Denis Arčon

The disorder-free non-BCS superconductor Cs3C60 emerges from an antiferromagnetic insulator parent state.

The body-centered cubic A15-structured cesium fulleride Cs3C60 is not superconducting at ambient pressure and is free from disorder, unlike the well-studied face-centered cubic A3C60 alkali metal fulleride superconductors. We found that in Cs3C60, where the molecular valences are precisely assigned, the superconducting state at 38 kelvin emerges directly from a localized electron antiferromagnetic insulating state with the application of pressure. This transition maintains the threefold degeneracy of the active orbitals in both competing electronic states; it is thus a purely electronic transition to a superconducting state, with a dependence of the transition temperature on pressure-induced changes of anion packing density that is not explicable by Bardeen-Cooper-Schrieffer (BCS) theory.

Polymorphism control of superconductivity and magnetism in Cs3C60 close to the Mott transition

The crystal structure of a solid controls the interactions between the electronically active units and thus its electronic properties. In the high-temperature superconducting copper oxides, only one spatial arrangement of the electronically active Cu2+ units—a two-dimensional square lattice—is available to study the competition between the cooperative electronic states of magnetic order and superconductivity. Crystals of the spherical molecular C603- anion support both superconductivity and magnetism but can consist of fundamentally distinct three-dimensional arrangements of the anions. Superconductivity in the A3C60 (A = alkali metal) fullerides has been exclusively associated with face-centred cubic (f.c.c.) packing of C603- (refs 2, 3), but recently the most expanded (and thus having the highest superconducting transition temperature, Tc; ref. 4) composition Cs3C60 has been isolated as a body-centred cubic (b.c.c.) packing, which supports both superconductivity and magnetic order. Here we isolate the f.c.c. polymorph of Cs3C60 to show how the spatial arrangement of the electronically active units controls the competing superconducting and magnetic electronic ground states. Unlike all the other f.c.c. A3C60 fullerides, f.c.c. Cs3C60 is not a superconductor but a magnetic insulator at ambient pressure, and becomes superconducting under pressure. The magnetic ordering occurs at an order of magnitude lower temperature in the geometrically frustrated f.c.c. polymorph (Néel temperature TN = 2.2 K) than in the b.c.c.-based packing (TN = 46 K). The different lattice packings of C603- change Tc from 38 K in b.c.c. Cs3C60 to 35 K in f.c.c. Cs3C60 (the highest found in the f.c.c. A3C60 family). The existence of two superconducting packings of the same electronically active unit reveals that Tc scales universally in a structure-independent dome-like relationship with proximity to the Mott metal–insulator transition, which is governed by the role of electron correlations characteristic of high-temperature superconducting materials other than fullerides.

Diluted magnetic semiconductors: Mn/Co-doped ZnO nanorods as case study

The structure and the magnetic properties of 3 and 5 mol% (based on the starting concentrations) Co- and Mn-doped ZnO nanorods, synthesized by a straightforward and experimentally simple nonaqueous sol–gel route based on benzyl alcohol as solvent, have been investigated by various characterization techniques, including X-ray diffraction with Rietveld refinement, high-resolution transmission electron microscopy, selected area electron diffraction, energy dispersive X-ray spectroscopy, magnetization measurements and electron paramagnetic resonance. The doped as-synthesized ZnO nanocrystals retain the wurtzite structure with a morphology in the form of nanorods grown along the [001] direction, whose dimensional parameters as well as degree of agglomeration depend on the type and level of doping. The Co-doped ZnO powders are ferromagnetic with a Curie temperature exceeding room temperature. Conversely, the Mn-doped samples show antiferromagnetic correlations with a possible transition to an antiferromagnetic ground state below TN = 10 K. The results suggest that the magnetic ground state is extremely sensitive to the type of dopant, which is in agreement with previous studies.

Spontaneous Magnetic Ordering in the Fullerene Charge-Transfer Salt (TDAE)C60

The zero-field muon spin relaxation technique has been used in the direct observation of spontaneous magnetic order below a Curie temperature (Tc) of ∼16.1 kelvin in the fullerene charge-transfer salt (tetrakisdimethylaminoethylene)C60 [(TDAE)C60]. Coherent ordering of the electronic magnetic moments leads to a local field of 68(1) gauss at the muon site at 3.2 kelvin (parentheses indicate the error in the last digit). Substantial spatially inhomogeneous effects are manifested in the distribution of the local fields, whose width amounts to 48(2) gauss at the same temperature. The temperature evolution of the internal magnetic field below the freezing temperature mirrors that of the saturation magnetization, closely following the behavior expected for collective spin wave (magnon) excitations. The transition to a ferromagnetic state with a Tc higher than that of any other organic material is now authenticated.

Orientational and Magnetic Ordering of Buckyballs in TDAE-C60.

Spin ordering in the low-temperature magnetic phase is directly linked to the orientational ordering of C60 molecules in organically doped fullerene derivatives. Electron spin resonance and alternating current susceptometry measurements on tetrakis(dimethylamino)ethylene-C60 (TDAE-C60) (Curie temperature Tc = 16 kelvin) show a direct coupling between spin and merohedral degrees of freedom. This coupling was experimentally demonstrated by showing that ordering the spins in the magnetic phase imprints a merohedral order on the solid or, conversely, that merohedrally ordering the C60 molecules influences the spin order at low temperature. The merohedral disorder gives rise to a distribution of π-lectron exchange interactions between spins on neighboring C60 molecules, suggesting a microscopic origin for the observed spinglass behavior of the magnetic state.

MnO(x) nanoparticles supported on a new mesostructured silicate with textural porosity.

