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We investigated the pressure dependence of electric transport in a superconducting sample, Ba0.77Na0.23Ti2Sb2O, to complete the phase diagram of superconducting transition temperature (Tc) against pressure (p). This superconducting sample exhibits a Tc value of 5.8 K at ambient pressure. Here, the superconductivity of the recently reported sample was investigated over a wide pressure range. The Tc value monotonously decreased with pressure below 8 GPa. Interestingly, the Tc value rapidly increased above 8 GPa and slowly declined with pressure above 11 GPa. Thus, a new superconducting phase was discovered above ∼9 GPa. The crystal structure of Ba0.77Na0.23Ti2Sb2O was also elucidated at 0-22.0 GPa with synchrotron X-ray powder diffraction. Consequently, an evident relation between the crystal structure and the superconductivity was revealed, namely, a clear structural phase transition was observed at 8-11 GPa, where the Tc value rapidly increased against pressure. This study provides detailed information on the superconductivity of Ba0.77Na0.23Ti2Sb2O under pressure, which will lead to a comprehensive understanding of pressure-driven superconductivity.

Herein, we report the preparation and characterization of BaBi3 clarified by DC magnetic susceptibility, powder X-ray diffraction (XRD), and electrical transport. The superconducting properties of BaBi3 were elucidated through the magnetic and electrical transport properties in a wide pressure range. The superconducting transition temperature, Tc, showed a slight decrease (or almost constant Tc) against pressure up to 17.2 GPa. The values of the upper critical field, Hc2, at 0 K, were determined to be 1.27 T at 0 GPa and 3.11 T at 2.30 GPa, using the formula, because p-wave pairing appeared to occur for this material at both pressures, indicating the unconventionality of superconductivity. This result appears to be consistent with the topological non-trivial nature of superconductivity predicted theoretically. The pressure-dependent XRD patterns measured at 0–20.1 GPa indicated no structural phase transitions up to 20.1 GPa, i.e., the structural phase transitions from the α phase to the β or γ phase which are induced by an application of pressure were not observed, contrary to the previous report, demonstrating that the α phase is maintained over the entire pressure range. Admittedly, the lattice constants and the volume of the unit cell, V, steadily decrease with increasing pressure up to 20.1 GPa. In this study, the plots of Tcversus p and V versus p of BaBi3 are depicted over a wide pressure range for the first time.

A superconducting KBi2 sample was successfully prepared using a liquid ammonia (NH3) technique. The temperature dependence of the magnetic susceptibility (M/H) showed a superconducting transition temperature (Tc) as high as 3.6 K. In addition, the shielding fraction at 2.0 K was evaluated to be 87%, i.e., a bulk superconductor was realized using the above method. The Tc value was the same as that reported for the KBi2 sample prepared using a high-temperature annealing method. An X-ray diffraction pattern measured based on the synchrotron X-ray radiation was analyzed using the Rietveld method, with a lattice constant, a, of 9.5010(1) A under the space group of Fd[3 with combining macron]m (face-centered cubic, no. 227). The lattice constant and space group found for the KBi2 sample using a liquid NH3 technique were the same as those reported for KBi2 through a high-temperature annealing method. Thus, the superconducting behavior and crystal structure of the KBi2 sample obtained in this study are almost the same as those for the KBi2 sample reported previously. Strictly speaking, the magnetic behavior of the superconductivity was different from that of a KBi2 sample reported previously, i.e., the KBi2 sample prepared using a liquid NH3 technique was a type-II like superconductor, contrary to that prepared using a high-temperature annealing method, the reason for which is fully discussed. These results indicate that the liquid NH3 technique is effective and simple for the preparation of a superconducting KBi2. In addition, the topological nature of the superconductivity for KBi2 was not confirmed.

A new superconducting sample, BaTi2Bi2O, was synthesized and characterized over a wide pressure range. The superconducting transition temperature, Tc, of BaTi2Bi2O was 4.33 K at ambient pressure. The crystal structure was tetragonal (space group of P4/mmm (No. 123)), according to the X-ray diffraction (XRD) pattern at ambient pressure. The XRD pattern was analyzed using the Le Bail method. The magnetic-field dependence of the magnetization at different temperatures was precisely investigated to elucidate the characteristics of the superconductivity. The pressure-dependent XRD patterns showed absence of structural phase transitions up to 19.8 GPa. The superconducting properties of BaTi2Bi2O were investigated under pressure. Tc monotonously increased with the pressure (p) up to 4.0 GPa and saturated above 4.0 GPa. The variations in the Tc-p plot were thoroughly analyzed. The Cooper pair symmetry (or superconducting pairing mechanism) was analyzed based on the magnetic field dependence of the superconductivity at ambient and high pressures, which indicated a sign of p-wave pairing for the superconductivity of BaTi2Bi2O, i.e., topologically nontrivial sign was suggested for BaTi2Bi2O.

