Progress in Solid State Chemistry 43 (2015) 1e36

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Progress in Solid State Chemistry

journal homepage: www.elsevier.com/locate/pssc

A2B0 B00 O6 perovskites: A review

Sami Vasala, Maarit Karppinen*
Laboratory of Inorganic Chemistry, Department of Chemistry, School of Chemical Technology, Aalto University, P.O. Box 16100, FI-00076 AALTO, Finland

a r t i c l e i n f o a b s t r a c t

Article history: The B-site substituted perovskite oxides A2B0 B00 O6 have in the recent decades gained an increasing
Available online 6 September 2014 amount of interest due to their various interesting properties and possible applications. Here we survey
the literature for ca. one thousand A2B0 B00 O6 perovskite compounds. Crystal structures and the various
Keywords: crystal chemistry features such as ordering and valence mixing of the B cations characteristic to these
Double perovskite oxides compounds are reviewed, together with their electronic and magnetic properties. Most importantly, the
Crystal structure
thorough examination of the research so far carried out allows us to make predictions for a number of
Cation ordering
new A2B0 B00 O6 compounds yet to be synthesized and reveal exciting but not yet fully explored puzzles
Valence mixing
Electronic properties
related to this family of functional oxide materials.
Magnetic properties © 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Perovskite A2B0 B00 O6 phase formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Cation combinations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Cation size mismatch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Possible novel compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Crystal structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1. Structure determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2. Disordered compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3. Rock-salt ordered compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.4. Effects of temperature and pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.5. Effects of bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.6. Octahedral distortions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.7. Other factors affecting crystal structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4. B-site cation ordering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.1. Degree of order and types of disorder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2. Detecting order . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.3. Charge and size difference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.4. Synthesis conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.5. Other contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.6. Charge disproportionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.7. Mixing of A- and B-site cations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.8. Layered compounds and other R2CuB00 O6 perovskites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5. B-site cation oxidation states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5.1. Exotic oxidation states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.2. Predicting oxidation states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.3. Mixed-valent compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.4. Effects of structure to oxidation states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
5.5. Cation disorder and synthesis conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
6. Electronic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

* Corresponding author. Tel.: þ358 50 384 1726; fax: þ358 9 462 373.
E-mail address: maarit.karppinen@aalto.fi (M. Karppinen).

http://dx.doi.org/10.1016/j.progsolidstchem.2014.08.001
0079-6786/© 2014 Elsevier Ltd. All rights reserved.
2 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36

6.1. Electronic structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

6.2. Electrical transport properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
6.3. Halfmetals and magnetoresistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6.4. Dielectrics and ferroelectrics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6.5. Superconductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6.6. Thermoelectric properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
6.7. Electro- and photocatalytic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7. Magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7.1. Basic magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7.2. Antiferromagnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
7.3. Magnetic frustration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
7.4. Ferromagnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
7.5. Ferrimagnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
7.6. Low-dimensional magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
7.7. Multiferroics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Supplementary material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

1. Introduction order in three different ways, as shown in Fig. 1 [16,17]. In the most
common case, the cations alternate in all three dimensions,
Compounds crystallizing in the perovskite structure are among creating a rock-salt-type arrangement, also known as the elpasolite
the most intensely studied materials in solid state chemistry and structure, after the mineral K2NaAlF6. Occasionally, the B0 and B00
physics [1]. Perovskites exhibit several fundamentally interesting cations may also form a layered order, where they alternate only in
chemical and physical properties; they can have electronic struc- one direction [16]. In rare cases a columnar order may take place,
tures ranging from insulating to metallic, and even halfmetallic with the two different B cations alternating in two directions, but
with spin-polarized electrical conductivity [2,3]; they can show this type of ordering has only been found when the A site is also
superconductivity [4]; they have magnetic orderings ranging from occupied by two different elements, and is not discussed here
antiferromagnetic to ferri- and ferromagnetic [5], but can also show further [17]. The possibility of cation ordering adds to the
magnetic frustration with no apparent long-range order [6,7]; they complexity and modifiability of the perovskite compounds. What is
can show ferroic atomic displacements [8], ionic conductivity [9] more, having two different B-site cations allows for interesting and
and catalytic properties [10]. What is more, perovskites may have novel combinations of different elements, ranging from 3d, 4d or 5d
many of these properties simultaneously, allowing for new com- transition metals through lanthanoides and actinoides to main
bined properties, such as multiferroicity [11]. As a result, perovskite group elements, many of them in various different oxidation states.
materials are also of great technological interest, with a range of As the B-site cations typically govern the most interesting proper-
possible applications such as dielectrics or piezoelectrics in elec- ties of perovskites, such as electrical conductivity and magnetic
tronic devices and sensors [1], magnetic memory components [3], order, this possibility of various combinations of elements together
electrode and electrolyte materials for fuel cells [12], and compo- with cation ordering allows for a wide range of interesting and
nents for solar cells [13], to name a few. possibly useful new materials.
This wide range of interesting properties stems largely from the In this work we survey the literature of about one thousand
exceptional structural and compositional flexibility of the perov- A2B0 B00 O6-type perovskite oxides reported from the 1950's to this
skite structure. The ideal cubic perovskite compound, ABX3, has a date [3,6,7,12,16,18e704]. We do consider both B-site ordered and
large cation at a twelve-coordinated A site, a smaller cation at an disordered compounds, although the ordered compounds will be in
octahedrally-coordinated B site, and an anion X, which most often our main focus. It should be noted that for simplicity all chemical
is oxygen. The BX6 octahedra form a corner-shared network, with formula are written as A2B0 B00 O6, even if the compound is disor-
remaining voids filled by the cation A. Importantly, the BX6 octa- dered; we moreover arrange the B0 and B00 elements such that the
hedra can expand/contract and tilt in order to compensate for non- former/latter has the lower/higher oxidation state (in case they
ideal ionic size ratios. Furthermore, in case of electronic in- have the same oxidation state, the order is based on the possible
stabilities, the octahedra can distort or the cations may shift from minimum/maximum oxidation states, or the atomic numbers).
their ideal positions. It is also possible to make partial substitutions Naturally, focusing only on A2B0 B00 O6-type oxide perovskites leaves
or create vacancies on any of the three sites of the structure. As a out many fascinating compounds. A great number of perovskite
result of this flexibility, the perovskite structure can accommodate halides, nitrides, sulfides and hydroxides exist [14,15]. Also, the
almost all of the elements of the periodic table, in one form or variety of B-site cation oxidation-state combinations could be
another [14,15]. widened by having two different aliovalent A-site cations, i.e.
Partial cation substitution is a very common method for A0 A00 B0 B00 O6. This would however expand the number of compounds
tailoring the properties of perovskite compounds. This substitution considerably and we thus limit our discussion only to compounds
can take place either at the A or the B site, and in varying degrees. with a single A-site cation. Having just one A-site cation makes
However, in the recent years there has been particular interest in comparisons of many properties also easier, as the possible effects
the case where exactly half of the B-site cations are substituted of A-site cation ordering [17] or size variance [705] do not have to
with another cation. In this case the two different cations, B0 and B00 , be considered. Perovskites with 1:2, 1:3, etc. B-site cation orderings
may remain disordered at the B site, or they can order, forming a so- are also not discussed here, as we focus only on the 1:1 substituted
called B-site ordered double-perovskite, A2B0 B00 X6. The cations can compounds. Moreover, even for the A2B0 B00 O6 compounds the
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
Fig. 1. Different B-site cation orderings found in A2B0 B00 O6 perovskites: (a) rock-salt, (b) layered and (c) columnar order.
reference list is far from complete; for example, for the Sr2FeMoO6
halfmetal a simple search comes up with over 600 publications!
Rather, our major goal in this review is to compile important data
for future reference for anyone interested in these compounds,
discuss general trends in properties, and reveal interesting but less
studied cases worth additional investigation.
We start with the phase formation and synthesis aspects
(Chapter 2), then proceed with factors affecting the crystal struc-
ture (Chapter 3), cation ordering (Chapter 4) and oxidation states
and charge fluctuation (Chapter 5), and finally discuss the elec-
tronic structures, and electrical (Chapter 6) and magnetic proper-
ties (Chapter 7). Chapter 8 is then a brief summary and outlook of
the future research trends of the B-site ordered double-perovskite
oxides. Not all the data collected are discussed in detail, and
additional data for the A2B0 B00 O6 perovskites reported in literature
can be found in the accompanying Supplementary material,
Tables S1 and S2, which make up an integral part of this review.
Here it should be mentioned that there are also a number of
previous excellent publications on various more specific areas
related to the topic. A book by Mitchell [14] compiles a great deal of
information on various perovskite and perovskite-related struc-
tures, including the A2B0 B00 O6 compounds. More specifically, in 1993
Anderson et al. [16] surveyed the literature for over 300 B-site
substituted double-perovskite oxides, both with one or two A-site
cations, and discussed their crystal structures and in particular the
B-site cation ordering. The present work can be seen as an exten-
sion of that review for the part of the A2B0 B00 O6 perovskites. Cation
ordering in perovskites has further been discussed by King and
Woodward [17], Davies et al. [706] and Howard et al. [707].
Goodenough [708] has discussed the transport properties of
perovskite compounds in general, including the double perovskites.
Finally, as the halfmetallic and magnetoresistance properties of
Sr2FeMoO6 and other similar compounds have been of great in-
terest in recent years, a few reviews of these compounds specif-
ically have also been written: Serrate et al. discussed their physical
properties in detail [709], whereas Karppinen and Yamauchi [710]
concentrated more on their chemistry.
2. Perovskite A2B′B00 O6 phase formation
There are nearly one thousand A2B0 B00 O6-type perovskite com-
pounds that have been reported in the literature, most of them
synthesized under ambient pressure. A number of new A2B0 B00 O6
compounds have also been realized through high-pressure (HP)
synthesis. In addition, there are several reported attempts to syn-
thesize compounds with the A2B0 B00 O6 stoichiometry, where a
perovskite compound was not formed. Fig. 2 illustrates graphically
the situation for the cases with A ¼ Ca, Sr, Ba or La, which are the
most common A-site cations; these compositions comprise most of
3
the reported compounds, totaling over 800. As is evident, there are
still many possible cation combinations left unstudied. However,
not all of these combinations actually form a perovskite compound,
and in this section we will take a look at some factors influencing
the A2B0 B00 O6 phase formation.
2.1. Cation combinations
Most of the A2B0 B00 O6 perovskites found in the literature have a
divalent cation at the A site, with over 720 compounds reported.
Most common divalent A cations are the alkaline earth elements,
Ca, Sr and Ba, followed by a smaller number of A ¼ Pb compounds.
In addition, there are seven compounds with A ¼ Cd, mainly tel-
lurides Cd2B0 TeO6, and five rather exotic compounds with A ¼ Mn,
namely Mn2B0 SbO6. Second most common are the compounds with
trivalent A cations, with more than 200 cases reported. The most
common trivalent A constituent is La, followed by the other rare
earth (R) elements. Also, four compounds with A ¼ Bi have been
reported. The prevalence of A2þ cations can be explained by their
larger size compared to the A3þ cations, as most trivalent ions are
somewhat small, limiting the size of the B-site cations.
The divalent A cation also allows for a larger range of oxidation
state combinations for the two B cations. Formation of a stoichio-
metric perovskite phase requires a combination of suitable B0 and
B00 cation oxidation states. The average B-site cation oxidation state
is four in case of an A2þ cation, but this can be accomplished by a
combination of B0 4þ/B00 4þ, B0 3þ/B00 5þ, B0 2þ/B00 6þ or B0 1þ/B00 7þ cations.
Thus elements with oxidation states ranging from one to seven can
be inserted into the A2þ 0 00
2 B B O6 perovskite's B site, covering all the
cations in the periodic table. On the other hand, for an A3þ cation
the average B-site cation oxidation state is three, which can be
accomplished by a combination of B0 3þ/B00 3þ, B0 2þ/B00 4þ or B0 1þ/B00 5þ
cations. Thus ions with oxidation states 6þ or 7þ are excluded.
While the A2þ and A3þ cations are common at the A site of
A2B0 B00 O6 perovskites, there appears to be only three reported ex-
amples of compounds with an A1þ cation: Na2ZrTeO6 [226,459] and
the high-pressure forms of Na2TiTeO6 and Na2SnTeO6, which at
ambient pressure have the ilmenite structure [466]. In case of A1þ
cations, the range of ionic radii is large, but the B-site cation
oxidation state combinations are limited to B0 5þ/B00 5þ, B0 4þ/B00 6þ and
B0 3þ/B00 7þ. Thus there are relatively few combination options
available, and fewer compositions are expected.
2.2. Cation size mismatch
In the ideal cubic single-perovskite ABO3 the AeO bond length
equals to the √2 * BeO bond length, based on simple geometric
considerations. It is, however, rather rare for the A and B cation
radii to match perfectly. Luckily, the perovskite structure allows
4 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36

Fig. 2. A2B0 B00 O6 compositions with A ¼ Ca, Sr, Ba or La reported in literature. Left column represents the B0 cation and top row the B00 cation. The colors indicate perovskite
compounds synthesized at ambient pressure (green) or stabilized using either high-pressure or high oxygen-partial-pressure synthesis (purple), and compounds with a hexagonal
non-perovskite structure with the A2B0 B00 O6 stoichiometry (yellow), and cases where a phase of the A2B0 B00 O6 composition does not form (red). (For interpretation of the references
to color in this figure legend, the reader is referred to the web version of this article.)

rather a large mismatch of ionic radii. This A and B cation size
mismatch is often described by the Goldschmidt tolerance factor
[711].
r þ rO
t ¼ pffiffiffi A
2ðrB þ rO Þ
where rA, rB, and rO are the ionic radii of A, B and O, respectively. For
A2B0 B00 O6 perovskites with two different B-site cations, an average
of the B-cation radii is typically used. When t < 1, the A-site cation
radius is smaller than ideal, and the perovskite structure compen-
sates for the cation size mismatch by tilting the BO6 octahedra. This
is discussed in more detail in Chapter 3, where we review the
structural features of A2B0 B00 O6 perovskites. With t > 1, the A-site
cation is too large and the strain caused by the radius mismatch
cannot be relieved by octahedral tilting. Typically various hexago-
nal structures are formed instead of a perovskite structure.
Commonly, and in this work too, tabulated ionic radii such as
those by Shannon [712], are used in calculating the tolerance factor.
However, especially in case of A2B0 B00 O6 perovskites the true ionic
radii may be quite different from the tabulated values. In A2B0 B00 O6
perovskites with t < 1, stress can be relieved by a change of bond
lengths, instead of octahedral tilting, and both tilting and bond
length change may take place simultaneously [46,55,126,231]. This
can be caused simply by a compression or stretching of bonds by
too large cations, or by polarization of the oxygen electron cloud by
the small, highly charged B00 cation, affecting the AeO or B0 eO
bonds.
Moreover, perovskites are not ideally ionic, but the bonds have a
considerable covalent nature. The p(BeO) bonds compete with the
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
s (AeO) bonds, and the s (B0 eO) bonds compete with the s(B00 eO)
bonds. The BeO bond can thus be affected by e.g. a change of the A-
site cation [90,92]. For example, Ca2MnWO6 has longer MneO
bonds than Sr2MnWO6 as the higher electronegativity of Ca
compared to Sr weakens the MneO bond [323]. Similarly, Ca2Co-
TeO6 has longer CoeO bonds than Sr2CoTeO6 [276]. The B00 eO bond
covalency can also affect the B0 eO bond length. For instance, in
Sr2MnWO6 the MneO bonds are longer than in Sr2MnMoO6 [323],
and in Ba2CoWO6 the CoeO bonds are longer than in Ba2CoMoO6
[72], due to the more covalent nature of W compared to Mo. Finally,
Chernorukov [59] noted that in case of a series of Ba2B0 UO6 com-
pounds with divalent B0 cations, increasing the size of B0 decreased
the UeO bond length as the larger ion pushed the oxygen further,
but increased the BaeO bond length due to increased unit-cell
volume. This change was non-linear, possibly due to a change in
ionicity of the bonds. However, the unit-cell volume increased
linearly with increasing size of the B0 cation, acting as a sort of an
averaging quantity. Thus it appears that the tolerance factor
calculated using tabulated ionic radii may not always be very pre-
cise. However, the correct bond lengths are not known beforehand,
so using tabulated values may be the only option for predicting the
stability and possible structural distortions of a compound. And as
we will see below, when the differences in the cations are taken
into account, the tolerance factor can be a rather useful predictive
tool also in case of the A2B0 B00 O6 perovskites.
With a large data set, some general trends may be found
despite small variations in the bond lengths. Fig. 3 plots the
number of A2B0 B00 O6 perovskite compounds reported in the
literature as a function of t. The reported compounds have t
values in the range of 0.85e1.07, although in case of some com-
pounds cation radii are not known, so t cannot be calculated. It
appears that at its smallest, the A-site cation radius is only 50%
larger than the average B-site cation radius (Sr2SrUO6,
Sm2NaIrO6), and the smallest reported average B0 eOeB00 bond
angles are around 137 (Ho2CoMnO6). This seems to be a limit of
the structure. On the other hand, at its largest the A-site cation
radius is about 170% larger than the average B-cation radius
(Ba2AlB00 O6, B00 ¼ Nb, Ta), setting another limit. A maximum in
number of compounds is found around t ¼ 0.93e1.01, where the
ionic radii match is rather close to ideal. There is a sharp drop in
the number of compounds for t > 1.01; as mentioned before, with
t > 1 the A-site cation is too large for the perovskite structure, and
various hexagonal structures are often formed. In this work we
have not specifically surveyed the literature for hexagonal com-
pounds, but looking at the compounds collected in
Supplementary material Table S1 it is evident that most reported
hexagonal A2B0 B00 O6 compounds have t > 1, and on the other
hand, above t z 1.05 very few perovskite A2B0 B00 O6 compounds
exist.
Fig. 3. Number of A2B0 B00 O6 compounds reported with different values of tolerance
factor t.
5
Fig. 4 shows a plot of the unit-cell volumes of A2B0 B00 O6 perov-
skites with A ¼ Ca, Sr, Ba or La as a function of t. The A-site cation
naturally affects the overall volume of the compounds, but as can be
seen from the plot, also for a certain A-site cation the unit-cell
volume decreases as t increases, in a rough correspondence to
Vegard's law. Some discrepancies and scatter is seen from the linear
dependency, in small part due to valence mixing, which will be
discussed later in more detail in Chapter 5. However, most of the
scatter is due to differences when comparing compounds with
different B00 cations. If we plot just single “families” of compounds
with fixed A and B00 cations, such as Ba2RB00 O6 with B00 ¼ Nb, Sb or Os
shown as an example in Fig. 5(a), an almost perfect linear behavior
is found. The different families of compounds however differ
slightly, probably due to different bond covalencies and bond
lengths between the different B00 cations.
Different types of B0 cations may also show different behaviors.
Especially interesting is the fact that the B0 ¼ R compounds seem to
behave differently from those with B0 being e.g. a 3d or 4d transition
metal. This is illustrated in Fig. 5(b) for the Ba2B0 OsO6 compounds:
when plotting the unit-cell volume against t, the B0 ¼ R compounds
form a straight line, as do the compounds with B00 ¼ In, Sc, Sr, Ca, Cd,
Zn, Mg or Cu, but the two lines differ from one another. It thus
appears that the bonding is different in the two groups of com-
pounds. It is also interesting to note that compounds with R ¼ La
often behave differently from those with other Rs, probably due to
the lack of f electrons. Also, if the B0 element is large (Ba, Sr, Ca)
compared to the A-site cation, the unit-cell volume will often
deviate from the expected value, possibly due to bond-length dis-
tortions. Finally, in some compounds with elements such as Ti or Bi
at the B site the unit-cell volume may also deviate from the ex-
pected value, possibly due to ferroelectric distortions. All in all it
appears that as long as the differences in the A, B and B00 cations are
taken into account, tolerance factor actually works quite well for
the A2B0 B00 O6 perovskites.
The tolerance factor probes the mismatch between the A- and B-
site cation radii. In the case of ABO3 single perovskites, this AeB
cation radius mismatch is the only one possible. But for the
A2B0 B00 O6 perovskites the B0 eB00 size difference is also of interest.
Looking at the compounds reported in literature, we find that the
difference in B-site cation radii can be quite large, as high as 0.85 Å
(or 160%) in case of Ba2KIO6. Many other compounds show large
differences in the B-site cation radii as well, so it appears that the B-
site cation radius ratio in the A2B0 B00 O6 perovskites is not very
restricted.
Fig. 4. Unit-cell volumes of A2B0 B00 O6 compounds with A ¼ Ca (white circles), Sr (gray
circles), Ba (black circles) and La (black triangles) as a function of tolerance factor.
6 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36

Fig. 5. Unit-cell volumes as a function of tolerance factor for (a) Ba2RB00 O6 with B00 ¼ Nb (black), Os (gray) and Sb (white), and (b) Ba2B0 OsO6 with B0 ¼ R (gray circles) or B0 ¼ In, Sc, Sr,
Ca, Cd, Zn, Mg or Cu (black triangles).

