We present the results of electrical resistivity, ac specific heat, magnetic susceptibility, X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) of the ternary iron arsenide EuFe2As2 single crystal under pressure. Applying pressure leads to a continuous suppression of the antiferromagnetism associated with Fe moments and the antiferromagnetic transition temperature becomes zero in the vicinity of a critical pressure Pc ~2.5-2.7 GPa. Pressure-induced re-entrant superconductivity, which is highly sensitive to the homogeneity of the pressure, only appears in the narrow pressure region in the vicinity of Pc due to the competition between superconductivity and the antiferromagnetic ordering of Eu2+ moments. The antiferromagnetic state of Eu2+ moments changes to the ferromagnetic state above 6 GPa. We also found that the ferromagnetic order is suppressed with further increasing pressure, which is connected with a valence change of Eu ions.
We have studied the Ce valence as a function of pressure in CeRhIn5 at 300 K and at 22 K using x-ray absorption spectroscopy in partial fluorescent yield mode. At room temperature, we found no detectable change in Ce valence greater than 0.01 up to a pressure of 5.5 GPa. At 22 K, the valence remains robust against pressure below 6 GPa, in contrast to the predicted valence crossover at P=2.35 GPa. This work yields an upper limit for the change in Ce-valence and suggests that the critical valence fluctuation scenario, in its current form, is unlikely.
A review is given of pressure induced valence transitions in f-electron systems calculated with the self-interaction corrected local spin density (SIC-LSD) approximation. These calculations show that the SIC-LSD is able to describe valence changes as a function of pressure or chemical composition. An important finding is the dual character of the f-electrons as either localized or band-like. A finite temperature generalisation is presented and applied to the study of the p-T phase diagram of the alpha to gamma phase transition in Ce.
Superconductivity can be realized in Eu-containing pnictides by application of chemical (internal) and physical (external) pressure, the intrinsic physical mechanism of which attracts much attention in physics community. Here we present the experimental evidence for the valence change of europium in compounds of EuFe2As1.4P0.6 exposed to ambient pressure and EuFe2As2 to high pressure by x-ray absorption measurements on L3-Eu edge. We find that the absorption spectrum of EuFe2As1.4P0.6 at ambient pressure shows clear spectra weight transfer from a divalent to a trivalent state. Furthermore, app…
We present accurate electrical resistivity measurements along the two principle crystallographic axes of the pressure-induced heavy-fermion superconductor CeRhIn5 up to 5.63 GPa. For both directions, a valence crossover line is identified in the p-T plane and the extrapolation of this line to zero temperature coincides with the collapse of the magnetic ordering temperature. Furthermore, it is found that the p-T phase diagram of CeRhIn5 in the valence crossover region is very similar to that of CeCu2Si2. These results point to the essential role of Ce-4f electron delocalization in both destroyi…
Simultaneous resistivity and a.c.-specific heat measurements have been performed under pressure on single crystalline CeCu2Si2 to over 6 GPa in a hydrostatic helium pressure medium. A series of anomalies were observed around the pressure coinciding with a maximum in the superconducting critical temperature, $T_c^{max}$. These anomalies can be linked with an abrupt change of the Ce valence, and suggest a second quantum critical point at a pressure $P_v \simeq 4.5$ GPa, where critical valence fluctuations provide the superconducting pairing mechanism, as opposed to spin fluctuations at ambient p…
It has been proposed that there are two types of superconductivity in CeCu2Si2, mediated by spin fluctuations at ambient pressure, and by critical valence fluctuations around a charge instability at a pressure P_v \simeq 4.5 GPa. We present in detail some of the unusual features of this novel type of superconducting state, including the coexistence of superconductivity and huge residual resistivity of the order of the Ioffe-Regel limit, large and pressure dependent resistive transition widths in a single crystal measured under hydrostatic conditions, asymmetric pressure dependence of the speci…
