Double perovskites and its application: A Review

Pratikshya Priyadarshini and S. K Parida

Department of Physics, ITER, Siksha O Anusandhan Deemed to be University, Bhubaneswar-751030, India

Corresponding author: santoshparida@soa.ac.in

Abstract
1. Introduction

A double perovskite oxide is any material with a crystal structure following the formula
AA’BB’O6. In recent decades double perovskite materials have attracted significant attention
because of their physical properties, technical applications and fundamental importance. Before
going to details of this we must have proper knowledge about what is perovskite.
The perovskite family is one of the most important families in solid state physics. A perovskite
was first discovered as the mineral which consists of Calcium Titanium Oxide ( CaTiO3 ). This
mineral was first discovered in 1839 by GUSTAV ROSE in the Ural Mountain of Russia and
named after Russian mineralogist L.A. PEROVSKI (1792 - 1856). Perovskite family shows
many engrossing and interesting features from both conceptual and application perspective.
Ferro electricity, Superconductivity, Magneto resistance, dielectric properties are commonly
observed characteristic in this family. The perovskite lattice is a FCC lattice that consists of
small B cation with oxygen octahedra and larger A cation which are 12 fold coordinated by
oxygen. The perovskite oxide materials have been considered as a prominent area of research in
applied solid state science. There are several types of perovskite structures exist in different
types such as; A2BO4 :- layered perovskite, ABO3 :- single perovskite , A2A’B2B’O9 :-triple
perovskite , AA’BB’O6 :- double perovskite etc. The perovskite structure with formula ABO3 (A
is a large cation, and B a small transition metal or lanthanide cation) can be described as a
framework of oxygen octahedral sharing corners. The enormous framework and configurational
space in perovskites materials have encourage experimentalists to multiply the site occupancies
by adding new elements to this structure. This addition leads to the elaboration of new materials
defined as double perovskite oxides, resulting from doubling the general formula of single
perovskite structure. Since the real studies in the early 1950’s, the A 2BB’O6 double perovskite (A
is an alkali or rare earth cation while B and B’ are transition metal cations) have undergo
significant scientific interest due to their physical properties and technological applications. Rare
earth element show different types of properties like magnetic, electrical, optical properties .In
recent decades rare earth based perovskites have attracted much interest due to it’s novel
functionalities like magneto resistance, multiferroicity, magnetocapacitance and photo catalytic
activities. Similarly, alkaline earth based double perovskites shows a large family of oxide
compounds with magnetic and electronic properties, half- metallicity, high-low field
magnetoresistance and wide variety of magnetic structures. All these features have attracted the
researchers to explore even more flexibility and degrees of freedom by conducting and
developing intensive researches on another family of mixed double perovskite materials of
general formula AA’BB’O6 ( A is an alkali earth cation, A’ a rare earth cation, while B and B’
are transition metal cation).In these compounds, depending on their ionic radius and charge the A
site and B site cations occupy distinct or indistinguishable crystallographic sites. Thus as a result
a variety of interesting properties have been highlighted such as magnetoelectricity, giant
magneto caloric effect, catalytic properties, half metallicity, multiferroicity, colossal
magnetoresistance etc.

2. Structure

In crystallography, the crystal structure of a solid substance is of considerable fundamental

interest. Numerous significant physical characteristics of the material, such as its electrical,
magnetic, or optical properties, can also be impacted by the crystal structure. Therefore,
understanding the crystal structure is frequently necessary in order to forecast or comprehend the
qualities of the material. Perovskite structure have general formula ABO 3, where A and B are
cations and O is anion, and the aristotype structure possesses Pm3m space group symmetry.

ABO3

La3+, Gd3+, Dy3+, Ce3+, Fe3+, Cr3+, Al3+,

Nd3+, Sm3+,Eu3+, Ga3+,Sc3+,In3+ etc
Tb3+ etc

The ideal perovskite structure is shown in figure below

The topology in case of perovskites is thermodynamically stable, but the structure may distort
due to bonding preferences of A, B and B’ cations. As earlier we have discussed that ideal
structure of perovskite is cubic but the structure can be distorted by tilting the BO 6 octahedra or
by cationic displacements. Octahedral tilting is the most common type.
From a structural perspective, the perovskite lattice is made up of larger cations that are eleven
fold coordinates of oxygen and tiny B cations that are contained within oxygen octahedra. ,
When two perovskite compounds are bombarded with each other, their respective bonding
strives to line up to frame a double perovskite structure. The general formula of double
perovskite is A2BB’O6 (where A is rare earth cations and B and B’ transition metal cations) and
aristotype structure possesses Fmˉ3m. The A2BB′O6 double perovskite structure, in which the
unit cell is doubled along all three axes, results from the arrangement of two distinct octahedral
cations in a three-dimensional checkerboard pattern (also known as rock salt ordering).

A2BB’O6

Ba2+, Mg2+, Ca2+, Sr2+, Fe, Cr, Co, Mo

Be2+, Ra2+ etc W etc

In B site ordering there are two types of B site patterning. More than 160 perovskite oxides, are
represented by rock salt ordering, are one form of pattern. The cations between B and B’ ordered
into alternate octahedral and other type is layered between B and B’. In the A2BB’O6 double
perovskite structure, B has partially filled and B’ has vacant orbital and vice versa. It presents an
unique opportunity for multiferroic behavior because of their ferromagnetic insulator properties
which include 1800 super exchange interaction between B and B’ cations through oxygen ions.
The functional characteristics of A2BB’O6 are influenced by the ordering of B and B’.