The pressure-induced change in the electronic structures of the superconductors ${\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$ and ${\mathrm{Ag}}_{x}{\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$ has been measured with high-resolution x-ray absorption spectroscopy. As a common feature for these compounds, we find that pressure causes the broadening of the Se $4p$ band and an energy shift of the Bi $6s$ band above the Fermi level up to the pressure of the first structural transition. These results, corroborated by density functional theory calculations, correlate with an increase of the carrier density, the disappearance of the band gap, and the emergence of superconductivity. The electronic structure changes significantly at the pressure of the first structural transition, which may be a trigger of the emergence of superconductivity, while above the pressure of the first phase transition it does not change much even around the second phase transition pressure, corresponding to the nearly constant ${T}_{\mathrm{c}}$ above the pressure of the second structural transition.

The crystal structures of Sb2Te3-ySey(y = 0.6 and y = 1.2) at 0 - 24 GPa were investigated by synchrotron X-ray diffraction (XRD). The stoichiometry of Sb2Te3-ySeyused in this study was determined to be Sb2Te2.19(9)Se0.7(2)for y = 0.6 and Sb2Te1.7(1)Se1.3(3)for y = 1.2, on the basis of energy-dispersive X-ray spectroscopy. The sample of Sb2Te2.19(9)Se0.7(2)showed a structural phase transition from a rhombohedral structure (space group No. 166,R3I…m) (phase I) to a monoclinic structure (space group No. 12,C2/m) (phase II), with increasing pressure up to ~9 GPa. A new structural phase (phase II') emerged at 17.7 GPa, a monoclinic structure with the space groupC2/c (No.15). Finally, a 9/10-fold monoclinic structure (space group No. 12,C2/m) (phase III) was observed at 21.8 GPa. In contrast, the sample of Sb2Te1.7(1)Se1.3(3) provided only phase I (space group No. 166,R3I…m) and phase II (space group No. 12,C2/m), showing one structural phase transition from 0 - 19.5 GPa. These samples were not superconductors at ambient pressure, but superconductivity suddenly appeared with increasing pressure. Superconductivity with superconducting transition temperatures (Tc's) of 2 and 4 K was observed above 6 GPa in phase I of Sb2Te2.19(9)Se0.7(2). In this sample, theTcvalues of 6 and 9 K were observed in phase II and phase II' or III of Sb2Te2.19(9)Se0.7(2), respectively. Superconductivity withTc's of 4 and 5 K suddenly emerged in Sb2Te1.7(1)Se1.3(3)at 13.6 GPa, which corresponds to phase II, and it evolved to 6.0 K under further increased pressure. ATcvalue of 9 K was finally found above 15 GPa. The magnetic field dependence ofTcin phase II of Sb2Te2.19(9)Se0.7(2)and Sb2Te1.7(1)Se1.3(3)followed ap-wave polar model, suggesting topologically nontrivial superconductivity.

We have produced a superconducting binary-elements intercalated graphite, CaxSr1−xCy, with the intercalation of Sr and Ca in highly-oriented pyrolytic graphite; the superconducting transition temperature, Tc, was ~3 K. The superconducting CaxSr1−xCy sample was fabricated with the nominal x value of 0.8, i.e., Ca0.8Sr0.2Cy. Energy dispersive X-ray (EDX) spectroscopy provided the stoichiometry of Ca0.5(2)Sr0.5(2)Cy for this sample, and the X-ray powder diffraction (XRD) pattern showed that Ca0.5(2)Sr0.5(2)Cy took the SrC6-type hexagonal-structure rather than CaC6-type rhombohedral-structure. Consequently, the chemical formula of CaxSr1−xCy sample could be expressed as ‘Ca0.5(2)Sr0.5(2)C6’. The XRD pattern of Ca0.5(2)Sr0.5(2)C6 was measured at 0–31 GPa, showing that the lattice shrank monotonically with increasing pressure up to 8.6 GPa, with the structural phase transition occurring above 8.6 GPa. The pressure dependence of Tc was determined from the DC magnetic susceptibility and resistance up to 15 GPa, which exhibited a positive pressure dependence of Tc up to 8.3 GPa, as in YbC6, SrC6, KC8, CaC6 and Ca0.6K0.4C8. The further application of pressure caused the rapid decrease of Tc. In this study, the fabrication and superconducting properties of new binary-elements intercalated graphite, CaxSr1−xCy, are fully investigated, and suitable combinations of elements are suggested for binary-elements intercalated graphite.

