High-pressure synthesis and superconductivity of LaGe5 containing a tunnel germanium network

Superconducting LaGe5 was synthesized by the reaction of La and Ge mixtures under a pressure of 5 GPa at 1200°C. It crystallized in the orthorhombic space group Immm (No. 71) with a=4.0290(6), b =6.307(1), and c=9.978(2) Å, V=253.54(6) Å3, and Z=2. Single-crystal studies revealed that LaGe5 had a germanium network with tunnels running along the a axis, where La atoms are located. There are two crystallographically different Ge sites in the structure La[(Gel)4(Ge2)1]. The tunnel network is composed of folded sp3-Gel layers coupled by eight coordinated Ge2 atoms. Electrical resistivity and magnetic-susceptibility measurements showed that the compound was a type-II superconductor with a transition temperature of 7.0 K

Pressure stability and low compressibility of intercalated cagelike materials: the case of silicon clathrates

We study the behavior under pressure (up to 35 GPa) of intercalated silicon clathrates, combining x-ray diffraction experiments and ab initio calculations. We show that endohedral doping does not introduce a strong modification of the compressibility of the empty clathrate network and that in particular cases can raise it to values equivalent to the one of the silicon diamond phase. Intercalation can also prevent the collapse of the cage structure up to pressures at least 3 times higher than in the empty clathrate. Further we find that the stability of all studied silicon clathrate networks as well as stressed silicon diamond is limited to average Si-Si interatomic distances higher than 2.30 Angstrom

A new class of low compressibility materials: Clathrates of silicon and related materials

We discuss the high pressure properties of different silicon clathrate structures that we have investigated by means of X-ray diffraction and ab initio calculations. Compressibility transition pressures or phase transformations are interpreted as a function of the nature of the guest atom intercalation, The compressibility of the clathrate structure is in all cases close to that of silicon diamond whereas transition pressures or the high pressure phases are extremely depending on the nature of the guest atom. We address the implications for obtaining a metallic material as hard as diamond

Structural distortion and suppression of superconductivity in stoichiometric B1-MoN epitaxial thin films

Molybdenum nitride films with the NaCl structure (B1-MoN) were epitaxially grown on α- Al2 O3 (001) and MgO(001) substrates at 973 K by pulsed laser deposition (PLD) under nitrogen radical irradiation. The highly crystalline epitaxial films enabled us to determine the three-dimensional cell parameters, which was motivated by theoretical calculations that B1-MoN, a predicted superconductor, is elastically unstable against tetragonal and trigonal distortions. On α- Al2 O3 (001), the B1-MoN phase (composition, Mo1 N0.98) was grown with its (111) planes parallel to the substrate surface. X-ray diffraction analysis with a multiaxes diffractometer detected only a small trigonal lattice distortion [a=0.4219(3) nm, α=89.28(5)°] with an expansion along the [111] direction perpendicular to the substrate surface. The film grown on MgO(001) had the MoN1.03 composition and showed a slight tetragonal distortion (a=0.4213 and c=0.424 nm) due to fitting to the MgO substrate lattice (a=0.4213 nm). These two stoichiometric films showed no superconductivity above 2 K. A lower nitrogen content (MoN0.86) film was obtained on α- Al2 O3 (001) using a higher deposition rate. The corresponding film had a much smaller lattice constant [a=0.4184(3) nm], and a similar distortion [α=89.41(5)°]. The B1- MoN0.86 film showed superconductivity with a transition temperature Tc =4.2 K. The suppression of the superconductivity of the former stoichiometric phase can be interpreted in terms of the lattice expansion

Superconductivity in doped sp3 semiconductors: The case of the clathrates

We present a joint experimental and theoretical study of the superconductivity in doped silicon clathrates. The critical temperature in Ba-8@Si-46 is shown to strongly decrease with applied pressure. These results are corroborated by ab initio calculations using MacMillan's formulation of the BCS theory with the electron-phonon coupling constant lambda calculated from perturbative density functional theory. Further, the study of I-8@Si-46 and of gedanken pure silicon diamond and clathrate phases doped within a rigid-band approach show that the superconductivity is an intrinsic property of the sp(3) silicon network. As a consequence, carbon clathrates are predicted to yield large critical temperatures with an effective electron-phonon interaction much larger than in C-60

Off-center rattling and thermoelectric properties of type-II clathrate (K, Ba)(24)(Ga, Sn, square)(136) single crystals

We report the synthesis and temperature-dependent structural, transport, and thermal properties of type-II clathrate K8+xBa16-xGa40-ySn96-z square(y+z) (1.2 <= x <= 2.8, 2.0 <= y <= 3.3, 0.8 <= z <= 6.6, square = framework vacancy). Single-crystal x-ray diffraction analysis reveals that the guest K+ and Ba2+ ions are preferentially incorporated into the hexakaidecahedral cages and dodecahedral cages, respectively. The guest site in the former splits into four sites 0.67 angstrom away from the center to the 32e site of the cage. The splitting is consistent with the presence of four minima in the electrostatic potential in the hexakaidecahedron. The thermopower is negative and relatively large, -50 similar to -120 mu V/K at 300 K, indicating that the dominant charge carriers are electrons. The thermal conductivity displays a glasslike behavior with a plateau at around 20 K. The analysis of the specific heat indicates that the motion of the K+ ion in the hexakaidecahedron can be described by the soft-potential model, including the tunneling term. The characteristic energy of 21 K for the soft mode is as low as that of the off-center rattling of the Ba2+ ion in type-I clathrate Ba8Ga16Sn30. The present result on the type-II clathrate verifies the idea that the low-energy off-center rattling in oversized cages of intermetallic clathrates couples to the acoustic phonons to lead to the glasslike thermal conductivity