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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.

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.

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.

Field-effect transistors (FETs) were fabricated using exfoliated single crystals of Mo(Se1-x Te-x)(2) with an x range of 0 to 1, and the transistor properties fully investigated at 295 K in four-terminal measurement mode. The chemical composition and crystal structure of exfoliated single crystals were identified by energy-dispersive x-ray spectroscopy (EDX), single-crystal x-ray diffraction, and Raman scattering, suggesting the 2H - structure in all Mo(Se1-x Te-x)(2). The lattice constants of a and c increase monotonically with increasing x, indicating the substitution of Se by Te. When x 0.4. In contrast, the polarity of a thick single-crystal Mo(Se1-x Te-x)(2) FET did not change despite an increase in x. The change of polarity in a thin single-crystal FET was well explained by the variation of electronic structure. The absence of such change in the thick single-crystal FET can be reasonably interpreted based on the large bulk conduction due to naturally accumulated electrons. The mu value in the thin single-crystal FET showed a parabolic variation, with a minimum mu at around x = 0.4, which probably originates from the disorder of the single crystal caused by the partial replacement of Se by Te, i.e., a disorder that may be due to ionic size difference of Se and Te.

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.

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.

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.

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.