Department of Chemistry, University of California Davis, Davis, California95616, United States.
Ames Laboratory and Department of Physics and Astronomy, Iowa State University, Ames, Iowa50011, United States.
Inorg Chem. 2023 Feb 13;62(6):2694-2704. doi: 10.1021/acs.inorgchem.2c03817. Epub 2023 Jan 31.
The solid solutions of YbREZnSb (RE = Sc, Y, La, Lu, and Gd; 0.2 ≤ ≤ 0.7) were prepared to probe the intermediate valency of Yb in YbZnSb. The substitution of Yb with RE elements should reduce or remove the intermediate valency of the remaining Yb ions. Large crystals are grown from Sn-flux, and the structure and magnetic susceptibility are presented. All compounds crystallize in the CaAlSb structure type and the RE ions show Yb site substitution preferences that correlate with size. Two compositions of YbYZnSb were investigated [ = 0.38(3), 0.45(3)] by temperature-dependent magnetic susceptibility and the broad feature in magnetic susceptibility measurements at 85 K in pristine YbZnSb attributed to valence fluctuation decreases and is absent for = 0.45(3). In compounds with nonmagnetic RE substitutions (Sc, Y, La, and Lu), temperature-dependent magnetic susceptibility shows a transition from intermediate valency fluctuation toward temperature-independent (Y, La, and Lu) or Curie-Weiss behavior and possibly low temperature heavy Fermion behavior (Sc). In the example of the magnetic rare earth substitution, RE = Gd, the Curie-Weiss-dependent magnetic moment of Gd is consistent with . Hall resistivity of YbYZnSb showed that the carrier concentration decreases with and the signature of the low-T intermediate valence state seen for = 0 is suppressed for = 0.38 and gone for = 0.45.
YbREZnSb(RE=Sc、Y、La、Lu 和 Gd;0.2≤ ≤0.7)的固溶体被制备来探测 YbZnSb 中 Yb 的中间价态。Yb 被 RE 元素取代应该会降低或消除剩余 Yb 离子的中间价态。大晶体从锡熔体制备,结构和磁化率被呈现。所有化合物都结晶为 CaAlSb 结构类型,RE 离子表现出与大小相关的 Yb 位取代偏好。通过温度相关的磁化率研究了两种 YbYZnSb 组成 [ = 0.38(3),0.45(3)],在原始 YbZnSb 中在 85 K 处磁化率的宽特征归因于价态波动的降低,对于 = 0.45(3)则不存在。在具有非磁性 RE 取代(Sc、Y、La 和 Lu)的化合物中,温度相关的磁化率显示出从中间价态波动向温度独立(Y、La 和 Lu)或 Curie-Weiss 行为以及可能的低温重费米子行为(Sc)的转变。在磁性稀土取代的例子中,RE=Gd,Gd 的 Curie-Weiss 依赖磁矩与 一致。YbYZnSb 的 Hall 电阻率表明,载流子浓度随 而降低,对于 = 0 观察到的低温中间价态的特征被 = 0.38 抑制,对于 = 0.45 则消失。