High-pressure synthesis and anomalous properties of new skutterudite-type compounds including heavy lanthanide

具有Im-3(T^5_h，#204)空间群的填充Skutterudite化合物LNT_4X_&lt；12&gt；(Ln=La，T=Fe，Ru，Os；X=P，As，Sb)因其在低温下具有多种物理性质而备受关注，如金属-绝缘体转变、多极有序、重费米子行为、非费米液体行为和奇异的超导电性。这一显著特征是由于强烈的p-f杂化效应、独特的能带结构和立方对称的Ln位上f电子的轨道自由度所致。我们在高温高压下制备了许多轻稀土的方解石。然而，很少有重稀土填充的方斜晶石被合成。我们首次用高压技术成功地制备了重稀土填充的新型方钛矿LNT_4P_(12)(Ln=重稀土，包括Y；T=Fe，Ru，Os)。合成并研究了新型填充型Skutterudite LnFe_4p&lt；12&Gt；(Ln=Tb，Dy，Ho，Er，Tm，Yb，Lu和Y)。LnFe_4P_(12)&Gt；(Ln=Gd，Tb，Dy，Ho，Er)是铁磁体。YFe_4P_(12)和LuFe_4P_(12)是超导体。Tm，Yb化合物在低温下都是顺磁性的。对于Ru系，在高压下制备了LfRu_4P_(12)&Gt；(Ln=Gd，Tb，Y)。Gdru_4p和TbRu_4p和TbRu_4p是反铁磁体。YRu4p&lt；12&gt；是一种转变温度为9K的新型超导体。对于Os系，制备并研究了新型填充型Skutterudite LNO_4P&lt；12&Gt；(Ln=Sm，Eu，Gd，Tb，Dy，Ho，Y)。LiNO_4P_(12)(Ln=Eu，Gd，Tb)是铁磁体。SMOS_4P_12是一种反铁磁体。Dy，Ho化合物在低温下都是顺磁性的。YOS_4P&lt；12&gt；是一种新的超导体，在这项工作中，我们发现了16个新的填充式的Skurudite和4个新的具有Skutterudite结构的超导体。

Filled skutterudite compounds LnT_4X_<12> (Ln=Lanthanide ; T=Fe,Ru,Os ; X=P,As,Sb) with space group Im-3 (T^5_h, #204) have attracted much attention because of wide variety of physical properties at low temperature, such as metal-insulator transition, multipole order, heavy-fermion behavior, non Fermi liquid behavior and exotic superconductivity. This remarkable feature is caused by a strong p-f hybridization effect, a unique band structure and an orbital degree of freedam due to f electron in Ln site with cubic symmetry.We have prepared many skutterudites with lighter lanthanide at high temperatures and high pressures. However, few filled skutterudites with heavy lanthanide have been synthesized. We have succeeded to prepare for the first time new filled skutterudites with heavy lanthanide, LnT_4P_<12> (Ln=heavy lanthanide, including Y ; T=Fe,Ru,Os) by the high-pressure technique. New filled skutterudites LnFe_4P_<12> (Ln=Tb,Dy,Ho,Er,Tm,Yb,Lu and Y) were prepared and studied. LnFe_4P_<12> (Ln=Gd,Tb,Dy,Ho,Er) are ferromagnets. YFe_4P_<12> and LuFe_4P_<12> are superconductors. Tm, Yb compounds are paramagnetic down to low temperature. For Ru system, LfRu_4P_<12> (Ln=Gd,Tb,Y) were prepared under high pressure. GdRu_4P_<12> and TbRu_4P_<12> are antiferromagnets. YRu_4P_<12> is a new superconductor (transition temperature Tc=9K). For Os system, new filled skutterudites LnOs_4P_<12> (Ln=Sm,Eu,Gd,Tb,Dy,Ho and Y) were prepared and studied. LnOs_4P_<12> (Ln=Eu,Gd,Tb) are ferromagnets. SmOs_4P_<12> is an antiferromagnet. Dy, Ho compounds are paramagnetic down to low temperature. YOs_4P_<12> is a new superconductor.In this work, we found 16 new filled skuterudites and 4 new superconductors with skutterudite-type structure.