The structure of double perovskite structure from single perovskite is shown in figure below

It is necessary to clarify the arrangement and position of the ions in order to comprehend the
physical properties of perovskites or any other material. The physical characteristics of double
perovskites are typically determined by the B cations.

3. Synthesis techniques
4. Properties
One of the subjects of solid state chemistry and physics that has received the greatest attention is
compounds that crystallize in the perovskite structure. Several fundamentally intriguing chemical
and physical characteristics are present in perovskites. The extraordinary structural and
compositional flexibility of the perovskite structure is largely responsible for this vast variety of
intriguing features. Let’s discuss some of electronic and magnetic properties.

4.1 Electronic properties

The B-site cations have a significant role in controlling the electronic properties of perovskite
compounds. The great flexibility of the A2BB’O6 perovskites is seen in the ability of combining
various main group elements, 3d, 4d and 5d transition metals, lanthanides and actinides with
different oxidation states at the two B sites . Thus, it should come as no surprise that the many
A2BB’O6 compounds have a variety of semiconducting, metallic, halfmetallic, dielectric,
ferroelectric, thermoelectric, and maybe even superconducting properties. The compounds with
the most intriguing electrical properties are often those containing various transition metal
elements, and what is particularly intriguing in the A2BB’O6 perovskites is the ability to
combine 3d and 4d/5d elements at the two B sites. Most A2BB’O6 perovskites are insulators or
semiconductors. Electrical conductivity of various types has been discovered in semiconducting
A2BB’O6 perovskites. The half metallicity found in some A2B0 B00O6 perovskite compounds
is perhaps the most interesting property.

4.1(a) Halfmetallic property

In general, halfmetallicity is a rare property found only in a few A2BB’O6 perovskites with B=
Fe, Cr. One spin channel in a halfmetallic compound is metallic, while the other has a band gap
and is insulating. Halfmetallicity is also experimentally difficult to detect. Halfmetals are
typically metallic compounds with an integer spin moment at T= 0k. However, Grain boundaries
in a polycrystalline solid, may conceal the exact nature of electrical conductivity, and cation
disorder or spin-orbit coupling may impact the measured moment or even defeat halfmetallicity.
A2FeMoO6 with A= Ca, Sr, Ba is the most thoroughly studied of the known A2BB’O6
halfmetallic perovskites. They are all halfmetallic, with high metallic conductivity and
significant negative tunneling magnetoresistance (TMR) behavior even at room temperature.
4.1(b) dielectric and ferroelectric

As discussed earlier, most of the perovskite compounds are insulator. Such compounds could be
used as dielectrics, which is one of the earliest practical applications for perovskite oxides. The
most common application is probably in microwave dielectrics for communications. Such
materials require high dielectric constant k > 20, low loss tangent tan δ < 10-5, and small
absolute temperature coefficient of resonant frequency. For example, most ferroelectrics have
high k but also strong temperature dependence, and only a few materials with high k also have
good thermal properties. The polarizabilities of the constituent ions influence the dielectric
polarization of a compound and in double perovskites different cation ions with varying
dielectric properties can be incorporated. Dielectric properties can also be affected by cation
ordering: for microwave applications, high ordering may be preferred because B-site cation
ordering reduces dielectric loss.

Ferroelectric compounds are of great interest because they have spontaneous electronic
polarization and often large dielectric constants. Perovskites with Pb at A site is the most studied
ferroelectrics.

4.2(c) thermoelectric properties

Only a few materials of double perovskite have had their thermoelectric properties measured. It
has been proposed that the low thermal conductivity encountered in A2BB’O6 perovskites is
caused by phonon scattering by the two different metals at the B site.

4.2(d) Electro and photo catalytic properties

A2BB’O6 perovskites have also been reviewed as electrode materials for solid oxide fuel cells
(SOFCs). Such materials would require high electrical conductivity and electrocatalytic activity
at relatively high operating temperatures. Compounds with transition metals at the B sites have
received the most attention because transition metals have catalytic activity and, in particular,
4d/5d metals can improve electrical conductivity.

Some A2BB’O6 perovskites have extremely low resistivities. These compounds would be
expected to reduce and decompose quickly, preventing them from working on the anode side of
the cells. La2NiFeO6 has been considered as a possible SOFC cathode, because of its low
resistivity.

Some insulating/semiconducting A2BB’O6 compounds may have photocatalytic properties, such

as hydrogen generation via water splitting. Adjusting the band gap and band energies in
photocatalytic compounds is critical for optimising optical absorption and redox behaviour. The
ability to combine various cations in A2BB’O6 perovskites results in a wide range of different
band gaps in the 0.5 eV range. Under visible light irradiation, Ba2PrBiO6 has been shown to
have good photocatalytic activity for the degradation of methylene blue and 2-propanol.
5. Applications

6. Conclusions

Acknowledgement: Authors would like to thank to the host Institute foe digital library facility
during the literature survey

Conflict of Interest: No conflict of interest

References