We systematically investigated the pressure dependence of electrical transport and the crystal structure of topological insulator, $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$, which showed no superconductivity down to 2.0 K at ambient pressure. The $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ crystal showed two structural phase transitions under pressure, from rhombohedral structure (space group No. 166, $R\overline{3}m$, termed phase I) to monoclinic structure (space group No. 12, $C2/m$, termed phase II), and from phase II to another monoclinic structure (space group No. 12, $C2/m$, termed phase III). Superconductivity appeared when applying pressure; actually the superconductivity of all $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ samples emerged in phase I. The superconducting transition temperature, ${T}_{\mathrm{c}}$, increased against pressure in a pressure range of 0--15 GPa for all $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ samples, and the maximum ${T}_{\mathrm{c}}$ was 5.45 K, recorded at 13.5 GPa in $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ at $x=0$ and $y=1.0$. The magnetic field (H) dependence of the R--T plot for $\mathrm{B}{\mathrm{i}}_{2\ensuremath{-}x}\mathrm{S}{\mathrm{b}}_{x}\mathrm{T}{\mathrm{e}}_{3\ensuremath{-}y}\mathrm{S}{\mathrm{e}}_{y}$ was measured to characterize the superconducting pairing mechanism of pressure-induced superconducting phase.

Metal intercalation to graphite produces various types of superconductors. The highest superconducting transition temperature Tc (onset temperature, Tconset, of 11.5 K) was found in Ca intercalated graphite, denoted CaC6. Tconset increased up to 15.1 K at 7.5 GPa, implying a positive pressure dependence. However, no new metal-intercalated graphite superconductors with Tconset higher than 11.5 K at ambient pressure have so far been reported. To search for new graphite superconductors, we successfully synthesized binary-element-intercalated graphite, CaxK1−xCy. Their structure resembles that of KC8. Tc increased continuously with increasing x. Furthermore, the pressure dependence of Tc in Ca0.6K0.4C8 was investigated over a wide pressure range from 0–43 GPa. Tc (= 9.6 K at 0 GPa) increased to 11.6 K at 3.3 GPa, and decreased to 2.0 K at 41 GPa. This behavior is similar to that of CaC6, albeit with a lower maximum Tc. X-ray diffraction patterns were measured under high pressures of 0–24 GPa, and suggest a structural transition at 15 GPa. Evidence is given for superconducting graphite involving binary metal intercalation.

The crystal structure of BiSbTeSe2 (Bi2-x Sb x Te3-y Se y (x = 1.0 and y = 2.0)) at 0-29 GPa is investigated through synchrotron x-ray diffraction (XRD) and two structural phase transitions are discovered. The stoichiometry of BiSbTeSe2 employed in this study is Bi1.19(4)Sb0.81(4)Te0.83(4)Se2.17(4), as determined from energy-dispersive x-ray spectroscopy. The sample demonstrated structural transitions, from a rhombohedral structure (space group no 166, R [Formula: see text] m) (phase I) to a monoclinic structure (space group no 12, C2/m) (phase II), and from phase II to a 9/10-fold monoclinic structure (space group no 12, C2/m) (phase III). The temperature dependence of resistance (R-T plot) exhibited a semiconducting behavior in a low pressure range and changed from semiconducting to metallic behavior with increasing pressure. Pressure-driven superconductivity is observed above 9.1 GPa in Bi1.19(4)Sb0.81(4)Te0.83(4)Se2.17(4). The pressure phase corresponds to phase II. The superconducting transition temperature, T c, increased with pressure. The maximum T c value is 8.3 K at 19.1 GPa. The magnetic field dependence of T c in phase II of Bi1.19(4)Sb0.81(4)Te0.83(4)Se2.17(4) is proceeded by a p-wave polar model, indicating topologically nontrivial superconductivity. In addition, the emergence of superconductivity and the change in superconducting behavior are closely associated with the structural transitions.

We synthesized the alkaline-earth metal-doped FeSe compounds (NH3) y AE x FeSe (AE: Ca, Sr and Ba), using the liquid NH3 technique, to determine their superconducting properties and crystal structures. Multiple superconducting phases were obtained in each sample of (NH3) y Ca x FeSe and (NH3) y Ba x FeSe, which showed two superconducting transition temperatures (T c's) as high as 37-39 K and 47-48 K at ambient pressure, hereinafter referred to as the 'low-T c phase' and 'high-T c phase', respectively. The high-T c phases in (NH3) y Ca x FeSe and (NH3) y Ba x FeSe were metastable, and rapidly converted to their low-T c phases. However, T c values of 38.4 K and 35.6 K were recorded for (NH3) y Sr x FeSe, which displayed different behavior than (NH3) y Ca x FeSe and (NH3) y Ba x FeSe. The Le Bail fitting of x-ray diffraction (XRD) patterns provided lattice constants of c = 16.899(1) A and c = 16.8630(8) A for the low-T c phases of (NH3) y Ca x FeSe and (NH3) y Ba x FeSe, respectively. The lattice constants of their high-T c phases could not be determined due to the disappearance of the high T c phase within a few days. The XRD pattern for (NH3) y Sr x FeSe indicated the coexistence of two phases with c = 16.899(3) A and c = 15.895(4) A. The former value of c in (NH3) y Sr x FeSe is almost the same as those of the low-T c phases in (NH3) y Ca x FeSe and (NH3) y Ba x FeSe. Therefore, the phase with c = 16.899(3) A in (NH3) y Sr x FeSe must correspond to the superconducting phase with the T c of 38.4 K, while the superconducting phase with T c = 35.6 K is assigned to the crystal phase with c = 15.895(4) A. For (NH3) y Sr x FeSe, a high-T c phase with T c = 47-48 K has not yet been obtained, but a new phase showing the T c value of 35.6 K was clearly obtained. This is the first systematic study of the preparation, crystal structure, and superconductivity of alkaline-earth metal-doped FeSe, (NH3) y AE x FeSe.