2.3. Possible novel compositions t ¼ 0.90e0.97, which would imply a relatively ideal perovskite
structure. Especially noteworthy are the A2MnOsO6 compounds, for
With the aforementioned limitations of tolerance factor and which the A ¼ Ca or Sr combinations do not form a perovskite
cation combinations, it is possible to make some estimation on the phase, and the A ¼ Ba compound is hexagonal. Some of these
number of possible A2B0 B00 O6 perovskite compounds. If we consider missing compounds could form under high pressure. For instance,
a single A1þ, A2þ or A3þ cation at the A site, tolerance factor in the Ca2InOsO6 was reported not to form under ambient pressure [21],
range of t ¼ 0.85e1.05 (perovskite phase possible, at least with HP but was later made by HP synthesis [306]. On the other hand,
synthesis), and exclude radioactive or other unsuitable cations A2B0 BiO6 perovskites with A ¼ Sr or Ba, B0 ¼ Co or Ni could not be
(such as B, C, N, etc.), we can by a simple calculation come up with synthesized even at a high pressure of over 80 kbar [70], which was
around 2.0  104 different perovskite combinations. Naturally, not assumed to be due to the crystal field strength being too weak to
all of these will actually form, but the calculation gives an idea of stabilize the 3þ oxidation state of Co or Ni.
the number of combinations that could be imagined and tried. It appears that often if no perovskite phase is formed, a multi-
Many of the combinations stem from the fact that in the A2B0 B00 O6 phase mixture is found [16,263,389]. For example, when synthe-
structure rare earth elements can be placed both at the A and B0 sis of La2CuVO6 was attempted, a mixture of La2CuO2 and LaVO4
sites. It is actually somewhat of a specialty of the A2B0 B00 O6 perov- was formed [389]. Similarly, attempting to synthesize Sr2CuMoO6
skites that the R cations can also occupy the B site, as in many other at ambient pressure resulted in a mixture of SrCuO2 and SrMoO4,
structures it is difficult to put R cations in an octahedral coordi- but with HP synthesis a perovskite phase was formed [568]. Oc-
nation due to their large size [246]. casionally pyrochlore, ilmenite or spinel phases are reported to
It is interesting to look at the cases reported in the literature form instead of perovskites [34,463,466]. In such cases HP synthesis
where a perovskite structure has not formed. Not all such failures could again provide perovskite compounds, especially in convert-
have of course been reported, but some have. Most of the failed ing pyrochlore phases into perovskites.
compounds with A ¼ Ba have t > 1, only exception being Ba2CeSbO6. There are some rather unexpected hexagonal phases reported in
Thus quite a few hexagonal phases with A ¼ Ba have been reported, the literature. The Sr2RRuO6 (R ¼ La, Ce, Pr or Nd) compounds are
as is evident in Fig. 2. On the other hand, most compositions with reported to be hexagonal [35], even though the A2LaRuO6 com-
A ¼ Ca, Sr or La that have been reported not to form a perovskite pounds with A ¼ Ca and Ba are perovskites. Also, many R2B0 TiO6
phase have tolerance factors in a reasonable range. Some of these compounds with B0 ¼ Cu or Mn are hexagonal. Ionic radii of the
compositions are collected as an example in Table 1 together with small 12-coordinated Rs are not well known, but estimation would
their calculated tolerance factors. As can be seen, most of these lead to t ¼ 0.85e0.88 for all of these compounds. In case of the
cases are A ¼ Ca compounds. While the ionic radius of Ca is small, R2CuTiO6 compounds, the occurrence of a hexagonal structure with
the tolerance factors of these compounds would fall in the range of non-octahedral B-site cation coordination has been explained by
the d0 nature of Ti4þ: due to the lack of d electrons there is no
octahedral crystal field stabilization energy to favor an octahedral
Table 1 coordination [16]. It has also been suggested that covalent cati-
Calculated tolerance factors for several A2B0 B00 O6 compositions reported in literature.
Compounds with the tolerance factor in parentheses have been reported not to form
onecation bonding may stabilize a hexagonal structure instead of
a perovskite structure at ambient pressure. the perovskite structure in some cases, especially when B0 ¼ Cr
[76,90,92]. Hong et al. [91] have proposed that this is partially the
Formula Tolerance factor
reason why Ba2CrTaO6 is hexagonal if synthesized at ambient
Ca Sr Ba pressure.
A2CoBiO6 (0.963) (1.021) Looking at the literature, synthesis of A2B0 B00 O6-type compounds
A2NiBiO6 (0.965) (1.023) with monovalent A cations have apparently been tried mainly with
A2CoMoO6 (0.937) 0.971 1.029 B00 ¼ Te. Besides the aforementioned three perovskites, there are
A2NiMoO6 (0.950) 0.984 1.043
A2CdOsO6 (0.902) (0.935) 0.991
many non-perovskites. Some A2B0 TeO6 compounds with A ¼ Li or
A2GaOsO6 (0.970) 1.005 Na and B0 ¼ Ge, Ti or Sn are layered analogues of the different ASbO3
A2MgOsO6 (0.953) 0.988 1.047 structures [459]. Similarly, Li2B0 TeO6 compounds with B0 ¼ Ti or Sn
A2MnOsO6 (0.928) (0.962) (1.020)h have structures similar to LiSbO6 [461] and Li2B0 TeO6 with B0 ¼ Zr or
A2ScOsO6 (0.941) 0.975 1.033
Hf have structures similar to LiNbO3, but with ordered B-site cat-
A2ZnOsO6 (0.949) (0.983) 1.042
A2GaReO6 (0.969) 1.004 ions [460]. Lithium is clearly too small for the A site considering a
A2InReO6 (0.927) 0.961 1.018 perovskite phase formation. On the other hand, A2GeTeO6 com-
A2ZnReO6 (0.947) 0.982 1.041 pounds with A ¼ K, Rb or Cs and large t values have the pyrochlore
h stands for a formation of a hexagonal structure. structure [337], whereas K2B0 TeO6 with B0 ¼ Ge or Sn were found
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
not to form [459]. However, other compositions than B00 ¼ Te could
perhaps provide more perovskite phases. Considering the ionic
radii of the alkali metals, at least with A ¼ Na or K some new
perovskite compounds could be synthesized.
As can be seen from Table S1 in the Supplementary material and
Fig. 2, HP synthesis has been successfully used in many cases to
stabilize new A2B0 B00 O6 perovskite compounds, especially in case of
compositions with high values of t that would otherwise form
hexagonal phases. Compressibility of the AeO bond is usually
higher than that of the BeO bonds, and thus high pressure can
effectively decrease t and transform the hexagonal compounds to
metastable perovskite forms. Therefore, it might be expected that
the non-perovskite A ¼ Ba compounds with t > 1 could be trans-
formed into perovskites with high pressure. The HP synthesis has
also been used to make some rather novel compounds, such as the
A ¼ Mn or Bi perovskites. High-pressure synthesis favors structures
with small unit-cell volumes, and as the perovskite structure pro-
vides a rather dense packing of ions, it often forms under high
pressure [713].
There are many reported cases where an A ¼ Pb composition
does not form a perovskite phase even if the A ¼ Ca, Sr, Ba ones do.
However, many such A ¼ Pb compounds have been synthesized
employing the HP synthesis. These compounds can be rather sen-
sitive to the synthesis conditions. For instance, in case of Pb2B0 B00 O6
with B ¼ Ni, Mg Cu, Co, Zn, Fe, Mn, Cd, Ca or Hg and B00 ¼ Mo, W or
Re, increasing the B0 -cation radius requires the synthesis pressure
to be increased and a precise control of the synthesis temperature
to avoid the pyrochlore phase [474]. The Pb2MnReO6 composition
makes a very exceptional case in that at ambient pressure below
about 725  C a perovskite phase forms faster than the competing
pyrochlore phase, and thus the pure perovskite phase can be syn-
thesized at relatively low temperatures if the synthesis time is short
enough [497]. Ramesha et al. [496] used different starting materials
and were able to make the perovskite phase at 550  C, whereas the
pyrochlore phase formed if the synthesis temperature was 600  C.
Similar sensitivity to synthesis parameters has been found with
other compounds too. For example, Ba2CrUO6 can form either a
cubic perovskite phase or a hexagonal phase depending on the
synthesis route [22]. This is probably due to the compound being
very close to a phase transition, with t ¼ 1.02. Also, Ca2CaUO6 can be
obtained with two different crystal structures depending on the
synthesis conditions: a metastable alpha phase (rhombohedral,
non-perovskite type) and a stable beta phase (monoclinic perov-
skite) [714].
Sometimes an additional oxygen source is needed in the HP
treatment, especially in order to get a correct oxygen stoichiometry
in compounds with elements that are reluctant to oxidize; using
high-pressure oxidation some interesting elements with high
nominal oxidation states have been achieved. For example, penta-
valent Fe has been stabilized in La2LiFeO6, and the rather unknown
Fe5þ radius in octahedral coordination was determined as ~0.49 Å
[414]. On the other hand, the similar La2LiB00 O6 compounds with
B00 ¼ Cr, Mn or Rh did not form a perovskite phase [413]. Ionic radii
of Cr5þ and Mn5þ are of the same order as that of Fe5þ, and it was
suggested that a higher pressure and quenching might help form
these phases. However, La2LiRhO6 could not be synthesized even at
8 GPa of O2 pressure [416]. There are no other reported examples of
Rh5þ perovskite compounds either, and it has been proposed that
the ionization potential of Rh might be too high to stabilize this
oxidation state [413]. However, the neighboring elements, Ru and
Ir, do exist at the pentavalent state, and in fact, using HP oxidation,
Ir has been oxidized to the hexavalent state in compounds A2B0 IrO6
with A ¼ Sr or Ba and B0 ¼ Ca, Sr, Zn, Mg or Ni [41,42,43,44,45,653].
The Ir6þ radius in octahedral coordination was determined to be
~0.52 Å [41], depending on the compound, as the reported IreO
7
bond lengths are apparently very structure-dependent [653]. There
are no examples of hexavalent Ru in the A2B0 B00 O6 compounds,
although Ru6þ has been stabilized in Na2RuO4 [715]. This com-
pound is, however, air sensitive. Compounds with V5þ are also
rather rare, with only Ba2BiVO6, Ba2YVO6 and La2LiVO6 reported.
Pentavalent V is quite small (0.54 Å), but so are many other cations
found at the B site of the A2B0 B00 O6 perovskites. Perhaps the reason
for the lack of V5þ compounds is in the coordination preference of
this element, as V5þ does prefer lower coordination in some com-
pounds. Occasionally such structural inhibitions may affect the
phase formation, as in case of the Ca2CuB00 O6 compounds, which
have been postulated not to form due to an incompatibility of a
large octahedral tilting and orbital ordering of the JahneTeller (JT)
active Cu2þ [716].
In contrast to the high oxygen pressure, inert or reducing at-
mospheres have also been used to stabilize cations with the un-
usually low oxidation states. For instance, cations such as V3þ, Ir3þ,
Ru3þ, Mo4þ, Nb4þ, Ta4þ, Os5þ, Re5þ, U5þ and W5þ are commonly
found in the A2B0 B00 O6 perovskites, as can be seen in the
Supplementary material Table S1. Interestingly, the rather rare Te5þ
was stabilized in Ba2TlTeO6 and Te5þ radius in octahedral coordi-
nation was determined as 0.615 Å in this compound [241].
Reducing synthesis conditions may help making more interesting
compounds with lower oxidations states. For example, A2VSbO6
(A ¼ Ca, Sr or Ba) with trivalent V might be obtained. In the liter-
ature, the HP synthesis of Mn2VSbO6 has been reported, although
the sample appeared not to be phase-pure [463].
3. Crystal structure
The crystal structure of a solid compound is of great funda-
mental interest in crystallography. The crystal structure can also
affect many of the material's important physical such as its elec-
trical, magnetic or optical properties. Thus, often in order to predict
or understand the material properties, knowing the crystal struc-
ture is essential.
First of all, the structure and space group of the A2B0 B00 O6 pe-
rovskites depends on the B-site cation ordering. Cation ordering is
discussed more thoroughly in Chapter 4, but looking at the
Supplementary material Table S1, we can see that by far the most
common type of B-site ordering is the rock-salt order, followed by a
much smaller number of disordered compounds. Thus, in this
discussion we will concentrate on rock-salt ordered compounds,
with a brief mention of the disordered ones. The few A2B0 B00 O6
perovskites with a layered B-site cation order all have JT active Cu2þ
at the B0 site, and they will be discussed together with other JT
distorted compounds in Chapter 3.6.
In case of perovskites, the topology is thermodynamically stable
but the structure may distort due to competing bonding prefer-
ences of the A, B0 and B00 cations [645,655]. The ideal perovskite
structure is cubic, but as described in the Introduction, the struc-
ture can be distorted by tilting or distortion of the BO6 octahedra, or
by cationic displacements [15]. Octahedral tilting is the most
common type of structural distortion, and the discussion is mostly
centered on this subject. Octahedral distortion and cationic dis-
placements due to electronic instabilities such as JT distortion or
ferroelectric (FE) displacement are less common, and they will be
briefly discussed in Chapter 3.6.
3.1. Structure determination
Here it should be noted that the crystal structure and space
group have been determined for only about two thirds of the
A2B0 B00 O6 compounds found in the literature. In addition, there is a
great deal of discrepancies in the determined structures
8 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
[53,180,599]. The Ba2LaIrO6 compound is an example of a case for
which the exact structure determination has been problematic. It
was first described as monoclinic P21/n [63,183], then as rhombo-
hedral R-3 [182], then as a mixture of monoclinic I2/m and rhom-
bohedral R-3 phases [181], and then again as just R-3 [180].
Similarly, Ba2LaRuO6 has been described either as triclinic I-1 [185],
monoclinic P21/n [186] or rhombohedral R-3 [184]. Some of the
discrepancies found in the literature are due to the fact that many of
the compounds were originally characterized in the 1950s and 60s,
and the diffraction methods at the time were not quite precise
enough to detect the tiniest distortions in the structure. Many of
these compounds have thus been assigned a cubic structure, but
have later been found to be slightly distorted.
However, even these days there are problems in precise struc-
ture determination. As we will see later, the crystal structure can be
affected by the cation ionic radii, B-site cation ordering, electronic
instabilities, bond covalency and other bonding preferences, syn-
thesis conditions and oxygen content. Sometimes there are two
phases with slightly different structures coexisting due to a struc-
tural transition, and detecting such phases may be difficult with
laboratory XRD [130]. Crystal twinning is also possible in A2B0 B00 O6
perovskites, especially when there is a transition from a high to low
symmetry structure with decreasing temperature [576]. Thus, poor
sample quality can hinder the structural determination [180].
However, there are also difficulties in the actual structural deter-
mination even with a high-quality sample due to the nature of
these compounds.
The correct crystal system could be determined from unit-cell
parameters. However, sometimes the structural distortions are
small, and the A2B0 B00 O6 perovskites, especially with A ¼ Sr, can have
notable pseudosymmetry. This means that just looking at unit-cell
parameters (i.e. peak splitting) may not reveal the true structure, as
sometimes only the peak intensities are affected
[228,553,610,707,717]. Such pseudosymmetry may be beyond the
detection limits of ordinary XRD analysis, and synchrotron
diffraction may be needed for proper structural assignment [179].
The different BO6-octahedron tiltings and the resulting space
groups can be recognized by their different diagnostic reflection
conditions [180]. However, sometimes two different space groups
can explain the same reflections if the peaks overlap, and some of
the reflections may be very weak [180,599]. Moreover, both the
cation ordering and octahedral tilting affect the same reflections, as
does displacement of the A cation, which makes the structure
determination more complicated than in case of normal perov-
skites [123,228,448,707,717]. Detecting the octahedral tilt is based
on oxygen positions, which can be difficult to detect with labora-
tory XRD, especially when heavy elements are present. For
example, the tetragonal space groups I4/m and I4/mmm are difficult
to distinguish as their only difference is a slight rotation of octa-
hedra [707]. Thus neutron diffraction (ND) analysis is often
required to verify small octahedral tiltings.
A reasonable starting point for the structural determination is
helpful, and the program SPUDS is often used for finding a possible
starting structure [717]. Furthermore, a good process of structure
determination in case of the A2B0 B00 O6 perovskites was described by
Barnes et al. [228]. Usually, a combination of (synchrotron) XRD and
ND is needed for precise analysis [123,227]. Another useful method
for tough cases is electron diffraction (ED), which can determine the
structure in local level. For example, careful ED studies have shown
the true symmetries in case of A2InNbO6 [173] and Pb2NiReO6 [499].
3.2. Disordered compounds
The ideal single perovskite ABO3 structure is cubic Pm-3m with
regular BO6 octahedra and BeOeB bond angles of 180 . When the A
cation is smaller than ideal, the BO6 octahedra can tilt in order to
optimize the A-site cation bonding, whereas the BeO coordination
sphere remains relatively unchanged [14,718]. This tilting of rela-
tively rigid octahedra can be described using the Glazer's notation
[15,719,720]. Studying the perovskite system, Glazer [719] found 23
possible tilt systems for the single perovskite system and assigned
space groups for those tiltings. Later, a group-theoretical analysis
for single perovskites reduced the number of possible space groups
to 15 [721], and of these six are commonly observed with a single A-
site cation [720].
Disordered A2B0 B00 O6 perovskites are described by the same
space groups as single perovskites. We have collected the numbers
of disordered A2B0 B00 O6 compounds with different Glazer tilt sys-
tems to Table 2. As can be seen, the most common tilt system is
abþa (Pnma) followed by a0a0a0 (Pm-3m). In addition, there are a
few compounds reported with aaa (R-3c) and a0a0c (I4/mcm)
tiltings, and one compound each with a0bb (Imma or Ibmm) and
aþbc (P21/m). Compared with a study by Lufaso et al. [720], the
frequency of these space groups is quite similar to ABO3 single
perovskites. A few compounds have been reported with some other
space groups, such as I2/c in case of Sr2B0 RuO6 with B0 ¼ Fe or Co
[6,544]. Also, some apparently disordered compounds have been
reported using space groups of ordered compounds, such as Fm-
3m, I4/m or P21/n.
3.3. Rock-salt ordered compounds
In case of an ideal cubic rock-salt ordered A2B0 B00 O6 perovskite,
the unit cell is doubled in all three crystallographic directions
compared to a single perovskite, resulting in a space group Fm-3m.
Similar octahedral tilting as with single perovskites is possible, but
the resulting space groups differ. Space groups for the 23 tilt sys-
tems were determined for the rock-salt ordered perovskites by
Woodward [15]. Again, group theoretical analyses by Howard et al.
[707] and Gateshki et al. [553] reduced the number of possible tilt
systems to 12. In addition, in case of A2B0 B00 O6 perovskites with a
single A-site cation, certain space groups are strongly favored, due
to having all A cations in the same coordination environment [718].
The other space groups are found only when two different A cations
are present. With single A-site cation, only seven groups remain
[717]. The most common systems are a0a0a0 (Fm-3m), aaa (R-3),
a0a0c (I4/m), a0bb (I2/m) and aþbb (P21/n) [65,180]. a0a0cþ
(P4/mnc) and abc (I-1) are much rarer, and in fact, Fu et al. [180]
have questioned the existence of compounds with the abc
tilting altogether.
We have collected the number of rock-salt ordered A2B0 B00 O6
perovskites with different tiltings in Table 3, excluding the A ¼ Pb or
Bi compounds that may have ferroelectric distortions. Lufaso et al.
[717] also surveyed the A2B0 B00 O6 compounds with different space
groups, and the frequency of different tiltings is again very similar.
The most common tilting is aþbb (P21/n) with over 300 com-
pounds. Five of these compounds have been assigned the space
group P21/c, which is another way of expressing the aþbb tilt
Table 2
Most common tilt systems for disordered A2B0 B00 O6 perovskites and the number of
compounds reported for each.
Glazer tilt Space group Number of compounds
a0a0a0 Pm-3m 11
aaa R-3c 5
a0a0c I4/mcm 4
a0bb Imma 1
abþa Pnma 45
aþbc P21/m 1
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
Table 3
Most common tilt systems for rock-salt ordered A2B0 B00 O6 perovskites and the
number of compounds reported for each.
Glazer tilt Space group Number of compounds
a0a0a0 Fm-3m 146
aaa R-3 19
a0a0c I4/m 44
a0a0cþ P4/mnc 0
a0bb I2/m 19
aþbb P21/n 310
abc I-1 2 pounds with B00 ¼ Mo, Sb, Nb or Ta are cubic if t > 0.97e0.98. The
system [707]. Also, a few compounds have been reported with
disordered space group Pnma, although acknowledged as P21/n by
the authors [345]. The second most common case with nearly 150
compounds reported is the cubic, no tilt a0a0a0 (Fm-3m), similarly
to the disordered compounds.
Following are smaller numbers of compounds with tilt systems
a0a0c (I4/m), aaa (R-3) and a0bb (I2/m). Instead of R-3 there
are some compounds assigned with a space group R-3m, with no
octahedral tilting. This is not a “Glazer” group, and it's possible that
these compounds are all in fact R-3, as the two space groups have
the same reflection conditions, and are thus difficult to distinguish
[53]. La2MgGeO6 has also been reported with space group R3 [386].
Several compounds (Ba2LaRuO6, Ba2SmMoO6, Ca2LaRuO6,
Sr2YNbO6 and Ba2SrWO6) have been assigned the triclinic space
group I-1 (or P-1, F-1), but also some higher symmetry group. In
these cases the higher symmetry appears reasonable, and has been
selected for this work. Only two compounds make a strong case for
the triclinic structure: Sr2MgMoO6 has been found to be metrically
tetragonal, but small changes in oxygen positions apparently make
it triclinic [633]. Also, Sr2FeIrO6 appears to have been described
only as I-1 [578]. Finally, Ba2PrIrO6 appears to be the only com-
pound that has been reported as a0a0cþ (P4/mnc), but it has also
been assigned other tilt systems, as noted also by Lufaso et al. [717].
Overall, there are no definitive examples of this tilt system found in
the literature.
The octahedral tilting takes place mainly to optimize the A-site
cation bonding in case of non-ideal ionic radius ratio. As described
in Section 2.2, the tolerance factor is a common way of expressing
the cation size mismatch. In case of the rock-salt ordered A2B0 B00 O6
double perovskites, a typical progress of octahedral tilting with
decreasing tolerance factor has been found as a0a0a0 (Fm-
3m) / a0a0c (I4/m) or aaa (R-3) / a0bb (I2/
m) / aacþ (P21/n) [65,114,179,180]. Looking at all the com-
pounds in the Supplementary material Table S1, this progression is
not immediately evident. Different groups of compounds behave
differently, and as discussed in Section 2.2, perovskites are not ideal
ionic compounds, so the cation radii are not exactly known. But
comparing similar “fixed B-cation families” can show this progress
of octahedral tilting. This is especially the case with, say, com-
pounds A2RB00 O6 with fixed A and B00 cations and various Rs, as the
electronegativities of the different Rs are all quite similar, so bond
covalency does not affect the comparison [114]. Similarly, the
progress is apparent with the A-site cation substitution, for
example in the Ba2xSrxInTaO6 system [179].
Some small deviations are found in the literature, though. The
structure of the Ba2RTaO6 compounds has been found to change
with decreasing t (increasing size of the R constituent) as Fm-
3m / I4/m / I2/m / R-3 [123]. However, only the end member
Ba2LaTaO6 was found to be in the borderline between I2/m and R-3.