UTe$_2$ is a recently discovered unconventional superconductor that has attracted much interest due to its many intriguing properties - a large residual density-of-states in the superconducting state, re-entrant superconductivity in high magnetic fields, and potentially spin-triplet topological superconductivity. Our ac calorimetry, electrical resistivity, and x-ray absorption study of UTe$_2$ under applied pressure reveals key new insights on the superconducting and magnetic states surrounding pressure-induced quantum criticality at P$_{c1}$ = 1.3 GPa. First, our specific heat data at low pre…
We present the pressure-temperature phase diagram of the antiferromagnet CeAg$_2$Si$_2$ established via resistivity and calorimetry measurements under quasi-hydrostatic conditions up to 22.5~GPa. With increasing pressure, the Néel temperature [$T_{\mathrm{N}}(p=0)=8.6$~K] slowly increases up to $T_{\mathrm{N}}=13.4$~K at 9.4~GPa and then vanishes abruptly at the magnetic critical pressure $p_{\mathrm{c}}\sim13$~GPa. For the first time, heavy fermion superconductivity is observed in CeAg$_2$Si$_2$ . Superconductivity emerges at $\sim 11$~GPa and persists over roughly 10~GPa. Partial- and bulk-t…
"F-free" CeOBiS$_2$ single crystals have successfully grown, thoroughly eliminating a concern about F-contamination by using a high-purity CsCl flux. The obtained crystals have a plate-like shape with a size of 1.0-3.0 mm in the well-developed plane. Single crystal X-ray structural analysis clearly revealed that the CeOBiS$_2$ crystallizes with a space group $P4/nmm$ (with lattice parameters of $a$ = 4.0189(6) Å, $c$ = 13.573(2) Å). The bond valence sum estimation and X-ray photoelectron spectroscopy analysis showed that the chemical state of Ce was in the mixed valence of Ce$^{3+}$ and Ce$^{4…
We report on a pressure-induced evolution of exotic superconductivity and spin correlations in CeIr(In$_{1-x}$Cd$_{x}$)$_5$ by means of In-Nuclear-Quadrupole-Resonance (NQR) studies. Measurements of an NQR spectrum and nuclear-spin-lattice-relaxation rate $1/T_1$ have revealed that antiferromagnetism induced by the Cd-doping emerges locally around Cd dopants, but superconductivity is suddenly induced at $T_c$ = 0.7 and 0.9 K at 2.34 and 2.75 GPa, respectively. The unique superconducting characteristics with a large fraction of the residual density of state at the Fermi level that increases wit…
We review the evidence supporting valence-fluctuation mediated superconductivity in CeCu2Si2 and CeCu2Ge2, where Tc reaches 2.4 K at high pressure. In these systems the valence and magnetic critical points, at p_V and p_c respectively, are well separated. Characteristic signatures associated with both phenomena are distinct. In contrast, the valence and spin fluctuation regions appear much closer in most Ce based compounds. Concerning d-transition metals, superconductivity in pure iron emerges in the pressure window 15-30 GPa with the onset of Tc up to almost 3 K. All relevant observations poi…
Mott insulator superconductor transition, via pressure and no external doping, is studied in orbitally non degenerate spin-\half systems. It is presented as another RVB route to high \tc superconductivity. We propose a `strong coupling' hypothesis which helps to view first order Mott transition as a self doping process that also preserves superexchange on metal side . We present a generalized t-J model where a conserved $N_0$ doubly occupied ($e^-$) sites and $N_0$ empty sites ($e^+$) hop in the background of $N - 2 N_0$ singly singly occupied (neutral) sites in a lattice of N sites. An equiva…
Despite almost 40 years of research, the origin of heavy-fermion superconductivity is still strongly debated. Especially, the pressure-induced enhancement of superconductivity in CeCu$_2$Si$_2$ away from the magnetic breakdown is not sufficiently taken into consideration. As recently reported in CeCu$_2$Si$_2$ and several related compounds, optimal superconductivity occurs at the pressure of a valence crossover, which arises from a virtual critical end point at negative temperature $T_{\rm cr}$. In this context, we did a meticulous analysis of a vast set of top-quality high-pressure electrical…
