A hidden pseudogap under the 'dome' of superconductivity in electron-doped high-temperature superconductors

The ground state of superconductors is characterized by the long-range order of condensed Cooper pairs: this is the only order present in conventional superconductors. The high-transition-temperature (high-T(c)) superconductors, in contrast, exhibit more complex phase behaviour, which might indicate the presence of other competing ground states. For example, the pseudogap--a suppression of the accessible electronic states at the Fermi level in the normal state of high-T(c) superconductors-has been interpreted as either a precursor to superconductivity or as tracer of a nearby ground state that can be separated from the superconducting state by a quantum critical point. Here we report the existence of a second order parameter hidden within the superconducting phase of the underdoped (electron-doped) high-T(c) superconductor Pr2-xCe(x)CuO4-y and the newly synthesized electron-doped material La2-xCe(x)CuO4-y (ref. 8). The existence of a pseudogap when superconductivity is suppressed excludes precursor superconductivity as its origin. Our observation is consistent with the presence of a (quantum) phase transition at T = 0, which may be a key to understanding high-T(c) superconductivity. This supports the picture that the physics of high-T(c) superconductors is determined by the interplay between competing and coexisting ground states.     

Magnetic-field-induced charge-stripe order in the high-temperature superconductor YBa2Cu3Oy

Electronic charges introduced in copper-oxide (CuO(2)) planes generate high-transition-temperature (T(c)) superconductivity but, under special circumstances, they can also order into filaments called stripes. Whether an underlying tendency towards charge order is present in all copper oxides and whether this has any relationship with superconductivity are, however, two highly controversial issues. To uncover underlying electronic order, magnetic fields strong enough to destabilize superconductivity can be used. Such experiments, including quantum oscillations in YBa(2)Cu(3)O(y) (an extremely clean copper oxide in which charge order has not until now been observed) have suggested that superconductivity competes with spin, rather than charge, order. Here we report nuclear magnetic resonance measurements showing that high magnetic fields actually induce charge order, without spin order, in the CuO(2) planes of YBa(2)Cu(3)O(y). The observed static, unidirectional, modulation of the charge density breaks translational symmetry, thus explaining quantum oscillation results, and we argue that it is most probably the same 4a-periodic modulation as in stripe-ordered copper oxides. That it develops only when superconductivity fades away and near the same 1/8 hole doping as in La(2-x)Ba(x)CuO(4) (ref.?1) suggests that charge order, although visibly pinned by CuO chains in YBa(2)Cu(3)O(y), is an intrinsic propensity of the superconducting planes of high-T(c) copper oxides.     

Superconductivity phase diagram of Na(x)CoO2*1.3H2O

The microscopic origin of superconductivity in the high-transition-temperature (high-T(c)) copper oxides remains the subject of active inquiry; several of their electronic characteristics are well established as universal to all the known materials, forming the experimental foundation that all theories must address. The most fundamental of those characteristics, for both the copper oxides and other superconductors, is the dependence of the superconducting T(c) on the degree of electronic band filling. The recent report of superconductivity near 4 K in the layered sodium cobalt oxyhydrate, Na(0.35)CoO2*1.3H2O, is of interest owing to both its triangular cobalt-oxygen lattice and its generally analogous chemical and structural relationships to the copper oxide superconductors. Here we show that the superconducting T(c) of this compound displays the same kind of behaviour on chemical doping that is observed in the high-T(c) copper oxides. Specifically, the optimal superconducting T(c) occurs in a narrow range of sodium concentrations (and therefore electron concentrations) and decreases for both underdoped and overdoped materials, as observed in the phase diagram of the copper oxide superconductors. The analogy is not perfect, however, suggesting that Na(x)CoO2*1.3H2O, with its triangular lattice geometry and special magnetic characteristics, may provide insights into systems where coupled charge and spin dynamics play an essential role in leading to superconductivity.     

Negative lattice expansion from the superconductivity--antiferromagnetism crossover in ruthenium copper oxides

The mechanism of high-transition-temperature (high-T(c)) superconductivity in doped copper oxides is an enduring problem. Antiferromagnetism is established as the competing order, but the relationship between the two states in the intervening 'pseudogap' regime has become a central puzzle. The role of the crystal lattice, which is important in conventional superconductors, also remains unclear. Here we report an anomalous increase of the distance between copper oxide planes on cooling, which results in negative thermal volume expansion, for layered ruthenium copper oxides that have been doped to the boundary of antiferromagnetism and superconductivity. We propose that a crossover between these states is driven by spin ordering in the ruthenium oxide layers, revealing a novel mechanism for negative lattice expansion in solids. The differences in volume and lattice strain between the distinct superconducting and antiferromagnetic states can account for the phase segregation phenomena found extensively in low-doped copper oxides, and show that Cooper pair formation is coupled to the lattice. Unusually large variations of resistivity with magnetic field are found in these ruthenium copper oxides at low temperatures through coupling between the ordered Ru and Cu spins.     

