresis, micro-cracking and so many more
needs to be accounted when it will be applied to real devices, the discovery
of bismuth ferrite being able to show large shape-memory effect only shows
that it is not an ordinary material. This alloy has great potentials that it can
be use in the future in nanoelectromechanical devices and other state-of-theart nanosystems.
Environmental threat
The treat that it impose to the environment is due to the use of lead.
Bismuth ferrite is a piezoelectric material that is a lead-based perovskite
compound. Lead that is used poses threats to neurotoxin that may seriously
affect human health, especially the young ones and to the environment. But
because of the threat it poses researchers of University of California in
Berkley together with the U.S. Department of Energys Lawrence Berkeley
national laboratory (Berkely Lab) have discovered a way to produce a leadfree alternative to the current crop of piezoelectric material by applying
compression to the thin films of bismuth ferrite. However, the by this method
bismuth ferrite crystal have the tendency to revert back to its original

rhombohedral-like phase but by alternating the material from squeezing and


relaxing, the researchers was able to shuffle the material back and forth
between the two phases.
Indeed alloys have shaped the world of technology and technology
shaped the world of alloys as well. Because of the pursuit to better living,
continuous discovery of alloys application has already been rampant and
have been beneficial to human race.

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Phys.org. Retrieved December 20, 2013, from
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Bismuth Ferrite (BiFe03) from READE (n.d.). In READE. Retrieved


December 24, 2013, from
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ferrite-bife03-bfo-multiferroic-bismuth-ferrite-powder-bismuth-ferritesputtering-targets-bismuth-ferrite-nanotubes-bismuth-ferritenanowires-bismuth-ferrite-nanocrystals-superconductivity-spontan?
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Bismuth Ferrite: Multiferroic and Lead-Free Piezoelectric Materials.
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PDF:

Synthesis and characterization of bismuth and its component (2009) by


Vishwambar Nath Shukla

Bismuth ferrite nanoparticles formation via a supercritical


hydrothermal synthesis method (2012) by J. Karimi, A., and Golzary, C

Synthesis and Properties of Bismuth Ferrite Multiferroic Nanoflowers


(2000s) by Chybczynska, K., awniczak, P., Hilczer, B., eska, B.,
Pankiewicz, R., Pietraszko, A., Kepinski, L., Kauski, T., Cieluch, P.,
Matelski F., and Andrzejewski, B.