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Schizophrenic electrons in ruthenium-based oxides †


R. J. Cava
Department of Chemistry, Princeton University, Princeton, NJ 08540, USA
Received 1st March 2004, Accepted 7th April 2004
First published as an Advance Article on the web 26th July 2004

Ruthenium and oxygen form many ternary compounds electronic–structural coupling can be expected either to be
in which the Ru 4d states and O 2p states are strongly overtly present or lurking in the background, for the ruthenium
hybridized. In some such compounds, this hybridization oxides this coupling appears to sometimes be important and
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leads to the loss of local magnetic moment character other times not, making them a uniquely interesting class of
for the Ru, and in others it does not. The factors that compounds. Electrons in ruthenates seem to have an equal
determine which is the case are often subtle and poorly chance of displaying itinerant or localized behavior, often
understood. The richness of structure types seen in ternary dependent on subtle structural or chemical influences, thus
Ru oxides leads to a corresponding richness in electronic motivating the title of this brief review.
and magnetic properties. This article briefly describes the Experimental and theoretical research in recent years has
author’s current views on these materials. shown that ferromagnetic, antiferromagnetic, and nonmagnetic
states are very close in energy for the ruthenates. This appreci-
ation of the character of the ruthenates was developed by solid
1 Introduction state chemistry groups in the US and Europe, and through
Many of the relationships coupling chemistry, crystal structure, detailed work by experimental and theoretical physicists on one
electronic properties, and magnetic properties in transition particular ruthenate, Sr2RuO4, and related perovskite-based
metal oxides remain poorly understood. Unexpected magnetic phases. The structural and chemical complexity available in
and electronic properties frequently surprise the community: ruthenates, when combined with this delicate balance between
the cuprate superconductors are good examples. This unpre- different magnetic states, offers the potential for observing
dictability of properties is due in large part to the presence of many surprising properties. Although the 3d oxides continue to
strong interactions between d electrons – generally too complex be the subject of much research, 4d oxides in general have seen
to be treated by the usual theoretical models. But the problem is little sophisticated experimental and theoretical study. Thus
much richer than that. Often, the electronic state of a transition they can be considered to be relatively early in their develop-
metal oxide is the result of subtle coupling between electronic ment. There is great untapped potential in the ruthenates for
and structural degrees of freedom. The 3d-based transition using solid state chemistry to influence the factors that
metal oxides, especially the perovskites, are renowned for are important in their determining balance between different
such complexities, supported with decades of observations of electronic states.
structure–property correlations. The properties of Sr2RuO4, and how they are related to those
The emergence in the past 5–10 years of correlations of a of the Ruddlesden–Popper phases Sr3Ru2O7 and SrRuO3, play
similar nature in ruthenium-based oxides was unanticipated. In the leading role in illustrating the complexities of the ruthen-
more extended orbitals, the 4d valence electrons of Ru are ates. Sr2RuO4 is superconducting, by an exotic microscopic
expected to show fewer tendencies toward localization than mechanism, near 1 K.1 Yoshi Maeno and his collaborators have
their 3d analogs, and weakened coupling between structural been the leaders in its characterization, and they have described
and electronic degrees of freedom. Unlike 3d oxides, for which its properties in great detail (see, e.g. refs. 2 and 3). The inter-
ested reader is referred to their work to learn about the proper-
† Based on the presentation given at Dalton Discussion No. 7, 5–7th ties of that compound. Here, I will paint that material and
July 2004, University of St Andrews, UK. related perovskite phases with a broader brush, but using them
as a central part of the argument about the uniqueness of the
ruthenates. I will concentrate mostly on the structures and
Robert Cava is a Professor in the Department of Chemistry at properties of non-perovskite ruthenates and will draw primarily
Princeton University. He took that position in 1997 after being from the work of our group, but will also describe the work
at Bell Laboratories (1979–1997), NIST (1978–1978), and of others.
receiving his PhD in Ceramics from MIT in 1978. He is a member
of the US National Academy of Sciences.
2 The perovskite and Ruddlesden–Popper phases
The ruthenate perovskites and their layered variants provide an
important testing ground for current ideas in the magnetism of
complex systems, and, in particular, the possible relationships
between ferromagnetism and superconductivity. Sr2RuO4 is
the n = 1, single layer member of the Ruddlesden–Popper
homologous series, Srn⫹1RunO3n⫹1 4–6 (Fig. 1). In this family
n represents the number of layers of corner-shared RuO6
DOI: 10.1039/ b403107e

octahedra in each grouping – these n layers are electronically


connected by Ru–O–Ru bonding before the electronic coupling
in the direction perpendicular to the layers is broken up by
O–O–O electronic overlap. As n increases, the proportion of
pure perovskite character increases, and therefore the structures
become more three-dimensional. The evolution of the electro-
Robert Cava
nic states from delocalized to ferromagnetic as n increases has