We investigated the temperature dependence of resistivity in thin crystals of FeSe1−xTex (x = 1.0, 0.95, and 0.9), though bulk crystals with 1.0 ≧ × ≧ 0.9 are known to be non-superconducting. With decreasing thickness of the crystals, the resistivity of x = 0.95 and 0.9 decreases and reaches zero at a low temperature, which indicates a clear superconducting transition. The anomaly of resistivity related to the structural and magnetic transitions completely disappears in 55- to 155-nm-thick crystals of x = 0.9, resulting in metallic behavior in the normal state. Microbeam x-ray diffraction measurements were performed on bulk single crystals and thin crystals of FeSe1−xTex. A significant difference of the lattice constant, c, was observed in FeSe1−xTex, which varied with differing Te content (x), and even in crystals with the same x, which was mainly caused by inhomogeneity of the Se/Te distribution. It has been found that the characteristic temperatures causing the structural and magnetic transition (T t), the superconducting transition (T c), and the zero resistivity (T c zero) are closely related to the value of c in thin crystals of FeSe1−xTex.

We prepared two superconducting phases, which are called “low-Tc phase” and “high-Tc phase” of (NH3)yNaxFeSe showing Tc’s of 35 and 44 K, respectively, at ambient pressure, and studied the superconducting behavior and structure of each phase under pressure. The Tc of the 35 K at ambient pressure rapidly decreases with increasing pressure up to 10 GPa, and it remains unchanged up to 22 GPa. Finally, superconductivity was not observed down to 1.4 K at 29 GPa, i.e., Tc < 1.4K. The Tc of the 44 K phase also shows a monotonic decrease up to 15 GPa and it weakly decreases up to 25 GPa. These behaviors suggest no pressure-driven high-Tc phase (called “SC-II”) between 0 and 25 GPa for the low-Tc and high-Tc phases of (NH3)yNaxFeSe, differing from the behavior of (NH3)yCsxFeSe,which has a pressure-driven high-Tc phase (SC-II) in addition to the superconducting phase (SC-I) observed at ambient and low pressures. The Tc-c phase diagram for both low-Tc and high-Tc phases shows that the Tc can be linearly scaled with c (or FeSe plane spacing), where c is a lattice constant. The reason why a pressure-driven high-Tc phase (SC-II) was found for neither low-Tc nor high-Tc phases of (NH3)yNaxFeSe is fully discussed, suggesting a critical c value as the key to forming the pressure-driven high-Tc phase (SC-II). Finally, the precise Tc-c phase diagram is depicted using the data obtained thus far from FeSe codoped with a metal and NH3 or amine, indicating two distinct Tc-c lines below c = 17.5A° .

We investigated the pressure dependence of electric transport and crystal structure of Ag-doped Bi2Se3. In the sample prepared by Ag doping of Bi2Se3, the Bi atom was partially replaced by Ag, i.e., Ag0.05Bi1.95Se3. X-ray diffraction patterns of Ag0.05Bi1.95Se3 measured at 0–30 GPa showed three different structural phases, with rhombohedral, monoclinic, and tetragonal structures forming in turn as pressure increased, and structural phase transitions at 8.8 and 24 GPa. Ag0.05Bi1.95Se3 showed no superconductivity down to 2.0 K at 0 GPa, but under pressure, superconductivity suddenly appeared at 11 GPa. The magnetic field (H) dependence of the superconducting transition temperature Tc was measured at 11 and 20.5 GPa, in order to investigate whether the pressure-induced superconducting phase is explained by either p-wave polar model or s-wave model.

