Hydride ion as a two-electron donor in a nanoporous crystalline semiconductor 12CaO.7Al2O3.
The 12CaO.7Al2O3 (C12A7) crystal with a nanoporous lattice framework exhibits high electrical conductivity with an activation energy of approximately 1.5 eV when equilibrated in a hydrogen atmosphere above approximately 800 degrees C. The high conductivity is preserved in a quenched state below approximately 600 degrees C with a reduced activation energy of approximately 0.8 eV. Such complex behavior in electrical conductivity is associated with incorporation of hydride ions (H-) in cages of the lattice framework. Electromotive force measurements reveal that the major carrier for the conductivity is electron with a small contribution by proton (H+), ruling out the possibility of direct intercage migration of the H- ion. A combination of these observations with the ab initio calculations leads to the conclusion that the electrons are thermally generated from the H- ion by the dissociation into two electrons and an proton, which is further converted to an OH- ion via reaction with an extraframework oxide ion (O2-). The energy difference between the initial (H- + O2-) and the final (2e- + OH-) states as evaluated by the theoretical calculation is as small as approximately 1 eV, which agrees well with an experimentally obtained enthalpy change, approximately 1.4 eV. Thus, internal equilibration between the extraframework hydrogen and the oxygen species is responsible for the thermal generation of the carrier electron. It is also suggested that the same conductive (2e- + OH-) state is reached by the photoirradiation of H- -containing C12A7. In this case the photoionization of H- forms an electron and an Ho atom, which then forms an OH- ion and another electron with thermal assistance. The persistence of photoinduced conductivity is explained by the slow kinetics of the reverse process at room temperature.
Hayashi
Katsuro
K
Frontier Collaborative Research Center and Materials and Structures Laboratory, Tokyo Institute of Technology, S2-13, 4259 Nagatsuta, Yokohama 226-8503, Japan. k-hayashi@lucid.msl.titech.ac.jp
Sushko
Peter V
PV
Shluger
Alexander L
AL
Hirano
Masahiro
M
Hosono
Hideo
H