Enhanced moments of Eu in single crystals of the metallic helical antiferromagnet EuCo2 yAs2

The compound EuCo{2-y}As2 with the tetragonal ThCr2Si2 structure is known to contain Eu{+2} ions with spin S = 7/2 that order below a temperature TN = 47 K into an antiferromagnetic (AFM) proper helical structure with the ordered moments aligned in the tetragonal ab plane, perpendicular to the helix axis along the c axis, with no contribution from the Co atoms. Here we carry out a detailed investigation of the properties of single crystals. Enhanced ordered and effective moments of the Eu spins are found in most of our crystals. Electronic structure calculations indicate that the enhanced moments arise from polarization of the d bands, as occurs in ferromagnetic Gd metal. Electrical resistivity measurements indicate metallic behavior. The low-field in-plane magnetic susceptibilities chi{ab}(T < TN) for several crystals are reported that are fitted well by unified molecular field theory (MFT), and the Eu-Eu exchange interactions Jij are extracted from the fits. High-field magnetization M data for magnetic fields H||ab reveal what appears to be a first-order spin-flop transition followed at higher field by a second-order metamagnetic transition of unknown origin, and then by another second-order transition to the paramagnetic (PM) state. For H||c, the magnetization shows only a second-order transition from the canted AFM to the PM state, as expected. The critical fields for the AFM to PM transition are in approximate agreement with the predictions of MFT. Heat capacity Cp measurements in zero and high H are reported. Phase diagrams for H||c and H||ab versus T are constructed from the high-field M(H,T) and Cp(H,T) measurements. The magnetic part Cmag(T, H = 0) of Cp(T, H = 0) is extracted and is fitted rather well below TN by MFT, although dynamic short-range AFM order is apparent in Cmag(T) up to about 70 K, where the molar entropy attains its high-T limit of R ln8.Comment: 29 pages, 30 figures including 62 subfigures, 8 tables, 84 reference

Magnetic phase transitions in Eu(Co1-xNix)(2-y)As-2 single crystals

The effects of Ni doping in Eu(Co1-xNix)(2-y)As-2 single crystals with x = 0 to 1 grown out of self-flux are investigated via crystallographic, electronic transport, magnetic, and thermal measurements. All compositions adopt the body-centered-tetragonal ThCr2Si2 structure with space group I4/mmm. We also find 3%-4% of randomly distributed vacancies on the Co/Ni site. Anisotropic magnetic susceptibility chi(alpha) (alpha = ab, c) data versus temperature T show clear signatures of an antiferromagnetic (AFM) c-axis helix structure associated with the Eu+2 spins 7/2 for x = 0 and 1 as previously reported. The chi(alpha)(T) data for x = 0.03 and 0.10 suggest an anomalous 2q magnetic structure containing two helix axes along the c axis and in the ab plane, respectively, whereas for x = 0.75 and 0.82 a c-axis helix is inferred as previously found for x = 0 and 1. At intermediate compositions x = 0.2, 0.32, 0.42, 0.54, and 0.65, a magnetic structure with a large ferromagnetic (FM) c-axis component is found from magnetization versus field isotherms, suggested to be an incommensurate FM c-axis cone structure associated with the Eu spins, which consists of both AFM and FM components. In addition, the chi(T) and heat capacity C-p(T) data for x = 0.2-0.65 indicate the occurrence of itinerant FM order associated with the Co/Ni atoms with Curie temperatures from 60 to 25 K, respectively. Electrical resistivity rho(T) measurements indicate metallic character for all compositions with abrupt increases in slope on cooling below the Eu AFM transition temperatures. In addition to this panoply of magnetic transitions, Eu-151 Mossbauer measurements indicate that ordering of the Eu moments proceeds via an incommensurate sine amplitude-modulated structure with additional transition temperatures associated with this effect

Non-Fermi-liquid types of behavior associated with a magnetic quantum critical point in Sr(Co1-xNix)(2)As-2 single crystals

