Intermetallic Charge Transfer and Colossal Negative Thermal Expansion in Perovskite BiNiO<sub>3</sub>

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  • AZUMA Masaki
    Materials and Structures Laboratory, Tokyo Institute of Technology
  • OKA Kengo
    Materials and Structures Laboratory, Tokyo Institute of Technology

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  • ぺロブスカイトBiNiO<sub>3</sub>におけるサイト間電荷移動と巨大負の熱膨張
  • ペロブスカイト BiNiO ₃ ニ オケル サイト カン デンカ イドウ ト キョダイフ ノ ネツ ボウチョウ

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BiNiO3 is a perovskite compound with unique Bi3+0.5Bi5+0.5Ni2+O3 oxidation state. Neutron powder diffraction and synchrotron X-ray absorption studies revealed the intermetallic charge transfer between Bi5+ and Ni2+ on pressurization or on heating at a moderate pressure leading to the shrinkage of the unit cell volume. Partial substitution of La3+ for Bi shifts the phase boundary between Bi3+0.5Bi5+0.5Ni2+O3 and Bi3+Ni3+O3 to the low pressure, low temperature side. Bi0.95La0.05NiO3 shows a negative thermal expansion with a dilatometric thermal coefficient of −82×10−6/K, three times as large as the existing compound.

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