‘Aromatic hydrocarbon’ implies an organic molecule that satisfies the (4 n + 2) π-electron rule and consists of benzene rings. Doping solid aromatic hydrocarbons with metals provides the superconductivity. The first discovery of such superconductivity was made for K-doped picene (K x picene, five benzene rings). Its superconducting transition temperatures ( T c ’s) were 7 and 18 K. Recently, we found a new superconducting K x picene phase with a T c as high as 14 K, so we now know that K x picene possesses multiple superconducting phases. Besides K x picene, we discovered new superconductors such as Rb x picene and Ca x picene. A most serious problem is that the shielding fraction is ⩽15% for K x picene and Rb x picene, and it is often ∼1% for other superconductors. Such low shielding fractions have made it difficult to determine the crystal structures of superconducting phases. Nevertheless, many research groups have expended a great deal of effort to make high quality hydrocarbon superconductors in the five years since the discovery of hydrocarbon superconductivity. At the present stage, superconductivity is observed in certain metal-doped aromatic hydrocarbons (picene, phenanthrene and dibenzopentacene), but the shielding fraction remains stubbornly low. The highest priority research area is to prepare aromatic superconductors with a high superconducting volume-fraction. Despite these difficulties, aromatic superconductivity is still a core research target and presents interesting and potentially breakthrough challenges, such as the positive pressure dependence of T c that is clearly observed in some phases of aromatic hydrocarbon superconductors, suggesting behavior not explained by the standard BCS picture of superconductivity. In this article, we describe the present status of this research field, and discuss its future prospects.

We prepared two superconducting phases of (NH3) y Li x FeSe0.5Te0.5, which show superconducting transition temperatures (T c’s) as high as 20.2 and 29.5 K at ambient pressure, here called the ‘low-T c phase’ and ‘high-T c phase’. The temperature dependence of electrical resistance (R) was measured for the low-T c phase of (NH3) y Li x FeSe0.5Te0.5 over a pressure (p) range of 0–14 GPa, and for the high-T c phase of (NH3) y Li x FeSe0.5Te0.5 over 0–19 GPa, yielding double-dome superconducting T c–p phase diagrams, i.e. two superconducting phases (SC-I and SC-II) were found for both the low-T c and high-T c phases under pressure. For the low-T c phase, the maximum T c was 20.2 K at 0 GPa for SC-I, and 19.9 K at 8.98 GPa for SC-II. For the high-T c phase, the maximum T c was 33.0 K at 1.00 GPa for SC-I, and 24.0 K at 11.5–13.2 GPa for SC-II. These results imply that the maximum T c value of the high pressure phase (SC-II) does not exceed the maximum value of the SC-I, unlike what was shown in the T c–p phase diagrams of (NH3) y Li x FeSe and (NH3) y Cs x FeSe investigated previously. Nevertheless, the double-dome T c–p phase diagram was found in metal-doped FeSe0.5Te0.5, indicating that this feature is universal in metal-doped FeSe1−z Te z . Moreover, no structural phase transitions were observed for either the low-T c or high-T c phases of (NH3) y Li x FeSe0.5Te0.5 over the wide pressure range of 0–15.3 GPa, and the T c-lattice constant (c) plots for both phases were recorded to determine the critical point separating SC-I and SC-II.

Herein, we investigated the pressure dependence of electric transport in a new type of superconducting metal iridate compound, SrIr2, that exhibits a superconducting transition temperature, T c, as high as 6.6 K at ambient pressure, in order to complete the T c-pressure (p ) phase diagram. Very recently, this sample's superconductivity was discovered by our group, but the superconducting behavior has not yet been clarified under pressure. In this study, we fully investigated this sample's superconductivity in a wide pressure range. The T c value decreased with an increase in pressure, but the onset superconducting transition temperature, [Formula: see text], increased above a pressure of 8 GPa, indicating an unconventional superconductivity different from a BCS-type superconductor. The magnetic field dependence of electric resistance (R) against temperature (R - T plot) recorded at 7.94 and 11.3 GPa suggested an unconventional superconductivity, followed by a p -wave polar model, supporting the deviation from a simple s-wave pairing. Moreover, we fully investigated the pressure dependence of crystal structure in SrIr2 and discussed the correlation between superconductivity and crystal structure. This is the first systematic study on superconducting behavior of a new type of metal iridate compound, MIr2 (M: alkali-earth metal atom), under pressure.

Na-intercalated FeSe0.5Te0.5 was prepared using the liquid NH3 technique, and a superconducting phase exhibiting a superconducting transition temperature (T-c) as high as 27 K was discovered. This can be called the high-T-c phase since a 21 K superconducting phase was previously obtained in (NH3)(y)NaxFeSe0.5Te0.5. The chemical composition of the high-T-c phase was determined to be (NH3)(0.61(4))Na-0.63(5) Fe0.85Se0.55(3) Te-0.44(2). The x-ray diffraction patterns of both phases show that a larger lattice constant c (i.e., FeSe0.5Te0.5 plane spacing) produces a higher T-c. This behavior is the same as that of metal-doped FeSe, suggesting that improved Fermi-surface nesting produces the higher T-c. The high-T-c phase converted to the low-T-c phase within several days, indicating that it is a metastable phase. The temperature dependence of resistance for both phases was recorded at different magnetic fields, and the critical fields were determined for both phases. Finally, the T-c versus c phase diagram was prepared for the metal-doped FeSe0.5Te0.5, which is similar to that of metal-doped FeSe, although the T-c is lower.

