Evidence of unconventional superconductivity on the surface of the nodal semimetal CaAg1-xPdxP.

Surface states of topological materials provide extreme electronic states for unconventional superconducting states. CaAg1-xPdxP is an ideal candidate for a nodal-line Dirac semimetal with drumhead surface states and no additional bulk bands. Here, we report that CaAg1-xPdxP has surface states that exhibit unconventional superconductivity (SC) around 1.5 K. Extremely sharp magnetoresistance, tuned by surface-sensitive gating, determines the surface origin of the ultrahigh-mobility "electrons." The Pd-doping elevates the Fermi level towards the surface states, and as a result, the critical temperature (Tc) is increased up to 1.7 K from 1.2 K for undoped CaAgP. Furthermore, a soft point-contact study at the surface of Pd-doped CaAgP proved the emergence of unconventional SC on the surface. We observed the bell-shaped conductance spectra, a hallmark of the unconventional SC. Ultrahigh mobility carriers derived from the surface flat bands generate a new class of unconventional SC.

Superconductivity in High-Entropy Antimonide M1-xPtxSb (M = Equimolar Ru, Rh, Pd, and Ir).

The high-entropy concept was applied to the synthesis of transition-metal antimonides, M1-xPtxSb (M = equimolar Ru, Rh, Pd, and Ir). High-entropy antimonide samples crystallized in a pseudo-hexagonal NiAs-type crystal structure with a P63/mmc space group were successfully synthesized through a conventional solid-state reaction and subsequent quenching. A detailed investigation of the composition and equilibration conditions confirmed the reversible phase transition between a multiphase state at low temperature and an entropy-driven single-phase solid solution at high temperatures. Electrical resistivity, magnetization, and heat capacity measurements of single-phase M1-xPtxSb (x = 0.2) samples revealed a bulk superconducting transition at 2.15(2) K. This study demonstrates that the high-entropy concept provides numerous opportunities for the discovery of new functional materials such as superconductors.

Regular-triangle trimer and charge order preserving the Anderson condition in the pyrochlore structure of CsW2O6.

Since the discovery of the Verwey transition in magnetite, transition metal compounds with pyrochlore structures have been intensively studied as a platform for realizing remarkable electronic phase transitions. We report on a phase transition that preserves the cubic symmetry of the ß-pyrochlore oxide CsW2O6, where each of W 5d electrons are confined in regular-triangle W3 trimers. This trimer formation represents the self-organization of 5d electrons, which can be resolved into a charge order satisfying the Anderson condition in a nontrivial way, orbital order caused by the distortion of WO6 octahedra, and the formation of a spin-singlet pair in a regular-triangle trimer. An electronic instability due to the unusual three-dimensional nesting of Fermi surfaces and the strong correlations of the 5d electrons characteristic of the pyrochlore oxides are both likely to play important roles in this charge-orbital-spin coupled phenomenon.

Giant isotropic negative thermal expansion in Y-doped samarium monosulfides by intra-atomic charge transfer.

Stimulated by strong demand for thermal expansion control from advanced modern industries, various giant negative thermal expansion (NTE) materials have been developed during the last decade. Nevertheless, most such materials exhibit anisotropic thermal expansion in the crystal lattice. Therefore, strains and cracks induced during repeated thermal cycling degrade their performance as thermal-expansion compensators. Here we achieved giant isotropic NTE with volume change exceeding 3%, up to 4.1%, via control of the electronic configuration in Sm atoms of SmS, (4 f)6 or (4 f)5(5d)1, by partial replacement of Sm with Y. Contrary to NTE originating from cooperative phenomena such as magnetism, the present NTE attributable to the intra-atomic phenomenon avoids the size effect of NTE and therefore provides us with fine-grained thermal-expansion compensators, which are strongly desired to control thermal expansion of microregions such as underfill of a three-dimensional integrated circuit. Volume control of lanthanide monosulfides via tuning of the 4 f electronic configuration presents avenues for novel mechanical functions of a material, such as a volume-change driven actuator by an electrical field, which has a different drive principle from those of conventional strain-driven actuators such as piezostrictive or magnetostrictive materials.

Progress of Research in Negative Thermal Expansion Materials: Paradigm Shift in the Control of Thermal Expansion.