This journal is © The Royal Society of Chemistry 2004 Dalton Trans., 2004, 2979–2987 2979
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approximately 10%, relaxes the structural distortions and


induces metallic conductivity, indicating Ca2RuO4 to be barely
in the insulating regime.15
The n = 2 compound, Sr3Ru2O7, was at first the subject of
controversy. In the initial characterization,16 the magnetic
susceptibility was found to show a broad peak around 15 K,
accompanied by Curie–Weiss behavior at high temperatures,
yielding θCW = ⫺15 K and a large local moment of 2.5 µB/Ru. In
a subsequent study,17 using what were called “single crystals” of
Sr3Ru2O7, ferromagnetic (FM) ordering at 104 K was reported.
This result was not supported by neutron diffraction results 18
and was inconsistent with magnetic susceptibility data for
single crystalline Sr3Ru2O7 prepared by the floating-zone
method.19 Although it has never been conclusively established,
it is very likely that the problem with the reports of ferro-
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magnetism in this compound are due to the intergrowth of


layers of SrRuO3 or Sr4Ru3O10 in the Sr3Ru2O7 -intergrowth of
foreign stacking sequences within crystals of one dominant
member is not an uncommon phenomenon in Ruddlesden–
Popper phases. Overlooking the possible presence of such
intergrowth phases, and other types of non-uniformity in
“single crystals”, is a common problem in physicists’ work on
complex chemical systems; one that could be remedied
by improved interactions between solid state chemists and
physicists in this field.
The intrinsic properties of Sr3Ru2O7 illustrate the delicate
balance between competing electronic states in the ruthenates.
It possesses what appear to be incommensurate antiferro-
magnetic spin fluctuations,20 and electrical transport measure-
ments have been interpreted in terms of skew scattering by
Fig. 1 The crystal structures of (a) SrRuO3, (b) CaRuO3, (c) Sr2RuO4 magnetic fluctuations.21 The Hall coefficient can be decom-
and (d) Sr3Ru2O7. Large grey circles, Sr atoms, large grey circles; Ru posed into normal and anomalous parts – analogous to the
atoms, blue circles; O atoms, small red circles. RuO6 octahedra are case of skew scattering in heavy fermion compounds and
emphasized. ferromagnetic metals. Observations suggest that the magnetic
correlations in Sr3Ru2O7 at ambient pressure undergo a qualita-
been the subject of considerable study, and illustrates in a single tive change as the temperature is lowered. At higher temper-
chemical system the complexities that the ruthenates afford. atures they are dominated by ferromagnetic interactions, but at
Structurally consisting of single layers of corner-shared low temperatures the system crosses over to antiferromagnetic-
RuO6 octahedra, Sr2RuO4 has been found to be electronically like behavior. Further, a transition to a ferromagnetic state
quasi two-dimensional (2D) as well. The magnetic susceptibility (a metamagnetic transition) has been observed for fields above
is temperature independent, implying the presence of delocal- 5 T at low temperatures.22 When hydrostatic pressure is applied,
ized electrons, but the Sommerfeld parameter describing the a “T = 0 K” paramagnetic to ferromagnetic quantum phase
linear contribution to the specific heat at low temperatures is transition was also found, similar to that seen in Sr2RuO4,
approximately 40 mJ mol Ru⫺1 K⫺2,7 indicating an enhanced but with slightly lower critical pressure.19 Thus Sr3Ru2O7
mass for the conduction electrons. This degree of mass displays nearly the full range of possible electronic states seen in
enhancement is near the low end of Sommerfeld parameters ruthenates in a single compound.
displayed by materials with unusual electronic states. Beyond Ferromagnetism has been reported for Sr4Ru3O10 23 at 104 K,
that, NMR measurements have revealed strong orbital depend- but given all the problems with intergrowths in this system,
ent magnetic correlations 8 and inelastic neutron scattering further work is required to verify its intrinsic properties.
measurements find incommensurate, antiferromagnetic spin However, the reported T c falls nicely in the evolution from
fluctuations 9 in this compound. A “T = 0 K” paramagnetic to nonmagnetic to ferromagnetic behavior as the number of layers
ferromagnetic phase transition has been observed under increases.
applied pressure.10 These observations suggest that this material The three dimensional perovskite SrRuO3, T c = 160 K, is one
is schizophrenic indeed, being close to ferromagnetic, anti- of only a few known ferromagnets among the 4d transition
ferromagnetic, and superconducting instabilities that compete metal oxides.24 The 3D perovskites themselves provide another
for dominance. Surprisingly, substitution of small amounts of good illustration of the delicate balance involved in determin-
non-magnetic Ti for Ru in Sr2RuO4 has recently been shown to ing electronic states in the ruthenates, as there is an evolution
tip the balance in favor of a magnetically ordered state.11,12 This from ferromagnetism to paramagnetism between SrRuO3 and
also occurs for the CaRuO3 perovskite, as described below, and CaRuO3. CaRuO3, more structurally distorted than SrRuO3
may be a unique characteristic of the ruthenates. due to rotation of the RuO6 octahedra, displays Curie–Weiss
Ca2RuO4 has the same basic crystal structure as Sr2RuO4, but magnetic behavior with a significant negative Weiss temper-
due to the presence of the smaller Ca atom has a substantially ature (⫺200 K) but no magnetic ordering.25 It appears to be one
distorted crystal structure, with tilting and rotation of the RuO6 of the only materials known in which clear Curie–Weiss law
octahedra, making the compound a Mott insulator.13 A further behavior of the susceptibility with negative θCW does not imply
structural distortion has been found to accompany a transition the dominance of antiferromagnetic spin interactions.26
to an insulating antiferromagnetically ordered state at low Electronic band structure calculations indicate that SrRuO3 and
temperatures 14 – the first example in this review of a common CaRuO3 are poised between nearly energetically equivalent
theme in the ruthenates – that they display subtle and not yet antiferromagnetic and ferromagnetic ground states.27 Although
fully understood coupling between structural and electronic it is tempting to attribute the differences between these two
degrees of freedom. Sr substitution for Ca at a very low level, materials to the larger deviations of the Ru–O–Ru bond angles