We have investigated the Mott transition in a quasi-two-dimensional Mott insulator EtMe$_3$P[Pd(dmit)$_2$]$_2$ with a spin-frustrated triangular lattice in hydrostatic pressure and magnetic field. In the pressure-temperature ($P$-$T$) phase diagram, a valence bond solid phase is found to neighbor the superconductor and metal phases at low temperatures. The profile of the phase diagram is common to those of Mott insulators with antiferromagnetic order. In contrast to the antiferromagnetic Mott insulators, the resistivity in the metallic phase exhibits anomalous temperature dependence, $ρ= ρ_0 +…
We report comprehensive high pressure studies on correlation between intercalated magnetic layers and superconductivity in EuFe2(As0.81P0.19)2 single crystal through in-situ high pressure resistance, specific heat, X-ray diffraction and X-ray absorption measurements. We find that an unconfirmed magnetic order of the intercalated layers coexists with superconductivity in a narrow pressure range 0-0.5GPa, and then it converts to a ferromagnetic (FM) order at pressure above 0.5 GPa, where its superconductivity is absent. The obtained temperature-pressure phase diagram clearly demonstrates that th…
Effects of inhomogeneous doping on the high-$T_c$ cuprate superconductors are studied within the framework of the t-J model. Especially, the boundary between two non-superconducting regions with doping rates much higher and lower than the optimal one is examined. It is found that, although there is no superconductivity in the bulk, a superconducting region appears at the boundary because singlet resonating valence bond order and holon condensation occur simultaneously in this region. The critical temperature of the induced superconductivity can be higher than that of the optimally doped sample…
Unconventional superconductivity frequently emerges as the transition temperature of a magnetic phase, typically antiferromagnetic, is suppressed continuously toward zero temperature. Here, we report contrary behavior in pressurized CeRhGe3, a non-centrosymmetric heavy fermion compound. We find that its pressure-tuned antiferromagnetic transition temperature (TN) appears to avoid a continuous decrease to zero temperature by terminating abruptly above a dome of pressure-induced superconductivity. Near 21.5 GPa, evidence for TN suddenly vanishes, the electrical resistance becomes linear in tempe…
Sulfur-doped SnSe single crystal was successfully synthesized using a melt and slow-cooling method. The chemical composition and valence state of the obtained sample were analyzed by X-ray photoelectron spectroscopy. The pressure range of a diamond anvil cell with boron-doped diamond electrodes was upgraded to 104 GPa using nano-polycrystalline diamond anvil to investigate a pressure effect for the sample. Electrical resistivity measurements of sulfur-doped SnSe single crystal showed the insulator-metal-superconductor transition by applying high pressure up to 75.9 GPa.
We measured the electrical resistivity of a BiS2-based compound EuFBiS2 under high pressure. Polycrystalline EuFBiS2 shows insulator-metal transition and pressure-induced superconductivity above 0.7 GPa. The superconducting transition temperature increases with increasing applied pressure and shows the maximum value around 8.6 K at 1.8 GPa.
The evolution of pressure induced superconductivity in single crystal as well as polycrystalline samples of BaFe2As2 has been investigated through temperature dependent electrical resistivity studies in 0-7 GPa pressure range. While the superconducting transition remains incomplete in polycrystalline sample, a clear pressure induced superconductivity with zero resistivity at the expense of magnetic transition, associated with spin density wave (SDW), is observed in the single crystal sample. The superconducting transition temperature (TC) is seen to increase upto a moderate pressure of about ~…
Pressure-induced superconductivity and its relation to corresponding Hall coefficient (RH) have been reported for Bi2Te3, one of known topological insulators. A full phase diagram is presented which shows a complex dependence of the superconducting transition temperature as a function of pressure over an extensive range. High-pressure RH measurements reveal a close relation of these complex behaviors, particularly, a dramatic change of dRH/dP before structural phase transition and a pressure-induced crossover on RH in the high pressure phase were observed.