This was assumed to be caused either by the large size of La, or its
lack of f electrons. As we noted in Section 2.2, La compounds often
deviate from other R cases when plotting the unit-cell volume as a
function of t. Also, (Ca,Sr,Ba)2CoWO6 and (Sr,Ba)2YMoO6 appear to
9
progress as Fm-3m / I4/m / P21/n with decreasing t, skipping the
I2/m symmetry [86,249].
As the different tilt systems are apparently governed by the
cation radius mismatch, it is interesting to consider at what values
of tolerance factor the structural transitions appear. There have
been some observations made in the literature, but they depend on
the chemistry of the compounds, and are not completely general.
The Ba2RB00 O6 compounds are the most studied in this respect, as it
is easy to change t by the choice of R. Typically, Ba2RB00 O6 com-
structure then changes with decreasing t to either I4/m or R-3 until
t ¼ 0.96e0.97 is reached, where a transition to I2/m or P21/n takes
place [53,65].
Fig. 6 shows the percentage of compounds reported with the
different space groups for all the rock-salt ordered A2B0 B00 O6 double
perovskites as a function of t. We can see that in general the tran-
sition from one tilt system to another is not clear cut and there is a
lot of overlap. Also, in this comparison valence mixing is not taken
into account, but instead all cations have been assigned integral
oxidation states. This causes relatively small difference and only for
a few compounds, however. What is seen is that in general,
monoclinic distortion aþbb (P21/n) is favored with t < 0.97 and
cubic a0a0a0 (Fm-3m) with t > 0.97. The remaining three most
common tilt systems are found for the intermediate values of t.
Occurrence of aaa (R-3) is at maximum at t ¼ 0.96e0.97, and
that of a0a0c (I4/m) at around t ¼ 0.97e1.00, whereas the number
of compounds with a0bb (I2/m) peaks at slightly lower values,
t ¼ 0.95e0.97. Thus in general these trends fit the aforementioned
progress of octahedral tilting.
3.4. Effects of temperature and pressure
The same progress in octahedral tilting can also take place with
a function of intrinsic variables, i.e. temperature or pressure. Of
these, temperature is the more thoroughly studied variable. Over
one hundred studies have been made of ca. 90 compounds, and the
results have been collected in Table S2 (in Supplementary material).
In all of the cases we could find, increase in temperature decreases
octahedral tilt and thus increases the crystal symmetry. Transition
to a cubic structure (a0a0a0) is the most commonly observed one.
Fig. 7 shows phase transition temperatures to a cubic structure for
A2B0 B00 O6 perovskites with A ¼ Ba and Sr, the most studied com-
positions found in the literature. A clear trend of decreasing tran-
sition temperature with increasing tolerance factor is seen, as
compounds with higher t are already closer to the ideal cubic
structure. There is great variability in the transition temperatures
found for a single compound by different groups, and the values
shown here are the most probable ones. Interestingly, compounds
Fig. 6. Percentages of A2B0 B00 O6 compounds reported with different space groups as a
function of tolerance factor.
10 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
Fig. 7. Phase transition temperatures to a cubic structure for several A2B0 B00 O6 com-
pounds with A ¼ Sr (white) or Ba (black). Inset: transition temperatures for Ba2RMoO6
with R ¼ Pr, Nd, Sm, Eu, Gd and Tb.
with A ¼ Sr tend have higher transition temperatures than those
with A ¼ Ba, even with similar tolerance factors. This could imply
that compounds with A ¼ Ba are in fact more symmetric at the
same value of tolerance factor. If we again look at just one “family”
of compounds, at best a rather linear trend in the transition tem-
peratures as a function of t can be seen, as for example the Ba2R-
MoO6 compounds in the inset in Fig. 7. Similar behavior was found
by Gateshki et al. [517] for several Sr2B0 WO6 compounds, although
in their case a more non-linear decrease in the transition temper-
ature was seen.
As can be seen from Fig. 7, many compounds transform to a
cubic structure near room temperature. There are also many other
compounds with, for example, R-3 e P21/n, or I4/m e P21/n tran-
sitions near room temperature (see Supplementary material
Table S2); for instance, Ba2LaTaO6 may be near an I2/m e R-3
phase transition [123]. This may explain some discrepancies with
the structures found in literature: slight changes in synthesis pro-
cedure or sample history could favor one structure instead of
another. Some compounds have also been found to exhibit two
phases coexisting at room temperature. These include Ba2BiIrO6
[33], Sr2CoWO6 [86,552], La2NiMnO6 [441,443,446], La2MgMnO6
[423,424] and the aforementioned Ba2LaIrO6 [181].
Some compounds, mainly those with B0 ¼ Fe, apparently have
structural transitions that are linked to magnetic ordering, and a
symmetry lowering is caused by the interplay between magnetic
and structural degrees of freedom. Sr2FeMoO6, the most well-
known example of the halfmetallic and ferrimagnetic double pe-
rovskites, has a structural transition at the magnetic ordering
temperature TC z 400 K, changing from tetragonal to cubic with
increasing temperature [584,594]. On the other hand, disordered
samples of Sr2FeMoO6 have been found to remain tetragonal at all
temperatures between 15 and 500 K [594]. Similarly, Ba2FeMoO6 is
reported to have a tetragonal I4/mmm structure, a “non-Glazer” tilt
system probably caused by the magnetic ordering, and to change to
cubic Fm-3m at TC z 320 K [140]. Finally, Ba2FeReO6 changes from
I4/mmm to Fm-3m at 305 K, and magnetic peaks have been found to
appear in ND measurements at the same temperature [696].
Compared to the effects of temperature, effects of pressure to
the crystal structure of A2B0 B00 O6 perovskites have been studied
much less. Lufaso et al. [38] have noted that for single perovskites,
typically the A2þB4þO3 compounds become more distorted with
increasing pressure, whereas A3þB3þO3 perovskites may become
less distorted. Whether pressure increases or decreases distortion
depends on the relative compressibility of the AO12 polyhedron
compared to that of the BO6 octahedron [599]. In general, in case of
the A2B0 B00 O6 perovskites, most compounds become more distorted
with increasing pressure, indicating that the AO12 polyhedra are
compressed more than the BO6 octahedra [418,599]. For instance,
Ba2BiB00 O6 with B00 ¼ Sb or Ta change from R-3 to I2/m [38,39],
Ba2YTaO6 from Fm-3m to I4/m [722] and Sr2CoWO6 from I4/m to
P21/n [723] with increasing pressure. Only exceptions are the
compounds with B0 ¼ Cu2þ, which are JT distorted. In these cases
the structural distortion is decreased with increasing pressure
[418,570]. The long CueO bonds apparently are compressed easier
than the short ones, and the tetragonal structure becomes more
cubic and less distorted with increasing pressure. The aforemen-
tioned examples are, however, all compounds with an A2þ cation,
and there appears to be no HP structural studies for A2B0 B00 O6
compounds with an A3þ cation. The more highly charged and often
smaller A3þ cations could be less compressible than the A2þ cations,
revealing a similar trend as with the single perovskites.
3.5. Effects of bonding
Geometric factors clearly can explain the major trends of
structural distortions in A2B0 B00 O6 perovskites, and the tolerance
factor can provide a decent prediction on the possible structural
distortions. However, as mentioned earlier, perovskites are not
completely ionic, so covalency and bonding properties affect the
structure. For example, properties of the A-site cation can affect the
structure in some cases [718]. Barnes et al. [228] have noted that
when t is close to 1, compounds with A ¼ Ba may have a higher
symmetry than the ones with A ¼ Sr, even if their tolerance factors
are similar. Similarly, Day et al. [46] have noted that the tetragonal-
to-cubic phase transition boundary is found at lower values of t in
compounds with A ¼ Ba than in compounds with A ¼ Sr. This was
assumed to be caused by a flexibility of the BaeO bond lengths that
help stabilize the cubic structure even at lower values of t. This
effect was also noted in the previous section in the structural
transition temperatures in Fig. 7.
The B-site cation bonding may also affect the crystal symmetry
of the A2B0 B00 O6 compounds. When one of the B-site cations is a p-
group element, such as Sb or Te, the compounds have been found to
be more distorted than when there are no p-group elements pre-
sent [226]. This behavior appears to be related to oxygen polari-
zation and the lack of p-bonding in case of the p-group elements:
the highly charged B00 cation would polarize the oxygen electron
could, but this polarization is weakest at 180 bond angles. How-
ever, in the absence of p-bonding, there is no preference for linear
bonds, and nonlinear bond angles may be favored in order to
maximize polarization, and the structure is distorted. Looking at
the compounds reported in the literature this effect is mostly
difficult to verify. For example, Sb is smaller than the corresponding
pentavalent transition metals Nb or Ta, so t is larger, and thus
B00 ¼ Sb compounds are often more symmetric than those with
B00 ¼ Nb or Ta. However, Sr2(Cr,Mn)B00 O6 with B00 ¼ Nb, Sb or Ta
appear to demonstrate the effect, with B00 ¼ Sb compounds having a
lower symmetry than the B00 ¼ Nb or Ta compounds (see
Supplementary material Table S1). Ba2MnTeO6 and Sr2NiTeO6 have
also lower symmetries than some other similar B00 6þ compounds
with smaller tolerance factors.
Special effort has been taken to understand why some A2B0 B00 O6
compounds adopt the tetragonal I4/m structure whereas others are
orthorhombic R-3 even with similar values of t, as these two
structures are direct competitors [253], and it is not always
immediately evident why one structure would be favored over
another. This division may be explained by either A- or B-site cation
bonding properties.
Effects of the A cation can be explained with bond covalence. For
single perovskites, the rhombohedral structure has the highest
Coulombic attraction, but also the highest repulsive energy: a
highly charged A cation together with relatively small octahedral
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
tilting stabilizes rhombohedral structure, as the attractive term
outweighs the repulsive one [114,253,718]. Similarly, looking at
Supplementary material Table S1, in A2B0 B00 O6 perovskites there are
some A ¼ La compounds reported as rhombohedral, whereas none
are tetragonal; the larger Coulombic attraction of the A3þ cation
appears to favor the rhombohedral structure. Also worth noting is
that in the reported A2B0 B00 O6 perovskites with an A2þ cation, most
of the tetragonal I4/m compounds have Sr as the A cation, while
very few have Ba. Conversely, most of the rhombohedral R-3
compounds have A ¼ Ba, whereas very few have A ¼ Sr. This could
be due to the increased electronegativity and covalence of Sr
compared to Ba [114,718].
The B-site cation can also affect whether a tetragonal or ortho-
rhombic structure is stabilized. Looking at the Supplementary
material Table S1, we can see that most of the A2B0 B00 O6 perov-
skites with A ¼ Sr or Ba having a space group R-3 have either some
p-group element (Bi, Sb, Te, Sn), or Ru or Ir at the B site. On the other
hand, tetragonal I4/m compounds generally have at the B site ele-
ments W, Ta, Nb, Mo, Re or Os. It thus appears that compounds with
a B-site cation from the right side of the periodic table are rhom-
bohedral, while the ones with elements from the left side are
tetragonal. There are a few exceptions, though. Sr2CrOsO6 is
rhombohedral, but it could be that Os is in the borderline between
the two structures. On the other hand, A2CuTeO6, A ¼ Sr, Ba and
Sr2MnSbO6 are tetragonal, but this is caused by the JT active Cu2þ or
Mn3þ ions. Sr2GaSbO6 is also tetragonal, even with Sb at the B site,
making this compound the most notable exception to the afore-
mentioned behavior.
Interestingly, the bonding preference of the B cations from the
two sides of the periodic table may be so strong that sometimes it
may not be possible to accommodate both kinds of elements in the
same structure. In case of Ba2NdNb1-xSbxO6 and Ba2Eu1-xPrxNb1-
xSbxO6 series, a phase segregation has been found with certain
values of x, indicating limited solubility between the Nb- and Sb-
containing perovskites [130]. However, in compounds such as
Ba2BiTaO6, both Bi and Ta coexist, although they occupy different B
sites.
There are two causes given in the literature for this structural
division between the different elements: covalency and p-bonding.
As for the covalency, increased covalency of a BeO bond favors a
coordination sphere around the A cation that maximizes Coulomb
attraction, resulting in a rhombohedral structure [114,718]; highly
covalent B00 eO bonds may determine the structure, whereas the
more ionic and flexible AeO or B0 eO bonds follow along [168].
Therefore, compounds with the relatively electronegative elements
from the right side of the periodic table, which form more covalent
bonds with oxygen, tend to be rhombohedral [53,55]. The cova-
lency picture is, however, difficult to quantify, as the precise elec-
tronegativities of elements with different oxidation states are not
well known [123,253].
The second explanation considers the effect of the number of
the B-site cation d electrons on the BeO p-bonding strength. When
the B-site cation has only a few d electrons, a structure with B0 -O-B00
bond angle closest to linear is favored, that being the tetragonal
structure. Thus, elements on the left side of the periodic table with
a small number of d electrons favor the tetragonal structure,
whereas elements from the right side of the periodic table with a
large number of d electrons favor the rhombohedral structure
[123,126,697]. In this case, the stability boundary between the two
structures was suggested to lie between d1 and d3 ions. Looking at
the compounds in Supplementary material Table S1, it would rather
appear that the stability boundary would be between d3 and d4
ions. Which one of these explanations is the correct one is not clear,
and both effects could contribute, as they are difficult to
distinguish.
11
3.6. Octahedral distortions
In addition to the octahedral tilting, distortion of the BO6 octa-
hedra due to electronic instabilities such as the JT effect, and
cationic displacement due to ferroic distortions can affect the
crystal structure of the A2B0 B00 O6 perovskites [15]. The structural
features of JT distorted A2B0 B00 O6 perovskites has been studied
before by Lufaso and Woodward [716], and Howard and Carpenter
[724] determined the possible space groups for compounds where
one cation is JT active by group theoretical analysis. The space
groups differ from non-JT compounds: for instance I4/mmm re-
places Fm-3m due to a cooperative JT distortion along the c axis
[553,724].
If we examine the compounds with the most prominent JT
active ions Cu2þ and Mn3þ, we can first of all note that Mn3þ
compounds are almost all disordered. This is due to the relatively
high oxidation state of Mn3þ, and the resulting small charge
difference between the B0 and B00 cations, which will hinder
cation ordering, as will be discussed in Section 4.3. Such disor-
dered compounds do not show cooperative JT distortions [716].
However, Sr2MnB00 O6 with B00 ¼ Nb, Ta or Sb all show a low de-
gree of cation ordering. Of these, only Sb is tetragonal with the c
axis ~3% longer than the a axis, indicating the presence of some
cooperative JT distortion. Slight differences in the amount of
short-to-medium range cation order may explain the difference
between the A ¼ Sb compound compared to the A ¼ Nb or Ta
compounds [716]. Similarly, Sr2MnRuO6 is reported to be disor-
dered, but also tetragonal with a ~3% c axis elongation. Replacing
Sr with Ca in this compound apparently shifts the cation oxida-
tion states from Mn3þ/Ru5þ towards Mn4þ/Ru4þ, and the weak JT
distortion disappears [314]. Finally, La2GaMnO6 has also found to
be locally JT distorted, but the disordered structure (Pnma) hides
the distortion [408].
The effect of JT distortion is seen much clearer in the Cu2þ
compounds. Here the difference between the two B-site cation
oxidation states can be larger than with Mn3þ, and the compounds
tend to be more ordered. The rock-salt ordered Cu2þ compounds
with A2þ cations are all tetragonal, with the c axis 5e10% longer
than the a axis, due to the long CueO bonds being cooperatively
ordered along the c axis, as seen in the Supplementary material
Table S1. The other B-site cation typically has a close to regular
octahedral coordination. Interestingly, these compounds tend to
have octahedral rotation about the c axis even with large values of t,
as also noted by Lufaso and Woodward [716]. On the other hand, it
appears that these compounds cannot withstand much octahedral
tilting, as apparently the tilting destabilizes the orbital order [716].
As discussed earlier, this may be the reason why the Ca2CuB00 O6
compounds have not been synthesized yet, even though their
tolerance factors would be reasonable.
As mentioned previously, the Cu containing JT distorted
A2B0 B00 O6 compounds are the only ones for which increasing pres-
sure decreases distortion. This is due to compressing of the long
CueO bonds faster than the short ones, which makes the com-
pounds more cubic-like [418]. Increasing the temperature also in-
creases symmetry by decreasing the octahedral rotation. For
Sr2CuWO6 and Ba2CuUO6 an I4/m / I4/mmm transition has been
observed, where the B0 eOeB00 bond angles change to 180 [96,553].
The JT distorted compounds may also to transform to a cubic
structure at high temperatures when the JT distortion disappears,
although this transition has only been detected in Sr2CuB00 O6 with
B00 ¼ W or Mo [553,568]. This transition temperature may be quite
different compared to the non-JT distorted compounds with similar
values of t, as is evident from the data in Table S2 (Supplementary
material). Rather strangely, it has been noted that in case of
Ba2CuUO6 the JT distortion appears to increase with increasing
12 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
temperature, which was assumed to be due to a coupling between
the JT distortion and the octahedral tilting [96].
The A3þ2Cu2þB00 4þO6 compounds with B00 ¼ Mn, Ti or Rh are all
disordered and show no cooperative JT effect. Again, this is
explained by the small difference in the B cation oxidation states.
On the other hand, A2CuIrO6 with A ¼ La or Nd and La2CuRuO6 have
been reported to be rock-salt ordered with at least partial cation
order, but to be monoclinic. Interestingly, in these compounds the a
and b axes are longer than the c axis, implying that the long CueO
bonds may in fact be preferably ordered within the ab plane.
The rather uncommon A2B0 B00 O6 perovskites with a layered B-
site cation ordering are all compounds with B0 ¼ Cu2þ, namely
R2CuSnO6 with R ¼ La, Nd, Pr or Sm and La2CuZrO6. These com-
pounds have all been described as monoclinic, space group P21/m,
with the CueO and B00 eO layers repeating along the a axis. The long
CueO bonds are ordered along the a axis, which is ~9% longer than
the b or c axes (see Table S1). The BO6 octahedra are rather strongly
tilted, causing a buckling of the CueO and B00 eO layers, and it has
been suggested that the stability of the layered structure might be
coupled to the size of octahedral rotation [716], as will be discussed
in more detail in Section 4.8.
There are a few reported examples of compounds exhibiting a
weak JT effect due to a d1 electron configuration, namely
Ba2B0 MoO6, B0 ¼ Nd or Sm and Ba2NaOsO6. This effect can be static,
with a corresponding structural distortion, or dynamic, with an
average structure of two distorted states [698]. The two Ba2B0 MoO6
compounds are tetragonally distorted, although the distortion is
very small [109,229,698], whereas Ba2NaOsO6 appears to be cubic
and the JT distortion is apparent only in the magnetic properties
[207]. Interestingly, Ba2RMoO6 compounds with smaller R, such as
Gd or Er, do not show this JT distortion, possibly due to a higher
tolerance factor and correspondingly more ideal structure
[160,575]. Finally, a weak JT effect has also been detected in some
B0 ¼ Co compounds. In case of Sr2CoFeO6, the CoO6 octahedra
appear to have slight JT distortion [525]. This was explained with a
presence of some JT active intermediate-spin Co3þ, caused by a
mixed-valence state. Also, in Sr2CoOsO6 a distortion in the CoO6
octahedron has been noted, and assigned as a weak JT distortion of
the high-spin d7 Co2þ [540]. Similar weak distortion may also take
place in La2CoIrO6 [360,540].
Additional distortion to the A2B0 B00 O6 perovskite crystal struc-
ture may be caused by a ferroelectric displacement of a cation. Pb2þ
or Bi3þ at the A site in particular can cause ferroic distortions, due to
the 6s2 lone electron pair of these ions. Of these, the A ¼ Pb com-
pounds are much more common, as can be seen from Table S1 in
Supplementary material. Only four A ¼ Bi compounds are re-
ported in the literature. Of these Bi2NiMnO6 has been found to be
ferroelectric below ca. 460e480 K [259,260] and Bi2CoMnO6 has a
ferroelectric transition above 600 K [259]. In Fig. 8, we plot the
transition temperatures from (anti)ferroelectric to paraelectric
Fig. 8. Phase transition temperatures to a cubic paraelectric structure for Pb2B0 B00 O6
compounds as a function of tolerance factor t.
structures as a function of the tolerance factor for some of the
A ¼ Pb compounds found in the literature. Relatively linear
behavior is found, indicating that the cation radius mismatch af-
fects also the ferroelectric distortions [487]. Many of the com-
pounds with lower values of t show relatively high transition
temperatures, above room temperature, useful for applications.
Ferroelectric properties of the A2B0 B00 O6 perovskites are discussed
further in Section 6.4.
In the ferroelectrically distorted case the exact structure of a
compound may be very complicated and the space groups found for
other A2B0 B00 O6 perovskites may not be adequate in describing these
structures [496,507]. Incommensurate structures are also possible,
as in case of Pb2CoWO6 [479,492], or Pb2MgTeO6, which has an
incommensurate structure below 194 K [492]. What is more, in case
of ferroelectric compounds, even above the paraelectric transition
temperature the A cation may not be at the ideal position, but have
a statistical distribution [502].
3.7. Other factors affecting crystal structure
Synthesis conditions have been found to affect the crystal
structure, and this may be one reason why for some compounds
several different space groups have been assigned [553]. For
example, the structure of Ba2CeNbO6 depends on the Ce starting
material used in the synthesis, and similar phenomenon has been
found in case of Ba2LaIrO6 [65]. Also, A2InNbO6 with A ¼ Ca, Sr or Ba
have been given various structures in literature, possibly due to
different synthesis conditions [173]. These discrepancies are
probably caused by the different reaction mechanisms of different
starting materials, which affect the required synthesis temperature
and time, as has been found in the case of La2CuTiO6 [398]. Espe-
cially too short annealing times may result in two phases coexist-
ing, most probably due to slow cation diffusion during the
synthesis, and this can cause difficulties in structural determination
[676]. Interestingly, in case of La2CoMnO6, an orthorhombic-to-
rhombohedral phase transition temperature depends on the cool-
ing rate during the synthesis. The oxidation states in a slow-cooled
sample appear to be Co2þ and Mn4þ or close, but in quenched
samples the balance is moved towards Co3þ and Mn3þ. This change
in the oxidation states changes the tolerance factor of the com-
pound, which then changes the phase transition temperature [725].
Oxygen vacancies can also affect the crystal structure and
symmetry. It has been noted by Kato et al. [726] that oxygen va-
cancies can change the structure of a compound to cubic, even with
low values of tolerance factor. Similarly, Sr2CoIrO6 changes from
monoclinic to tetragonal [530], and Sr2CoSbO6 from rhombohedral
to cubic [546] with the introduction of oxygen vacancies. It is thus