2980 Dalton Trans., 2004, 2979–2987


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from the ideal 180⬚ in CaRuO3, this has not yet been fully charged ions on the A-site, – “charge disorder” on the magnet-
addressed theoretically for the 4d derived t2g orbitals and ically inactive site – can suppress ferromagnetism, even more
oxygen 2p orbitals involved in this case. Structure and magnet- strongly than changing the Ru–O–Ru bond angle.
ism are clearly deeply connected in the 3D ruthenate perov- I have been preaching for some years about the highly
skites, but in a subtle and as yet poorly understood manner. anomalous character of CaRuO3. More detailed investigation
CaRuO3, cited in the past as a simple paramagnetic material of its properties appears to me to be well warranted. The
with antiferromagnetic spin interactions, thus establishing a perovskite/Ruddlesden–Popper family illustrates fully the range
baseline for “normal” behavior in this system, is therefore in of unusual electronic states displayed by the ruthenates and
actuality quite problematic, and so the evolution of properties their sensitivity to temperature, pressure, disorder, dimension-
in the ruthenate perovskites is not even simple at the zero-order ality, and structural distortion. A full theoretical picture
level. that integrates all the observed behavior has not yet been
Recently, a new context for understanding CaRuO3 has been established. Continuing in-depth characterization of materials
proposed, in which it is considered to be a nearly ferromagnetic in this family will yield ample information to ground such a
metal, rather than a classical Curie–Weiss antiferromagnet.26,27 picture. For the ruthenates, however, many other structural
Small amounts of disorder introduced into CaRuO3 by partial families displaying unusual electronic states can also be studied.
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substitution of Ru by non-magnetic, isovalent Ti induce Some of those materials are described briefly in the following
clear ferromagnetic behavior at low temperatures: magnetic sections.
hysteresis loops are observed at 5 K for as little as 2% Ti
substitution.28 This is highly unusual behavior. CaRuO3 itself 3 Hexagonal perovskites
therefore seems to be in as yet not well understood electronic
state that can be tipped to ferromagnetism by the introduction Although chemically related to the strontium ruthenates,
of very small amounts of disorder in the Ru–O network. BaRuO3 displays crystal structures based on a distinctly
In one study 29 on these ruthenate perovskites, a previously different structure type, with no analogs in the Sr–Ru–O or
unobserved structure–property effect was uncovered when Ca–Ru–O systems. BaRuO3 has three crystallographic forms,
comparison was made between the magnetic properties and representatives of the “hexagonal Perovskite” family. Known as
structures of isoelectronic CaRuO3, SrRuO3, La0.5Na0.5RuO3, the 9-layer, 6-layer, and 4-layer compounds, they have different
and their solid solutions. Through chemical doping experi- amounts of corner- and face-sharing of RuO6 octahedra – in
ments, a stronger suppression of the ferromagnetism in SrRuO3 turn resulting in different relative contributions of Ru–Ru
through solid solution with La0.5Na0.5RuO3 than through and Ru–O–Ru interactions to the electronic structure. The
solid solution with CaRuO3 was found. Through determination properties differ considerably, even though the chemical
of the structures of the solid solutions in the SrRuO3– compositions are identical.
La0.5Na0.5RuO3 case and comparison to the known data for The crystal structures of the two most well characterized
SrRuO3–CaRuO3, the effects of structural distortion due to forms of BaRuO3 are shown schematically in Fig. 3.30,31 The
rotations of the RuO6 octahedra were normalized out (Fig. 2). more commonly found 9-layer (9L) form consists of units
The results show that solid solutions involving differently of three RuO6 octahedra sharing faces in a partial chain,
facilitating direct Ru–Ru d orbital interactions within the
group, with each of these triple units of octahedra connected to
its neighbors along the hexagonal axis by perovskite-like corner
sharing with nearly 180⬚ Ru–O–Ru bonds. The stacking pattern
repeats after nine octahedra. Similarly, the less common 4-layer
(4L) form consists of units of two octahedra sharing faces
connected to each other by perovskite-type corner sharing, with
a repeating stacking pattern along the hexagonal axis after four
octahedra. Thus the two forms differ in the relative amounts of
direct Ru–Ru and oxygen mediated Ru–O–Ru interactions.