Resonance in the electron-doped high-transition-temperature superconductor Pr0.88LaCe0.12CuO4-delta

In conventional superconductors, the interaction that pairs the electrons to form the superconducting state is mediated by lattice vibrations (phonons). In high-transition-temperature (high-T(c)) copper oxides, it is generally believed that magnetic excitations might play a fundamental role in the superconducting mechanism because superconductivity occurs when mobile 'electrons' or 'holes' are doped into the antiferromagnetic parent compounds. Indeed, a sharp magnetic excitation termed 'resonance' has been observed by neutron scattering in a number of hole-doped materials. The resonance is intimately related to superconductivity, and its interaction with charged quasi-particles observed by photoemission, optical conductivity, and tunnelling suggests that it might play a part similar to that of phonons in conventional superconductors. The relevance of the resonance to high-T(c) superconductivity, however, has been in doubt because so far it has been found only in hole-doped materials. Here we report the discovery of the resonance in electron-doped superconducting Pr0.88LaCe0.12CuO4-delta (T(c) = 24 K). We find that the resonance energy (E(r)) is proportional to T(c) via E(r) approximately 5.8k(B)T(c) for all high-T(c) superconductors irrespective of electron- or hole-doping. Our results demonstrate that the resonance is a fundamental property of the superconducting copper oxides and therefore must be essential in the mechanism of superconductivity.     

Plutonium-based superconductivity with a transition temperature above 18 K

Plutonium is a metal of both technological relevance and fundamental scientific interest. Nevertheless, the electronic structure of plutonium, which directly influences its metallurgical properties, is poorly understood. For example, plutonium's 5f electrons are poised on the border between localized and itinerant, and their theoretical treatment pushes the limits of current electronic structure calculations. Here we extend the range of complexity exhibited by plutonium with the discovery of superconductivity in PuCoGa5. We argue that the observed superconductivity results directly from plutonium's anomalous electronic properties and as such serves as a bridge between two classes of spin-fluctuation-mediated superconductors: the known heavy-fermion superconductors and the high-T(c) copper oxides. We suggest that the mechanism of superconductivity is unconventional; seen in that context, the fact that the transition temperature, T(c) approximately 18.5 K, is an order of magnitude greater than the maximum seen in the U- and Ce-based heavy-fermion systems may be natural. The large critical current displayed by PuCoGa5, which comes from radiation-induced self damage that creates pinning centres, would be of technological importance for applied superconductivity if the hazardous material plutonium were not a constituent.     

Spin correlations in the electron-doped high-transition-temperature superconductor Nd2-xCexCuO4+/-delta

High-transition-temperature (high-T(c)) superconductivity develops near antiferromagnetic phases, and it is possible that magnetic excitations contribute to the superconducting pairing mechanism. To assess the role of antiferromagnetism, it is essential to understand the doping and temperature dependence of the two-dimensional antiferromagnetic spin correlations. The phase diagram is asymmetric with respect to electron and hole doping, and for the comparatively less-studied electron-doped materials, the antiferromagnetic phase extends much further with doping and appears to overlap with the superconducting phase. The archetypal electron-doped compound Nd2-xCexCuO4+/-delta (NCCO) shows bulk superconductivity above x approximately 0.13 (refs 3, 4), while evidence for antiferromagnetic order has been found up to x approximately 0.17 (refs 2, 5, 6). Here we report inelastic magnetic neutron-scattering measurements that point to the distinct possibility that genuine long-range antiferromagnetism and superconductivity do not coexist. The data reveal a magnetic quantum critical point where superconductivity first appears, consistent with an exotic quantum phase transition between the two phases. We also demonstrate that the pseudogap phenomenon in the electron-doped materials, which is associated with pronounced charge anomalies, arises from a build-up of spin correlations, in agreement with recent theoretical proposals.     