apparent that oxygen vacancies can increase symmetry compared
to stoichiometric samples. This could be due to increased repulsion
between the cations caused by the missing anions, which would
work to maximize the cationecation distance.
4. B-site cation ordering
What truly separates the complex A2B0 B00 O6 perovskites from the
ABO3 single perovskites is the possibility for the two B-site cations
to order. Such order-disorder phenomena are of fundamental in-
terest, but the ordering also affects many of the physical properties
of these compounds. For instance, the halfmetallic and magneto-
resistance properties of Sr2FeMoO6 are strongly affected by the
degree of B-site cation order [709,710,727]. Also, the ferroelectric
properties of the A ¼ Pb compounds depend on the B-site cation
order as will be discussed in Section 6.4.
Different types of B-site cation ordering are possible, as has been
mentioned in the Introduction. Most commonly the compounds are
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
either rock-salt ordered or disordered. There are over 650 reported
rock-salt ordered A2B0 B00 O6 compounds and about 100 disordered
ones, and they are the ones we focus on here. Third possibility is the
layered order. However, only five A2B0 B00 O6 compounds are reported
layered and we will discuss them separately in Section 4.8.
4.1. Degree of order and types of disorder
The degree of B-site cation order can be quantified as a first
approximation by a simple long-range order parameter, defined as
S ¼ 2gB  1
where gB is the occupancy of a B-site cation at its correct site. The
completely ordered double perovskite corresponds to S ¼ 1 and the
completely disordered one to S ¼ 0. However, partial cation
ordering is also possible. What is more, the range of cation order in
a single compound can vary widely due to different synthesis
conditions, which allows for the control of cation order in some of
the A2B0 B00 O6 compounds. In the Supplementary material Table S1,
we can find several compounds for which a range of cation order-
ings have been found. For example, Ca2FeSbO6 has been reported
mainly with a high degree of order, S z 0.9 [135,150,302], but also
as completely disordered [301]. Similarly, Pb2ScNbO6 has been re-
ported with a wide range of S varying from 0 to 0.92 [502,503].
The disorder of the B-site cations can take place in different
ways, as presented in Fig. 9. Simplest is the antisite (AS) defect,
where B0 and B00 cations simply change places. Small amount of such
point-like AS defects are always expected to be present due to
configurational entropy. Another common type of defect is the
antiphase boundary (APB), which separates two ordered domains
with reversed B0 and B00 site occupancies. In a way this can be
considered as accumulation of AS defects in one place, resulting in
the correct periodicity of the ordered phase, but in reverse order
[727]. In fact, in the A2B0 B00 O6 perovskites these APBs have often
been found [172,510]. For example, cation ordering in Sr2FeMoO6
has been studied quite extensively, as the physical properties are
very sensitive to ordering, and it appears that APBs are favored over
AS defects [292,727]. Also, in case of Sr2MgMoO6, the B-site cation
disorder takes place as extended APBs instead of simple AS defects
[633]. Interestingly, in their study, Faik et al. [512] found that
Sr2AlSbO6 had APBs, whereas Sr2CoSbO6 had only AS defects. Thus
the nature of cation disorder may depend on composition, perhaps
because of differences in melting points and synthesis conditions. It
was noted by Dass et al. [446], that in case of La2NiMnO6 prolonged
annealing may lower the amount of AS defects, but the APBs are not
affected.
The aforementioned Pb2ScNbO6 is an interesting example. A
study by Perrin et al. [503] found that seemingly partially ordered
samples contained ordered and disordered domains, and APBs
were found within the ordered domains. In addition, even the
Fig. 9. B-site cation disorder schemes: (a) completely ordered, (b) antisite disorder and (c) antiphase boundary.
13
disordered structure may contain very short range ordering [502].
Similarly, in case of Sr2FeMoO6, a high degree of short range order
has been found even in very disordered samples [727]. This phe-
nomenon was also noted in Section 3.6 in case of the JT distorted
Mn3þ compounds, which appear disordered but have slight
tetragonal distortions, indicative of short-range cation ordering.
These results show that the cation ordering in A2B0 B00 O6 perovskites
can be rather complicated in the microstructural level. Stenger and
Burggraaf [728] have also pointed out that the use of long-range
order parameter is limited to materials with spatially homoge-
neous order, which is often possible only when the system has
reached equilibrium with respect to the cation order. In case of non-
homogeneous samples containing ordered domains within disor-
dered matrix, using a fraction of the ordered domains may be more
appropriate. Finally, Woodward [226] has suggested dividing the
A2B0 B00 O6 perovskites into five categories depending on the nature
of cation ordering: 1) disordered (possibly with or without short
range order), 2) weakly ordered, 3) partially ordered, 4) highly or-
dered with APBs, 5) highly ordered without APBs.
4.2. Detecting order
The B-site cation order is most often determined by diffraction
studies. Due to the cation ordering and corresponding doubling of
the unit cell, supercell reflections are generated. These supercell
reflections would be a clear indication of order [16], but as
described earlier, combination of octahedral tilting and cation
ordering can affect the same reflections, and it sometimes becomes
difficult to separate the two effects. Also, detecting cation ordering
is difficult with XRD if the two B-site cations have similar number of
electrons. This problem has been noted for example in case of
La2NiMnO6 [448], Ba2RTaO6 [123] and Ba2RRuO6 [184]. Certain
compositions may actually have exactly the same electron count on
both the B0 and B00 cations, as in A3þ2Ca2þTi4þO6, A2þ2In3þSb5þO6,
A2þ2Sr2þMo6þO6, A2þ2Y3þNb5þO6, A2þ2Sc3þV5þO6 or
A2þ2Tl3þBi5þO6. Cation ordering in such cases may be detected
indirectly from oxygen positions [30,695]. However, oxygen is
difficult to reliably detect with XRD, and NPD may be needed in
order to detect order, as it is insensitive to the number of electrons
and can also detect oxygen positions more reliably. On the other
hand, the high scattering length of oxygen can cause difficulties in
determining B-site cation order, and combination of XRD and NPD
may again be needed [37,239,397]. Diffraction studies may also
distinguish between AS and APB type disorder from the broadening
of the supercell peaks [510,512,727]. Electron microscopy may also
help to detect local order in apparently disordered compounds, and
the ordered/disordered domains of Pb2Sc(Nb,Ta)O6 mentioned
above were found using this method [503]. Finally, Mo €ssbauer
spectroscopy is a very powerful method for detecting cation
ordering if suitable elements, such as Fe, are present in the sample
under study [729].
14 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
4.3. Charge and size difference
When considering the factors affecting B-site cation order, it
should be noted that entropy would always favor some degree of
disorder [92]. However, as many of the A2B0 B00 O6 compounds are
reported to be very highly ordered, there must be other energetic
terms favoring order. It is well accepted, that the main factor
causing B-site cation order in these compounds is the difference in
the B0 and B00 cation oxidation states, DZB ¼ jZB00 eZB0 j. Broadly
speaking, when DZB < 2 the compounds are disordered and when
DZB > 2 the compounds are ordered [16,17,510,730,731]. This can be
explained simply by considering the electrostatic repulsion be-
tween the B-site cations: when DZB is large, placing two highly
charged B00 cations close to each other will be energetically unfa-
vorable compared to the ordered arrangement where the B00 cation
is surrounded only by the less charged B0 cations. In more quanti-
fied terms, the Madelung energy of ordering in the A2B0 B00 O6 pe-
rovskites increases with increasing charge difference [92,732].
When the difference in the B-site cation oxidation states is large
enough, increase in the electrostatic repulsion overcomes the
entropic term and the cations are ordered [616]. The Madelung
energy of ordering has been calculated for cubic and tetragonal
A2þ2B0 B00 O6 perovskites [733,734]: if DZB ¼ 0, there is no change in
Madelung energy with ordering and consequently there is no en-
ergy gain in cation ordering compared to a disordered case. How-
ever, the Madelung energy of ordering is proportional to DZ2B. Thus
the energy increases quickly with DZB, and the ordering energy can
become a significant fraction of the total energy, 13% in case of
Ba2LiReO6 with DZB ¼ 6.
Second commonly noted factor affecting the cation order is the
ionic radius difference, DrB ¼ jrB00 erB0 j. Generally, the larger the
difference, the more probable ordering is. If difference in the ionic
radii is large enough, increase in lattice strain overcomes the
entropic considerations, and the cations are ordered [616]. Galasso
and Darby [735] determined the effect of ionic radius difference to
ordering in small number of compounds with M3þ/Nb5þ cation
combinations. Their results suggested that a difference in radii
higher than 7e17% would be enough to cause ordering.
Here we look at the cation ordering of the compounds collected
in Supplementary material Table S1. Fig. 10 and Table 4 summarize
the different cases: a general trend is found, with the degree of B-
site cation order increasing with increasing charge and size dif-
ference. The simplest cases are the A3þ2B0 3þB00 3þO6 compounds
Fig. 10. Charge difference versus ionic radius difference for disordered (white) and
ordered (black) A2B0 B00 O6 compounds. The symbols for disordered (ordered) com-
pounds have been raised (lowered) for clarity.
Table 4
Summary of cation orderings found in different A2B0 B00 O6 compounds.
DZB Compound Ordering
0 A2þ2B0 4þB00 4þO6 Disordered with DrB < 0.17 Å. Ordered above
A3þ2B0 3þB00 3þO6 Disordered
2 A1þ2B0 4þB00 6þO6 Ordered
A2þ2B0 3þB00 5þO6 Disordered, partially ordered or ordered
with increasing DrB
A3þ2B0 2þB00 4þO6 Most compounds at least partially ordered
4 A2þ2B0 2þB00 6þO6 Mostly highly ordered
A3þ2B0 1þB00 5þO6 Ordered
6 A2þ2B0 1þB00 7þO6 Ordered
with DZB ¼ 0, which are all disordered. Interestingly, some of the
A2þ2B0 4þB00 4þO6 compounds, even with DZB ¼ 0, have been reported
to be ordered. Most of these ordered compounds have DrB > 0.17 Å
or ~24%, whereas compounds with a smaller size difference are
disordered. There are a few exceptions, though. Ba2PrBiO6 appears
to be highly ordered even with DrB ¼ 0.05 Å. However, this com-
pound has been reported to have some valence mixing between the
B-site cations [60,61], so it may actually have DZB > 0. Similarly,
Ba2TbBiO6 and Sr2TbIrO6 which are on the borderline of ordering
with DrB ~ 0.14 Å appear to have valence mixing, and are ordered.
La2(Mn,Fe)IrO6 are also ordered with DrB < 0.17, but the oxidation
states of the B-site cations are not known well, and valence mixing
is a possibility in these compounds as well. Finally, Sr2CoTiO6 with
DrB ¼ 0.08 Å has been reported with a low degree of order, S ¼ 0.07,
and is thus practically disordered. Thus a relatively sharp order-
disorder transition is seen at around DrB z 0.17 Å in case of the
A2þ2B0 4þB00 4þO6 compounds showing that the effect of ionic radius
on ordering is notable in these compounds.
Conversely, the A2þ2B0 2þB00 6þO6, A2þ2B0 1þB00 7þO6 and
A3þ2B0 1þB00 5þO6 perovskites with a high charge differences of DZB ¼ 4
or 6 are for the most part very highly ordered. There are, however,
some examples with relatively low ordering, such as Sr2FeTeO6,
Sr2ZnIrO6 and Sr2MnMoO6, all of which have been reported with
S < 0.8. Interestingly, they are all found within the A2þ2B0 2þB00 6þO6
compounds. This is probably mostly due to the fact that these com-
pounds have in general been studied more than the corresponding
DZB ¼ 4 compounds A3þ2B0 1þB00 5þO6. The disorder may also in some
cases be due to partial electron transfer between the two B-site cat-
ions, which effectively lowers DZB, or due to oxygen vacancies, which
can also lower the cation order, as will be discussed in Section 4.5. In
case of the A3þ2B0 1þB00 5þO6 compounds, no charge transfer is possible
due to the nature of the monovalent B0 cations, which are all alkali
metals. An especially intriguing case is Pb2MnTeO6, which is the only
one of these compounds that has been reported to be disordered,
even though the p-group element Te would be expected to improve
cation ordering, as will be discussed in Section 4.5.
The most interesting order-disorder phenomena are found
when DZB ¼ 2, where a wide range of partial order may take place.
As is seen in Fig. 10, both ordered and disordered compounds can be
found in the whole range of DrB of these compounds, although it
appears that there are more disordered compounds found at lower
values of DrB.
Fig. 11(a) shows the degree of order for the A2þ2B0 3þB00 5þO6
perovskites as a function of DrB. The figure shows a general trend of
increasing cation order with increasing DrB. In general, the com-
pounds are almost completely ordered if DrB > 0.2 Å or ~35%. Only
notable exceptions are Ba2B0 RuO6 with B0 ¼ Gd or Bi, which are
found to be disordered even with high values of DrB ¼ 0.37 and
0.47 Å, respectively. Below DrB ¼ 0.2 Å, the compounds show a wide
range in degree of order, from disordered to fully ordered, but it
appears that the lower value of S are more common with lower
values of DrB.
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
Fig. 11. Degree of B-site cation order for (a) A2þ2B0 3þB00 5þO6 and (b) A3þ2B0 2þB00 4þO6 perovskites as a function of B-site cation radius difference.
The degree of order for the A3þ2B0 2þB00 4þO6 perovskites as a
function of DrB is shown in Fig. 11(b). In contrast to the
A2þ2B0 3þB00 5þO6 perovskites, these compounds do not show a clear
trend in the degree of order with respect to DrB, although the
number of samples is rather low. The compounds appear to be split
broadly in two: some have a relatively high degree of order,
whereas some whole “families” of compounds are disordered. For
example, all of the R2CuTiO6, R2CuMnO6 and R2MnTiO6 compounds
are disordered, even though for these compounds DrBs are rela-
tively large, 0.13e0.23 Å. On the other hand, many other similar
compounds, such as R2NiMnO6 or R2CoRuO6, are quite highly or-
dered with DrB ¼ 0.13e0.16 Å. It would thus appear that certain
“families” behave differently, which could be due to different
bonding behavior with different cation combinations.
Finally, the A1þ2B0 4þB00 6þO6 compounds with DZB ¼ 2, are all
reported to be fully ordered. However, there are only three exam-
ples of these compounds, two of which are high-pressure synthe-
sized samples. As will be discussed in the next section, HP may
improve cation order.
4.4. Synthesis conditions
The charge, and to some extent cation radius differences are the
major factors affecting the B-site cation order. In the case DZB ¼ 2, a
wide range in the degree of order is often possible, as discussed,
and in these cases there are many additional contributions affecting
the cation ordering. Among the most important are synthesis
conditions, especially synthesis temperature. It has been found in
case of Sr2AlB00 O6, B00 ¼ Nb or Ta, that the synthesis of the perovskite
phase begins with relatively fast formation of a partially ordered
phase, which then orders during annealing [510]. Similar results
have been found in many other cases, such as Ba2YTaO6 [255],
(Sr,Ba)2InNbO6 [172], Ba2InTaO6 [178], Sr2MnSbO6 [320] and
Sr2(Al,Co)SbO6 [512]. Such an ordering process takes place by a
thermally activated diffusion of cations. The process is kinetically
controlled and higher temperatures and longer annealing times
tend to increase order. At equilibrium, high order would be ex-
pected. However, at higher temperatures the entropy term TDS
would cause more cation disorder, and the ordering process be-
comes thermodynamically limited. Thus, the thermodynamic and
kinetic factors compete and some optimal temperature for
maximum ordering may often be found.
The optimal annealing temperature depends on the composi-
tion. The single most studied compound in this respect is again
Sr2FeMoO6, due to the fact that the magnetic and magnetoresistive
properties greatly depend on the ordering [709,710], with the
optimal properties often found with high degree of order. For
Sr2FeMoO6, highest degree of order has been obtained around
1420 K: below this temperature the ordering process is under ki-
netic control, above it under thermodynamic control. Thus, long
15
annealing at this temperature maximizes the cation order
[579,590,594,736,737,738,739]. Sr2MnSbO6 shows some B-site or-
der (S z 0.2e0.3) if annealed at 1370e1470 K, although longer
annealing times lower the degree of order. At ~1570 K, a disordered
compound was obtained [320]. In case of Sr2AlNbO6, the highest
order has been found when annealing at around 1670 K, whereas
for Sr2AlTaO6 the cation order did not reach maximum even at
1870 K [510]. What is more, higher degree of order was obtained
with Sr2AlNbO6 than with Sr2AlTaO6. These differences were
assumed to be caused by the different melting points of these
compounds. It is interesting to consider the possibility that in some
cases the low degree of cation ordering could be caused because the
compound would need very low annealing temperatures to order,
but synthesis at such temperatures becomes impossible. More
reactive precursors or soft-chemical synthesis methods might help
in controlling the cation order in such cases. Finally, La2CoMnO6 has
a high degree of order when annealed at 1060 K, and low when
annealed at 1640 K [367]. In their study Kyo ^men [725,740] found
that the B-site order of this compound freezes around 1400 K, and
the order parameter of quenched samples changes quite abruptly
around this temperature. In case of this compound, the change in
cation order may be related to a change in the cation valences:
ordered samples annealed at low temperatures appear to have a
Co2þ/Mn4þ cation combination, while the more disordered samples
quenched from high temperatures may be closer to Co3þ/Mn3þ.
Besides temperature, the pressure during synthesis may also
affect the cation order. Cation disorder has been found to increase
the unit-cell volume in the A2B0 B00 O6 perovskites, due to electro-
static repulsion between the highly charged B00 cations [510,736].
Conversely, it would be expected that reducing the lattice volume
by external pressure would make the ordered structure energeti-
cally more favorable compared to the disordered case [736]. This
has been shown in case of Sr2FeReO6, where HP-synthesized
samples had S z 1, compared to S ¼ 0.5 found for samples syn-
thesized at ambient pressure [603].
4.5. Other contributions
Besides the synthesis conditions, other factors such as cation
bonding properties have also been found to affect the B-site
ordering. However, it is difficult to verify these weaker contribu-
tions because of the overwhelming effect of synthesis conditions to
the ordering.
Firstly, it has been noted that a smaller A-site cation may
somewhat increase the B-site cation order [730,731]. This effect is
due to the fact that with a smaller A-site cation, the B-site cations
will be closer together, and their electrostatic repulsion will be
higher. Thus the Madelung energy of ordering is increased as the A-
site cation radius decreases. Therefore, chemical pressure would
work similarly to external pressure discussed in the previous
16 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
section. However, this effect appears to very weak [510], and might
also be explained by changes in melting point [228].
Secondly, compounds with a main group element at the B00 site,
such as Sb5þ, have been found to be somewhat more ordered than
those with a comparable transition metals, such as Nb5þ or Ta5þ
[226,227,510,583,607]. As was discussed in Section 3.5, in case of
highly charged p-group cations at the B00 site, polarization of the
oxygen electron cloud is important. In disordered compounds the
B00 eOeB00 ion arrangement is common, but in this case polarization
is not optimal due to the oxygen electrons being pulled equally
from both sides. The polarization is maximized with complete
ordering, where only B0 eOeB00 arrangements are possible. In
addition, p-bonding may affect the ordering: the lack of d orbitals
available for p-bonding in the p-group elements means that there is
no additional bonding energy available with the B00 eOeB00
arrangement of a disordered case [226,227,510].
Finally, oxygen content can also affect the B-site cation ordering;
oxygen vacancies lower the B-site order, as has been noted for
example by Kato et al. [726]. In case of Sr2MgMoO6, it has been
found that samples containing oxygen vacancies had lower degree
of B-site cation order than oxygen stoichiometric samples [633].
The explanation given was that Mg tries to avoid the lower coor-
dination caused by an oxygen vacancy, and the cation disorder is
increased so that the oxygen in MoeOeMo bonds can be removed.
Similarly, with replacing Mo6þ by Nb5þ in Sr2MgMoO6, more oxy-
gen vacancies are created, and the B-site cation order is decreased
[741]. Other defects in the structure can affect cation ordering as
well, as in the case of Sr2AlTaO6, where changing the Al/Ta stoi-
chiometry can either increase or decrease the cation degree of or-
der [510].
4.6. Charge disproportionation
A very special case of B-site cation ordering is caused by a charge
disproportionation of the B-site cation of a single perovskite ABO3.
The most well-known example of this is perhaps BaBiO3, where the
Bi charge is ordered, Bi(4d)þ/Bi(4þd)þ, forming a rock-salt ordered
double perovskite Ba2BiBiO6 [27,28,29,30]. The setup is somewhat
different from two different B-site cations, but the result is a B-site
ordered double perovskite. Compared to cation ordering, charge
ordering is quick and easy to achieve, as no ionic diffusion is
required, and only electron transfer and small anion displacements
to compensate for the different ionic radii take place [30]. Thus, the
kinetic factors that often limit the cation order in the A2B0 B00 O6
perovskites are absent in the charge ordered compounds. Also, it
could be assumed that there are fewer defects in the ordering, as
the electrons can move easily to remedy any imbalances.
The other difference compared to cation ordering is that the
charge ordering typically depends sensitively on temperature. At
high temperatures the charges can be delocalized due to thermal
energy and typically an ordering temperature is found, below
which the charges localize. However, the charge ordering is often
not complete at this transition temperature. Thus the cation
oxidation states are not ideal integers, and may change with tem-
perature. In case of Ba2Bi(4d)þBi(4þd)þO6, at its highest d appears to
be ~0.5, but can also depend on synthesis conditions [32]. The
charge disproportionation in this compound is also very robust,
persisting even at high temperatures of at least 920 K [695].
There are at least two other compounds that have a charge-
ordered double-perovskite structure. Y2NiNiO6 has a charge
ordering temperature of ~580 K, and the ordering is accompanied
by a metal-insulator transition [693]. Again, the charge dispropor-
tionation is apparently not complete; at its maximum the cation
oxidation states reach about Ni2.65þ and Ni3.35þ. Finally, CaFeO3 has
a charge disproportionation at ~290 K, close to room temperature
[742]. Here the Fe oxidation states are found to be around Fe3.45þ
and Fe4.55þ. Interestingly, SrFeO3 does not show such a charge
disproportionation [743], indicating that structural distortions are
essential for the charge ordering in CaFeO3 [744].
4.7. Mixing of A- and B-site cations
An interesting phenomenon related to the B-site cation order is
the possibility for the A- and B-site cations to change places
[122,265,272,285,286,287]. Typically this does not occur, as the size
difference between the A- and B-site cations is quite large. However,