Many cerium-based heavy fermion (HF) compounds have pressure-temperature phase diagrams in which a superconducting region extends far from a magnetic quantum critical point. In at least two compounds, CeCu2Si2 and CeCu2Ge2, an enhancement of the superconducting transition temperature was found to coincide with an abrupt valence change, with strong circumstantial evidence for pairing mediated by critical valence, or charge transfer, fluctuations. This pairing mechanism, and the valence instability, is a consequence of a f-c Coulomb repulsion term U_fc in the hamiltonian. While some non-supercon…
We show theoretically that the nuclear spin-lattice relaxation rate (T_1T)^{-1} and the spin susceptibility exhibit divergent behaviors toward zero temperature at the quantum critical point (QCP) of the first-order valence transition. Remarkable enhancement in (T_1T)^{-1} and the spin susceptibility is induced by valence fluctuations even at the valence-crossover temperature far away from the QCP. This mechanism well explains peculiar behaviors observed recently in YbAuCu_4 and also gives a systematic explanation for YbXCu_4 for X=In, Au, Ag, Tl, and Pd from the viewpoint of the closeness to t…
The sodium rhodate NaRh2O4 was synthesized for the first time and characterized by neutron and x-ray diffraction studies, measurements of magnetic susceptibility, specific heat, electrical resistivity, and the Seebeck coefficient. NaRh2O4 crystallizes in the CaFe2O4-type structure, which is comprised of a characteristic RhO6 octahedra network. The compound is metallic in nature, probably reflecting the 1 to 1 mixed valence character of Rh(III) and Rh(IV) in the network. For further studies of the compound, the Rh valence was varied significantly by means of an aliovalent substitution: the full…
We design and investigate the physical properties of new indium compounds AInX$_{3}$ (A = alkali metals, X = F or Cl). We find nine new In based materials in their ground state and are thermodynamically stable but are not reported in ICSD (Inorganic Crystal Structure Database). We also discuss several metastable structures. This new series of materials display multiple valences, charge and bond disproportionation, and dimerization. The most common valence of In is 3+. We also find two rare alternatives, one has In$^{2+}$ with In-In dimerization and the other shows valence disproportionation to…
The roles of critical valence fluctuations of Ce and Yb are discussed as a key origin of several anomalies observed in Ce- and Yb-based heavy fermion systems. Recent development of the theory has revealed that a magnetic field is an efficient control parameter to induce the critical end point of the first-order valence transition. Metamagnetism and non-Fermi liquid behavior caused by this mechanism are discussed by comparing favorably with CeIrIn5, YbAgCu4, and YbIr2Zn20. The interplay of the magnetic order and valence fluctuations offers a key concept for understanding Ce- and Yb-based system…
We show that superconductivity is absent within the 1/2-filled band triangular lattice repulsive Hubbard model that has been proposed for organic charge-transfer solids. We posit that organic superconductivity is rather reached from a Bond-Charge Density Wave that either constitutes the insulating state proximate to superconductivity, or is extremely close in energy to the antiferromagnetic state, and replaces the latter under pressure. The Bond-Charge Density Wave can be described within an effective attractive $U$ extended Hubbard Hamiltonian with repulsive nearest neighbor interaction $V$. …
The mechanism of how critical end points of the first-order valence transitions (FOVT) are controlled by a magnetic field is discussed. We demonstrate that the critical temperature is suppressed to be a quantum critical point (QCP) by a magnetic field. This results explain the field dependence of the isostructural FOVT observed in Ce metal and YbInCu_4. Magnetic field scan can lead to reenter in a critical valence fluctuation region. Even in the intermediate-valence materials, the QCP is induced by applying a magnetic field, at which the magnetic susceptibility also diverges. The driving force…
Low-temperature (T) heat-capacity measurements under hydrostatic pressure of up to p=2.1 GPa have been performed on single-crystalline CeCu2Si2. A broad superconducting (SC) region exists in the T-p phase diagram. In the low-pressure region antiferromagnetic spin fluctuations and in the high-pressure region valence fluctuations had previously been proposed to mediate Cooper pairing. We could identify these two distinct SC regions. We found different thermodynamic properties of the SC phase in both regions, supporting the proposal that different mechanisms might be implied in the formation of s…
