A3B2B'O9 perovskites; making use of cation disorder to synthesize new magnets

Lead Research Organisation: University of Oxford
Department Name: Oxford Chemistry

Abstract

Solids are very complex materials. They contain millions of atoms, each of which interacts with those immediately around it and, sometimes, with those somewhat further away. Each atom usually has between four and twelve neighbours, and of course they all have other neighbours so the complexity of the interactions increases rapidly as you move out from your starting point. If the atoms are arranged regularly in space, then the solid is said to be crystalline and it is easier to deal with these than those where the atoms are not periodically arranged, known as amorphous materials.
Even in a crystalline solid it is difficult to understand what interactions are taking place. Sometimes there are sites in a crystal that we know are occupied by an atom, but we cannot be sure what type of atom it will be. That is, the atom at a particular point could be either of two different chemical elements. If we know what type of element is at every site in the crystal, then the compound is said to be structurally ordered; if we cannot be sure, then it is said to be disordered. If the crystal is structurally ordered, then it is relatively straightforward to predict what properties the crystal might have, although the number of interactions in which it takes part is still so large that it is rarely trivial to do so accurately. If the compound is structurally disordered then it is very difficult to predict what will happen because there the environment of every atom is somewhat random in nature. Often the presence of disorder prevents the compound having useful properties, for example being a good electrical conductor or a strong magnet. The challenge facing chemists is to turn the tables on nature and make new compounds whose natural disorder is responsible and essential for endowing the compound with useful properties. The research described in this proposal aims to show that oxides containing lanthanum, nickel and antimony show useful magnetic properties only because of the fact that some of the magnetic atoms (nickel) are mixed up with antimony on one set of sites in the structure.

Planned Impact

The research described in this proposal is fundamental solid-state chemistry, although it lies close to the border with solid-state physics and could be regarded as multi-disciplinary. The aim is to synthesize a range of compounds and identify the factors that cause some of them to behave as 'relaxor ferromagnets", i.e. to show a large magnetisation once exposed to a magnetic field but none before the field is applied. The work is thus a long way from "materials science", which is essentially about taking a known compound with established properties and processing it in some way that allows it to be used as a device. Thus the work will enhance the knowledge economy, and I expect it to be regarded as internationally competitive. The project will provide good training for post-graduate students.
The work has the potential to improve quality of life if a compound is found that, with suitable processing, can be developed into a useful magnetic material. However, this development could not begin until the proposed research is complete. If such a material can eventually be developed it would contribute to wealth creation and economic prosperity and could attract R&D investment from global business. This might involve the formation of a spin-out company to develop new products. Those who work on the project would gain skills and expertise that would be useful in non-academic professions.