Fig. 2 Comparison of the suppression of the ferromagnetism in


SrRuO3 for the charge-disordered SrRuO3–La0.5Na0.5RuO3 solid
solution and the conventional SrRuO3–CaRuO3 solid solution. Both
systems maintain the 4⫹ oxidation state of the Ru. The data
characterizing the magnetism (saturation magnetization and θCW) have
been plotted for the same degree of structural distortion (Ru–O–Ru
angle) in both systems. It can be seen that the structural distortion (data
labeled “SD”) from the ideal perovskite lattice with 180⬚ Ru–O–Ru
bonds suppresses the ferromagnetism, but that the off-site charge Fig. 3 The crystal structures of (a) 4-layer and (b) 9-layer BaRuO3.
disorder (data labeled “CD”) introduced by mixing in La3⫹ and Na⫹ on Large blue circles, Ba atoms; grey circles, Ru atoms; small red circles;
the Sr2⫹ site has an even stronger effect. O atoms. RuO6 octahedra are emphasized.

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The electrical resistivities of the 4-layer and 9-layer forms of of the 9L phase appear to be particularly sensitive to the level
BaRuO3 have been measured;32,33 representative data are shown of disorder in the sample. This, along with the absence of local
in Fig. 4. For both phases the room temperature resistivities are moment behavior, suggests a qualitative similarity to Sr2RuO4.
in the 200–500 µΩ cm range. The 4-layer phase shows metallic It would be of interest to see whether very high purity prepar-
behavior to low temperatures – residual resistivities on the ations may show superconductivity. If the electronic states are
order of 100 µΩ cm are seen. The inset to Fig. 4 shows that the indeed analogous in Sr2RuO4 and 4-layer and/or 9-layer
resistivities approximately follow the form ρ = ρ0 ⫹ AT2 at low BaRuO3, then one would have to conclude that the layered
temperatures along both characteristic directions. The 9-layer structure of the latter compound is not fundamental to its
variant shows at first a metallic resistivity with decreasing magnetic and electronic state, in spite of clear implications
temperature, but then a crossover to a more resistive phase at that can be drawn from comparison between phases in the
low temperatures. The resistivity does not continue to rise perovskite-based family. Further study of these phases would
below 10 K in the out-of plane direction, but rather saturates be of great interest.
to a maximum value. Both the 9L and 4L phases appear to be The 6-layer (6L) variant of BaRuO3 has not been character-
electronically isotropic.35 ized. However, it is possible to synthesize 6L phases stabilized
by the addition of a third metal element. These compounds
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have the hexagonal barium titanate structure type, with pairs of


face-shared RuO6 octahedra interconnected by corner-sharing
MO6 octahedra. This structure leads to a considerable amount
of regular perovskite character, with Ru–O–M–O–Ru angles
near 180⬚. The structure repeats every six layers of octahedra.
These compounds have the general formula Ba3MRu2O9 where
for the transition metals M = at least Mn, Fe, Co, Ni, Cu, and
Zn 37–41 (many other variants with M selected from other
elemental groups are also known): electronically active 3d
elements may therefore be present in addition to the Ru. The
compounds are all semiconductors, and, for the Cu, Ni and Co
analogs, there is a magnetic transition at approximately 100 K.
Unlike pure BaRuO3, then, in these compounds the Ru bears a
local moment. For Ba3CoRu2O9, for example, the ordered
magnetic moments determined 15 K are 2.8 and 1.3 µB for Co
and Ru, respectively.40,41 Comparing the magnetic properties of
these phases with those of BaRuO3 itself, it is seen that the
addition of the transition element (albeit in large proportions)
has induced local moment behavior on the Ru.
Although BaRuO3 itself is a metallic conductor, all of the
Fig. 4 The resistivities of 9-layer and 4-layer BaRuO3 for the in-plane