We report syntheses of new superconducting metal-doped MoSe2 materials (MxMoSe2). The superconducting MxMoSe2 samples were prepared using a liquid NH3 technique and can be represented as ‘(NH3)yMxMoSe2’. The Tcs of these materials were approximately 5.0 K, independent of x and the specific metal atom. X-ray diffraction patterns of (NH3)yNaxMoSe2 were recorded using polycrystalline powders. An increase in lattice constant c showed that the Na atom was intercalated between MoSe2 layers. The x-independence of c was observed in (NH3)yNaxMoSe2, indicating the formation of a stoichiometric compound in the entire x range, which is consistent with the x-independence of Tc. A metallic edge of the Fermi level was observed in the photoemission spectrum at 30 K, demonstrating its metallic character in the normal state. Doping of MoSe2 with Li and K also yielded superconductivity. Thus, MoSe2 is a promising material for designing new superconductors, as are other transition metal dichalcogenides.

The superconducting transition temperature T-c of ammoniated metal-doped FeSe (NH3)(y)MxFeSe (M: metal atom) has been scaled with the FeSe plane spacing, and it has been suggested that the FeSe plane spacing depends on the location of metal atoms in (NH3)(y)MxFeSe crystals. Although the crystal structure of (NH3)(y)LixFeSe exhibiting a high T-c (similar to 44 K) was determined from neutron diffraction, the structure of (NH3)(y)MxFeSe exhibiting a low T-c (similar to 32 K) has not been determined thus far. Here, we determined the crystal structure of (NH3)(y)Cs0.4FeSe (T-c = 33 K) through the Rietveld refinement of the x-ray diffraction (XRD) pattern measured with synchrotron radiation at 30 K. The XRD pattern was analyzed based on two different models, on-center and off-center, under a space group of 14/mmm. In the on-center structure, the Cs occupies the 2a site and the N of NH3 may occupy either the 4c or 2b site, or both. In the off-center structure, the Cs may occupy either the 4c or 2b site, or both, while the N occupies the 2a site. Only an on-center structure model in which the Cs occupies the 2a and the N of NH3 occupies the 4c site provided reasonable results in the Rietveld analysis. Consequently, we concluded that (NH3)(y)Cs0.4FeSe can be assigned to the on-center structure, which produces a smaller FeSe plane spacing leading to the lower T-c.

We produced a new superconducting binary elements intercalated graphite, CaxCs1−xCy, by the intercalation of Ca and Cs in highly-oriented pyrolytic graphite using the metal-alloy method. The superconducting CaxCs1−xCy sample was synthesized with the nominal x value of 0.8, i.e., Ca0.8Cs0.2Cy; its superconducting transition temperature, T c, was 7.4 K. Energy dispersive x-ray (EDX) spectroscopy provided the stoichiometry of Ca0.8(1)Cs0.2(1)Cy. The x-ray powder diffraction (XRD) pattern showed that Ca0.8(1)Cs0.2(1)Cy took on a CsC8-type hexagonal structure rather than a CaC6-type rhombohedral structure, suggesting that the chemical formula is 'Ca0.8(1)Cs0.2(1)C8'. The pressure dependence of T c for Ca0.8(1)Cs0.2(1)C8 was determined from the temperature dependence of its resistance under pressure, which exhibited a positive pressure dependence of T c below 9.3 GPa, and a rapid decrease above 9.3 GPa. We studied the pressure dependence of the crystal structure of Ca0.8(1)Cs0.2(1)C8, and the correlation between the T c and structure is fully discussed below.

We report experimental observation of the proximity-induced supercurrent in superconductor–multilayer graphene–superconductor junctions. We find that the supercurrent is a linearly decreasing function of the junction length (separation of the superconducting electrodes), which is quite different from the usual behavior of exponential dependence. We suggest that this behavior originates from the intrinsic large contact resistance between the multilayer and the superconducting electrodes.

We experimentally studied current–voltage characteristics of superconductor/thin graphite film/superconductor Josephson junctions. A reentrant behavior in the differential conductance was observed at low bias voltages just above the structure due to supercurrent. The gate voltage dependence of the conductance peak shows that the origin of the reentrant behavior is different from that for the conventional reentrant behavior seen in a disordered normal metal coupled to a superconductor.

We previously discovered multiple superconducting phases in the ammoniated Na-doped FeSe material, (NH3)yNaxFeSe. To clarify the origin of the multiple superconducting phases, the variation of Tc was fully investigated as a function of x in (NH3)yNaxFeSe. The 32 K superconducting phase is mainly produced in the low-x region below 0.4, while only a single phase is observed at x = 1.1, with Tc = 45 K, showing that the Tc depends significantly on x, but it changes discontinuously with x. The crystal structure of (NH3)yNaxFeSe does not change as x increases up to 1.1, i.e., the space group of I4/mmm. The lattice constants, a and c, of the low-Tc phase (Tc = 32.5 K) are 3.9120(9) and 14.145(8) Å, respectively, while a = 3.8266(7) Å and c = 17.565(9) Å for the high-Tc phase (~46 K). The c increases in the high Tc phase, implying that the Tc is directly related to c. In (NH3)yLixFeSe material, the Tc varies continuously within the range of 39 to 44 K with changing x. Thus, the behavior of Tc is different from that of (NH3)yNaxFeSe. The difference may be due to the difference in the sites that the Na and Li occupy.