Origin of the metallic properties of heavily boron-doped superconducting diamond

The physical properties of lightly doped semiconductors are well described by electronic band-structure calculations and impurity energy levels. Such properties form the basis of present-day semiconductor technology. If the doping concentration n exceeds a critical value n(c), the system passes through an insulator-to-metal transition and exhibits metallic behaviour; this is widely accepted to occur as a consequence of the impurity levels merging to form energy bands. However, the electronic structure of semiconductors doped beyond n(c) have not been explored in detail. Therefore, the recent observation of superconductivity emerging near the insulator-to-metal transition in heavily boron-doped diamond has stimulated a discussion on the fundamental origin of the metallic states responsible for the superconductivity. Two approaches have been adopted for describing this metallic state: the introduction of charge carriers into either the impurity bands or the intrinsic diamond bands. Here we show experimentally that the doping-dependent occupied electronic structures are consistent with the diamond bands, indicating that holes in the diamond bands play an essential part in determining the metallic nature of the heavily boron-doped diamond superconductor. This supports the diamond band approach and related predictions, including the possibility of achieving dopant-induced superconductivity in silicon and germanium. It should also provide a foundation for the possible development of diamond-based devices.     

Antiferromagnetic order as the competing ground state in electron-doped Nd1.85Ce0.15CuO4

Superconductivity in the high-transition-temperature (high-T(c)) copper oxides competes with other possible ground states. The physical explanation for superconductivity can be constrained by determining the nature of the closest competing ground state, and establishing if that state is universal among the high-T(c) materials. Antiferromagnetism has been theoretically predicted to be the competing ground state. A competing ground state is revealed when superconductivity is destroyed by the application of a magnetic field, and antiferromagnetism has been observed in hole-doped materials under the influence of modest fields. None of the previous experiments have revealed the quantum phase transition from the superconducting state to the antiferromagnetic state, because they failed to reach the upper critical field B(c2). Here we report the results of transport and neutron-scattering experiments on electron-doped Nd1.85Ce0.15CuO4 (refs 13, 14), where B(c2) can be reached. The applied field reveals a static, commensurate, anomalously conducting long-range ordered antiferromagnetic state, in which the induced moment scales approximately linearly with the field strength until it saturates at B(c2). This and previous experiments on the hole-doped materials therefore establishes antiferromagnetic order as a competing ground state in the high-T(c) copper oxide materials, irrespective of electron or hole doping.     

Room-temperature electronic phase transitions in the continuous phase diagrams of perovskite manganites

Highly correlated electronic systems--such as transition-metal oxides that are doped Mott insulators--are complex systems which exhibit puzzling phenomena, including high-temperature superconductivity and colossal magnetoresistivity. Recent studies suggest that in such systems collective electronic phenomena are important, arising from long-range Coulomb interactions and magnetic effects. The qualitative behaviour of these systems is strongly dependent on charge filling (the level of doping) and the lattice constant. Here we report a time-efficient and systematic experimental approach for studying the phase diagrams of condensed-matter systems. It involves the continuous mapping of the physical properties of epitaxial thin films of perovskite manganites (a class of doped Mott insulator) as their composition is varied. We discover evidence that suggests the presence of phase boundaries of electronic origin at room temperature.     

Superconductivity in two-dimensional CoO2 layers

Since the discovery of high-transition-temperature (high-T(c)) superconductivity in layered copper oxides, many researchers have searched for similar behaviour in other layered metal oxides involving 3d-transition metals, such as cobalt and nickel. Such attempts have so far failed, with the result that the copper oxide layer is thought to be essential for superconductivity. Here we report that Na(x)CoO2*yH2O (x approximately 0.35, y approximately 1.3) is a superconductor with a T(c) of about 5 K. This compound consists of two-dimensional CoO2 layers separated by a thick insulating layer of Na+ ions and H2O molecules. There is a marked resemblance in superconducting properties between the present material and high-T(c) copper oxides, suggesting that the two systems have similar underlying physics.     

A universal scaling relation in high-temperature superconductors

Since the discovery of superconductivity at elevated temperatures in the copper oxide materials there has been a considerable effort to find universal trends and correlations amongst physical quantities, as a clue to the origin of the superconductivity. One of the earliest patterns that emerged was the linear scaling of the superfluid density (rho(s)) with the superconducting transition temperature (T(c)), which marks the onset of phase coherence. This is referred to as the Uemura relation, and it works reasonably well for the underdoped materials. It does not, however, describe optimally doped (where T(c) is a maximum) or overdoped materials. Similarly, an attempt to scale the superfluid density with the d.c. conductivity (sigma(dc)) was only partially successful. Here we report a simple scaling relation (rho(s) proportional, variant sigma(dc)T(c), with sigma(dc) measured at approximately T(c)) that holds for all tested high-T(c) materials. It holds regardless of doping level, nature of dopant (electrons versus holes), crystal structure and type of disorder, and direction (parallel or perpendicular to the copper-oxygen planes).     