The compound SrCo2As2 with the body-centered tetragonal ThCr2Si2 structure is known to remain paramagnetic down to a temperature T=0.05 K, but inelastic neutron scattering studies have shown that both ferromagnetic (FM) and antiferromagnetic (AFM) fluctuations occur in single crystals. Thus it is of interest to study how the magnetism evolves on doping SrCo2As2. Previous work on polycrystalline samples of Sr(Co1−xNix)2As2 indicated the development of AFM order for 0Ab initioelectronic-structure calculations for x=0 and 0.15 indicate that a flat band with a peak in the density of states just above the Fermi energy is responsible for this initial magnetic-ordering behavior on Ni doping. The AFM ordering is observed in the range 0.013≤x≤0.25 with the ordered moments aligned in the ab plane and with a maximum ordering temperature TN=26.5 K at x=0.10. The Curie-Weiss-like T dependence of χ in the paramagnetic (PM) state indicates dominant FM interactions. The behavior of the anisotropic susceptibilities below TN suggests a planar helical magnetic ground state with a composition-dependent pitch based on a local-moment molecular-field-theory model, with FM interactions in the ab plane and weaker AFM interactions along the helix c axis. However, the small ordered (saturation) moments ∼0.1μB per transition metal atom, where μB is the Bohr magneton, and the values of the Rhodes-Wohlfarth ratio indicate that the magnetism is itinerant. The high-field M(H) isotherms and the low-field χ−1(T\u3eTN) data were successfully analyzed within the framework of Takahashi\u27s theory of FM spin fluctuations. The Cp(T) at low T exhibits Fermi-liquid behavior for 0≤x≤0.15, whereas an evolution to a logarithmic non-Fermi-liquid (NFL) behavior is found for x=0.2 to 0.3. The logarithmic dependence is suppressed in an applied magnetic field. The low-Tρ(H=0,T) data show a T2 dependence for 0≤x≤0.20 and a power-law dependence ρ(H=0,T)=ρ0+ATn with ndependence, suggesting both doping- and magnetic-field-tuned quantum critical phenomena. These low-T NFL types of behavior observed in the Cp and ρ measurements are most evident near the quantum critical concentration x≈0.3 at which a T=0 composition-induced transition from the AFM phase to the PM phase occurs

Lanthanide-based complexes as efficient physiological temperature sensors

A new molecular thermometric sensor based on the terbium(III) complex [C2mim][Tb(fod)4] (C2mim – 1-methyl-3-ethylimidazolium, fod− - tetrakis-6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate), doped with 0.015% of its europium(III) analogue (1, [C2mim][Tb(fod)4]0.99985:[C2mim][Eu(fod)4]0.00015), was prepared and its thermochromic behaviour evaluated from ambient temperature up to 75 °C, including in the physiological range (35–45 °C). It was found that the intensity ratio of the 5D4→7F5 (TbIII) and 5D0→7F2 (EuIII) transitions is correlated with temperature having three different linear regimes. Visual colorimetry allowed the evaluation of the temperature in different ranges from green at ambient temperature, to yellow and finally red at higher temperatures. The TbIII complex emission intensity is extremely sensitive to small temperature variations, particularly between 25 and 35 °C, were it reaches only 40% of the initial intensity. Confinement of the dopped TbIII tetrakis-complex in the organic polymeric matrix poly(methylmethacrylate) (PMMA) induced higher thermal stability in 1, together with a strong temperature dependence of the most intense emissive transition of the TbIII complexes. The photoluminescence quantum yield of polymer-lanthanide hybrid materials increased significantly compared with that of 1. Under 366 nm irradiation, the hybrid material presents a green colour at 25 °C that evolves to yellow at 30 °C and to a white tone at 35 °C.publishe

Highly Luminescent Salts Containing Well-Shielded Lanthanide-Centered Complex Anions and Bulky Imidazolium Countercations

In this paper, we report on the syntheses, structures, and characterization of four molten salts containing imidazolium cations and europium(III)- or terbium(III)-centered complex anions. In the complex anions, the lanthanide centers are wrapped by four pseudodiketonate anionic ligands, which prevent them from contacting with high-frequency oscillators and allow them to show intense characteristic europium(III) or terbium(III) emission, small line widths, high color purity, high quantum yields (30−49%), and long decay times (\u3e2 ms)