(perpendicular to c) and perpendicular-to-plane directions in the members of the M = 3d element Ba3MRu2O9 family are
hexagonal crystals, normalized to their 300 K resistivities to facilitate non-metallic.41 This result is not surprising for M = Zn because
comparison. Inset – the low-temperature resistivities of the 4-layer the zinc orbital–oxygen orbital overlap is expected to be poor.
phase plotted vs. T 2. For the other 3d metals, however, this is unexpected, as the
overlap should be better; nonmetallic behavior over a wide
The magnetic susceptibilities for both phases are small and range of electron counts is, however, observed. At room tem-
paramagnetic, and only weakly temperature dependent, con- perature the Ru–Ru distances between face shared octahedra
sistent with the full absence of local moment of the Ru ions. (∼2.6 Å) are short enough to allow good direct Ru orbital
The susceptibilities are due to Pauli paramagnetism of the overlap and sharing of electrons. The 180⬚ Ru–O–M–O–Ru
conduction electrons. The observed susceptibility values, bonds are expected to have the correct geometry to allow con-
∼3–8 × 10⫺4 emu mol-Ru⫺1 Oe, suggest a rather high density of duction through the octahedral site, thus coupling the
states at the Fermi level within the standard free-electron ruthenium dimers. This, however, does not seem to occur. The
model. For the 4L phase this would correspond to a linear term temperature dependence of the resistivities suggests that the M
in the specific heat (γ) of as much as 50 mJ mol⫺1 K⫺2. The atoms in the octahedral sites effectively lead to localization of
linear term can be lower if the susceptibility is enhanced by the charge carriers and isolation of the Ru dimers, implying
spin fluctuations. Interestingly, this estimate is consistent with that the energies of the 3d transition metal states are quite
the prefactor of the T 2 term in the resistivity for this phase, different from those of the Ru.
assuming that it is dominated by electron-electron scatter- There is substantially less detailed characterization of the
ing.34,35 For the 9-layer phase, the susceptibility is equivalent to hexagonal perovskites than of the usual perovskite phases.
that of the 4-layer phase at 400 K but then decreases smoothly Indications are that there are interesting electronic properties to
to approximately half that value by 4.2 K. Following the above be uncovered in this structural family with further work.
rationale, the average value would correspond to linear term in
the specific heat of as much as 30 mJ mol⫺1 K⫺2. Comparing
this with the directly measured specific heat result,36 one
4 Pyrochlores
concludes that the susceptibility for this phase is enhanced by a Compounds with the pyrochlore structure can be represented
factor of 3–4. by the general formula A2(B2O6)O⬘ – emphasizing that the
The residual resistivities, on the order of 100 µΩ cm, attri- structure consists of a rigid three-dimensional B2O6 network of
butable to impurity scattering, are very high, in comparison to corner-sharing BO6 octahedra, with A and O⬘ atoms occupying
superconducting Sr2RuO4 single crystals (where the residual interstitial sites. Oxygen vacancy formation, if it occurs, prefers
resistivity is about 1 µΩ cm 1). The T 2 behavior in resistivity at the interstitial O⬘ site. The chemical variables commonly used
low temperatures in the 4L phase indicates Fermi liquid to modify the physical properties of these compounds are
behavior. In the 9L form, after an initially metallic behavior, oxygen vacancy content and metal-site substitution.42 The B2O6
a transition to a more resistive state is observed, apparently array of the pyrochlore structure is shown in Fig. 5.
accompanied by the development of a very small ferromagnetic The electronic properties of the ruthenate pyrochlores are
moment parallel to the chain direction. Further, the properties not comprehensively understood, though they have been of

