No Arabic abstract
Unusual phases and phase transitions are seen at the magnetic-nonmagnetic boundary in Ce, Eu and Yb-based compounds. EuNi$_2$P$_{2}$ is a very unusual valence fluctuating Eu system, because at low temperatures the Eu valence stays close to 2.5 instead of approaching an integer value. Eu valence and thus the magnetic property in this system can be tuned by Ge substitution in P site as EuNi$_2$Ge$_{2}$ is known to exhibit antiferromagnetc (AFM) ordering of divalent Eu moments with $T_N$ = 30 K. We have grown EuNi$_2$(P$_{1-x}$Ge$_x$)$_2$ (0.0 $leq$ $x$ $leq$ 0.5) single crystals and studied their magnetic, thermodynamic and transport properties. Increasing Ge doping to $x >$ 0.4 results in a well-defined AFM ordered state with $T_N$ = 12 K for $x$ = 0.5. Moreover, the reduced value of magnetic entropy for $x$ = 0.5 at $T_N$ suggests the presence of valance fluctuation/ Kondo effect in this compound. Interestingly, the specific heat exhibits an enhanced Sommerfeld coefficient upon Ge doping. Subsequently, electronic structure calculations lead to a non-integral valence in EuNi$_2$P$_{2}$ but a stable divalent Eu state in EuNi$_2$Ge$_{2}$ which is in good agreement with experimental results.
The intermediate valent systems TmSe and SmB6 have been investigated up to 16 and 18 GPa by ac microcalorimetry with a pressure (p) tuning realized in situ at low temperature. For TmSe, the transition from an antiferromagnetic insulator for p<3 GPa to an antiferromagnetic metal at higher pressure has been confirmed. A drastic change in the p variation of the Neel temperature (Tn) is observed at 3 GPa. In the metallic phase (p>3 GPa), Tn is found to increase linearly with p. A similar linear p increase of Tn is observed for the quasitrivalent compound TmS which is at ambiant pressure equivalent to TmSe at p=7 GPa. In the case of SmB6 long range magnetism has been detected above p=8 GPa, i.e. at a pressure slightly higher than the pressure of the insulator to metal transition. However a homogeneous magnetic phase occurs only above 10 GPa. The magnetic and electronic properties are related to the renormalization of the 4f wavefunction either to the divalent or the trivalent configurations. As observed in SmS, long range magnetism in SmB6 occurs already far below the pressure where a trivalent Sm3+ state will be reached. It seems possible, to describe roughly the physical properties of the intermediate valence equilibrium by assuming formulas for the Kondo lattice temperature depending on the valence configuration. Comparison is also made with the appearance of long range magnetism in cerium and ytterbium heavy fermion compounds.
The magnetic ground state of the Eu$^{2+}$ moments in a series of Eu(Fe$_{1-x}$Co$_{x}$)$_{2}$As$_{2}$ single crystals grown from the Sn flux has been investigated in detail by neutron diffraction measurements. Combined with the results from the macroscopic properties (resistivity, magnetic susceptibility and specific heat) measurements, a phase diagram describing how the Eu magnetic order evolves with Co doping in Eu(Fe$_{1-x}$Co$_{x}$)$_{2}$As$_{2}$ is established. The ground-state magnetic structure of the Eu$^{2+}$ spins is found to develop from the A-type antiferromagnetic (AFM) order in the parent compound, via the A-type canted AFM structure with some net ferromagnetic (FM) moment component along the crystallographic $mathit{c}$ direction at intermediate Co doping levels, finally to the pure FM order at relatively high Co doping levels. The ordering temperature of Eu declines linearly at first, reaches the minimum value of 16.5(2) K around $mathit{x}$ = 0.100(4), and then reverses upwards with further Co doping. The doping-induced modification of the indirect Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between the Eu$^{2+}$ moments, which is mediated by the conduction $mathit{d}$ electrons on the (Fe,Co)As layers, as well as the change of the strength of the direct interaction between the Eu$^{2+}$ and Fe$^{2+}$ moments, might be responsible for the change of the magnetic ground state and the ordering temperature of the Eu sublattice. In addition, for Eu(Fe$_{1-x}$Co$_{x}$)$_{2}$As$_{2}$ single crystals with 0.10 $leqslant$ $mathit{x}$ $leqslant$ 0.18, strong ferromagnetism from the Eu sublattice is well developed in the superconducting state, where a spontaneous vortex state is expected to account for the compromise between the two competing phenomena.
The low-temperature electron spin resonance (ESR) spectra and the static magnetization data obtained for the stoichiometric single crystals of $beta$-Na$_{0.33}$V$_2$O$_5$ indicate that this quasi-one-dimensional mixed valence (V4+/V5+) compound demonstrates at $T_N=22$ K the phase transition into the canted antiferromagnetically ordered state. The spontaneous magnetization of $3.4times 10^{-3}$ $mu_B$ per V$^{4+}$ ion was found to be oriented along the two-fold $b$ axis of the monoclinic structure, the vector of antiferromagnetism is aligned with the $a$ axis and the Dzyaloshinsky vector is parallel to the $c$-axis. The experimental data were successfully described in the frame of the macroscopic spin dynamics and the following values for the macroscopic parameters of the spin system were obtained: the Dzyaloshinsky field $H_D=6$ kOe, the energy gaps of two branches of the spin wave spectrum $Delta_1=48$ GHz and $Delta_2=24$ GHz.
Neutron diffraction and magnetization measurements of the magneto refrigerant Mn1+yFe1-yP1-xGex reveal that the ferromagnetic and paramagnetic phases correspond to two very distinct crystal structures, with the magnetic entropy change as a function of magnetic field or temperature being directly controlled by the phase fraction of this first-order transition. By tuning the physical properties of this system we have achieved a maximum magnetic entropy change exceeding 74 J/Kg K for both increasing and decreasing field, more than twice the value of the previous record.
In this study, we synthesized single crystals of Na$_{x}$CoO$_{2}$ with $xsim0.8$ using the optical floating zone technique. A thorough electrochemical treatment of the samples permitted us to control the de-intercalation of Na to obtain single crystal samples of stable Na ordered phases with $x=0.5-0.8$. Comparisons of the bulk magnetic properties with those observed in the Na ordered powder samples confirmed the high quality of these single crystal phases. The ab plane resistivity was measured for the Na ordered samples and it was quite reproducible for different sample batches. The data were analogous to those found in previous initial experimental studies on single crystals, but the lower residual resistivity and sharper anti-ferromagnetic transitions determined for our samples confirmed their higher quality.