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Contemporary Superconducting Materials View Online 40TH ANNIVERSARY ARTICLE www.rsc.org/chemcomm | ChemComm Contemporary superconducting materials R. J. Cava DOI: 10.1039/b512643f Superconductors currently under active study are briefly described from a chemical perspective. The author’s current views on those superconductors, the role of theory in searching for new superconductors, and possibilities for new superconducting materials that might be found in the future are presented. Introduction field, and have also found new super- complexity for the kinds of relatively conductors, both in focused searches simple compounds that can support New superconductors are currently being and by accident in synthetic programs superconductivity. Some materials of discovered in the world at about the with other goals. Many excellent, detailed current interest are described in the rate of 2 to 4 per year. Although the reviews of superconductivity and the following. transition temperature to the zero resis- known superconducting materials are tance state is a critical characteristic, 1–5 available (see e.g. ). This brief essay Sr2RuO4 other characteristics such as critical is directed at the chemical reader inter- The magnetic properties of ruthenium- current, critical magnetic field, and pro- ested in learning about recently dis- based oxides range from ferromagnetism cessability are equally important for covered superconducting materials, to antiferromagnetism to Pauli paramag- possible applications. From a scientific and considering some speculations of netism, and the electronic properties perspective, the underlying cause of mine about the possibilities for new range from insulating to metallic. This superconductivity can often raise fore- superconductors. front issues in condensed matter physics, unusually wide variation comes from the and has been investigated actively for fact that Ru–O networks are poised at Recently discovered the cusp between localized and deloca- many materials—ranging from those superconductors lized electron behavior, with strong with T s as low as 1 K (e.g. Sr RuO ) c 2 4 Ru–O orbital hybridization. Further, to those with Tcs above 100 K (e.g. the From the chemist’s perspective, the most Downloaded on 05 January 2011 ferromagnetic and antiferromagnetic copper oxide superconductors). The interesting superconductors are those states at low temperatures are close search for new superconductors has for which many chemical or structural Published on http://pubs.rsc.org | doi:10.1039/B512643F in energy. The CaO and SrO-based largely been the domain of condensed variants can be found. Disappointingly, Ruddlesden Popper (AO) (RuO ) matter physicists knowledgeable in the the superconductors found in recent n+1 2 n series embodies all this complexity in synthesis of intermetallic or oxide com- years have either literally been ‘‘one a single family. Ca3Ru2O7 is a Mott– pounds. Chemists have much to offer the of a kind’’ or very nearly so. I remain Hubbard insulator, CaRuO3 is a optimistic that new families remain to be paramagnet that can be tipped into found, but it could be that our searches Department of Chemistry, Princeton Institute ferromagnetism with slight chemical are pushing into the periphery of the for the Science and Technology of Materials, doping, SrRuO3 is a ferromagnet, Princeton University, Princeton, NJ, USA stability and chemical and structural Sr3Ru2O7 is a metamagnet (becomes ferromagnetic, but only under a modest Robert Cava is Chair of the Depart- applied field) and Sr2RuO4 (Fig. 1) is 6 ment of Chemistry at Princeton and a superconducting at 1 K. There has been Professor in Chemistry and Materials. a remarkable amount of work on this He is a Fellow of the American superconductor in the past decade (see, Physical Society and the American e.g. ref. 7). It looks like the super- Ceramic Society, and a member of the conducting wave function has p-wave US National Academy of Sciences. He symmetry, implying that the super- was Acting Director of the Princeton conductivity is a result of a ferromag- Materials Institute from 2001 to 2002. netic-like interaction between electrons. He began at Princeton in 1997 after Perhaps surprisingly, this 1 K super- working at Bell Laboratories from 1979 to 1997, where he was a Distinguished conductivity has motivated the study Member of Technical Staff. He was and discovery of many new ruthenium a National Research Council oxides. The delicately sensitive super- Postdoctoral Fellow at NIST from conductivity of this type (a few hundred 1978 to 1979 after receiving his Ph.D. parts per million impurities are sufficient in Ceramics from MIT in 1978. to kill it—a purity level not commonly achieved in synthesis of complex oxides) This journal is ß The Royal Society of Chemistry 2005 Chem. Commun., 2005, 5373–5377 | 5373 View Online Fig. 2 The layered crystal structure of MgB2, recently discovered to be superconducting at 39 K, a compound that has been available for purchase from chemical