2982 Dalton Trans., 2004, 2979–2987


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erties of Y2Ru2O7. In fact, the electronic structure calculations


suggest that Y2Ru2O7 should be weakly metallic, similar to
Bi2Ru2O7. One factor such calculations do not include is
electron–electron correlation. Recently Y2Ir2O7 was found to be
a Mott–Hubbard insulator, which is a direct result of electronic
correlation.49 However, in that pyrochlore, iridium is in d5
electronic configuration, yielding a one electron half-filled a1g
band, expected to maximize the influence of correlations. In
Bi2Ru2O7, ruthenium is d4 with one electron fewer; therefore
electronic correlation should be reduced.
Bi2Ru2O7 is a poor metal, with paramagnetic magnetic
susceptibility, and the experimentally determined density of
states at EF is reported as ∼4 states/eV-Ru.50 We proposed that
the t2g band splitting intrinsic to the D3d Ru-site symmetry leads
to the low value of N(EF) and semi-metallic character for
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Fig. 5 The pyrochlore crystal structure of Bi2Ru2O7. Bi atoms, large Bi2Ru2O7. The Fermi level in Bi2Ru2O7 lies in a sharp density of
grey circles, Ru atoms, small purple circles, O atoms, small red circles. states valley, and subtle changes such as A-site disorder may
RuO6 octahedra are emphasized. have a dramatic effect on the electronic properties. While the
electronic properties of Bi2Ru2O7 are nicely explained in a
interest for some time.43 Bi2Ru2O7 and Pb2Ru2O6.5 are weakly conventional band picture, the electronic properties of Y2Ru2O7
metallic, displaying no local moment on Ru and temperature are not. Unlike CaRuO3, Bi2Ru2O7 cannot be made to display
independent resistivities over a broad temperature range. ferromagnetism by small percentages of substitution of foreign
Conversely, Y2Ru2O7 and the Ln2Ru2O7 series are insulators, atoms,51 suggesting that ruthenates in the pyrochlore structure
although formally isostructural and isoelectronic to their are very far from the kinds of magnetic instabilities and exotic
metallic counterparts. Some publications consider the small electronic states that make the perovskite phases so interesting.
Ru–O–Ru bond angle for lanthanide and yttrium pyrochlores Aside from figuring out for certain the cause of the insulating
as a possible explanation for their decreased conductivity: 44,45 behavior in the Ln2Ru2O7 variants, the ruthenate pyrochlores
as the bond angle decreases, orbital overlap will also decrease, have not yet shown the kind of properties that suggest they are
resulting in a narrowed band and decreased mobility. However, worthy of continuing detailed study.
the difference in Ru–O–Ru bond angle between metallic
Bi2Ru2O7 and non-metallic Pr2Ru2O7 is less than 2⬚, making it
unlikely that this is the primary reason for the difference in 5 Hollandites
properties. It has also been proposed that hybridization of Bi The tetragonal hollandite crystal structure consists of double
and Ru states present at the Fermi energy in Bi2Ru2O7 leads to a chains of edge sharing RuO6 octahedra running parallel to the
wider conduction band relative to pyrochlores with lanthanide crystallographic c axis (Fig. 6). Alkali or alkaline earth atoms
A-site elements.46 occupy large tunnels running in the same direction.52 These
The RuO6 coordination polyhedron in Bi2Ru2O7 has been tunnels may be occupied in the relative proportion 1 : 6 or 1 : 4,
described as a regular octahedron (symmetry Oh). More yielding for example ruthenate hollandites with the formulas
precisely, however, the symmetry is trigonal antiprismatic BaRu6O12 and KRu4O8. These have formal Ru oxidation states
(symmetry D3d). There is a compression of the ideal octahedron of 3.67⫹ and 3.75⫹, respectively. The structure is highly
along a three-fold axis. The degree of compression can be one-dimensional in character. 1D metals are an important in
measured by the angle (α) between the three-fold symmetry axis contemporary condensed matter physics: electron–electron
and the Ru–O bond. In an ideal octahedron, α = 54.7⬚, while in interactions in 1D can lead to a breakdown of Fermi liquid
Bi2Ru2O7, α ∼ 58.5. For Ru4⫹, which has four t2g electrons, this theory. The hollandites provide the opportunity to study these
distortion and lowering of symmetry can cause what would be a unusual 1D phenomena in ruthenates.
partially filled band for a regular octahedron to split into a
completely filled band and an empty band for a triangular
antiprism.42,47
Electronic band structure calculations performed for
Bi2Ru2O7 showed that the ruthenium t2g states are split, in good
agreement with what is expected for D3d symmetry.48 The Fermi
energy (EF) lies at the top of a filled band (eg⬘) of four electrons
per ruthenium, while directly above EF an empty band (a1g) is
found which can accommodate two electrons per ruthenium.
These bands overlap slightly, and the density of states at
the Fermi energy is lowered almost to zero. The Bi2Ru2O7
pyrochlore can therefore be classified as a semi-metal. Similar
Fig. 6 The hollandite crystal structure. The double chains of edge
band splitting occurs for Y2Ru2O7, Ln2Ru2O7 and others.
shared RuO6 octahedra are shown. The large one-dimensional tunnels
The Ru–O–Ru angle between corner-shared octahedra is are also seen. The large “A” ions (grey circles) occupy these tunnels in
120⬚ in Y2Ru2O7 and 133⬚ in Bi2Ru2O7. This difference has different proportions with different periodicities along the RuO2 chain
several effects on the electronic structure. The primary effect is direction.
that in Y2Ru2O7, there is a 1 eV gap between the split ‘t2g’
band and the higher energy eg band. In Bi2Ru2O7, where the Fig. 7(a) shows the temperature dependences of the resistivity
Ru–O–Ru angle is increased, the two bands overlap somewhat. parallel and perpendicular to the ruthenium–oxygen chains in
Secondly, the overall band width of calculated ‘t2g’ states for BaRu6O12.53 The resistivity along the chains is metallic over the
Bi2Ru2O7 is ∼2 eV, while in Y2Ru2O7 the band width is about whole temperature range (0.3–300 K), showing slope changes
1.5 eV. This narrowing effect would be less pronounced in around 210 and 100 K (Fig. 2(a)). The magnetic susceptibility
Pr2Ru2O7, also an insulator, where the difference in Ru–O–Ru χ(T ) exhibits similar features around the same temperatures.53
angle from that in Bi2Ru2O7 is smaller. It is not clear whether Interestingly, a semiconducting to metallic crossover in the
the 25% decrease in band width can cause the insulating prop- a-axis resistivity is seen around 210 K. The high temperature

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electronic character. It is not known why there is such a


dramatic difference in properties between the BaRu6O12 and
alkali ruthenate hollandites, but it may be related to the differ-
ent ratio of A ions to RuO2 units: the different A atom
periodicities (and charges) along the tunnels likely impose
different periodic potentials on the Ru–O chains, possibly
influencing the properties. Further work to establish the nature
of the unconventional electronic state of BaRu6O12 would be of
considerable interest.