when A ¼ Ca and B0 ¼ R, the size difference may be very small, and in
such compounds A-B cation mixing has been found. The mixing is
not necessarily complete, but the degree of mixing depends on the R
radius: closer it is to the radius of Ca, the more the cations mix
[272,286]. For example, in case of Ca2LuRuO6, only ~4% of Lu is found
at the A site, whereas Ca2LaRuO6 has in fact been found to be CaL-
aCaRuO6, i.e. La is completely at the A site [272]. This is quite
reasonable, as La is slightly larger than Ca. However, in case of
Ca2RB00 O6 with B00 ¼ Nb, Ta or Ru, it has been found that the cation
mixing happens already when rR < rCa, i.e. before geometrical con-
siderations [125,272]. This is probably due to the higher valent R ion
preferring a higher oxygen coordination environment of the A site.
4.8. Layered compounds and other R2CuB00 O6 perovskites
The discussion of cation ordering has so far considered only the
rock-salt ordered or disordered compounds. But in case of the
A2B0 B00 O6 perovskites, a layered ordering is also possible, as has
been discussed earlier. This type of B-site cation order has only been
found in five R2CuB00 O6 compounds where B00 ¼ Sn or Zn. Of these,
La2CuSnO6 was first discovered by Anderson et al. [393]. Later,
R2CuSnO6 with R ¼ Nd, Pr or Sm and La2CuZrO6 were synthesized
using high pressure [394,395]. Anderson et al. [16] also studied
several other compositions R2CuB00 O6 with B00 ¼ Ge, Mn, Ti, Ir, Sn, Zr,
or Pb, but none of these compounds formed a layered structure.
It has been postulated that the layered ordering is only possible
in a narrow range of balancing properties: the difference in the B-
site cation oxidation states should be DZB ¼ 2; the two B-site cat-
ions should have different coordination geometries to provide
distinct sites, in this case the JT distorted CuO6 octahedra and the
more ideal B00 O6 octahedra; B00 should be large enough in order to
allow for the cooperative JT effect of Cu and to improve A-cation
bonding by a buckling of the B00 O2 layers [16,716]. However, due to
the small number of compounds forming the layered structure, it is
not clear whether these conditions are all necessary or if they are
even sufficient for the layered ordering to take place.
It is interesting to look at the cation ordering found in different
La2CuB00 O6 compounds: with B00 ¼ Mn, Rh or Ti the compounds are
disordered, with B00 ¼ Sn, Zr they are layered and with B00 ¼ Ir, Ru
they are rock-salt ordered. The ordering in these compounds
actually follows the difference in B-site cation ionic radii, DrB:
compounds with small DrB ¼ 0.01e0.04 are layered, those with DrB
~0.11 are rock-salt ordered and the ones with large DrB ¼ 0.13e0.2
are disordered. This progress is somewhat counterintuitive, as the
compounds with large DrB would be expected to have higher de-
gree of order. It would thus appear that the JT distorted Cu com-
pounds behave rather differently from the other A2B0 B00 O6
perovskites when it comes to cation ordering.
5. B-site cation oxidation states
The oxidation states of the elements in the A2B0 B00 O6 perovskites
are of interest, as they can affect the cation ordering and all the
physical properties in these compounds. Compounds with
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
elements in exotic oxidation states may provide new interesting
physical properties. Valence mixing, or degeneracy [745], is an
especially interesting and important phenomenon: many A2B0 B00 O6
perovskites with B-site cation valence mixing have been found to
be metallic or halfmetallic, whereas integer-valent compounds are
usually insulators [709]. Here we discuss the B-site cation oxidation
states in A2B0 B00 O6 perovskites together with two ways of predicting
them using tabulated standard-electrode potentials and by
comparing unit-cell volumes.
5.1. Exotic oxidation states
The A-site cation in perovskites is most often a single-valent ion,
such as an alkaline-earth element. The B-site elements on the other
hand can often have several oxidation states. Elements found in the
A2B0 B00 O6 perovskites that commonly appear with more than one
oxidation states are the transition metals, Bi, some rare earth ele-
ments such as Ce, Pr or Tb, and actinoides U and Pu. Furthermore,
some rather exotic oxidation states have been stabilized in the
A2B0 B00 O6 perovskites. The cases of Te5þ, Fe5þ and Ir6þ were dis-
cussed in Section 2.3. Also, Ni3þ appears to be present in some
compounds, such as Ba2NiNbO6 and La2NiCoO6, although they may
be oxygen nonstoichiometric. However, in Y2NiNiO6 the charge
disproportionation results in Ni oxidation state of approximately
3.35þ [693]. Also, Bi appears be present as Bi4þ in compounds such
as A2þ2B0 BiO6 with B0 ¼ Ti or Ce, although the B0 ¼ Ti compound has
not been properly characterized. Finally, by stoichiometry, Cr
should exist as Cr4þ in Ca2CrTiO6, although the compound quite
probably has oxygen vacancies.
Some new compounds with elements in novel oxidation states
might also be possible. In the reported compounds Cu is almost
always found in the oxidation state 2þ, but could perhaps exist also
as 1þ or 3þ. La2CuRhO6 has been found to be mixed valent, with
apparent Cu oxidation state higher than 2þ [372,390]. Also, with
the aforementioned exception of Ba2TlTeO6, Te is found only at the
oxidation state of 6þ, but might also exist as Te4þ. Lead at the B site
is usually found as 2þ in these compounds, but in Ba2PbBiO6 the
oxidation state should be 34þ, depending on the oxidation state
of Bi. It might be possible to stabilize Pb4þ in other compounds as
well, although the synthesis of several A3þ2CuPb4þO6 compounds
has been found to be unsuccessful [16]. Antimony appears to be
found only as Sb5þ, but could perhaps exist as Sb3þ as well. In all
these cases the ionic radii of the ions would be reasonable
considering the formation of an A2B0 B00 O6 perovskite phase, so it
could be possible to synthesize some more compounds with these
elements and oxidation states.
Demazeau et al. [43,413] have discussed what should be consid-
ered to stabilize uncommonly high oxidation states in transition
metals: 1) structure of the local surroundings, governing the crystal
field energy, and thus the electronic population of the d orbitals, 2)
nature of the cations, affecting the bond covalency, and 3) synthesis
conditions. For instance, in the high oxidation state B00 ¼ Ir6þ com-
pounds the IreO bonds are very strong, and they may require weak
competing B0 -O bonds, such as CaeO or SreO. Electropositive A or B0
site cations can lower the O p orbital energies, allowing for additional
electron transfer from the highly oxidized B00 cation to oxygen and
thus help stabilize a high oxidation state on the B00 cation [41,745,746].
The A2B0 B00 O6 perovskites form quite a suitable structure in this sense,
as many different elements can be placed in the A or B sites in order to
stabilize different oxidation states.
5.2. Predicting oxidation states
An interesting, and more complicated case is found when both
of the B-site cations can have more than one oxidation states. In
17
such a case, the oxidation states of the two B-site cations can vary
depending on the cation combinations, and may be difficult to
predict. Several experimental methods exist for determination of
the oxidation states, such as x-ray absorption spectroscopy (XAS),
x-ray photoelectron spectroscopy (XPS), Mo €ssbauer spectroscopy,
etc., but only a few A2B0 B00 O6 compounds have been properly
characterized. It would also be advantageous to be able to predict
the oxidation states in advance, before the synthesis.
The oxidation state combination of the two B-site cations is
determined by their relative orbital or band energies, as will be
discussed in Section 6.1. Interestingly, the standard-electrode
reduction potentials, such as those collected by Bratsch [747] or
Milazzo and Caroli [748], correspond to these orbital energies to
some degree and can be used to predict the oxidation states, as will
be discussed in more detail below. They can predict the cation
oxidation states usually when the difference between the redox
potentials is large. However, for many ions redox potentials are not
well known, and as the potentials are measured in aqueous solu-
tions, a rather different environment from the solid compounds,
the results are ambiguous if the difference in the redox potentials is
small.
Another way to examine the cation oxidation states is by
comparing the unit-cell volumes of different compounds. Different
combinations of B-cation oxidation states can have different
average B-cation radii, and therefore different unit cell volumes
[77,134,310,317,521,536,548]. Therefore, comparing the unit-cell
volume of a compound to those of other similar compounds may
give a hint of the cation oxidation states. Plotting the unit-cell
volumes of different “families” of compounds as a function of the
calculated tolerance factor results in a linear behavior, as discussed
in Section 2.2. However, if a compound doesn't fit in the line, this
could indicate a different average B-cation radius, i.e. different
oxidation states. This is exemplified in Fig. 12, where the unit-cell
volumes of Ba2RIrO6 with R ¼ LaeNd, SmeLu and Y are shown as
a function of t. It can be seen that using the ionic radii of R3þ and
Ir5þ, a good linear behavior is found for all compounds, with the
exception of R ¼ Ce and Pr. This would indicate a different oxidation
state combination in the case of these two compounds compared to
the rest of the Ba2RIrO6 compounds. Indeed, in the literature, the
other lanthanides and Y have been found to be in the oxidation
state of 3þ, whereas Ce and Pr have been considered to be in the
oxidation state of 4þ or close [63,165,217,218,219,220]. If we now
assume a different oxidation state combination for these two
compounds, and change the radii of R and Ir (and thus the calcu-
lated t) accordingly (assuming a linear dependency of cation radius
with oxidation state) until these compounds fit with the line, we
obtain for these compounds an average cation oxidation-state
combination of R3.7þ/Ir4.3þ. This is in decent agreement with the
Fig. 12. Unit-cell volumes for Ba2RIrO6 with R ¼ LaeNd, SmeLu and Y as a function of
tolerance factor using radii of R3þ and Ir5þ (white). Black circles represent the R ¼ Ce
and Pr compounds with oxidation state combinations adjusted to fit the other
compounds.
18 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
expected B0 4þ/Ir4þ combination, and the deviation may be due to
inaccuracy of the analysis, or due to actual valence mixing between
the two B-site cations, as the precise oxidation states in these two
compounds have not been determined.
With large amount of structural data collected, this comparison
can be done for quite a few compounds. However, the comparison
works best for A ¼ Ba, Sr, Ca or La compounds, because in these
cases there are more samples to compare to. There are also some
complications in the comparison. As described in Section 2.2, we
have to separate the B0 ¼ R compounds from other elements, and if
a B cation is too large compared to A (such as Ba, Sr or Ca) or La, the
unit-cell volumes may deviate from the expected. It is also possible
for the different B cation oxidation-state combinations to have the
same average ionic radii, in which case they cannot be differenti-
ated. Also, the spin state of a cation can affect its ionic radius; for
the most part the 3d transition metals are found in a high-spin
state, whereas the 4d/5d metals are low-spin, as will be discussed
in Section 6.1, but Co especially may have intermediate-spin or low-
spin configurations. On the other hand, cation disorder appears to
have relatively little effect. Unit-cell volumes are larger for disor-
dered compounds, but effect is relatively small in the scale of this
comparison [510].
This is a rather coarse analysis, but it highlights some interesting
compounds which might need further investigations, either
because of apparent charge transfer between the cations, or
because of unexplained discrepancies in the unit-cell volume
compared to other compounds. There are several compounds that
appear to have anomalously small or large unit-cell volumes. This is
seen in many Bi compounds, such as Ba2CrBiO6, Ba2BiRuO6 or
Ba2BiSbO6. Also, many Ti or Ir containing compounds have unex-
pectedly large unit-cell volumes. Similar behavior is found with
some Co compounds: low spin-states are possible for Co, but they
would decrease the unit-cell volume rather than increase it. Oxy-
gen vacancies could affect the unit-cell volumes of Co compounds,
though.
The prediction made by standard electrode potentials and
comparison of unit-cell volumes can be compared with oxidation
states determined by other methods. For example, Ce in Ba2CeB00 O6
with B00 ¼ Nb or Ta is found as Ce3þ, as determined by XAS mea-
surements [65]. The redox potentials would also indicate so, as the
Ce4/3þ redox potential (~1.6 V) is much larger than those of Nb5/4þ
(~0.25 V) or Ta5/4þ (~0.97 V). Also, the unit-cell volume com-
parison fits with Ce3þ. Similarly, a XAS study has found that
A2MnReO6, A ¼ Sr or Ba contain Mn2þ and Re6þ [200]. Again, both
the redox potentials (~1.51 V for Mn3/2þ and ~0.40 V for Re6/5þ) and
unit-cell comparisons support this picture. Finally, La2B0 VO6 with
B0 ¼ Mn, Co or Ni appear to be close to B0 2þ/V4þ as determined by
XAS, with a possibility of slight charge transfer in the B0 ¼ Mn case
[380]. Here the redox potentials would predict B0 2þ/V4þ oxidation
states, whereas the unit-cell comparison is more ambiguous due to
the small number of La2B0 VO6 compounds. It is interesting to note
that La2FeVO6 has not been characterized very well, but based on
the redox potentials it could have some degree of valence mixing.
Also, La2CrVO6 has not been synthesized, but it would be predicted
to have Cr3þ and V3þ based on the redox potentials. Thus there
could be an interesting change in vanadium valence in this series.
Finally, Co in La2CoFeO6 would appear to be in an intermediate-spin
state based on the unit-cell comparison. In the literature, low-spin
state has been reported based on magnetic properties [358].
Some additional cases can be found that could perhaps warrant
further study. All La2B0 B00 O6 compounds with B0 ¼ 3d transition
metal and B00 ¼ Ru, Rh or Ir appear intriguing: the analysis by redox
potentials or unit-cell volumes do not give conclusive answers to
the possible oxidation states of the B site cations in these com-
pounds. The redox potentials of Ru, Rh and Ir are not well known
and many of these compounds have large variations in reported
unit-cell volumes. However, there are some interesting behaviors
noted in these compounds. For example La2MnRhO6 has Mn3þ/
Rh3þ, as determined by XAS [390], and La2MnRuO6 would appear to
have Mn3þ/Ru3þ as well [374,422]. On the other hand, La2MnIrO6
may have Mn2þ/Ir4þ [427]. Moreover, the B00 ¼ Rh or Ru cases are
disordered, whereas the B00 ¼ Ir compound is ordered, which sup-
ports this picture. Thus moving from 4d to 5d metal on the B00 site
would appear to change the oxidation state balance. Also, R2B0 RhO6
with B0 ¼ Mn, Fe or Co appear to have B0 3þ/Rh3þ oxidation states,
whereas B0 ¼ Ni probably has Ni2þ/Rh4þ. On the other hand, the
B0 ¼ Cu compound has been reported to be mixed valent [372,390].
So there is again a possibility of a change in the cation oxidation
state balance with a change of the B0 cation. Similarly, in case of
La2B0 IrO6 with B0 ¼ Mn, Fe or Co, the unit-cell comparison would
indicate possible discrepancies in the cation oxidation states.
However, the reported unit-cell volumes of these compounds have
large variations, making the analysis uncertain.
5.3. Mixed-valent compounds
Compounds that appear to have non-integer oxidation states are
especially interesting, as they may have valence mixing. The
A2FeB00 O6 compounds with A ¼ Ca, Sr, Ba and B00 ¼ Mo, Re are the
most well-known mixed-valent A2B0 B00 O6 perovskites. The valence
mixing in case of the A2FeMoO6 has been verified in several studies
by XAS [583,749,750], Mo € ssbauer spectroscopy [146,751,752],
nuclear magnetic resonance (NMR) spectroscopy [753], XPS [583],
examining the cation bond lengths [582,583,588] and from elec-
tronic properties [145,591]. All of these studies point at mixed Fe2/
3þ
and Mo5/6þ valences, although there have been some discrep-
ancies in the details, most probably due to differences in synthesis
conditions, surface effects and differences between the analysis
methods. Also, these materials have been found to degrade over
time [750]. Similarly, for the B00 ¼ Re compounds mixed Fe2/3þ and
Re5/6þ valences have been found by XAS [583], Mo €ssbauer spec-
troscopy [138,153,295] and studying the cation bond-lengths [603].
The unit-cell volume comparison results in around 50e65% of
Fe3þ/Mo5þ oxidation-state combinations for the A2FeMoO6 com-
pounds, indicating mixed valence. Similar result is obtained from
the redox potentials: the Fe3/2þ potential of ~0.79 V is very close to
the Mo6/5þ potential of ~0.65 V. For comparison, Sr2FeWO6 has
been found with Fe2þ/W6þ as the W orbitals are too high in energy
to overlap with the Fe orbitals [754]. This is also shown by the unit-
cell comparison and the reduction potentials: W6/5þ reduction
potential of ~0.03 V is notably smaller than that of Fe3/2þ, indi-
cating a reluctance of W6þ to reduce. In the B00 ¼ Re compounds, the
unit-cell comparison indicates valence mixing for the A ¼ Sr and Ba
compounds, but oxidation states close to Fe3þ/Re5þ for A ¼ Ca.
Interestingly, the electronic properties of A ¼ Ca also differ from
those of A ¼ Sr or Ba, as will be discussed in Section 6.3. The redox
potential of Re6/5þ (~0.40 V) is also reasonably close to that of Fe3/2þ
allowing for valence mixing.
There are a few other compounds that have been suggested to
have valence mixing in the literature. A2VMoO6 with A ¼ Ca or Sr
appear to have V3/4þ/Mo4/5þ valence mixing. The compounds are
found to be metallic and Pauli paramagnetic [332,667]. Unit cell
comparison is inconclusive due to a small difference between the
tolerance factors of V3þ/Mo5þ and V4þ/Mo4þ combinations, but the
redox potentials of V4/3þ (~0.34 V) and Mo5/4þ (~0.40 V) are almost
identical, supporting valence mixing. Sr2MnRuO6 has been found to
be mixed valent by XAS measurements [640] and by examining
cation bond lengths [314]; both the redox potentials and unit-cell
volumes also indicate valence mixing. Finally, La2CuRhO6 is
apparently mixed valent, as mentioned earlier [372,390], and
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
mixed valence has also found in the iridates Sr2NiIrO6 [653] and
Ca2MnIrO6 [310]. In these three cases the unit-cell volume com-
parisons are either not possible due to small amount of compounds,
or would show no valence mixing. Similarly, predictions by redox
potentials are ambiguous for these compounds.
There are a number of more uncertain cases in which some degree
of valence mixing could be possible based on the unit-cell volume
comparison. For example, the lanthanoides Ce, Pr and Tb may often
be found in oxidation states between 3þ and 4þ. This has been noted
in case of the A2RBiO6 compounds by Harrison et al. [60] and Mat-
sushita et al. [61]. Similarly, possible valence mixing is indicated in
Sr2FeUO6, Ba2BiIrO6 and Ba2FeBiO6. In some cases such as A2B0 MoO6
with B0 ¼ Mn or Co, the unit-cell volume comparison results in a small
amount of apparent valence mixing. These results could be due to an
inaccuracy of the method, or due to a slight virtual electron transfer
[536]. Martínez-Lope et al. [72] have also suggested that Ba2CoB00 O6
with B00 ¼ Mo or W could have dynamic electron transfer between Co
and Mo/W. These compounds are black, but not metallic, so true
valence mixing seems to be excluded.
5.4. Effects of structure to oxidation states
An interesting possibility is to change the B-site cation
oxidation-state combinations with the crystal structure. The
different B-cation oxidation state combinations correspond to
different tolerance factors, and this can affect which combination is
more stable [63].
The A2FeMoO6 compounds with A ¼ Ca, Sr or Ba are again
perhaps the most studied examples. In general, it has been found
that with a large A cation (Ba) the charge balance moves more to-
wards Fe2þ/Mo6þ, whereas a smaller A cation (Ca) results in
oxidation states closer to Fe3þ/Mo5þ, although the exact details
have varied slightly from study to study [146,291,755]. The average
B-site cation radius is smaller with the valence combination of
Fe3þ/Mo5þ than with Fe2þ/Mo6þ. Thus a small A site cation favors
the smaller Fe3þ/Mo5þ combination and a large A-site cation moves
the balance towards Fe2þ/Mo6þ, in order to improve the tolerance
factor, i.e. in order to decrease strain and structural distortions. This
effect is seen in many other cases as well. In Ca2MnRuO6 the B-site
cation oxidation states are close to Mn4þ and Ru4þ, whereas
Sr2MnRuO6 is mixed valent, as discussed previously [314,318]. This
effect is also observed in the unit-cell volume comparison. Simi-
larly, the B-site cation oxidation state combination in Ba2-xSrxTbIrO6
is found to change from Tb3þ/Ir5þ to Tb4þ/Ir4þ with increasing x at
around x ¼ 0.35 [234,661]. Finally, the slight valence mixing noted
in La2MnVO6 has also been proposed to be due to a relief of strain
caused by the rather large Mn2þ cation [380]. Here it would be
interesting to see if a smaller lanthanide in the A site would change
the oxidation-state balance more towards Mn3þ/V3þ.
The unit-cell volume comparison suggests a few more inter-
esting cases. For instance, the B-site cation oxidation states in
A2BiB00 O6, B00 ¼ Nb or Ta would appear to be Bi3þ/B00 5þ when A ¼ Ba,
but B00 3þ/Bi5þ with A ¼ Ca. The A ¼ Sr compounds have not been
synthesized. This change in the oxidation states could happen in
order to improve the tolerance factor in case of the A ¼ Ca com-
pounds: the tolerance factor in these compounds would increase
from 0.87 to 0.91 with changing the valence states from Bi3þ/B00 5þ
to Bi5þ/B00 3þ. This behavior would be quite extraordinary, as Nb5þ
and Ta5þ are not expected to be easily reduced, as indicated by their
redox potentials. Similar behavior appears in case of A2CeTaO6 with
A ¼ Sr or Ba: the B-cation oxidation states would fit best with Ce3þ/
Ta5þ in case of A ¼ Ba, but with Ce4þ/Ta4þ when A ¼ Sr. The toler-
ance factor would again improve in case of the A ¼ Sr compound
from 0.90 to 0.92 with the change in the valence states. Finally, the
B-site cation oxidation states in Ca2FeWO6 appear closer to Fe3þ/
19
W5þ than Fe2þ/W6þ. In case of A ¼ Sr and Ba the oxidation states are
clearly Fe2þ/W6þ, which has also been found by XAS and
Mo €ssbauer spectroscopy [581,583,613,614]. The tolerance factor of
Ca2FeWO6 would increase from 0.93 to 0.95 with such a change in
oxidation states. This behavior would be very intriguing when
considering the mixed valence found in the A2FeMoO6 compounds.
However, Ca2FeWO6 has not been extensively characterized, so the
unit-cell volume may be erroneous.
The unit-cell volume comparison would also suggest valence
mixing in certain compounds caused by the chemical pressure.
Sr2PbMoO6 would appear mixed valent, whereas Ba2PbMoO6
clearly has a Pb2þ/Mo6þ combination. However, mixing of A- and B-
site cations could be possible in case of the A ¼ Sr compound, as the
ionic radii of Sr2þ (1.44 Å) and Pb2þ (1.49 Å) are almost identical.
The unit-cell volumes of Ca2B0 ReO6 with B0 ¼ Mn or Co would also
indicate valence mixing, although there are not many compounds
to compare to, and these compounds are also reported to be in-
sulators. In comparison, in Sr2B0 ReO6 with B0 ¼ Mn or Co, the
oxidation states are B0 2þ/Re6þ, as also determined by studying bond
lengths or using XAS [200,541]. Similarly, Ca2NiOsO6 would appear
mixed valent, whereas Sr2NiOsO6 appears to have Ni2þ/Os6þ. In all
these cases the tolerance factor of the A ¼ Ca compound would be
improved by the charge transfer. However, while bond lengths may
change due to strain, as noted in Section 2.2, it is not obvious if this
correspond to actual charge transfer between the cations. Still,
these compounds appear interesting, and would perhaps require a
closer investigation.
5.5. Cation disorder and synthesis conditions
The B-site cation disorder has been found to have an effect on
