Insulating state and metallic phase transition of heavily sodium-doped low-silica X (LSX) zeolites

Electrical resistivity was measured for Na-doped low-silica X (LSX) zeolite at various Na-loading densities. Many s-electrons are introduced into the regular array of zeolite nanocages by the loading of guest Na atoms. The average Na-loading density per unite cage, n  , was changed from 0 to ≈12≈12. Nonmagnetic and insulating properties are observed for n≲11n≲11. A drastic decrease in the resistivity is observed at n≈12n≈12, indicating that the insulating phase is changed to metallic one by the addition of less than one Na-atom per unite cage. At the same time, a remarkable increase in paramagnetic susceptibility is observed at room temperature. Insulating states are explained by spin-singlet clusters which are assigned to the self-trapped s-electron pairs (small bipolarons) due to the strong electron–phonon interaction against the Coulomb repulsive interaction between two s-electrons. Pairs of s-electrons occupy successively the quantum states of clusters in zeolite cages with increasing the Na-loading density. The metallic phase transition is explained by the formation of large polarons which are mobile over many cages through the zeolite windows. The increase in the paramagnetic susceptibility is explained by the thermal excitation of small polarons expected in the adiabatic potential.

► We measured temperature dependence of electrical resistivity in Na-doped LSX zeolite.
► Insulating and nonmagnetic phase is observed at doping less than 11 Na atoms per cage.
► Metallic and paramagnetic phase suddenly appears at doping 12 Na atoms per cage.
► Phase transition is explained by the drastic change of polaron states.
► Small and large polarons are expected to coexist dynamically in metallic phase.