6 La3Ru3O11 and La4Ru6O19


In all the perovskite-based families, the magnetic and electronic
character derives from the special characteristics of transition
metal–oxygen orbital hybridization. The ruthenates are distinct
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Fig. 7 Temperature dependence of the electrical resistivity with from many 3d-based chemical systems, as structure types other
current flowing parallel (ρc) and perpendicular (ρa) to the Ru–O chain
direction for BaRu6O12.
than classical perovskites are relatively straightforward to
synthesize. Two such materials are La4Ru6O19 and La3Ru3O11.
behavior shows that the electronic system at high temperatures The crystal structures of La4Ru6O19 57 and La3Ru3O11 58 are
is effectively 1D. As the temperature is lowered, the interchain derivatives of the cubic KSbO3 structure type, which is known
coupling increases, leading to a 1D to 3D crossover in to compete with perovskites for stability in several chemical
properties and metallic resistivity perpendicular to the chain systems. The structure of both compounds contains pairs of
direction at low temperatures edge-shared RuO6 octahedra, effectively forming Ru2O10
The resistivity of BaRu6O12 is sensitive to disorder.53 The dimers, which are connected to other dimers through corner-
value of the residual resistivity ratio (RRR), quantifying the shared oxygen. The structures are shown in Fig. 8(a) and (b).
level of disorder, was found to vary from crystal to crystal, The result is a 3D Ru–O network. The formal Ru oxidation
ranging from 11.3 to 2.6 among 50 crystals measured. All sam- state is ⫹4.33. La3Ru3O11 and La4Ru6O19 therefore have an
ples measured down to 0.3 K showed a drop in ρ| |(T ) below identical Ru–O network geometry and identical formal Ru
2 K. The sharpness and the relative size of the drop, as well as oxidation state. In La4Ru6O19, the Ru–Ru distance across the
the slope above the drop, depended sensitively on the “RRR”. shared edge of the octahedra in the dimers is 2.49 Å, smaller
(RRR, the residual resistivity ratio, is the ratio of the resistivity than the shortest Ru–Ru distance in Ru metal (2.65 Å) or that
at 300 K to the resistivity at 4.2 K. Because the low-temperature in RuO2 (3.11 Å), indicating the presence of Ru–Ru bonding. In
resistivity is largely determined by impurity scattering the RRR La3Ru3O11, in contrast, the Ru–Ru distance in the dimers is very
is a good measure of sample purity.) large, indicating that no metal-metal bonding is present.
It has been proposed 53 that the observed properties indicate
that there is a quantum phase transition 54 in BaRu6O12. A
slightly increasing resistivity seen in the RRR = 2.6 sample
above the 2-K resistivity drop suggests that a weakly localized
ground state might be present in this material, induced by
disorder. Further, in the high RRR sample, application of a
magnetic field suppresses the resistivity drop, resulting in an
upturn on decreasing temperature. The characteristic temper-
ature below which the resistance shows an upturn increases as
the field increases, showing that the field stabilizes the tendency
toward electron localization. The observed change in resistivity,
tuned by a magnetic field, was proposed to be a true quantum
phase transition between two fundamentally different ground
states – one metallic and the other weakly localized. The
magnetic field induced weakly localized ground state in
BaRu6O12 is unique among ruthenates.
Surprisingly, the electronic behavior of the alkali hollandites,
typified by KRu4O8 and RbRu4O8, is completely different.55 Fig. 8 Two crystallographic units cells of (a) La4Ru6O19 and (b)
La3Ru3O11. RuO6 octahedra are shown as shaded polyhedra (with Ru
The susceptibilities of KRu4O8 and RbRu4O8 are basically tem- inside). A virtually identical Ru–O network is seen for each. La and
perature independent, with small magnitudes, on the order of non-network O are shown by closed and open circles, respectively.
1 × 10⫺4 emu mol Ru⫺1 Oe⫺1, consistent with temperature
independent Pauli paramagnetism. KRu4O8 and RbRu4O8 are Electronic structure calculations 59 on La3Ru3O11 show a
good metallic conductors, with reasonable RRR, between manifold of delocalized states (broad bands several eV wide) –
40 and 50. Their residual resistivities are very small, on the similar to those seen in ruthenate perovskites, due to strong
order of 3 µΩ cm⫺1 at 4 K – not quite in the range needed to Ru–O orbital hybridization. However, similar calculations for
observe superconductivity in Sr2RuO4 56 but very good. For La4Ru6O19 revealed not only the presence of the usual Ru–O
KRu4O8, a low-resistivity sample cooled down to 0.3 K showed derived broad bands, but also additional localized electronic
no anomalous behavior of any kind, in sharp contrast to the states (narrow bands) near the Fermi energy. Analysis has
case of the BaRu6O12 hollandite. Specific heat measurements shown that the localized states originate from the Ru–Ru bonds
revealed that the Sommerfeld parameter γ is approximately the in the dimers in La4Ru6O19. Thus both localized and delocalized
same for both KRu4O8 and RbRu4O8, given by γ = 3 mJ mol electronic states are expected to be present near the Fermi
Ru⫺1 K⫺2. This suggests only minimal enhancement of the energy in this material. The result is a unique compound – with
carrier mass compared to the free electron mass, and is con- both localized and delocalized states coming from different
siderably lower, for example, than the 40 mJ mol Ru⫺1 K⫺2 kinds of orbitals derived from the same atoms.
found for Sr2RuO4.7 Thus of all the known ruthenates, the While La3Ru3O11 displays electronic and magnetic behavior
alkali hollandites appear to be the most conventional in typical of metallic oxides, La4Ru6O19 has a number of highly