To meet strong demands for the control of thermal expansion necessary because of the advanced development of industrial technology, widely various giant negative thermal expansion (NTE) materials have been developed during the last decade. Discovery of large isotropic NTE in ZrW2O8 has greatly advanced research on NTE deriving from its characteristic crystal structure, which is now classified as conventional NTE. Materials classified in this category have increased rapidly. In addition to development of conventional NTE materials, remarkable progress has been made in phase-transition-type NTE materials using a phase transition accompanied by volume contraction upon heating. These giant NTE materials have brought a paradigm shift in the control of thermal expansion. This report classifies and reviews mechanisms and materials of NTE to suggest means of improving their functionality and of developing new materials. A subsequent summary presents some recent activities related to how these giant NTE materials are used as practical thermal expansion compensators, with some examples of composites containing these NTE materials.

Colossal negative thermal expansion in reduced layered ruthenate.

Large negative thermal expansion (NTE) has been discovered during the last decade in materials of various kinds, particularly materials associated with a magnetic, ferroelectric or charge-transfer phase transition. Such NTE materials have attracted considerable attention for use as thermal-expansion compensators. Here, we report the discovery of giant NTE for reduced layered ruthenate. The total volume change related to NTE reaches 6.7% in dilatometry, a value twice as large as the largest volume change reported to date. We observed a giant negative coefficient of linear thermal expansion α=-115 × 10-6 K-1 over 200 K interval below 345 K. This dilatometric NTE is too large to be attributable to the crystallographic unit-cell volume variation with temperature. The highly anisotropic thermal expansion of the crystal grains might underlie giant bulk NTE via microstructural effects consuming open spaces in the sintered body on heating.

Giant barocaloric effect enhanced by the frustration of the antiferromagnetic phase in Mn3GaN.

First-order phase transitions are accompanied by a latent heat. Consequently, manipulating them by means of an external field causes a caloric effect. Although transitions from antiferromagnetic to paramagnetic states are not controlled by a magnetic field, a large barocaloric effect is expected when strong cross-correlations between the volume and magnetic order occur. Here we examine how geometric frustration in itinerant antiferromagnetic compounds can enhance the barocaloric effect. We study the thermodynamic behaviour of the frustrated antiferromagnet Mn3GaN, and report an entropy change of 22.3 J kg(-1) K(-1) that is concomitant with a hydrostatic pressure change of 139 MPa. Furthermore, the calculated value of the adiabatic temperature change reaches 5 K by depressurization of 93 MPa. The giant barocaloric effect in Mn3GaN is caused by a frustration-driven enhancement of the ratio of volume change against the pressure coefficient of the Néel temperature. This mechanism for enhancing the barocaloric effect can form the basis for a new class of materials for solid-state refrigerants.

Magnetovolume effects in manganese nitrides with antiperovskite structure.

Magnetostructural correlations in antiperovskite manganese nitrides were investigated systematically for stoichiometric and solid solution Mn3Cu1-x A x N (A = Co, Ni, Zn, Ga, Ge, Rh, Pd, Ag, In, Sn or Sb). This class of nitrides is attracting great attention because of their giant negative thermal expansion, which is achieved by doping Ge or Sn into the A site as a relaxant of the sharp volume contraction on heating (spontaneous volume magnetostriction ωs) because of the magnetovolume effects. The physical background of large ωs and mechanism of how the volume contraction becomes gradual with temperature are central concerns for the physics and applications of these nitrides. An entire dataset of thermal expansion, crystal structure and magnetization demonstrates that the cubic triangular antiferromagnetic state is crucial for large ωs. The intimate relationship between ωs and the magnetic structure is discussed in terms of geometrical frustration related to the Mn6N octahedron and magnetic stress concept. The results presented herein also show that ωs depends on the number of d electrons in the A atom, suggesting the important role of the d orbitals of the A atom. Not all the dopants in the A site, but the elements that disturb the cubic triangular antiferromagnetic state, are effective in broadening the volume change. This fact suggests that instability neighboring the phase boundary is related to the broadening. The relation between the gradual volume change and the local structure anomaly is suggested by recent microprobe studies.

Negative thermal expansion materials: technological key for control of thermal expansion.

Most materials expand upon heating. However, although rare, some materials contract upon heating. Such negative thermal expansion (NTE) materials have enormous industrial merit because they can control the thermal expansion of materials. Recent progress in materials research enables us to obtain materials exhibiting negative coefficients of linear thermal expansion over -30 ppm K-1. Such giant NTE is opening a new phase of control of thermal expansion in composites. Specifically examining practical aspects, this review briefly summarizes materials and mechanisms of NTE as well as composites containing NTE materials, based mainly on activities of the last decade.