We have studied new superconductors prepared by metal doping of two-dimensional (2D) layered materials, FeSe and FeSe0.5Te0.5, using ethylenediamine (EDA). The superconducting transition temperatures (T(c)s) of metal-doped FeSe and metal-doped FeSe0.5Te0.5, i.e., (EDA)(y)MxFeSe and (EDA)(y)MxFeSe0.5Te0.5 (M: Li, Na, and K), were 31-45 K and 19-25 K, respectively. The stoichiometry of each sample was clarified by energy dispersive x-ray (EDX) spectroscopy, and the x-ray powder diffraction pattern indicated a large expansion of lattice constant c, indicating the cointercalation of metal atoms and EDA. The pressure dependence of superconductivity in (EDA)(y)NaxFeSe0.5Te0.5 has been investigated at a pressure of 0-0.8GPa, showing negative pressure dependence in the same manner as (NH3)(y)NaxFeSe0.5Te0.5. The T-c-c phase diagrams of MxFeSe and MxFeSe0.5Te0.5 were drawn afresh from the T-c and c of (EDA)(y)MxFeSe and (EDA)(y)MxFeSe0.5Te0.5, showing that the T-c increases with increasing c but that extreme expansion of c reverses the T-c trend.

The pressure dependence of the superconducting transition temperature (Tc) and unit cell metrics of tetragonal (NH3)yCs0.4FeSe were investigated in high pressures up to 41 GPa. The Tc decreases with increasing pressure up to 13 GPa, which can be clearly correlated with the pressure dependence of c (or FeSe layer spacing). The Tcvs. c plot is compared with those of various (NH3)yMxFeSe (M: metal atoms) materials exhibiting different Tc and c, showing that the Tc is universally related to c. This behaviour means that a decrease in two-dimensionality lowers the Tc. No superconductivity was observed down to 4.3 K in (NH3)yCs0.4FeSe at 11 and 13 GPa. Surprisingly, superconductivity re-appeared rapidly above 13 GPa, with the Tc reaching 49 K at 21 GPa. The appearance of a new superconducting phase is not accompanied by a structural transition, as evidenced by pressure-dependent XRD. Furthermore, Tc slowly decreased with increasing pressure above 21 GPa and at 41 GPa superconductivity disappeared entirely at temperatures above 4.9 K. The observation of a double-dome superconducting phase may provide a hint for pursuing the superconducting coupling-mechanism of ammoniated/non-ammoniated metal-doped FeSe.

We experimentally investigated electrical transport in thin graphite films about 10 nm thick connected to superconducting leads. Proximity-induced superconductivity was observed and the critical supercurrent strongly depends on the gate voltage. From the maximum-to-minimum ratios of the critical supercurrent and the normal state resistance, we conclude that the major part of the supercurrent flows in a few graphene layers close to the gate electrode.

Alkali-metal-intercalated FeSe materials, (NH3)(y)M0.4FeSe (M: K, Rb, and Cs), have been synthesized using the liquid NH3 technique. (NH3)(y)Cs0.4FeSe shows a superconducting transition temperature (T-c) as high as 31.2 K, which is higher by 3.8 K than the T-c of nonammoniated Cs0.4FeSe. The T(c)s of (NH3)(y)K0.4FeSe and (NH3)(y)Rb0.4FeSe are almost the same as those of nonammoniated K0.4FeSe and Rb0.4FeSe. The T-c of (NH3)(y)Cs0.4FeSe shows a negative pressure dependence. A clear correlation between T-c and lattice constant c is found for ammoniated metal-intercalated FeSe materials, suggesting a correlation between Fermi-surface nesting and superconductivity.

We report the observation of zero resistivity (\ensuremath{\rho}) in a hydrocarbon superconductor, and describe the temperature dependence of \ensuremath{\rho} in metal-doped hydrocarbons. The resistivity of K-doped picene (K${}_{x}$picene) has been recorded from pellet samples in a four-terminal measurement mode. A drop in $\ensuremath{\rho}$ is observed below 7 K for K${}_{3.1}$picene and below 11 K for K${}_{3.5}$picene, which clearly displays zero resistivity. The resistivity drop at 7 K is consistent with the superconducting critical temperature (${T}_{\mathrm{c}}$) obtained from the magnetic susceptibility of the 7 K phase of K${}_{3}$picene, while the drop at 11 K is inconsistent with the ${T}_{\mathrm{c}}$'s of both the 7 and 18 K phases of K${}_{3}$picene reported previously. The temperature dependence of \ensuremath{\rho} for both samples exhibits granular-metal-like behavior in the normal state.