suppliers for many years. (The red spheres are B and the blue spheres are Mg). This structure type, which contains honeycomb layers of boron structurally and electronically analogous to graphite, is found for many transition metal and lanthanide borides. In the case of MgB2, a critical deviation from full transfer of charge from Mg to B results in the presence of holes in the sigma bonding orbitals of the B honeycomb layer. In contrast, these sigma orbitals are filled in graphite, and superconductivity occurs at lower temperatures when electrons are doped into states that are not as effectively coupled to the lattice vibrations. Fig. 1 The layered crystal structure of the 1 K superconductor Sr2RuO4. (The Sr are shown as large blue spheres and the diboride superconductors Nb12xB2 and transform for example from one to RuO6 octahedra are shown as polyhedra; (Zr,Mo)B2 (with Tcs less than 10 K) have another via simple chemical or physical the Ru are internal to the octahedra and been known since the 1960s, but MgB is means. In recent years fundamental the O are small red spheres). The low 2 special because no d orbitals are involved research has been performed on a hand- temperature superconductivity in this compound is only seen in crystals with in the electronic system. In the crystal ful of materials where the two states are unusually high purity and is believed to structure (Fig. 2), the boron forms a very nearly perfectly balanced. From my be unconventional in character. This honeycomb plane, analogous to the C viewpoint, ZrZn2 is the most interesting structure type is commonly found for layers in graphite. The magnesium forms of these.10 It is very weakly ferromag- transition metal oxides, and many studies a triangular layer between the B layers. If netic, with a small ordered magnetic of two-dimensional conductivity and MgB2 were strictly ionic, then it would be moment and a ferromagnetic ordering Downloaded on 05 January 2011 magnetism have been performed on isoelectronic with graphite. Critically, the temperature of 28 K (note that it is made compounds like this one. The first of the Mg to B charge transfer is not complete, from non-ferromagnetic elements) but Published on http://pubs.rsc.org | doi:10.1039/B512643F ‘‘High Tc superconductors’’ discovered, and the in-plane boron–boron sigma La Ba CuO , has the same basic also, while ferromagnetic, becomes 1.85 0.15 4 states, which are filled in the case of crystal structure, with some subtle but superconducting at 0.3 K (!). Under a important differences due to the differ- graphite, are only partly filled in the case modest applied pressure, both the ferro- ence in d orbital occupancy. of MgB2, leading to metallic conduc- magnetism and superconductivity go tivity. The modulation of the in-plane away at the same time, indicating that B–B bonds by a phonon therefore they are intimately coupled. Related strongly impacts the electronic system, 11 behavior is seen for UGe2, where has so far made Sr2RuO4 one of a kind: and gives rise to the very high Tc. ferromagnetism transforms into 1 K superconducting Sr2RuO4 can only be Surprisingly, there appear to be two superconductivity under applied pres- obtained in crystals grown by the float- superconducting systems of electrons in sure, though the presence of the magnetic ing zone method, a method that naturally MgB2—the pi electron states give rise state in the ambient pressure material results in zone-refining of a crystal’s to a lower energy system of super- is less surprising in this case, as U impurity content. conducting carriers as well! The conse- often displays a local magnetic moment. quences of this are still under study. These materials have suggested an MgB 2 Maddeningly, this important super- interesting new class of superconductors conductor is one of a kind—no addi- MgB is an interesting case, and with a that is likely to have more members— 2 tional new superconductors with high T s T of 39 K8,9 can be considered the c marginally magnetic materials where c grew from its discovery. ultimate electron–phonon coupled super- subtle changes in pressure or temperature conductor. It was discovered to be super- tip the balance to marginal super- ZrZn , UGe conducting in 2001 after being available 2 2 conductivity. These are classic examples as a commercial chemical reagent for Magnetic ordering and superconduc- of materials that display a ‘‘quantum several decades. This is an example of tivity are both cooperative states of critical point’’—materials that display a the surprises in store in this field: who electrons at low temperatures, and there- crossover in physical properties very could imagine that a simple binary fore in some cases can be competitors. near zero Kelvin, where quantum 12 compound with a Tc of nearly 40 K For almost all materials, one state is the effects must rule. Surprisingly, highly could lie undiscovered for so long? The clear winner, and it is not possible to unexpected properties are found in such 5374 | Chem.
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