the oxidation states in the A2B0 B00 O6 perovskites. As discusses above,
Fe in Sr2FeMoO6 has been found to be in a mixed valent state.
However, Mo € ssbauer studies indicate that antisite Fe is in fact close
to the oxidation state of 3þ, possibly because the AS Fe is sur-
rounded by other Fe ions, which inhibits charge transfer from Mo
[751]. Similarly, ordered La2B0 MnO6 with B0 ¼ Co or Ni have been
reported to have the oxidation state combinations of B0 2þ/Mn4þ,
but more disordered samples appear to have oxidation states closer
to B0 3þ/Mn3þ [362,441,446,448,699,756]. For example, Asai [449]
found using NMR that in La2NiMnO6 the ordered compound had
Mn4þ, but AS Mn appeared be in the oxidation state of 3þ. Ac-
cording to XAS the oxidation states in ordered La2CoMnO6 are Co2þ/
Mn4þ or close, but quenched sample with high degree of disorder
had more Co3þ/Mn3þ [725,757]. The two La2B0 MnO6 compounds
may in fact be synthesized in two different phases with different
magnetic ordering temperatures, depending on synthesis condi-
tions, and the different properties appear to be related to the
different cation oxidation-states [447,757].
6. Electronic properties
The electronic properties of perovskite compounds are largely
governed by the B-site cations. The great flexibility of the A2B0 B00 O6
perovskites is seen in the possibility of combining various main-
group elements, 3d, 4d and 5d transition metals, lanthanoides
and actinoides with different oxidation states at the two B sites. It is
thus no surprise that a range of different semiconducting, metallic,
halfmetallic, dielectric, ferroelectric, thermoelectric and possibly
even superconducting properties have been found in the various
A2B0 B00 O6 compounds. Often the compounds with the most
intriguing electrical properties tend to be those containing various
transition metal elements, and what is of especial interest in the
A2B0 B00 O6 perovskites is the possibility to combine 3d and 4d/5d
elements at the two B sites.
20 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
6.1. Electronic structure
The electrical properties of a solid are broadly speaking gov-
erned by the overall band structure, together with the balance
between inter-atomic interactions, described by the electronic
bandwidth W, and the intra-atomic electroneelectron interactions,
U. In case of an empty conduction band (e.g. d0 transition metal
oxides) the compounds are band insulators. With partially occupied
conduction band, when W < U, the electrons are localized, and
when W > U, they can be itinerant.
The electronic bandwidth of an A2B0 B00 O6 perovskite depends
largely on the spatial orbital overlap between the different ele-
ments, which again is strongly dependent on the crystal structure.
In case of perovskites, W can often be estimated with two param-
eters: bond angle and length [142,326]. Typically, the bandwidth is
narrow in perovskites with a 3d transition metal elements at the B-
site, due to the relatively contracted nature of the 3d orbitals and
the corresponding weak overlap with the O 2p orbitals, especially
in case of p-bonds. For the same reason the inter-electronic
repulsion in 3d metals is often notable, so W < U is often found.
On the other hand, the 4d/5d orbitals are generally more extended,
and as a result the bandwidth is often wider in compounds where
the B-site cation is a 4d/5d transition metal [638]. Thus spin delo-
calization is more commonly observed with the 4d/5d elements. In
fact, the compounds reported metallic or close to metallic in the
Supplementary material Table S1 tend to have a 4d or 5d element at
the B00 site, with only a few exceptions, as will be discussed in the
Section 6.2.
An interesting case is Ru, which has often been considered to be
in the borderline between localized and delocalized electron
behavior [185,193,334,387]. In case of A2B0 B00 O6 compounds with
B00 ¼ Ru, a decrease in the unit-cell volume (increase in orbital
overlap) has been found to increase Ru d electron delocalization,
although actual delocalization has not been observed. This is
despite the fact that compounds such as CaRuO3 and SrRuO3 are
metals [319]. In the ordered A2B0 B00 O6 compounds, it seems possible
that the B0 cation could inhibit complete delocalization of the B00
cation electrons by physically separating the B00 O6 octahedra.
This effect of electron delocalization by isolation depends on the
nature of the two B-site cations, however. Compared to single pe-
rovskites with one B-site cation, with two B-site cations, in addition
to spatial overlap, energetic overlap and symmetry of the orbitals of
the two B-site cations must also be considered. In case of a tran-
sition metal at the B00 site in octahedral coordination, the p* con-
duction band is largely derived from the B00 t2g orbitals. If the B0
cation is a main group element, with no orbital mixing with the p*
band due to symmetry, the B0 cation has practically no contribution
to the conduction band [47]. Such compounds are found to be
insulating. If the B0 -site cation does have accessible d orbitals, the
orbital mixing depends on the energetic overlap of the orbitals.
These orbital energies correspond roughly to the redox potentials
discussed in Section 5.2. If the band energies of the two B-site
cations are very different, there is poor orbital mixing [47,540].
Sr2FeWO6 for example has tungsten band energy raised above the
iron ones, making it insulating [754]. While the two cations may
not be completely electronically isolated, the resulting bandwidth
may remain narrow, and with W < U the electrons will remain
localized. Also, even if the orbital energies would otherwise over-
lap, there is generally no t2g and eg orbital mixing due to their
different symmetries, although structural distortion may allow
some sep interactions [93,274,391].
Matching of the two B-site cation orbital energies is a relatively
rare occurrence, as several factors affect the energies. For transition
metals, orbital energies decrease moving right in the periodic table
due to the increase in nuclear charge [77,536,595,758]. Similarly,
crystal field splitting decreases moving right in the periodic table,
due to decrease in ionic radius, and corresponding decrease in bond
covalency. In addition, there are some notable differences between
3d and 4d/5d transition metal elements. 3d metals tend to have
crystal field splitting energies smaller or comparable to the elec-
troneelectron repulsion. As a consequence they are usually found
in a high-spin state. On the other hand, 4d/5d metals have higher
crystal field splitting energies and weaker inter-electronic repul-
sion due to their more extended orbitals, and they are found in a
low-spin state. High cation charge also increases crystal field
splitting, and the 4d/5d elements in A2B0 B00 O6 perovskites tend to be
found in high oxidation states [45,427,429,514,627,653,758]. This
high oxidation state also means there are fewer d electrons, and
thus the relevant electrons in 4d/5d elements are often found in t2g
orbital, whereas in the high-spin 3d elements with the lower
oxidation states the relevant electrons are often in eg orbitals,
which may in some cases hinder electron transfer due to symmetry.
A low-spin state may be possible for 3d metals too. Strong
covalency of the B00 eO bond may compete with the B0 eO bond and
weaken the B0 cation crystal field energy due to reduction of elec-
tron density around the B0 cation. This may be especially important
in case of Co3þ, where crystal field splitting is of similar energy to
the electronic repulsion [134,759]. For instance, Ba2CoB00 O6 with
B00 ¼ Nb or Ta have been suggested to have possible low-spin or
intermediate-spin Co3þ [75,80]. Similarly, La2CoFeO6 has been
proposed to have low-spin Co3þ [358], and comparing the unit-cell
volume to other similar compounds would suggest so as well.
Finally, Ouchetto et al. [340] found that in a series of R2B0 PtO6
compounds with B0 ¼ Mg, Co, Ni or Zn, the Co compounds have
smaller than expected unit-cell volumes, indicating a possible low-
spin state for Co.
In 4d and 5d metals spin-orbit coupling (SOC) is also strongly
enhanced compared to 3d metals, where SOC is quite weak
compared to other energies [156,514,653]. This can cause notable
changes to the electronic structure, especially in case of compounds
that would otherwise be halfmetals, as will be discussed in Section
6.3. In case of Ir4þ and Ir5þ compounds, SOC has been found to
affect electronic structure especially, as it can split the otherwise
degenerate t2g orbitals [617]. However, structural distortions can lift
d-orbital degeneracy and quench orbital moment, so crystal
structure is again of importance.
As a conclusion it can be seen that electron itinerancy in the
A2B0 B00 O6 perovskites becomes possible only in relatively rare cases
with good orbital energy overlap and correct symmetries, and these
considerations explain why metallic behavior is found only in a few
A2B0 B00 O6 compounds, as will be discussed in the next section.
6.2. Electrical transport properties
Most A2B0 B00 O6 perovskites are insulators or semiconductors,
with about 160 such compounds reported in the literature.
Furthermore, there are several compounds listed in Table S1 in
Supplementary material for which electronic transport properties
have not been determined, but which are reported to have a large
band gap or a light color indicative of the insulating behavior.
Different types of electrical conductivity have been found in the
semiconducting A2B0 B00 O6 perovskites. Commonly the conduction
happens by thermally-excited small-polaron hopping, but occa-
sionally Mott variable-range hopping (VRH) conduction is
observed. The VRH behavior is rather reasonable in case of disor-
dered compounds like Sr2MnRuO6 [638] or Sr2CoSbO6 [545].
However, certain compounds have been found to show VRH at low
temperatures, but small-polaron hopping-type conduction at high
temperatures. For example, A2CoIrO6 with A ¼ La or Sr [359] and
Sr2B0 MoO6 with B0 ¼ Cr or Mn [141] have been found to exhibit this
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
behavior. It was noted by Popov et al. [200] that structural distor-
tions, cation disorder or oxygen vacancies can generate an impurity
band near the Fermi level, and localization of electrons in the im-
purity band could lead to VRH-type conduction. At higher tem-
peratures, more typical thermally-excited conductivity will prevail.
There are a few semiconducting compounds found in the liter-
ature with rather low electrical resistivities. For instance, La2NiFeO6
and Sr2CoIrO6 have both been reported with resistivities in the
order of 103e104 U cm. The Sr2B0 MoO6 compounds with B0 ¼ Ti
or Zr also have low resisitivities in the 103 U cm range, and also
low Seebeck coefficient values of ~5 mV/K, reminiscent of a metal.
Such compounds could be close to a metal-insulator border. On the
other hand, La2CoMnO6 shows large variations in reported re-
sistivity values, probably due to variations in oxygen content and
the formation of the different phases depending on synthesis
conditions, as discussed in Section 4.4. In this vein, many com-
pounds have been reported with largely varying resistivity values,
as in polycrystalline solids grain boundaries can cause orders of
magnitude difference in resistivity [29,584,760]. Thus some of the
insulating compounds with low resistivities could in fact be poor
metals which just appear insulating due to grain boundaries. This
could be the case with La2NiCoO6 for example [438]. Finally, there
are many compounds reported to be black, but for which re-
sistivities have not been measured. Especially interesting are the
many Mo-, Os- and Ir-containing compounds which have not been
thoroughly characterized. While they are probably small band-gap
semiconductors, they might warrant further study.
Very few of the A2B0 B00 O6 perovskites are reported to be metallic.
There are only six clear cases, with ten more compounds showing
either borderline metallic behavior of metal-insulator transitions.
Most of the metallic compounds belong to the halfmetallic ferri-
magnets, which will be discussed in more detail in the next section.
Of the remaining compounds, A2VMoO6 with A ¼ Ca or Sr are
especially interesting. They are metallic and Pauli paramagnetic,
although the resistivity again depends on annealing conditions. As
described in Section 5.3, they have V3/4þ/Mo4/5þ valence mixing,
which causes the metallic behavior [332,667]. The other com-
pounds with possible valence mixing discussed earlier could have
metallic conductivities as well, although Sr2MnRuO6 and
La2CuRhO6 for example have been reported to show insulating
behavior [314,372,390,431,639].
Some of the A2B0 B00 O6 compounds have been reported to show
metal-insulator transitions (MITs) with changing temperature.
Sr2CoTiO6 has an MIT at around 700 K [550], and as discussed
before, the charge disproportionation in Y2NiNiO6 is accompanied
by a MIT at ~580 K [693]. The crystal structure can also affect the
appearance of MIT, due to changes in orbital overlap, as for example
Ca2MnMoO6 has an MIT at 209 K [141], whereas Sr2MnMoO6 is an
insulator [535,538,595].
6.3. Halfmetals and magnetoresistance
Perhaps the most intriguing property of the A2B0 B00 O6 perov-
skites is the halfmetallicity found in compounds such as Sr2FeMoO6
[3,709]. In a halfmetallic compound, one spin channel is metallic,
while the other has a band-gap, and is insulating [761]. In an ideal
case the electron transport is thus completely spin-polarized. Such
properties would be useful for example in spintronic devices. The
properties of the halfmetallic A2B0 B00 O6 compounds have been well
reviewed [93,709,710], and there is no reason to repeat everything
here.
Halfmetallicity is a rare property in general, and is found only in
a few A2B0 B00 O6 perovskites with B0 ¼ Fe, Cr. Halfmetallicity is also
somewhat difficult to detect experimentally. Typically halfmetals
should be metallic compounds with an integer spin moment at
21
T ¼ 0 K [761]. However, grain boundaries in a polycrystalline solid
may mask the true nature of electrical conductivity, and cation
disorder or spin-orbit coupling may affect the measured moment,
or even destroy halfmetallicity.
Of the known A2B0 B00 O6 halfmetallic perovskites, A2FeMoO6 with
A ¼ Ca, Sr, Ba are the most thoroughly studied ones. They are all
found to be halfmetallic with high metallic conductivity and
notable negative tunneling magnetoresistance (TMR) behavior
even at room temperature. The Fe and Mo bands have a good en-
ergetic overlap allowing for orbital mixing, and the halfmetallic
nature is caused by a Fe t2geO 2peMo t2g hybridization resulting in
a partially filled down-spin band and the fortunate positioning of
the Fermi level in a gap in the up-spin channel
[93,560,709,762,763]. Here it is interesting to note that Pb2FeMoO6
has been reported to be an insulator, even though the B-site cation
arrangement is identical to the halfmetallic compounds. However,
this compound has not been thoroughly studied and appears to be
disordered, which could explain the difference.
From an application point of view, the room-temperature TMR
found in the A2FeMoO6 perovskites is of great interest [3,140]. Here
the spin-polarized electron tunneling happens through grain
boundaries: single crystal samples have been found not to have any
significant magnetoresistance properties [585]. Similarly, properly
annealed high-quality polycrystalline samples with few grain
boundaries showed practically no TMR [584]. The TMR properties
are also affected by the A-site cation, with best properties found
with either A ¼ Ca or Sr, while A ¼ Ba shows a weaker effect [146];
as discussed in Section 5.4, the A-site cation affects the B-site charge
balance in these compounds. The electrical properties are also
affected by the B-site cation order. In general it has been found that
the higher degree of order corresponds with the lower resistance,
and the properties change around S ¼ 0.90 from polaronic to itin-
erant [737]. Cation disorder also destroys the halmetallic nature of
these compounds and lowers the TMR effect [764,765]. However,
with a small amounts of disorder the MR effect may actually be
improved [739,765].
Looking at the series Sr2FeB00 O6 with B00 ¼ W, Re, Os is instruc-
tive, as it shows the effect of decreasing band energy when moving
right in the periodic table. The band energy of W is too high
compared to that of Fe, as has been discussed, resulting in an
oxidation state combination of Fe2þ/W6þ. As a consequence there is
no valence mixing and the compound is insulating [588,604,754].
Re orbitals, on the other hand, are in suitable energies compared to
those of Fe, forming mixed valence state similar to Sr2FeMoO6.
Finally, Os orbitals are too low in energy compared to Fe orbitals,
and a Fe3þ/Os5þ combination results: the Os down-spin t2g-derived
band is full and the compound is insulating [294,600].
Of these compounds, Sr2FeReO6 appears to be similar to Sr2Fe-
MoO6. Early electronic-structure calculations for Sr2FeReO6 found
the same halfmetallic nature as in Sr2FeMoO6, and the compound
shows itinerant electron behavior and magnetoresistance [605].
However, it appears that the stronger SOC of Re compared to that of
Mo destroys the halfmetallic nature in the A2FeReO6 perovskites
[300,766,767]. The spin polarization in these compounds is still very
high, but not complete. Also, while the A ¼ Sr and Ba compounds are
metallic, the A ¼ Ca case is insulating, although it has also been
found to have metal-insulator transition around 150 K [296,297,768].
The compound appears to be close to metallic, but structural dis-
tortions cause an insulating state [154,156,696]. Interestingly, the
rather similar compound Ca2FeMoO6 is still metallic. This difference
has been explained by the smaller radius of Re, which results in
weaker hybridization with oxygen and a narrower bandwidth,
causing the insulating behavior [768]. Similarly to Pb2FeMoO6,
Pb2FeReO6 has been reported to be an insulator, although with a
relatively low resistivity and a relatively high degree of order.
22 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
In addition to the B ¼ Fe compounds, certain A2B0 B00 O6 perov-
skites with B0 ¼ Cr have also been found to be halfmetallic. The
A2CrMoO6 compounds are apparently not halfmetallic, but perhaps
close. These compounds have been reported as insulators, although
in the A ¼ Sr case thermopower appears metallic and very similar to
that of Sr2FeMoO6 [144]. Compared to A2FeMoO6, the B0 ¼ Cr
compounds are generally highly disordered: the charge balance
appears to be very close to Cr3þ/Mo5þ, so the difference in oxidation
states is small. Thus a further study of these compounds might be
interesting if the degree of order could be improved.
The compounds Sr2CrB00 O6, B00 ¼ W, Re, Os again form an
interesting series. Here the B00 ¼ W compound is a halfmetal,
B00 ¼ Re is metallic, and B00 ¼ Os again has a full down-spin t2g band
and is insulating [560,769]. Sr2CrWO6 is somewhat similar to
Sr2FeMoO6 as it is also found to be halfmetallic [93], and shows
similar MR effect to Sr2FeMoO6 [566]. The samples appear metallic
or insulating depending on synthesis conditions, but thin films are
metallic [566]. The compound has been reported with relatively
low degree of order, which could affect the properties. The SOC of
W is stronger than that of Mo, but apparently not strong enough to
destroy the halfmetallic nature in this compound [770]. On the
other hand, Sr2CrReO6 is metallic, but the strong SOC of Re again
destroys the halfmetallic nature. The spin polarization is still high,
but the compound shows poor magnetoresistivity
[563,709,770,771]. Of the other A2CrB00 O6 compounds with B00 ¼ W,
Re or Os, those with A ¼ Ba are all hexagonal. Ca2CrOsO6 is an
insulator for the same reason as Sr2CrOsO6, whereas Ca2CrWO6 and
Ca2CrReO6 are insulators due to lattice distortions [274,280].
Finally, magnetoresistance behavior has also been noted in
La2CoMnO6, which shows relatively high magnetoresistive effect,
even though it is apparently not halfmetallic [367,368].
6.4. Dielectrics and ferroelectrics
As discussed earlier, most of the A2B0 B00 O6 perovskites are in-
sulators. Such compounds could find use as dielectrics, and this is
among the oldest practical applications conceived for perovskite
oxides [1]. Perhaps the most common application would be in
microwave dielectrics for communications [426]. Typical re-
quirements for such materials include high dielectric constant
k > 20, low loss tangent tan d < 105, and small absolute temper-
ature coefficient of resonant frequency <25 ppm/K near room
temperature. For example, most ferroelectrics have high k, but also
strong temperature dependency and very few materials with high k
have also good thermal properties [402,466,772]. However, it is
often possible to mix compounds with positive and negative tem-
perature coefficient to adjust the total coefficient to zero [706,773].
As most compounds have a positive temperature coefficient, it is
important to find compounds with negative ones to compensate. A
series of A2B0 B00 O6 compounds with A ¼ Ca, Sr or Ba; B0 ¼ La, Nd, Sm
or Yb; B00 ¼ Nb or Ta was studied by Takata and Kageyama [773],
who found several compounds with k > 20 and either positive or
negative temperature coefficients. Similarly, many A2B0 WO6 com-
pounds with A ¼ Sr or Ba and B0 ¼ Co, Ni or Zn have been reported
with large k values and negative temperature coefficients [774].
Dielectric polarization of a compound is dependent on the po-
larizabilities of the constituent ions [466], and in the A2B0 B00 O6
perovskites many different cations with varying dielectric proper-
ties can be incorporated. What is more, dielectric compounds,
when used as substrates or buffer layers, require a good match of
lattice parameters with the active compound. The benefit of the
A2B0 B00 O6 perovskites is the wide range of lattice parameters
possible due to the large number of cation combinations
[162,177,263]. Dielectric properties can also depend on the cation
ordering: for microwave applications, high ordering may be
preferred as the dielectric loss is usually reduced by the B-site
cation ordering [232,668].
Sometimes the reported dielectric constants of the A2B0 B00 O6 are
very high, even “colossal”. For instance, for Ca2CrTiO6 k values in
the order of 104 have been reported at room temperature [284].
High values of k have been reported also for La2CuTiO6 [403],
La2NiRuO6 with B0 ¼ [377] and La2B0 MnO6 with B0 ¼ Mg, Co or Ni
[423,775,776]. Commonly in these compounds the dielectric losses
are also large. While the reported colossal k compounds are
intriguing, they are also somewhat puzzling. Transition metal ox-
ides are quite prone for such high k values, but the cause of this
behavior is not always clear. Ferroelectricity may sometimes
explain this behavior, but in its absence it would appear that in
many cases interfacial barrier effects are the cause for high values of
dielectric constant [777]. Therefore, the dielectric properties might
not be intrinsic to the compounds.
Ferroelectric compounds have a spontaneous electronic polari-
zation and often large dielectric constants, and as such they are of
great interest [706]. The most studied ferroelectrics are perovskites
with Pb at the A site, due to the polarization of the lone 6s2 electron
pair of Pb2þ [504]. As was discussed in Section 3.6, many ferro-
electric Pb2B0 B00 O6 perovskites have relatively high transition tem-
peratures, above room temperature. However, many of the A ¼ Pb
compounds have been described as antiferroelectric, with only a
few compounds, such as Pb2ScB00 O6 with B00 ¼ Nb or Ta being
ferroelectric (see Supplementary data Table S2). Compounds with
A ¼ Bi3þ may also show ferroelectric distortions, although very few
examples of such A2B0 B00 O6 compounds exist.
In Pb2B0 B00 O6 ferroelectrics, the B-site cation ordering is very
important for the dielectric properties. Highly ordered compounds
are usually classical ferro- or antiferroelectrics. On the other hand,
disordered compounds or compounds showing short-range order
often show relaxor ferroelectric properties, with a diffuse dielectric
anomaly that depends on frequency [502,503,505,778,779]. In
addition, some compounds may show both relaxor and normal-like