Hidden magnetism and quantum criticality in the heavy fermion superconductor CeRhIn5

With only a few exceptions that are well understood, conventional superconductivity does not coexist with long-range magnetic order (for example, ref. 1). Unconventional superconductivity, on the other hand, develops near a phase boundary separating magnetically ordered and magnetically disordered phases. A maximum in the superconducting transition temperature T(c) develops where this boundary extrapolates to zero Kelvin, suggesting that fluctuations associated with this magnetic quantum-critical point are essential for unconventional superconductivity. Invariably, though, unconventional superconductivity masks the magnetic phase boundary when T < T(c), preventing proof of a magnetic quantum-critical point. Here we report specific-heat measurements of the pressure-tuned unconventional superconductor CeRhIn5 in which we find a line of quantum-phase transitions induced inside the superconducting state by an applied magnetic field. This quantum-critical line separates a phase of coexisting antiferromagnetism and superconductivity from a purely unconventional superconducting phase, and terminates at a quantum tetracritical point where the magnetic field completely suppresses superconductivity. The T --> 0 K magnetic field-pressure phase diagram of CeRhIn5 is well described with a theoretical model developed to explain field-induced magnetism in the high-T(c) copper oxides, but in which a clear delineation of quantum-phase boundaries has not been possible. These experiments establish a common relationship among hidden magnetism, quantum criticality and unconventional superconductivity in copper oxides and heavy-electron systems such as CeRhIn5.     

Magnetic order close to superconductivity in the iron-based layered LaO1-xFxFeAs systems

Following the discovery of long-range antiferromagnetic order in the parent compounds of high-transition-temperature (high-T(c)) copper oxides, there have been efforts to understand the role of magnetism in the superconductivity that occurs when mobile 'electrons' or 'holes' are doped into the antiferromagnetic parent compounds. Superconductivity in the newly discovered rare-earth iron-based oxide systems ROFeAs (R, rare-earth metal) also arises from either electron or hole doping of their non-superconducting parent compounds. The parent material LaOFeAs is metallic but shows anomalies near 150 K in both resistivity and d.c. magnetic susceptibility. Although optical conductivity and theoretical calculations suggest that LaOFeAs exhibits a spin-density-wave (SDW) instability that is suppressed by doping with electrons to induce superconductivity, there has been no direct evidence of SDW order. Here we report neutron-scattering experiments that demonstrate that LaOFeAs undergoes an abrupt structural distortion below 155 K, changing the symmetry from tetragonal (space group P4/nmm) to monoclinic (space group P112/n) at low temperatures, and then, at approximately 137 K, develops long-range SDW-type antiferromagnetic order with a small moment but simple magnetic structure. Doping the system with fluorine suppresses both the magnetic order and the structural distortion in favour of superconductivity. Therefore, like high-T(c) copper oxides, the superconducting regime in these iron-based materials occurs in close proximity to a long-range-ordered antiferromagnetic ground state.     

Superconductivity in diamond

Diamond is an electrical insulator well known for its exceptional hardness. It also conducts heat even more effectively than copper, and can withstand very high electric fields. With these physical properties, diamond is attractive for electronic applications, particularly when charge carriers are introduced (by chemical doping) into the system. Boron has one less electron than carbon and, because of its small atomic radius, boron is relatively easily incorporated into diamond; as boron acts as a charge acceptor, the resulting diamond is effectively hole-doped. Here we report the discovery of superconductivity in boron-doped diamond synthesized at high pressure (nearly 100,000 atmospheres) and temperature (2,500-2,800 K). Electrical resistivity, magnetic susceptibility, specific heat and field-dependent resistance measurements show that boron-doped diamond is a bulk, type-II superconductor below the superconducting transition temperature T(c) approximately 4 K; superconductivity survives in a magnetic field up to Hc2(0) > or = 3.5 T. The discovery of superconductivity in diamond-structured carbon suggests that Si and Ge, which also form in the diamond structure, may similarly exhibit superconductivity under the appropriate conditions.     

Real-space imaging of an orbital Kondo resonance on the Cr(001) surface

The Kondo effect is usually connected with the interaction between a localized spin moment and itinerant electrons. This interaction leads to the formation of a narrow resonance at the Fermi level, which is called the Abrikosov-Suhl or Kondo resonance. Scanning tunnelling microscopy is an ideal technique for real-space investigations of complicated electronic structures and many-body phenomena, such as the formation of the Kondo resonance or d-wave pairing in high-T(c) superconductors. Theory has predicted that similar, Kondo-like many-electron resonances are possible for scattering centres with orbital instead of spin degrees of freedom--the quadruple momenta in uranium-based compounds or two-level systems in metallic glasses are examples of such 'pseudo-Kondo' scattering centres. Here we present evidence for the orbital Kondo resonance on a transition-metal surface. Investigations of an atomically clean Cr(001) surface at low temperature using scanning tunnelling microscopy reveal a very narrow resonance at 26 meV above the Fermi level, and enable us to visualize the orbital character of the corresponding state. The experimental data, together with many-body calculations, demonstrate that the observed resonance is an orbital Kondo resonance formed by two degenerate d(xz), d(yz) surface states.     