Electrostatic carrier-doping is attracting serious attention as a meaningful technique for producing interesting electronic states in two-dimensional (2D) layered materials. Ionic-liquid gating can provide the critical carrier density required to induce the metal-insulator transition and superconductivity. However, the physical properties of only a few materials have been controlled by the electrostatic carrier-doping during the past decade. Here, we report an observation of superconductivity in a 2D layered material, LaOBiS2, achieved by the electrostatic electron-doping. The electron doping of LaOBiS2 induced metallic conductivity in the normally insulating LaOBiS2, ultimately led to superconductivity. The superconducting transition temperature, Tc, was 3.6 K, higher than the 2.7 K seen in LaO1-xFxBiS2 with an electron-doped BiS2 layer. A rapid drop in resistance (R) was observed at low temperature, which disappeared with the application of high magnetic fields, implying a superconducting state. This st...

Potassium-doped picene (K3.0picene) with a superconducting transition temperature (T C) as high as 14 K at ambient pressure has been prepared using an annealing technique. The shielding fraction of this sample was 5.4% at 0 GPa. The T C showed a positive pressure-dependence and reached 19 K at 1.13 GPa. The shielding fraction also reached 18.5%. To investigate the chemical composition and the state of the picene skeleton in the superconducting sample, we used energy-dispersive x-ray (EDX) spectroscopy, MALDI-time-of-flight (MALDI-TOF) mass spectroscopy and x-ray diffraction (XRD). Both EDX and MALDI-TOF indicated no contamination with materials other than K-doped picene or K-doped picene fragments, and supported the preservation of the picene skeleton. However, it was also found that a magnetic K-doped picene sample consisted mainly of picene fragments or K-doped picene fragments. Thus, removal of the component contributing the magnetic quality to a superconducting sample should enhance the volume fraction.

This article reviews new superconducting phases of carbon-based materials. During the past decade, new carbon-based superconductors have been extensively developed through the use of intercalation chemistry, electrostatic carrier doping, and surface-proving techniques. The superconducting transition temperature T c of these materials has been rapidly elevated, and the variety of superconductors has been increased. This review fully introduces graphite, graphene, and hydrocarbon superconductors and future perspectives of high-T c superconductors based on these materials, including present problems. Carbon-based superconductors show various types of interesting behavior, such as a positive pressure dependence of T c. At present, experimental information on superconductors is still insufficient, and theoretical treatment is also incomplete. In particular, experimental results are still lacking for graphene and hydrocarbon superconductors. Therefore, it is very important to review experimental results in detail and introduce theoretical approaches, for the sake of advances in condensed matter physics. Furthermore, the recent experimental results on hydrocarbon superconductors obtained by our group are also included in this article. Consequently, this review article may provide a hint to designing new carbon-based superconductors exhibiting higher T c and interesting physical features.

We report electronic structure and physical properties of metal doped picene as well as selective synthesis of the phase exhibiting 18 K superconducting transition. First, Raman scattering is used to characterize the number of electrons transferred from the dopants to picene molecules. The charge transfer leads to a softening of Raman scattering peaks, which enables us to determine the number of transferred electrons. From this we have identified that three electrons are transferred to each picene molecule in the superconducting doped-picene solids. Second, we report the pressure dependence of Tc in 7 and 18 K phases of K3picene. The 7 K phase shows a negative pressure-dependence, while the 18 K phase exhibits a positive pressure-dependence which cannot be understood with a simple phonon mechanism of BCS superconductivity. Third, we report a new synthesis method for superconducting K3picene by a solution process with monomethylamine, CH3NH2. This method enables one to prepare selectively the K3picene sample exhibiting 18 K superconducting transition. The discovery of suitable way for preparing K3picene with Tc = 18 K may facilitate clarification of the mechanism of superconductivity.

Magnetic response of a superconductor/normal‐metal (S/N) concentric disk is studied by use of a ballistic Hall magnetometer, which enables us to investigate the mutual proximity effects in a single and a micrometer‐sized sample. The core of the sample is a type‐I superconductor whose diameter is comparable to the coherence length and the magnetic penetration depth. The core and the surround are prepared by an improved double‐angle evaporation method to realize their metallic contacts. At T = 1.3 K, the pair breaking effect on the S has been predominant. We have observed the smaller diamagnetic susceptibility, the larger critical field, and the less stable vortex states in the S/N sample than in only S sample. These results are attributed to the suppression of the surface superconductivity, which effectively decreases the diameter of the superconductor.

Superconducting proximity effects in a ferromagnetic metal are directly observed by means of 59 Co NMR in Co/Al bilayers. Below the superconducting transition temperature, the resonant frequency decreases and the nuclear spin-lattice relaxation rate divided by temperature, 1/T1T, increases. These results indicate the reduction of magnetic moment in the Co layer. We discuss the spatial variation of the local magnetic moment and its temperature dependence by analyzing the resonance line shapes.