Local structure of LiNiO studied by neutron diffraction

中性子回折によるLiNiOの局所構造研究

Chung, J.-H.*; Proffen, T.*; 社本 真一  ; Ghorayeb, A. M.*; Croguennec, L.*; Tian, W.*; Sales, B. C.*; Jin, R.*; Mandrus, D.*; 江上 毅*

Chung, J.-H.*; Proffen, T.*; Shamoto, Shinichi; Ghorayeb, A. M.*; Croguennec, L.*; Tian, W.*; Sales, B. C.*; Jin, R.*; Mandrus, D.*; Egami, Takeshi*

LiNiOは、これまでS=1/2の三角格子系としてよく研究されてきたが、そのスピン相関に関してはまだよくわかっていない。そこではヤーンテラー効果による軌道状態も問題となるが、これまで長距離の格子歪みは見つかっていない。今回これまで行われたことのない幅広い実空間での結晶PDF解析を行うことで、短距離から長距離までさまざまな格子歪みが見つかった。この結果は10nmのドメインを持つナノ構造軌道秩序モデルで説明される。この局所的な軌道秩序状態が基となって、複雑な磁気特性が現れていると思われる。

LiNiO (S=1/2) forms a triangular lattice with the possible magnetic frustration, but the exact state of spin correlation has not yet been known. While there is no signature of long-range Jahn-Teller distortion, local JT distortion has been suspected. We have performed neutron diffraction and atomic pair-density function analyses up to unprecedented large distances to discover a number of unusual features, such as anomalous peak broadening, local JT distortion, sharp oxygen-oxygen distance correlations, and inverted temperature dependence of medium range correlation. These observations are best explained by local orbital ordering of Ni ions into three sublattices. This orbital ordering, however, cannot develop into long-range order because of the strain field it generates, and domains of about 10 nm in size are formed. Domains are susceptible to random pinning by impurities ssite disorderd resulting in the loss of structural long-range order. We suggest that this local orbital ordering is the basis for the complex magnetic properties observed in this compound.