Publications

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Description Before this grant began we had shown that La3Ni2SbO9 adopts a monoclinic variant of the perovskite structure with two crystallographically-distinct six coordinate sites in the unit cell. One of these is occupied exclusively by Ni2+ cations while the other accommodates a random 2:1 distribution of Sb5+ and Ni2+ cations. A study of La3Ni2SbO9 by SQUID magnetometry had revealed behaviour characteristic of a ferromagnet or ferrimagnet with a Curie temperature of 105 K. However, no evidence of long-range magnetic ordering could be detected in a neutron diffraction pattern collected at 5 K. This apparent inconsistency was accounted for by postulating that the bulk magnetisation observed in the magnetometer arises from the presence of ferrimagnetic domains that are too small to appear ordered in a diffraction experiment conducted in zero field, but whose constituent spins are aligned by an applied magnetic field. Consistent with this explanation, a subsequent neutron diffraction study showed that an increasing level of magnetic Bragg scattering is seen when the sample is subjected to an increasing applied magnetic field. That study also revealed that very weak magnetic scattering is present in the absence of a field, presumably from the largest domains in the sample. The net magnetisation within the domains is a consequence of the unequal distribution of the magnetic Ni2+ cations over the two six-coordinate sites; the nearest-neighbour superexchange along a nearly-linear Ni - O - Ni pathway will always be antiferromagnetic, but the spin-up cations outnumber those with spin-down by a factor of two. By analogy with the relaxor ferroelectric Pb3MgNb2O9, La3Ni2SbO9 was classified as a relaxor ferromagnet.
The aims of the work funded by this grant were firstly to determine the circumstances under which relaxor ferromagnetism occurs, secondly to make new compounds, isostructural with La3Ni2SbO9, in which the ferromagnetism is long-range rather than short range and, thirdly, to increase the onset temperature of the magnetism, be it long- or short-range. All the new compounds described below were studied by X-ray diffraction, neutron diffraction, electron microscopy and magnetometry. Some were also studied by µSR.
We initially investigated the consequences of replacing Sb5+ by W6+ and Te6+ and showed that CaLn2Ni2WO9 (Ln = La, Pr, Nd) behave as spin glasses below~30 K, i.e. they show neither long-range nor short-range ferromagnetism because competing magnetic interactions frustrate the formation of a magnetically ordered phase. Similar behaviour was observed in SrLa2Ni2TeO9, although in that case the magnetic interactions are disrupted by a complex microstructure. Spin-glass behaviour was also observed when Sb5+ was replaced by Nb5+ to form La3Ni2NbO9 but La3Ni2TaO9 showed relaxor ferromagnetism, albeit with a slightly lower onset temperature, ~85 K, than La3Ni2SbO9. A study of the mixed system La3Ni2SbxTayNb1-x-yO9 confirmed that the presence of Sb5+ and/or Ta5+ results in relaxor behaviour but the introduction of Nb5+ converts the system to a spin glass.
We also studied the consequences of replacing Ni2+ by other magnetic cations. In contrast to La3Ni2SbO9, LaSr2CrSbO9 and SrLa2FeCoSbO9 showed long-range magnetic order below ~150 K and 215 K, respectively, thus fulfilling two of our three aims. The cation ordering pattern that facilitates magnetic ordering in the latter compound is, we believe, unique.
Not all the compounds we prepared made a positive contribution to the principal theme of our work, but they all had interesting properties. For example, unlike LaSr2CrSbO9, Ca2PrCr2NbO9 and Ca2PrCr2TaO9 do not show the same type of cation ordering as La3Ni2SbO9 and they are therefore not candidates for relaxor behaviour. However, they do show the phenomenon of magnetisation reversal and our observation of this behaviour gave rise to a secondary project. Further examples are provided by Ca2CeCr2TiO9, where the cation disorder enabled us to study the growth of antiferromagnetic clusters as a function of temperature, and Sr3Fe2TeO9 where we identified an usual, albeit not unique, cation ordering pattern that does not support ferromagnetism. As in the case of SrLa2Ni2TeO9, a complex microstructure was identified and characterised but in this case it gives rise to antiferromagnetic ordering rather than spin glass behaviour.
With regard to our aim of understanding when relaxor behaviour is likely to occur in A3B2B'O9 triple perovskites (B is magnetic, B' is not), we have seen conventional long-range magnetic order in compounds containing Cr3+ and Fe3+ cations but not in those containing Ni2+. We have seen relaxor behaviour in some Ni2+ compounds and spin glass behaviour in others. Cr3+ interacts magnetically through p orbitals, Fe3+ through both p and s orbitals and Ni2+ only through s orbitals. It is therefore reasonable to hypothesise that the availability of p orbitals leads to long-range magnetic order in this structure, whereas relaxor behaviour may occur if only s orbitals are available. We must then explain why some Ni2+ compounds are relaxors and others are spin glasses, even if they the same cation ordering pattern and essentially defect-free microstructures; the contrast between the behaviour of La3Ni2NbO9 and La3Ni2TaO9 is particularly striking. In order for spin-glass formation to occur there must be competition between different magnetic interactions. The dominant interaction in all our materials will be antiferromagnetic s superexchange along a Ni - O - Ni pathway, although one of the Ni sites is diluted by B'. We propose that the competing interaction is along a Ni - O - B' - O - Ni s pathway. The strength of this interaction will depend on the energy of the outer d orbitals of B' which will lie in the sequence Ta5+ >Nb5+> Sb5+. If the energy match is optimal in the case of Nb5+ then the competition will be strongest and spin-glass formation is most likely. In the case of Sb5+ and Ta5+ the Ni - O - Ni is dominant and magnetically ordered microdomains are able to form. Their growth may be limited by short-range structural ordering among the diamagnetic and magnetic cations, a phenomenon that the subject of another investigation (performed by a student who is not funded by EPSRC) that is nearing completion. We note that we have only been able to prepare Cr3+ and Fe3+ systems, with the possibility of p-mediated magnetic interactions, in which B' = Sb5+. The longer pathway is therefore not competitive and spin glass formation would not be expected. The formation of a long-range ordered state rather than a relaxor can be attributed to the absence of short-range structural order, which would be consistent with the smaller difference in size and charge between Sb5+ and Cr3+ or Fe3+ compared to Ni2+.
Exploitation Route The results described in the publications associated with this grant provide a basis for the design of new perovskite-related materials that show a spontaneous magnetisation at temperatures approaching ambient.
Sectors Aerospace, Defence and Marine,Electronics