A multi-component Fermi surface in the vortex state of an underdoped high-Tc superconductor

To understand the origin of superconductivity, it is crucial to ascertain the nature and origin of the primary carriers available to participate in pairing. Recent quantum oscillation experiments on high-transition-temperature (high-T(c)) copper oxide superconductors have revealed the existence of a Fermi surface akin to that in normal metals, comprising fermionic carriers that undergo orbital quantization. The unexpectedly small size of the observed carrier pocket, however, leaves open a variety of possibilities for the existence or form of any underlying magnetic order, and its relation to d-wave superconductivity. Here we report experiments on quantum oscillations in the magnetization (the de Haas-van Alphen effect) in superconducting YBa(2)Cu(3)O(6.51) that reveal more than one carrier pocket. In particular, we find evidence for the existence of a much larger pocket of heavier mass carriers playing a thermodynamically dominant role in this hole-doped superconductor. Importantly, characteristics of the multiple pockets within this more complete Fermi surface impose constraints on the wavevector of any underlying order and the location of the carriers in momentum space. These constraints enable us to construct a possible density-wave model with spiral or related modulated magnetic order, consistent with experimental observations.     

Interplay of electron-lattice interactions and superconductivity in superconductivity in Bi2Sr2CaCu2O8+delta

Formation of electron pairs is essential to superconductivity. For conventional superconductors, tunnelling spectroscopy has established that pairing is mediated by bosonic modes (phonons); a peak in the second derivative of tunnel current d2I/dV2 corresponds to each phonon mode. For high-transition-temperature (high-T(c)) superconductivity, however, no boson mediating electron pairing has been identified. One explanation could be that electron pair formation and related electron-boson interactions are heterogeneous at the atomic scale and therefore challenging to characterize. However, with the latest advances in d2I/dV2 spectroscopy using scanning tunnelling microscopy, it has become possible to study bosonic modes directly at the atomic scale. Here we report d2I/dV2 imaging studies of the high-T(c) superconductor Bi2Sr2CaCu2O8+delta. We find intense disorder of electron-boson interaction energies at the nanometre scale, along with the expected modulations in d2I/dV2 (refs 9, 10). Changing the density of holes has minimal effects on both the average mode energies and the modulations, indicating that the bosonic modes are unrelated to electronic or magnetic structure. Instead, the modes appear to be local lattice vibrations, as substitution of 18O for 16O throughout the material reduces the average mode energy by approximately 6 per cent--the expected effect of this isotope substitution on lattice vibration frequencies. Significantly, the mode energies are always spatially anticorrelated with the superconducting pairing-gap energies, suggesting an interplay between these lattice vibration modes and the superconductivity.     

Microscopic electronic inhomogeneity in the high-Tc superconductor Bi2Sr2CaCu2O8+x

The parent compounds of the copper oxide high-transition-temperature (high-Tc) superconductors are unusual insulators (so-called Mott insulators). Superconductivity arises when they are 'doped' away from stoichiometry. For the compound Bi2Sr2CaCu2O8+x, doping is achieved by adding extra oxygen atoms, which introduce positive charge carriers ('holes') into the CuO2 planes where the superconductivity is believed to originate. Aside from providing the charge carriers, the role of the oxygen dopants is not well understood, nor is it clear how the charge carriers are distributed on the planes. Many models of high-Tc superconductivity accordingly assume that the introduced carriers are distributed uniformly, leading to an electronically homogeneous system as in ordinary metals. Here we report the presence of an electronic inhomogeneity in Bi2Sr2CaCu2O8+x, on the basis of observations using scanning tunnelling microscopy and spectroscopy. The inhomogeneity is manifested as spatial variations in both the local density of states spectrum and the superconducting energy gap. These variations are correlated spatially and vary on the surprisingly short length scale of approximately 14 A. Our analysis suggests that this inhomogeneity is a consequence of proximity to a Mott insulator resulting in poor screening of the charge potentials associated with the oxygen ions left in the BiO plane after doping, and is indicative of the local nature of the superconducting state.