2984 Dalton Trans., 2004, 2979–2987


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unusual electronic properties.60 At room temperature, the resist- magnetic phase transition at low temperatures, in which the
ivity is 2.5 mΩ cm, much larger than the ∼10⫺5 Ω cm typically magnetic moment of Ru is largely lost. Similar to Sr3Ru2O7,
observed for RuO2. Below 30 K, a linear T -dependence in which has double (100) perovskite planes of RuO6 octahedra,
resistivity is observed. Linear resistivity is frequently cited as La4Ru2O10 contains double (110) perovskite planes (Fig. 10).
one of the characteristics of the cuprate superconductors La4Ru2O10 has two closely related crystal structures: a mono-
(where it persists to much higher temperatures) that show that clinic structure at high temperature and a triclinic structure at
they are unconventional materials. Specific heat measurements low temperature. The structural transition between the two
revealed that C(T )/T of La4Ru6O19 at H = 0 displays a mini- forms at 170 K results in a slight atomic displacement that leads
mum around 5 K, which rises below 1 K with a ln T behavior to an ordered array of long and short O–Ru–O bonds within
and approaches a value of ∼60 mJ mol Ru⫺1 K⫺2 at low temper- the double perovskite planes.
atures (Fig. 9). The magnetic susceptibility also shows unusual
behavior. These features observed for La4Ru6O19 are quite
similar to those of the intermetallic, heavy Fermion com-
pounds. Both the linear T -dependence resistivity and T ln T
behavior in specific heat were found in CeCu6⫺xAux, the canon-
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ical example of a system close to a “quantum critical point”


between an antiferromagnetically ordered and non-magnetic
ground state.61 Therefore the linear resistivity and T ln T
behavior in specific heat have been taken as primary indications
of non-Fermi liquid behavior in La4Ru6O19, yet another strange
electronic ground state engendered in ruthenates.

Fig. 10 Comparison of the layered crystal structures of Sr3Ru2O7 and


La4Ru2O10. In the former, the layers of RuO6 octahedra are 100
perovskite layers. In the latter, the layers are of the 110 perovskite type.

The formal valence for Ru in La4Ru2O10 is 4⫹, yielding four


electrons in t2g orbitals. Magnetic susceptibility measurements
reveal Curie–Weiss behavior at temperatures above 170 K, with
θCW = ⫺71 K, and a moment of 2.53 µB, close to that for the
expected S = 1 spin configuration of Ru4⫹. For the low-T phase,
Curie–Weiss behavior was again observed, but with θCW = ⫺23
K, and a much reduced moment of 0.39 µB, corresponding
roughly to an S = 0 spin configuration. A dramatic loss of local
magnetic moment has therefore occurred at the structural phase
transition.
Fig. 9 The specific heat data for La4Ru6O19 in various applied fields. In both crystal structures, even considering crystal field
Inset: raw data. Main panel, the data with the Schottky anomaly due effects brought on by the low symmetry, band structure calcu-
to the nuclear spin component subtracted. The ln T dependence of the lations suggest that La4Ru2O10 should be metallic. However,
H = 0 data at low temperatures is emphasized with a dashed line. resistivity measurements showed that both the high-T phase
and low-T phase are insulating. At high temperatures, the
Metal-metal bonding is known to be present in many 4d and resistivity follows an Arrhenius behavior, ρ(T ) ∼ exp(T 0/T ),
5d transition metal oxides. The electronic consequences of the with T 0 values near 1100 K, corresponding to a band gap of
formation of localized states due to the presence of metal-metal approximately 0.1 eV. Below T = 160–170 K, the Arrhenius law
bonding have not been well explored in the context of con- was not found to describe the temperature dependence well.
temporary condensed matter physics. The large size of the The observation of insulating behavior with a well-defined gap
relevant orbitals typically results in wide bands in itinerant 4d indicates that the simple electron band picture that works well
and 5d transition metal oxides, leading to a large kinetic energy. for some ruthenates is not applicable to La4Ru2O10, most likely
From the physics point of view, the driving force for the local- due to the presence of strong Coulomb interactions.
ization of electrons in these compounds must ultimately be The magnetic transition is coupled to a subtle structural
related to the reduction of kinetic energy. The price to pay for distortion in which a slight atomic displacement leads to an
the localization is the increase in repulsive Coulomb inter- ordered array of long and short O–Ru–O bonds (Fig. 11). This
action, which can apparently be minimized through many-body type of magnetic transition–structural transition coupling has
screening by other conduction electrons originating from been of considerable interest recently in other classes of
metal–oxygen bonding. The delicate balance between these two materials, such as the manganate perovskites. La4Ru2O10
tendencies of electronic motion, localized vs. itinerant, has been appears to be the first clear example of orbital ordering in
proposed to place the system at a “self-organized” critical state. ruthenium based oxides, i.e. where energetically degenerate
Such a unique situation may lead to novel collective occupied sub-orbitals order in specific directions in a crystal
phenomena. La4Ru6O19 clearly falls in the class of the most structure. La4Ru2O10 displays orbital ordering in 4d t2g orbitals
exotic of the ruthenates in terms of its electronic properties. rather than 3d eg orbitals, as has been observed in other com-
pounds and so is representative of a new class of materials.
Such an “orbital ordering” affect, a topic of considerable
7 La4Ru2O10 62 current interest for 3d oxides, is quite surprising to find in a 4d
As a final example, I describe a new layered compound, oxide where the orbitals are expected to be more diffusely
La4Ru2O10, which has been found to display an unusual distributed.

Dalton Trans., 2004, 2979–2987 2985


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12 K. Pucher, J. Hemberger, F. Mayr, V. Fritsch, A. Loidl,


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