Tom Lancaster

Enhancement of the superconducting transition temperature of FeSe by intercalation of a molecular spacer layer

The discovery of high-temperature superconductivity in a layered iron arsenide has led to an intensive search to optimize the superconducting properties of iron-based superconductors by changing the chemical composition of the spacer layer between adjacent anionic iron arsenide layers. Superconductivity has been found in iron arsenides with cationic spacer layers consisting of metal ions (for example, Li(+), Na(+), K(+), Ba(2+)) or PbO- or perovskite-type oxide layers, and also in Fe(1.01)Se (ref. 8) with neutral layers similar in structure to those found in the iron arsenides and no spacer layer. Here we demonstrate the synthesis of Li(x)(NH(2))(y)(NH(3))(1-y)Fe(2)Se(2) (x~0.6; y~0.2), with lithium ions, lithium amide and ammonia acting as the spacer layer between FeSe layers, which exhibits superconductivity at 43(1) K, higher than in any FeSe-derived compound reported so far. We have determined the crystal structure using neutron powder diffraction and used magnetometry and muon-spin rotation data to determine the superconducting properties. This new synthetic route opens up the possibility of further exploitation of related molecular intercalations in this and other systems to greatly optimize the superconducting properties in this family.

Coexistence of static magnetism and superconductivity in SmFeAsO 1− x F x as revealed by muon spin rotation

The recent observation of superconductivity with critical temperatures (Tc) up to 55 K in the pnictide RFeAsO(1-x)F(x), where R is a lanthanide, marks the first discovery of a non-copper-oxide-based layered high-Tc superconductor. It has raised the suspicion that these new materials share a similar pairing mechanism to the cuprate superconductors, as both families exhibit superconductivity following charge doping of a magnetic parent material. In this context, it is important to follow the evolution of the microscopic magnetic properties of the pnictides with doping and hence to determine whether magnetic correlations coexist with superconductivity. Here, we present a muon spin rotation study on SmFeAsO(1-x)F(x), with x=0-0.30 that shows that, as in the cuprates, static magnetism persists well into the superconducting regime. This analogy is quite surprising as the parent compounds of the two families have rather different magnetic ground states: itinerant spin density wave for the pnictides contrasted with the Mott-Hubbard insulator in the cuprates. Our findings therefore suggest that the proximity to magnetic order and associated soft magnetic fluctuations, rather than strong electronic correlations in the vicinity of a Mott-Hubbard transition, may be the key ingredients of high-Tc superconductors.

Spin waves and revised crystal structure of honeycomb iridate Na2IrO3.

We report inelastic neutron scattering measurements on Na2IrO3, a candidate for the Kitaev spin model on the honeycomb lattice. We observe spin-wave excitations below 5 meV with a dispersion that can be accounted for by including substantial further-neighbor exchanges that stabilize zigzag magnetic order. The onset of long-range magnetic order below T(N)=15.3  K is confirmed via the observation of oscillations in zero-field muon-spin rotation experiments. Combining single-crystal diffraction and density functional calculations we propose a revised crystal structure model with significant departures from the ideal 90° Ir-O-Ir bonds required for dominant Kitaev exchange.

Control of the competition between a magnetic phase and a superconducting phase in cobalt-doped and nickel-doped NaFeAs using electron count.

Dinah R. Parker, Matthew J. P. Smith, Tom Lancaster, Andrew J. Steele, Isabel Franke, Peter J. Baker, Francis L. Pratt, Michael J. Pitcher, Stephen J. Blundell, ∗ and Simon J. Clarke † Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, United Kingdom Clarendon Laboratory, University of Oxford, Parks Road, Oxford OX1 3PU, United Kingdom ISIS Facility, STFC-Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, OX11 0QX, United Kingdom (Dated: September 16, 2010)