behavior simultaneously due to inhomogeneous cation ordering
[778]. As discussed in Section 4.4, order may depend on synthesis
conditions, and can in such cases be controlled. Among the most
studied compounds are Pb2ScB00 O6 with B00 ¼ Nb or Ta, in which the
cation order can be changes with synthesis conditions in a wide
range [501,502,503,505,731,780,781,782]. Typically compounds
annealed at high temperatures and quenched are disordered
relaxor ferroelectrics, whereas samples annealed at low tempera-
tures are ordered classical ferroelectrics.
6.5. Superconductivity
The high-Tc cuprate superconductors are perovskite-related
layered compounds, where the superconducting behavior is
linked to the CueO layers. In the A2B0 B00 O6 perovskites, similar
CueO layers are found in case of the layered compounds such as
La2CuSnO6, as discussed in Section 4.8. These compounds might
thus be expected to show superconductivity as well. Unfortunately,
they do not. This is due to a positioning of the Cu orbitals in these
compounds, as shown by Anderson et al. [396], who discussed the
differences in electronic structure between La2CuO4 and
La2CuSnO6. Compared to La2CuO4, in La2CuSnO6 the intervening Sn
and a cation size mismatch cause a weaker CueO orbital overlap,
which lowers the Cu dx2y2 orbital energy. With doping, holes are
thus introduced in the higher energy Cu dz2 orbitals instead of
dx2y2 as in the superconducting cuprates [396]. Decreasing the
CueCu distance would be expected to improve the orbital overlap.
However, smaller A-site cation does not improve the situation, as it
only buckles the layers more [395]. Smaller B00 cation might be
more helpful, but such compounds are not layered.
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
On the other hand, superconducting properties with
Tc z 30e40 K have been reported for some rock-salt ordered
compounds, such as Sr2Y(Ru1xCux)O6 with small amount of
x z 0.05e0.2 [223,672,673,783]. However, it has been debated
whether superconductivity in Sr2Y(Ru1xCux)O6 is in fact intrinsic
[784], or caused by impurities [785,786]. Nonetheless, it is inter-
esting to consider in this context that Ru-containing compounds
have often been found to be on a borderline between localized and
itinerant electron behaviors, as discussed earlier [387].
6.6. Thermoelectric properties
Thermoelectric properties have been measured for only a few
A2B0 B00 O6 perovskites. Both n- and p-type conduction have been
found, and in some cases very high Seebeck coefficient values have
been reported, as shown in the Supplementary material Table S1.
However, these compounds are often also highly resistive, indicating
typical insulating behavior. Some interesting cases are found, how-
ever. For example, Ba-for-Sr substituted Sr2FeMoO6 has shown a
relatively high thermoelectric performance, with the dimensionless
figure of merit ZT z 0.3 at 1100 K [586]. Sr2B0 RuO6 with B0 ¼ Y or Er
have also been shown to exhibit high Seebeck coefficients and low
thermal conductivities at high temperatures, but the compounds are
highly insulating, and thus their performance remains low [576]. Of
all the compounds reported in literature, La2CuRhO6 apparently has
the highest power factor at room temperature, with P z 0.4 mW/
cm K2 [372]. This is similar to the power factor value found for pure
Bi2Te3 [787]. If the thermal conductivity of this compound is low, it
could have promising thermoelectric properties.
Thermal conductivity has rarely been measured for the A2B0 B00 O6
perovskites, with only four cases found in the literature. However,
most of these compounds show quite low values of thermal con-
ductivity. In case of La2GaMnO6, thermal conductivity of ~2 W/m K
was found, apparently affected by a dynamic, local JT distortion
which suppresses phonon contribution to the thermal conductivity
[409]. Sr2CoReO6 shows a thermal conductivity of ~0.9 W/m K
[542], whereas in the series Sr2-xA00 xFeMoO6 with A00 ¼ Ba or La the
conductivity varies in the range of ~0.6e1.0 W/m K [586]. Finally,
the aforementioned Sr2B0 RuO6 compounds with B0 ¼ Y or Er have
shown very low thermal conductivities of ~0.2 W/m K at 300 K
[576]. These values are comparable to those found for the new high
ZT material SnSe7 [788], which has a thermal conductivity in the
range of ~0.3e0.6 W/m K, depending on the temperature, and to
those of various Bi2Te3-based compounds [787]. It has been pro-
posed that the low thermal conductivity found in the A2B0 B00 O6
perovskites could be due to a phonon scattering by the two
different metals at the B site [586]. Therefore this behavior could be
inherent to these compounds.
6.7. Electro- and photocatalytic properties
Certain A2B0 B00 O6 perovskites have also been studied as electrode
materials for solid oxide fuel-cells (SOFCs). Such materials would
require a good electrical conductivity at the relatively high operating
temperature and electrocatalytic activity. Mixed ionic-electronic
conductivity is also beneficial, as it can improve the catalytically
active surface area of the electrode. Compounds with transition
metals at the B sites have been studied most, as transition metals tend
to show catalytic activity, and especially 4d/5d metals can improve
the electrical conductivity, as discussed in Section 6.1. However, many
of the 4d/5d metals are relatively rare and expensive and thus
B00 ¼ Mo and Nb compounds are most studied in this respect.
Anode materials used in the fuel side of a fuel cell need to
withstand highly reducing conditions, which limits the number of
elements that can be used. Sr2MgMoO6 was found to be a
23
promising anode material for SOFC applications as it shows a great
stability under reducing conditions [12,536]. The compound also
showed good cell performance and sulfur tolerance. This com-
pound shows a decent electrical conductivity of ~1e10 S/cm when
it is reduced, and the resulting oxygen vacancies may allow for ionic
conductivity as well [12]. Sr2FeMoO6 [789] and Ba2FeMoO6 [790]
have also been found to provide good fuel-cell performances, and
these compounds are also highly conducting. A2B0 MoO6 with A ¼ Sr
or Ba and B0 ¼ Mn, Co or Ni have been shown to work as SOFC
anodes, although their cell performances were somewhat low
[12,537,790]. What is more, Co2þ and Ni2þ are prone to reduction to
metals under the reducing conditions of the SOFC anode [536].
Finally, Sr2B0 NbO6 compounds with B0 ¼ Mn, Fe, Cr have also been
considered as anode materials for SOFCs [559,596,636]. However,
these compounds generally have poor electrical conductivities.
Sr2MnNbO6 for example is a p-type conductor, so the conductivity
decreases under reducing conditions. Of these compounds, only
Sr2FeNbO6 appear promising with an n-type conductivity of ~2 S/
cm at 1170 K under reducing conditions. However, no fuel cell
performance test has been reported for this material.
As discussed in Section 6.2, some A2B0 B00 O6 perovskites are found
with very low resistivities, most notably the various R2NiMnO6 or
R2CoMnO6 combinations. These compounds would be expected to
reduce and decompose very easily and could not work on the anode
side of the cells. However, they could work as cathodes. Somewhat
surprisingly, no reports were found for fuel cell tests with these
compounds. La2NiFeO6 has also been considered as a possible SOFC
cathode, as it has a very low resistivity [439]. Other compounds
reported in the literature with relatively low resistivities that are
also expected to be stable in the cathode environment and do not
contain expensive elements include A2þ2MnSbO6, A2þ2CoTiO6,
A3þ2CuMnO6 and A3þ2GaMnO6.
Some of the insulating/semiconducting A2B0 B00 O6 compounds
could have photocatalytic properties, for example for hydrogen
generation by water splitting. In case of photocatalytic compounds,
adjusting the band gap and band energies is of importance for the
optimization of the optical absorption and redox behavior [47]. In
A2B0 B00 O6 perovskites, the possibility of combining various cations
results in a wide range of different band gaps in the range of 0e5 eV
as is seen in the Supplementary material Table S1. At least Ba2RBiO6
compounds have been studied as possible photocatalysts, and
especially Ba2PrBiO6 has been shown to possess good photo-
catalytic activity for degradation of methylene blue and 2-propanol
under visible light irradiation [61,62]. This activity was assumed to
be related to the apparent valence mixing in this compound.
7. Magnetic properties
The A2B0 B00 O6 perovskites are a great playground for magnetic
properties, as various combinations of different paramagnetic cat-
ions are possible at all of the three cation sites, allowing for a wide
range of magnetic behaviors. While many of these compounds are
antiferromagnetic (AFM), compared to many other oxides, relatively
many ferromagnetic (FM) or ferrimagnetic (FiM) compounds are
found in the A2B0 B00 O6 perovskites, some with very high TC values. In
addition, the cation degree of order is of great importance consid-
ering the magnetic properties: several disordered compounds have
been found to exhibit spin-glass-type behavior, with no apparent
long-range magnetic order. In case of JT distorted A2CuB00 O6 com-
pounds, low-dimensional magnetic properties have also been found.
7.1. Basic magnetic properties
In case of a single paramagnetic B-site cation in an A2B0 B00 O6
perovskite, the superexchange interactions take place over a
24 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
relatively long distance. What is interesting is that the strength of
the 90 B0 eOe(B00 )eOeB0 nearest-neighbor (NN) interactions and
the 180 B0 eOeB00 eOeB0 nextenearesteneighbor (NNN) in-
teractions can often be of the same order, and can compete
[106,673]. The relative strength of these interactions depends on
the nature of the paramagnetic ions. For example, it has been noted
that the 90 B0 eOeOeB0 interactions are stronger compared to 180
B0 eOeB00 eOeB0 in certain Ru compounds, due to the fact that the eg
orbitals of Ru are empty, so only p-interactions possible [578].
Similarly we would expect compounds with full t2g orbitals and
half-filled eg orbitals to have relatively stronger 180 interactions.
In case of two magnetic B-site cations, things are a bit more
complicated. There may be short-range B0 eOeB00 interactions
between the B-site cations, as well as long-range B0 eOe(B00 )e
OeB0 and B00 eOe(B0 )eOeB00 ones. It would perhaps be expected
that the short-range B0 eOeB00 interactions would be the strongest
interaction in the system, dominating the magnetic ordering.
However, in A2B0 B00 O6 perovskites, the B0 eOe(B00 )eOeB0 super-
exchange interactions may sometimes be stronger than B0 eOeB00
interactions, due to weaker energetic orbital overlap of the two
different B-site cations. This has been shown for example in case
of Sr2CoOsO6, where the two B-cation sublattices order inde-
pendently and at different temperatures [540]. Several com-
pounds with B0 ¼ R and B00 ¼ transition metal, such as various
A2RRuO6 compounds, Sr2TbIrO6 and Ba2NdOsO6, show the same
behavior of the two B-cation sublattices ordering at different
temperatures. Apparently the orbital mixing between the lanta-
noides and the transition metals is weak enough that the long-
range superexchange interactions dominate the magnetic
ordering. As was discussed in Section 6.1, the energetic overlap of
the two B-site cation orbitals is often poor in the A2B0 B00 O6 pe-
rovskites. Thus it could be relatively common for the long-range
B0 -O-(B00 )-O-B0 superexchange to be stronger than the short
B0 eOeB00 interaction in these compounds.
It is also possible to place a paramagnetic cation on the A site of
the A2B0 B00 O6 perovskites. Compounds with Mn2þ or a para-
magnetic R at the A site are known. In such cases there may be
magnetic coupling between the A and B site cations. For example, in
Mn2FeSbO6 the Mn and Fe spins are coupled, resulting in an
elliptical spin-spiral with an incommensurate propagation vector
[465]. It is even possible to have paramagnetic ions on all three
cation sites, as in Nd2NiMnO6, where Ni and Mn order FM to each
other at 200 K, whereas Nd is ordered AFM to the B-site cations at
45 K [336,471]. However, often the interactions between the A and
B cations are weak. In R2LiRuO6 for example, the RueO-(Li)eOeRu
interaction are stronger than the ReOeR or ReOeRu interactions
[351]. This is probably again largely due to the weak orbital mixing
between the lantanoid and transition metal ions. Interestingly, it
has been noted that Pb on the A site can enhance magnetic prop-
erties due to additional superexchange interactions using the Pb 6s
electrons [791]. Comparing compounds with A ¼ Sr or Pb, where
the A-site ionic radii are almost identical, it can be seen that at least
in case of A2B0 NbO6 with B0 ¼ Co, Fe, A2NiReO6, A2MnWO6 and
A2FeTiO6 the magnetic ordering temperatures are higher with
A ¼ Pb than with A ¼ Sr. However, this effect is not seen in A2FeB00 O6
with B00 ¼ Mo or Re due to the fact that in these compounds the
magnetic properties are not simply caused by superexchange in-
teractions, but are governed by the hopping of electrons, reminis-
cent of a double-exchange interaction [709].
The magnetic properties depend on the spatial orbital overlap of
the different ions, and this overlap is dependent on structure, as
discussed in Section 6.1. For example, in case of A0 A00 FeMoO6 com-
pounds with A0 , A00 ¼ Ca, Sr or Ba, a good correlation with TC and the
bandwidth estimated using bond lengths and angles has been
found [142]. Similarly, TN values found for several other B00 ¼ Mo or
W compounds have a relatively linear dependency on electronic
bandwidth [326].
As discussed in Section 3.6, JT distortion due to d1 configuration
(t12g) is rare, but has been found occasionally in A2B0 B00 O6 perov-
skites. In case of Ba2SmMoO6, the appearance of JT distortion co-
incides with TN, and it seems that the comparatively high value of
TN ¼ 130 K is affected by the orbital ordering [229]. Similarly, in
Ba2NdMoO6 JT distortion affects magnetic ordering, but there is less
of a correlation between orbital and magnetic order [109,616,698].
Finally, as discussed in Section 3.6, in case of Ba2NaOsO6 the JT
distortion is dynamic, and not evident in the structure, but the
effect is seen in the magnetic properties, where the destruction of
orbital degeneracy results in a weak ferromagnetic ordering. The
similar compound Ba2LiOsO6 is AFM, indicating a rather fine bal-
ance between these two compounds [207].
As discussed in Section 6.1, in case of 4d/5d metals both spin-
orbit coupling and spin delocalization by bond covalency are
strongly enhanced compared to 3d metals. Thus the magnetic
moment of the 4d/5d elements can be notably reduced from the
spin-only values. This has been noted for example in case of many
compounds with Ru [185,242], Re [200,201,541] or Os [115,208]. Ir
is an especially interesting case due to a strong SOC, comparable to
crystal field splitting or inter-electronic interactions. For instance,
Ir5þ with a typical low-spin d4 configuration would be expected to
be paramagnetic, but the strong SOC can lift the t2g orbital de-
generacy creating a nonmagnetic ground state [578,617]. For this
reason many Ir5þ compounds, such as Ba2HoIrO6 [164] or R2NaIrO6
[433], are found to have either no magnetic ordering of the Ir
sublattice, or a reduced moment at Ir [360,520]. In case of R2LiIrO6,
a nonmagnetic ground state is found for Ir at low temperatures, and
magnetic properties are caused by the R ions at the A site. However,
an Ir contribution to the magnetic properties is found at higher
temperatures [350]. The effect of SOC can be quenched by struc-
tural distortions, as in case of Sr2YIrO6, which shows a magnetic
transition at low temperature due to a non-cubic crystal field [617].
Spin-orbit coupling may be present in 3d transition metals as
well, as for example in case of high-spin 3d6 and 3d7 states with
degenerate t2g orbitals. Indeed, unquenched orbital moment is
found in many Co2þ compounds with the 3d7 electron configura-
tion. For instance, Sr2CoMoO6 [532], A2CoTeO6 with A ¼ Ca or Sr
[276,549] and La2CoMnO6 [757] have been reported with meff values
larger than what would be expected from spin only. The high-spin
3d6 Fe2þ should be affected too, and at least Sr2FeWO6 and Sr2Fe-
TeO6 show higher than expected values of meff.
Magnetic properties of compounds with paramagnetic lantha-
noid ions on the B site can be complicated by the possible low-
energy excited states that are of the order of kT around room
temperature. Thus the population of such low lying excited states
must be taken into account when calculating magnetic suscepti-
bility. This is seen for example in Ba2ROsO6 with R ¼ Eu or Nd
[115,208] and Ba2RIrO6 with R ¼ Sm, Eu or Yb [129]. An interesting
case is Ba2HoSbO6, which shows no sign of long-range magnetic
order due to splitting of the electronic states of Ho by crystalline
electric-field, resulting in a non-magnetic ground state [169].
7.2. Antiferromagnets
Most of the A2B0 B00 O6 perovskites reported with a magnetic
ordering are found to be AFM, and some sort of AFM order has been
reported for over 200 compounds. A single B0 (or B00 ) cation in an
ideal cubic A2B0 B00 O6 perovskite forms a face-centered cubic (FCC)
lattices, and few common types of magnetic orderings are found for
such a FCC array of cations when the magnetic interactions are
mainly AFM. These are the type I, II and III orderings, presented in
Fig. 13. Which of these orderings is favored depends on the relative
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
Fig. 13. Common antiferromagnetic orderings found in the A2B0 B00 O6 perovskites: (a)
type I, (b) type II and (c) type III.
strengths of the NN and NNN interactions between the magnetic
ions. Type I is favored when the NN interactions are stronger than
the NNN interactions. This results in eight of the twelve NN cations
being ordered AFM, while NNN cations all ordered FM. Type II is
found when the NN interactions are weak compared to the NNN
interactions, and all six NNN cations are ordered AFM. Type III order
is an intermediate form when the NN interactions are relatively
strong, but the NNN interactions are still significant. Here eight of
the twelve NN cations are ordered AFM, similarly to type I, but two
of the six NNN cations are ordered AFM [185,193,351,378,549,674].
The relative strength of the NN and NNN interactions depends
on spatial and energetic orbital overlap and symmetry, as discussed
previously. It has been remarked that the strength of the NN in-
teractions should decrease more rapidly than that of the NNN in-
teractions with increasing unit-cell volume [193]. There are,
however, only a few examples of such behavior found in the
compounds reported in literature. The magnetic ordering in
A2LaRuO6 changes from type I to type III when A changes from Ca to
Ba indicating that the NN interactions are weakened relative to the
NNN interactions. However, the NNN apparently remain significant
as BaLaRuO6 does not reach type II ordering. Similarly, the magnetic
order in A2MnTeO6 changes from type I to type II when A changes
from Sr to Ba. Here the type III order is apparently skipped, but it
would be interesting to see if this magnetic order would be found in
Sr2-xBaxMnTeO6 with some value of x. Finally, Ca2CoTeO6 is found to
have type I order, but Sr2CoTeO6 is reported with either Type I [549]
or type II order [276].
Makowski [351] has noted that the type I AFM order is common in
compounds with a combination of a R and a 4d/5d element, whereas
type II is common if both B-site cations are transition metals. Looking
at the compounds in Supplementary material Table S1 this behavior
is seen to some extent. Type I compounds are mostly those with
B00 ¼ Ru with either B0 ¼ R or Li. This could be due to the fact that Ru
has empty eg orbitals, resulting only in p-interactions, with strong 90
NN coupling, as discussed in Section 7.1. On the other hand, all of the
type II compounds have either Mn, Fe, Co, Ni or Cu on the B0 site. This
again could be due to these 3d elements having electrons on the eg
orbitals, allowing for s-interactions, which would enhance the 180
NNN coupling. However, the division between the type I and II
compounds is not completely clear, as Ca2CoTeO6, Sr2CoUO6 and
Sr2B0 SbO6 with B0 ¼ Cr or Fe are found with a type I AFM ordering. In
25
these compounds the p-interactions may compete with the sigma-
interactions, and it would be interesting to study the magnetic
ordering of corresponding compounds with larger A-site cations in
order to see if type II or type III ordering would be stabilized. Finally, it
appears that only the aforementioned Ba2LaRuO6 has been verified to
have a type III AFM ordering.
In the case of two paramagnetic B-site ions, the different B cat-
ions may order at the same temperature or at different tempera-
tures, depending on the interactions between them, as was
discussed in Section 7.1 [119]. The resulting magnetic ordering may
vary, but in case of A2RRuO6 compounds with paramagnetic R, two
interpenetrating type I AFM lattices have been found. On the other
hand, Sr2CoOsO6 is the only reported case with two interpenetrating
type II magnetic lattices [540]. In addition to the relatively
straightforward type I, II or III orders, some more special magnetic
orderings may take place. For example, Lu2MnCoO6 shows an up-up-
down-down spin arrangement along the c axis [462], whereas
La2NaRuO6 has an incommensurate magnetic structure [435].
Weak ferromagnetism has often been noted in the otherwise
AFM A2B0 B00 O6 perovskites [359,573,673]. Sometimes this is caused
by effects such as actual competing FM superexchange interactions
[675], microdomains [499] or borderline metallicity [207]. How-
ever, in most cases the weak FM behavior appears to be caused by
DzyaloshinskyeMoriya (DM) interactions and canting of spins
[648]. Many of the compounds showing weak FM behavior are
highly ordered, but structurally distorted. For example, it has been
noted that La2MgIrO6 is AFM, whereas La2ZnIrO6 appears FM even
though the compounds are otherwise almost identical [792]. This is
due to the fact that Zn is actually a spin canted AFM, and there is
apparently a very fine balance in the magnetic properties between
these compounds [793]. Similarly, Sr2ErRuO6 shows a weak FM
effect, while Ba2ErRuO6 does not. This is again down to the fact that
Sr2ErRuO6 has lower symmetry, which allows for the DM-
interactions to take place [127]. Also, it is interesting to note that
Ba2CoUO6 has been reported as FM, whereas Sr2CoUO6 is found to
be canted AFM. However, the TC, q and meff values of these two
compounds are practically identical, suggesting that the two
compounds could actually have similar magnetic orderings. Finally,
the few A2B0 B00 O6 perovskites with a layered ordering have also
been found to exhibit weak FM behavior, probably due to the fact
that in these compounds the B cation octahedra are strongly tilted.
Metamagnetic, or spin-flop, transitions have also been noticed
in many AFM A2B0 B00 O6 perovskites. This transition is caused by spin
reorientation due to an external magnetic field, and can happen if
in an AFM system the spontaneous AFM interactions are weak.
When the external magnetic field overcomes the AFM coupling, the
long-range ordered AFM structure can be destroyed, resulting in a
FM-like behavior [541]. For instance, A2NaOsO6 with A ¼ Pr or Nd
show spin-flop transitions from AFM to FM ordering, depending on
temperature and the external field [434]. These kinds of transitions
have also been reported at least in Sr2NiReO6 [541], Ba2B0 RuO6 with
B0 ¼ Gd or Ho [164,304], Sr2YIrO6 [617], Nd2LiRuO6 [351], and
Sr2B0 RuO6 with B0 ¼ Gd, Ho or Y [620,622,674]. It is interesting to
note that most of these spin-flop compounds have very small
values of q z0 K. This would indicate that in these compounds the
overall AFM ordering is weak, probably due to competing FM in-
teractions. The only exception is Sr2YIrO6, where the magnetic in-
teractions are complicated by the strong SOC of Ir5þ [183]. Other
AFM compounds with small values of q could perhaps show similar
spin-flop transitions.
7.3. Magnetic frustration
Magnetically frustrated compounds are of interest for funda-
mental solid-state physics. Compounds with low magnetic moment
26 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36