A two-step synthesis of a novel mesostructured silicate, KIL-2, and its manganese-containing analogue, Mn/KIL-2, has been developed. KIL-2 possesses interparticle mesopores with pore dimensions between 5 and 60 nm and a surface area of 448 m(2). The mesopores are formed by the aggregation of silica nanoparticles, which creates a network with interparticle voids. The particle size and the pore diameters depend on the temperature of the ageing step (first step) and on the solvothermal treatment in ethanol (second step), respectively. Mn/KIL-2 contains octahedrally coordinated Mn(3+) (80%) and tetrahedrally coordinated Mn(2+) (20%) ions. Mn(3+) ions are present in the extra-framework MnO(x) nanoparticles with typical dimensions of 2 nm, which are homogeneously distributed throughout the material. Mn(2+) ions occur as isolated manganese framework sites. The material is also able to retain its structure characteristics after the hydrothermal treatment in boiling water. Because of its non-toxic nature and cost-effective synthesis, Mn/KIL-2 thus exhibits properties that are needed for an environment-friendly catalyst.

Solvothermal and surfactant-free synthesis of crystalline Nb2O5, Ta2O5, HfO2, and Co-doped HfO2 nanoparticles

A simple route to niobium, hafnium and tantalum oxide nanocrystals using a nonaqueous sol-gel route based on the solvothermal reaction of the corresponding metal chlorides with benzyl alcohol is presented. This approach can easily be extended to the preparation of high quality Co-doped HfO(2) nanoparticles of uniform size and shape and with a homogenous distribution of the magnetic ions. The structural characterization of all these nanomaterials as well as the magnetic properties of pure and doped hafnia, with special attention to the doping efficiency, are discussed. The obtained Co-doped hafnia exhibits paramagnetic properties with very weak antiferromagnetic interactions between Co ions moments.

A comparative study of magnetic properties of LiFePO4 and LiMnPO4

A detailed comparative study of the magnetic properties of LiFePO4 and LiMnPO4 samples is presented. Magnetic susceptibility, electron paramagnetic resonance and 7Li NMR experiments were performed on samples as prepared for electrochemical studies. The ground state of LiFePO4 seems to be that of a collinear antiferromagnet and very robust against crystal imperfections. On the other hand, our LiMnPO4 samples possess a weak ferromagnetic ground state with a transition temperature TN = 42 K. We suggest that solitons may be very important magnetic excitations in these systems and that pinning of solitons below TN together with frustration plays a decisive role in the formation of the weak ferromagnetic state in LiMnPO4. The differences between the magnetic properties of these two samples reflect also the differences between their electronic structures and may thus be important for the electrochemistry of LiFePO4 and LiMnPO4.

Phonon-Modulated Magnetic Interactions and Spin Tomonaga-Luttinger Liquid in the p-Orbital Antiferromagnet CsO2

The magnetic response of antiferromagnetic CsO2, coming from the p-orbital S=1/2 spins of anionic O2(-) molecules, is followed by 133Cs nuclear magnetic resonance across the structural phase transition occurring at T(s1)=61  K on cooling. Above T(s1), where spins form a square magnetic lattice, we observe a huge, nonmonotonic temperature dependence of the exchange coupling originating from thermal librations of O2(-) molecules. Below T(s1), where antiferromagnetic spin chains are formed as a result of p-orbital ordering, we observe a spin Tomonaga-Luttinger-liquid behavior of spin dynamics. These two interesting phenomena, which provide rare simple manifestations of the coupling between spin, lattice, and orbital degrees of freedom, establish CsO2 as a model system for molecular solids.

Oxygen self-doping in hollandite-type vanadium oxyhydroxide nanorods.

A nonaqueous liquid-phase route involving the reaction of vanadium oxychloride with benzyl alcohol leads to the formation of single-crystalline and semiconducting VO 1.52(OH) 0.77 nanorods with an ellipsoidal morphology, up to 500 nm in length and typically about 100 nm in diameter. Composition, structure, and morphology were thoroughly analyzed by neutron and synchrotron powder X-ray diffraction as well as by different electron microscopy techniques (SEM, (HR)TEM, EDX, and SAED). The data obtained point to a hollandite-type structure which, unlike other vanadates, contains oxide ions in the channels along the c-axis, with hydrogen atoms attached to the edge-sharing oxygen atoms, forming OH groups. According to structural probes and magnetic measurements (1.94 mu B/V), the formal valence of vanadium is +3.81 (V (4+)/V (3+) atomic ratio approximately 4). The experimentally determined density of 3.53(5) g/cm (3) is in good agreement with the proposed structure and nonstoichiometry. The temperature-dependent DC electrical conductivity exhibits Arrhenius-type behavior with a band gap of 0.64 eV. The semiconducting behavior is interpreted in terms of electron hopping between vanadium cations of different valence states (small polaron model). Ab initio density-functional calculations with a local spin density approximation including orbital potential (LSDA + U with an effective U value of 4 eV) have been employed to extract the electronic structure. These calculations propose, on the one hand, that the electronic conductivity is based on electron hopping between neighboring V (3+) and V (4+) sites, and, on the other hand, that the oxide ions in the channels act as electron donors, increasing the fraction of V (3+) cations, and thus leading to self-doping. Experimental and simulated electron energy-loss spectroscopy data confirm both the presence of V (4+) and the validity of the density-of-states calculation. Temperature-dependent magnetic susceptibility measurements indicate strongly frustrated antiferromagnetic interactions between the vanadium ions. A model involving the charge order of the V (3+) sites is proposed to account for the observed formation of the magnetic moment below 25 K.