Rare 4f^2-based heavy-fermion behaviors have been revealed recently in Pr-based filled skutterudites PrFe4P12 and PrOs4Sb12. Recent studies on the thermal properties on both compounds are reported, putting emphasis on the field-induced ordered phase found in PrOs4Sb12.
Quasi-particle spin susceptibility ($chi^{qp}$) for various heavy-fermion (HF) superconductors are discussed on the basis of the experimental results of electronic specific heat ($gamma_{el}$), NMR Knight shift ($K$) and NMR relaxation rate ($1/T_1$) within the framework of the Fermi liquid model for a Kramers doublet crystal electric field (CEF) ground state. $chi^{qp}_{gamma}$ is calculated from the enhanced Sommerfeld coefficient $gamma_{el}$ and $chi^{qp}_{T_1}$ from the quasi-particle Korringa relation $T_1T(K^{qp}_{T_1})^2=const.$ via the relation of $chi^{qp}_{T_1}=(N_Amu_B/A_{hf})K^{qp}_{T_1}$ where $A_{hf}$ is the hyperfine coupling constant, $N_A$ the Abogadoros number and $mu_B$ the Bohr magneton. For the even-parity (spin-singlet) superconductors CeCu$_2$Si$_2$, CeCoIn$_5$ and UPd$_2$Al$_3$, the fractional decrease in the Knight shift, $delta K^{obs}$, below the superconducting transition temperature ($T_c$) is due to the decrease of the spin susceptibility of heavy quasi-particle estimated consistently from $chi^{qp}_{gamma}$ and $chi^{qp}_{T_1}$. This result allows us to conclude that the heavy quasi-particles form the spin-singlet Cooper pairs in CeCu$_2$Si$_2$, CeCoIn$_5$ and UPd$_2$Al$_3$. On the other hand, no reduction in the Knight shift is observed in UPt$_3$ and UNi$_2$Al$_3$, nevertheless the estimated values of $chi^{qp}_{gamma}$ and $chi^{qp}_{T_1}$ are large enough to be probed experimentally. The odd-parity superconductivity is therefore concluded in these compounds. The NMR result provides a convincing way to classify the HF superconductors into either even- or odd- parity paring together with the identification for the gap structure, as long as the system has Kramers degeneracy.
Only few selected examples among the great diversity of anomalous rare earth skutterudite are reviewed. Focus is first given on PrFe4P12 in comparison with URu2Si2. For PrFe4P12, great progress has been made on determining the nature of the order parameter (OP). A non magnetic order parameter with a multipolar component emerges here while for URu2Si2 the nature of the so-called hidden order remains mysterious. The two systems have several similarities in their temperature--pressure (T, P) and magnetic field--temperature (H, T) phase diagrams, in their spin dynamics, in their nesting character and in their high sensitivity to impurities. Advances on one side must stimulate new views on the other. Besides general considerations on the choice of the OP, a simple basic problem is the treatment of the Kondo coupling in a system with low charge carrier number for the cases of uncompensated and compensated semi-metal. An interesting problem is also the possible decoupling between exciton modes and itinerant carriers.
We report on systematic study of superconducting characteristics and Pr crystalline-electric-field (CEF) levels of filled-skutterudite pra ($T_{rm c}$ = 2.33 K). The temperature dependences of the upper critical field $H_{rm c2}$ and the Ginzburg-Landau (Maki) parameter $kappa_2$ suggest an s-wave clean-limit superconductivity. The electronic specific heat coefficient $gamma sim 95$ mJ/K$^2$mol, being $sim 1.5$ times larger than that for lra, indicates $4f$-originating quasiparticle mass enhancement. Magnetic susceptibility $chi(T)$ indicates that the CEF ground state is a $Gamma_1$ singlet and a $Gamma_4^{(1)}$ triplet first excited state lies at $Delta_{rm CEF}sim 30$ K above. Systematic comparison among pos, prs, pra and La-based reference compounds suggests that inelastic exchange- and aspherical-charge-scatterings of conduction electrons from CEF-split $4f$ levels play an essential role for the quasiparticle mass enhancement and the value of $T_{rm c}$ in the Pr-based filled skutterudites.
A technique for measuring the electrical resistivity and absolute thermopower is presented for pressures up to 30 GPa, temperatures down to 25 mK and magnetic fields up to 10 T. With the examples of CeCu2Ge2 and CeCu2Si2 we focus on the interplay of normal phase and superconducting properties. With increasing pres- sure, the behaviour of CeCu2Ge2 evolves from that of an antiferromagnetically ordered Kondo system to that characteristic of an intermediate valence compound as the Kondo temperature increases by about two orders of magnitude. In the pressure window 8-10 < P < 20 GPa, a superconducting phase occurs which com- petes at low pressure with magnetic ordering. For CeCu2Si2 the effective mass of carriers is probed by both the coefficient of the Fermi liquid law and the ini- tial slope of the upper critical field. The magnetic instability is studied no- tably for CeRu2Ge2 and Yb-based compounds for which pressure-induced magnetic ordering tends to develop. Finally, contrary to conventional wisdom, we argue that in heavy fermions a large part of the residual resistivity is most likely not independent of temperature; tentatively ascribed to Kondo hole, it can be very pressure as well as sample dependent. [electrical resistivity, thermoelectric power, heavy fermion, magnetic order, superconductivity]
Comprehensive magnetic-field-orientation dependent studies of the susceptibility and de Haas-van Alphen effect have been carried out on single crystals of the filled skutterudites PrOs$_4$As$_{12}$ and LaOs$_4$As$_{12}$ using magnetic fields of up to 40~T. Several peaks are observed in the low-field susceptibility of PrOs$_4$As$_{12}$, corresponding to cascades of metamagnetic transitions separating the low-field antiferromagnetic and high-field paramagnetic metal (PMM) phases. The de Haas-van Alphen experiments show that the Fermi-surface topologies of PrOs$_4$As$_{12}$ in its PMM phase and LaOs$_4$As$_{12}$ are very similar. In addition, they are in reasonable agreement with the predictions of bandstructure calculations for LaOs$_4$As$_{12}$ on the PrOs$_4$As$_{12}$ lattice. Both observations suggest that the Pr 4$f$ electrons contribute little to the number of itinerant quasiparticles in the PMM phase. However, whilst the properties of LaOs$_4$As$_{12}$ suggest a conventional nonmagnetic Fermi liquid, the effects of direct exchange and electron correlations are detected in the PMM phase of PrOs$_4$As$_{12}$. For example, the quasiparticle effective masses in PrOs$_4$As$_{12}$ are found to decrease with increasing field, probably reflecting the gradual suppression of magnetic fluctuations associated with proximity to the low-temperature, low-field antiferromagnetic state.