Magnetic and non-magnetic phases of a quantum spin liquid

A quantum spin-liquid phase is an intriguing possibility for a system of strongly interacting magnetic units in which the usual magnetically ordered ground state is avoided owing to strong quantum fluctuations. It was first predicted theoretically for a triangular-lattice model with antiferromagnetically coupled S = 1/2 spins. Recently, materials have become available showing persuasive experimental evidence for such a state. Although many studies show that the ideal triangular lattice of S = 1/2 Heisenberg spins actually orders magnetically into a three-sublattice, non-collinear 120° arrangement, quantum fluctuations significantly reduce the size of the ordered moment. This residual ordering can be completely suppressed when higher-order ring-exchange magnetic interactions are significant, as found in nearly metallic Mott insulators. The layered molecular system κ-(BEDT-TTF)2Cu2(CN)3 is a Mott insulator with an almost isotropic, triangular magnetic lattice of spin-1/2 BEDT-TTF dimers that provides a prime example of a spin liquid formed in this way. Despite a high-temperature exchange coupling, J, of 250 K (ref. 6), no obvious signature of conventional magnetic ordering is seen down to 20 mK (refs 7, 8). Here we show, using muon spin rotation, that applying a small magnetic field to this system produces a quantum phase transition between the spin-liquid phase and an antiferromagnetic phase with a strongly suppressed moment. This can be described as Bose–Einstein condensation of spin excitations with an extremely small spin gap. At higher fields, a second transition is found that suggests a threshold for deconfinement of the spin excitations. Our studies reveal the low-temperature magnetic phase diagram and enable us to measure characteristic critical properties. We compare our results closely with current theoretical models, and this gives some further insight into the nature of the spin-liquid phase.

Strong H...F hydrogen bonds as synthons in polymeric quantum magnets: structural, magnetic, and theoretical characterization of [Cu(HF2)(pyrazine)2]SbF6, [Cu2F(HF)(HF2)(pyrazine)4](SbF6)2, and [CuAg(H3F4)(pyrazine)5](SbF6)2.

Three Cu(2+)-containing coordination polymers were synthesized and characterized by experimental (X-ray diffraction, magnetic susceptibility, pulsed-field magnetization, heat capacity, and muon-spin relaxation) and electronic structure studies (quantum Monte Carlo simulations and density functional theory calculations). [Cu(HF(2))(pyz)(2)]SbF(6) (pyz = pyrazine) (1a), [Cu(2)F(HF)(HF(2))(pyz)(4)](SbF(6))(2) (1b), and [CuAg(H(3)F(4))(pyz)(5)](SbF(6))(2) (2) crystallize in either tetragonal or orthorhombic space groups; their structures consist of 2D square layers of [M(pyz)(2)](n+) that are linked in the third dimension by either HF(2)(-) (1a and 1b) or H(3)F(4)(-) (2). The resulting 3D frameworks contain charge-balancing SbF(6)(-) anions in every void. Compound 1b is a defective polymorph of 1a, with the difference being that 50% of the HF(2)(-) links are broken in the former, which leads to a cooperative Jahn-Teller distortion and d(x(2))(-y(2)) orbital ordering. Magnetic data for 1a and 1b reveal broad maxima in chi at 12.5 and 2.6 K and long-range magnetic order below 4.3 and 1.7 K, respectively, while 2 displays negligible spin interactions owing to long and disrupted superexchange pathways. The isothermal magnetization, M(B), for 1a and 1b measured at 0.5 K reveals contrasting behaviors: 1a exhibits a concave shape as B increases to a saturation field, B(c), of 37.6 T, whereas 1b presents an unusual two-step saturation in which M(B) is convex until it reaches a step near 10.8 T and then becomes concave until saturation is reached at 15.8 T. The step occurs at two-thirds of M(sat), suggesting the presence of a ferrimagnetic structure. Compound 2 shows unusual hysteresis in M(B) at low temperature, although chi vs T does not reveal the presence of a magnetic phase transition. Quantum Monte Carlo simulations based on an anisotropic cubic lattice were applied to the magnetic data of 1a to afford g = 2.14, J = -13.4 K (Cu-pyz-Cu), and J(perpendicular) = -0.20 K (Cu-F...H...F-Cu), while chi vs T for 1b could be well reproduced by a spin-1/2 Heisenberg uniform chain model for g = 2.127(1), J(1) = -3.81(1), and zJ(2) = -0.48(1) K, where J(1) and J(2) are the intra- and interchain exchange couplings, respectively, which considers the number of magnetic nearest-neighbors (z). The M(B) data for 1b could not be satisfactorily explained by the chain model, suggesting a more complex magnetic structure in the ordered state and the need for additional terms in the spin Hamiltonian. The observed variation in magnetic behaviors is driven by differences in the H...F hydrogen-bonding motifs.