and frustration may offer interesting new physical phenomena and Table 5
el temperatures, Weiss constants and effective magnetic moments for A2B0 B00 O6
Ne
degenerate ground states [192]. In the magnetically frustrated
perovskites for which frustration factor values higher than 10 are found.
compounds long-range order often takes place at some tempera-
ture TN, typically much lower than q. However, at temperatures Formula TN q (K) meff (mB)
between TN and q some exotic magnetic states may occur [671]. Ba2CaIrO6 55 573 3.9
Frustrated behavior has been found in the A2B0 B00 O6 perovskites in Ba2EuRuO6 42 1000 8.17
various forms, making these compounds of great interest in this Ba2FeBiO6 40e50 880 to 820
Ba2FeSbO6 12 210
field.
Ba2FeTaO6 22 519 8.6
A single B0 - (or B00 -) site cation in an ideal cubic A2B0 B00 O6 Ba2LaRuO6 29.5 304 4
perovskite forms an FCC lattice, as described was in the previous Ba2LuReO6 33 703 2.3
section. This results in a formation of edge-shared tetrahedral Ba2LuRuO6 35 630 4.4
592
structure of the B0 cations, and in such a case AFM NN interactions Ba2SmRuO6 42/54 5.16
Ba2YbOsO6 2.4 106.1 4.86
can be geometrically frustrated [653,671]. NNN interactions may Ba2YReO6 25/50 726 to 616 1.93e2.32
lift this frustration, although cases with small spin values may form Ba2YRuO6 36 630 to 571 4.5e4.64
exceptions [248,249]. Aharen has shown in their study this effect of Ca2CoTeO6 7e10 90 to 78 5.5
the spin value [247,250,251]: La2LiRuO6 and Ba2YRuO6 with S ¼ 3/2 Ca2LaRuO6 12 158 to 115 3.72e4.27
Ca2LuRuO6 14 162 to 104.9 3.18e3.67
were found to be magnetically ordered, but frustrated. On the other
Ca2YRuO6 14e16 176 to 155 3.74e4.02
hand, La2LiReO6 and Ba2YReO6 with S ¼ 1, or La2LiMoO6 and Sr2CoNbO6 19 650 4.9
Ba2YMoO6 with S ¼ ½ showed magnetic anomalies or short-range Sr2EuRuO6 31 399 3.1
order, but no clear long-range order. Sr2YIrO6 1.3 229 0.91
This geometric frustration is exemplified in many A2B0 B00 O6 pe-
rovskites, such as A2RSbO6 with A ¼ Sr or Ba and R ¼ Dy, Gd or Ho,
where no magnetic order is found down to 2 K [120]. Also, valence- Frustrated magnetic behavior may also be caused by B-site
bond glass behavior has been reported in Ba2B0 MoO6 with B0 ¼ Y or cation disorder, which can result in a range of different competing
Lu. These compounds again show no clear magnetic transition, but interactions [795]. Many A2B0 B00 O6 perovskites show spin-glass-like
instead a gradual spin-freezing with decreasing temperature behavior, and most of these compounds have notable cation dis-
[192,248,249]. However, structural distortions may destroy geo- order [6,451,608]. For example, ordered ruthenate compounds are
metric frustration [435]. This is seen in the Ba2RMoO6 compounds mostly found to be AFM ordered, whereas disordered ones show
with large R, or small tolerance factor, which do have magnetic either FM or spin-glass-like behavior [351]. There are about ten
long-range order [192,249]. Similarly, smaller A-site cation can A2B0 B00 O6 compounds that appear to be spin-glasses, with several
distort the structure and lift the degeneracy, causing long-range others that have spin-glass -like behavior. For example, spin-glass
order to take place. This happens in case of Sr2YMoO6, which has behavior has been found in the disordered Sr2FeB00 O6 compounds
a weak FM order, albeit with a large degree of spin glassiness with B00 ¼ Nb, Ta or Ru [6,150,597,598,607]. On the other hand,
[249,616]. Sr2FeSbO6 with a higher degree of cation order has been reported to
The geometric frustration of the NN interactions may be be largely magnetically ordered, but with clusters of frustrated
destroyed by the NNN interactions, but the two different in- spins [598,607]. As has been discussed before, La2B0 B00 O6 with B0 ,
teractions may also be a cause for frustration. The AFM NN and NNN B00 ¼ Co, Ni, Mn can have various degrees of cation order, depending
interactions would favor different magnetic orderings, and thus on the synthesis conditions, and in case of La2NiMnO6 quenched
frustration in the spin orientation is expected if the interactions are samples with B-site disordered show frustrated magnetic behavior
comparable. It was previously discussed that the type III AFM order [446]. Finally, Sr2CaReO6 [515] and Sr2MgReO6 [7] have been re-
is found when the NN interactions are only slightly stronger than ported with spin-glass-like behavior even with very high degree of
the NNN interactions. It could be that compounds found in the B-site cation order [796]. Such compounds are very rare, as usually
borderline of type II and type III ordering could show frustrated spin-glassiness requires some kind of structural disorder.
behavior. Frustrated NN and NNN interactions have been noted in In most cases the spin-glass behavior is not thoroughly verified,
certain A2CuB00 O6 compounds with B00 ¼ Mo, W, which form a quasi- and the true magnetic behavior may be different. Some apparent
two-dimensional lattice of Cu2þ ions due to the JT distortion of the spin-glass compounds may in fact have canted AFM ordering [610].
CuO6 octahedra [104,105,568,569]. The NN and NNN interactions Similarly, compounds with FM coupled clusters or small magnetic
between the Cu ions in these compounds are apparently of similar domains may in some cases appear similar to spin-glass
strength, and are somewhat frustrated. [320,541,638]. Spin-glass behavior has also been noted in oxygen
The frustration factor f ¼ jqj/TN is often used in order to non-stoichiometric samples, and as the oxygen content of most
quantify the amount of magnetic frustration. Generally, f > 10 compounds in not known, this could in some cases be partly
would already indicate a presence of magnetic frustration [794]. responsible for the spin-glass -like behavior [374].
There is a number of A2B0 B00 O6 compounds, presented in Table 5,
which do show magnetic long-range order at temperatures of up 7.4. Ferromagnets
to 55 K, but which at the same time have very high values of q,
and as a consequence calculated frustration factors of f > 10. Such There are in general very few FM oxides, as typically the
compounds could therefore have frustrated magnetic in- superexchange interactions favor antiparallel spin orientations
teractions. A second possibility is a borderline delocalization of (AFM or FiM). The Goodenough-Kanamori rules state that FM
electrons, which would cause Pauli paramagnetic-type behavior, superexchange happens only with half-filled/empty or half-filled/
with increased q [334]. In this case, however, the value of meff full orbital combinations of the interacting cations [427,429,797].
would also be expected to increase. Of the compounds in Table 5, Ferromagnetism is thus uncommon in stoichiometric single pe-
at least A2B0 RuO6 with A ¼ Ca or Ba, B0 ¼ La, Lu or Y and Ba2FeTaO6 rovskites, as with only one B-site cation these orbital filling com-
show anomalously large values of meff. The remaining compounds binations are not possible, and FM ordering in compounds such as
on the other hand do not show clear effects of spin delocalization. SrRuO3 is caused by itinerant charge carriers [798,799]. However,
the A2B0 B00 O6 perovskites with two different B-site cations allows
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
for combinations where superexchange FM can happen between
the neighboring cations. Therefore it is not surprising that many of
the FM oxides are either A2B0 B00 O6 perovskites or spinels [429,798].
About 30 A2B0 B00 O6 compounds have been reported to be FM, as
seen in Supplementary material Table S1. However, most of these
are various R2B0 MnO6 combinations with B0 ¼ Co, Ni. As has been
discussed earlier, these compounds can show a range of cation
order depending on the synthesis conditions. The ordered cases
show superexchange mediated FM due to a combination of
partially filled Co2þ/Ni2þ eg orbitals and empty Mn4þ eg orbitals
[366,800]. However, cation disorder is common in these com-
pounds, and can weaken the FM order due to AFM CoeOeCo,
NieOeNi or MneOeMn interactions [363,449,471]. All other re-
ported FM compounds also have some 3d metal, most often Mn, on
at least one B site, with the exception of Sr2GdIrO6, which is a
special case with a weak FM order caused by Gd, as Ir5þ has an
effectively zero magnetic moment due to the strong SOC, as dis-
cussed in Section 7.1. Most of the FM compounds are highly ordered
insulators, although La2NiCoO6 may be a metal or borderline metal,
as discussed in Section 6.2. Thus in the FM A2B0 B00 O6 compounds the
FM nature appears to be due to superexchange interactions be-
tween the two B-site cations, and not by itinerant electrons.
The TC values of the FM A2B0 B00 O6 perovskites are typically quite
low, below room temperature. Two exceptions are Bi2CuMnO6 and
Pb2FeTiO6, where apparently superexchange interactions using the
6s2 lone electron-pair increase TC, as discussed in Section 7.1. Here it
should also be noted that the existence of Pb2FeTiO6 has not been
confirmed, and that it has been reported that Fe solubility limit in
PbTiO3 is only 10% [801]. Finally, Ba2CrMoO6 has been reported as
FM with relatively high TC ¼ 310 K, whereas A2CrMoO6 with A ¼ Ca
or Sr apparently have FiM ordering. The behavior between FM and
FiM compounds may be difficult to distinguish, but the saturation
moment with A ¼ Ba is higher than what would be expected for FiM
order of Cr3þ and Mo5þ, whereas with A ¼ Ca or Sr the saturation
moments are quite low, fitting better with FiM order. However, the
nature of magnetic ordering in these compounds would require
experimental verification.
Synthesis of several more A2B0 B00 O6 perovskites with expected
FM superexchange interactions have been tried, but often these
compounds have been found to have B-site cation disorder and
magnetic frustration [450]. La2CrFeO6 for example is disordered
and AFM ordered with weak FM component. However, an artificial
superlattice of LaFeO3 and LaCrO3 has been found to show FM
behavior [382,802]. La2B0 IrO6 with B0 ¼ Mn or Fe were also been
predicted to be FM [798], and of these B0 ¼ Mn is indeed found to be
a B-site cation ordered FM, whereas B0 ¼ Fe has only partial cation
order, and is AFM with competing FM interactions.
Few rare compounds are found to be FM with only one para-
magnetic B site cation. One example is Ca2CrSbO6, which is FM even
though Sr2CrSbO6 is found to be AFM [281]. The FM nature of the
A ¼ Ca compound is caused by tilting of the BO6 octahedra and a
resulting FM exchange interactions. Ba2NaOsO6 is also weakly FM,
and as discussed before, this is caused by the slight JT distortion of
Os [207]. Similarly, La2GaMnO6 is found to be FM due to orbital
fluctuations of the JT active Mn3þ ion [409]. Thus the FM behavior in
all these compounds with a single paramagnetic B-site cation is
caused by different structural distortions.
7.5. Ferrimagnets
FiM ordering requires two magnetic cations with different
moments to be ordered AFM to each other, resulting in a net
magnetic moment. In case of A2B0 B00 O6 perovskites one might
expect this behavior to be rather common, as with quite a few B-site
cation combinations the two cations have differing but non-zero
27
magnetic moments. However, there are only about 30 com-
pounds reported with FiM ordering, and many of these belong to
the halfmetallic compounds, discussed in Section 6.3: their mag-
netic ordering is not simply due to superexchange interactions, but
by the itinerant electrons. It thus seems that in most cases the two
B-cation sublattices are ordered AFM within themselves, which
results in a zero net moment. As we discussed earlier, in A2B0 B00 O6
perovskites the long range B0 eOeB00 eOeB0 interactions may indeed
be stronger than the short range B0 eOeB00 interactions, leading to a
relatively weak coupling between the two different B cation
sublattices.
Here it should be noted that it is sometimes difficult to distin-
guish FiM and FM behavior from susceptibility measurements, as
their behavior may be superficially similar. Typically for FM com-
pounds q > TC, and for FiM q < TC, but determining q from Curi-
eeWeiss fit may be difficult if TC is high. The saturation moment
could also help distinguishing between the two orderings, but SOC,
cation disorder or oxygen vacancies may hinder such analysis [300].
We noted in the previous section the difference between A2CrMoO6
with A ¼ Ca or Sr, which have been reported to be FiM, and A ¼ Ba,
which has been reported as FM. Similarly, some A2B0 UO6 with
B0 ¼ Mn, Fe, Co or Ni are reported FM, while others as FiM. For
example, Sr2NiUO6 has been claimed to be FiM, while BaNiUO6 is
reported to be FM, but the two compounds have similar values of TC
and meff, indicating that they could in fact have the same magnetic
ordering. U6þ is diamagnetic, which would exclude the possibility
of FiM ordering in these compounds. However, it has been postu-
lated that a slight valence mixing could cause a small moment on U
in case of some of the A2B0 UO6 compounds, and thus make the
compounds FiM [612].
The A2B0 B00 O6 compounds reported FiM appear to be split into
two different types. The compounds in the first group have rela-
tively high values of TC > 300 K, and many of them are metallic. This
group consists of various halfmetallic or nearly halfmetallic com-
pounds discussed in Section 6.3, with A2B0 B00 O6 with B0 ¼ Cr or Fe
and B00 ¼ Mo, Re or Os, and Sr2CrWO6. On the other hand, the
compounds in the second group have low values of TC < 200 K, and
are insulating. This group is largely made of various compounds
with B0 ¼ Mn or Ni and B00 ¼ Re or U, A2FeUO6 and Ca2CrB00 O6 with
B00 ¼ Mo or W. This separation into two groups shows the effect of
the band energy overlap and electron itinerancy to the magnetic
properties. An interesting case is also found in A2FeOsO6, where
A ¼ Ca is FiM, whereas A ¼ Sr is AFM with canted spins. Here an
increase in lattice distortion causes the change in magnetic
ordering when moving from Sr to Ca [294].
Structure is of course important in all of these compounds, and
often TC reaches maximum when t z 1, as orbital overlap is
maximized [93]. Fig. 14 shows the TC values for the A2CrWO6 and
A2B0 B00 O6 compounds with A ¼ Ca, Sr or Ba; B0 ¼ Cr or Fe; B00 ¼ Mo or
Re as a function of the tolerance factor. In general, TC reaches a
maximum around t z 1, which in these compounds corresponds to
A ¼ Sr. The only exception is the A2FeReO6 series, where Ca2FeReO6
has the highest value of TC. It has been assumed that the increased
lattice distortion in this compound could introduce an additional s-
coupling, increasing TC [152]. On the other hand, unquenched
orbital moment has detected in the A2FeReO6 compounds, and the
moment is correlated with the crystal structure, with smaller A
cation resulting in a larger moment. Intriguingly, the TC in these
compounds follows the effective total spin moment rather linearly
[563,767].
B-site cation disorder is also found to affect the magnetic
properties of the FiM compounds, and the most studied case is
again Sr2FeMoO6. The saturation magnetization Ms especially is
sensitive to the cations disorder, decreasing relatively linearly as
Ms ¼ 4S, as predicted by a simple model with AS defects [710,738].
28 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36
Fig. 14. TC as a function of tolerance factor for (a) A2FeMoO6 (black circles) and
A2FeReO6 (white circles), and (b) A2CrMoO6 (white triangles), A2CrWO6 (black squares)
and A2CrReO6 (white squares) with A ¼ Ca, Sr or Ba.
With proper synthesis, high degree of order and high magnetiza-
tion are achieved [590].
7.6. Low-dimensional magnetism
Low-dimensional magnetic properties have been found in some
A2B0 B00 O6 perovskites. Most obvious cases are the R2CuB00 O6 com-
pounds with layered ordering. For example, La2CuSnO6 shows a
relatively broad susceptibility maximum, indicative of low
dimensional magnetic interactions [394,396]. However, the CuO2
layers in these compounds are strongly buckled, which probably
decreases the low-dimensional nature of these compounds, and as
a result they show spin canted properties.
Rather more clear low-dimensional behavior has been found in
many rock-salt ordered A2CuB00 O6 compounds with diamagnetic B00
such as Mo [568,569], W [95,104,105,106,568,569] or Te [95]. Here
the JT distortion of Cu2þ creates magnetic anisotropy and the Cu
ions effectively form a square lattice in the ab-plane of the unit cell,
with weaker magnetic interactions along the c direction. Of these
compounds, Ba2CuWO6 [104] and Sr2CuB00 O6 with B00 ¼ Mo or W
[569] have been shown to have three-dimensional long-range
magnetic order, but only at relatively low temperatures. It is
interesting to note that Ba2CuUO6 generally does not show such
low-dimensional magnetic properties [98,100], although a broad-
ened maximum in susceptibility has also been found, but this was
assumed to be due to cation disorder [97,101]. In addition,
Ba2CuOsO6 shows a slightly broadened susceptibility maximum
[94], whereas Sr2CuOsO6 does not [570]. Thus the low-dimensional
magnetic properties in these compounds are relatively sensitive to
the exact composition, allowing for an adjustment of the magnetic
properties with cation substitution.
7.7. Multiferroics
Multiferroic compounds with a coupling of spontaneous ferro-
electric polarization and ferromagnetic ordering are of great in-
terest, with a wide range of applications in electronic devices and
sensors [79,489]. This phenomenon is rather rare, however, as
displacive ferroelectric distortion generally requires elements with
empty d orbitals, whereas partial d-orbital filling is required for
magnetic ordering [803]. The most common solution for this
problem is to separate the two properties to different ions. Thus
many of the multiferroic perovskites are compounds with magnetic
B site cations such as Fe or Mn combined with an A-site cation such
as Pb or Bi, where the ferroelectric polarization is caused by the
lone 6s2 electron pair [260,495,497].
In case of the ferroelectric A2B0 B00 O6 perovskites, the A ¼ Pb
compounds are more thoroughly studied compared to the A ¼ Bi
cases, as discussed in Sections 3.6 and 6.4. Many of the A ¼ Pb
compounds have ferroelectric transitions above room temperature,
although most are antiferroelectric. A suitable combination of Pb
and a paramagnetic B cation could result in multiferroicity
[474,478], but there are not that many FM A2B0 B00 O6 perovskites
with A2þ cations, as these compounds are more often FiM, as dis-
cussed previously. Also, in many of FM cases the TC values are rather
low. However, as discussed earlier, the 6s2 electron pair can
enhance the magnetic ordering temperature [791]. Pb2FeTiO6 has
been reported to be both FM and ferroelectric at room temperature,
and the two properties may also be coupled [490]. However, as was
mentioned earlier, another report has found the Fe solubility limit
in PbTiO3 to be only 10%, which casts a doubt on these results [801].
As discussed in Section 7.4, the most common FM A2B0 B00 O6 pe-
rovskites are compounds with A3þ cations and some 3d transition
metals such as Mn on the B-sites. Thus multiferroic properties
could be found within various A ¼ Bi3þ compound. In this vein
Azuma et al. [260] synthesized the compound Bi2NiMnO6 to
combine the required properties. The compound is indeed ferro-
electric below ~460e480 K and FM, but only below 140 K [259,260].
8. Conclusions
The A2B0 B00 O6 perovskite oxides have been reported with a wide
range of properties: structural distortions, order-disorder phe-
nomena of the B-site cations, and various electronic structures and
magnetic orderings are of fundamental interest, but compounds
with properties such as spin-polarized electron transport, high
dielectric constant, low thermal conductivity or multiferroicity are
also in key position considering future technologies. However,
many of the compounds reported in the literature have not been
thoroughly examined, and it was partially the purpose of this work
to bring up such cases in order to find novel compounds with useful
properties.
The properties of perovskite compounds are largely governed by
the B-site cations. The A2B0 B00 O6 perovskite system is an interesting
platform for the study of the effects of the B-site cations, as almost
any element from the periodic table can be inserted into the two B
sites, many of them with various oxidation states. The B-site cation
oxidation states in many of the existing A2B0 B00 O6 compounds are
not well determined, however. In this work we made some pre-
dictions on the B-cation oxidation states based on the standard
electrode potentials of the elements and the unit-cell volumes of
the compounds. Several cases with a possible change in oxidation
states in a series of compounds, or compounds with possible
valence mixing were identified. However, these predictions are not
based on direct experimental data for the oxidation states, and they
should be verified by experimental methods.
The A2B0 B00 O6 perovskites exhibit various electrical transport
properties, ranging from insulators to metals and halfmetals. The
electrical properties of most compounds have not been measured,
but many are expected to be insulators due to the d0 nature of the B-
site cations. Such compounds could be good dielectrics, as many
double perovskites have been found to have high dielectric con-
stants. Semiconducting compounds with small band gaps are also
prevalent in the double perovskites, and could be useful as fuel-cell
 S. Vasala, M. Karppinen / Progress in Solid State Chemistry 43 (2015) 1e36 29

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