Coexistence of magnetic fluctuations and superconductivity in the pnictide high temperature superconductor SmFeAsO1-xFx measured by muon spin rotation.

Muon spin rotation experiments were performed on the pnictide high temperature superconductor SmFeAsO1-xFx with x=0.18 and 0.3. We observed an unusual enhancement of slow spin fluctuations in the vicinity of the superconducting transition which suggests that the spin fluctuations contribute to the formation of an unconventional superconducting state. An estimate of the in-plane penetration depth lambda ab(0)=190(5) nm was obtained, which confirms that the pnictide superconductors obey an Uemura-style relationship between Tc and lambda ab(0);(-2).

Experimentally determining the exchange parameters of quasi-two-dimensional Heisenberg magnets

Though long-range magnetic order cannot occur at temperatures T > 0 in a perfect two-dimensional (2D) Heisenberg magnet, real quasi-2D materials will invariably possess nonzero inter-plane coupling J? driving the system to order at elevated temperatures. This process can be studied using quantum Monte Carlo calculations. However, it is difficult to test the results of these calculations experimentally since for highly anisotropic materials in which the in-plane coupling is comparable with attainable magnetic fields J? is necessarily very small and inaccessible directly. In addition, because of the large anisotropy, the Neel temperatures are low and difficult to determine from thermodynamic measurements. Here, we present an elegant method of assessing the calculations via two independent experimental probes: pulsed-field magnetization in fields of up to 85T, and muon-spin rotation.

Compositional Control of the Superconducting Properties of LiFeAs

The response of the superconducting state and crystal structure of LiFeAs to chemical substitutions on both the Li and the Fe sites has been probed using high-resolution X-ray and neutron diffraction measurements, magnetometry, and muon-spin rotation spectroscopy. The superconductivity is extremely sensitive to composition: Li-deficient materials (Li(1-y)Fe(1+y)As with Fe substituting for Li) show a very rapid suppression of the superconducting state, which is destroyed when y exceeds 0.02, echoing the behavior of the Fe(1+y)Se system. Substitution of Fe by small amounts of Co or Ni results in monotonic lowering of the superconducting transition temperature, T(c), and the superfluid stiffness, rho(s), as the electron count increases. T(c) is lowered monotonically at a rate of 10 K per 0.1 electrons added per formula unit irrespective of whether the dopant is Co and Ni, and at higher doping levels superconductivity is completely suppressed. These results and the demonstration that the superfluid stiffness in these LiFeAs-derived compounds is higher than in all of the iron pnictide materials underlines the unique position that LiFeAs occupies in this class.

Muon spin relaxation investigation of magnetic ordering in the hybrid organic-inorganic perovskites [(CH3)2NH2]M(HCOO)3 (M=Ni,Co,Mn,Cu)

Muon spin relaxation measurements are reported on samples of dimethylammonium metal formates containing magnetic divalent nickel, cobalt, manganese, and copper ions. These hybrid organic-inorganic perovskites exhibit weak ferromagnetism and are, apart from the copper system, multiferroics with well separated magnetic and antiferroelectric transitions. We use muons to follow the sublattice magnetization, observing the effect of the spin reorientation transitions below TN and the criticality approaching TN. The multiferroic samples have three-dimensional antiferromagnetic interactions, but the copper sample shows quasi-one-dimensional behavior due to its Jahn-Teller distorted structure, with a ratio of its inter- and intrachain exchange constants j/J=0.037.