Extending the La Solubility Limit in Sr$_3$Ir$_2$O$_7$ through High-Pressure High-Temperature Synthesis
通过高压高温合成扩展Sr$_3$Ir$_2$O$_7$中的La溶解度极限
Cheng Peng, Weiwei Xie
AI总结 采用高压高温合成方法,将La掺杂双层铱酸盐(Sr$_{1-x}$La$_x$)$_3$Ir$_2$O$_7$的La溶解度显著提高至x=0.23,发现高掺杂下出现铁磁相变和金属性行为,揭示了常规合成无法获得的电子和磁态。
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La掺杂的双层铱酸盐为研究自旋轨道辅助莫特态在电子掺杂下的演化提供了重要平台,但常规常压合成所实现的La溶解度有限。本文报道了采用高压高温技术制备的名义La掺杂(Sr$_{1-x}$La$_x$)$_3$Ir$_2$O$_7$(x=0.05, 0.10, 0.15, 0.20)的合成和物理性质。单晶X射线衍射精修,辅以扫描电子显微镜-能量色散X射线光谱(SEM-EDX),揭示了显著增强的La掺入,名义x=0.05和0.15分别对应实际组成约为(Sr$_{0.89}$La$_{0.11}$)$_3$Ir$_2$O$_7$和(Sr$_{0.77}$La$_{0.23}$)$_3$Ir$_2$O$_7$。在名义x=0.20时,双层相不再稳定,而是转变为立方钙钛矿Sr$_{1-x}$La$_x$IrO$_3$。(Sr$_{0.89}$La$_{0.11}$)$_3$Ir$_2$O$_7$在186 K附近表现出类铁磁转变,伴随磁滞和微妙的晶格异常,表明自旋-晶格耦合。尽管电子掺杂水平高,该化合物仍保持强绝缘性,与母体Sr$_3$Ir$_2$O$_7$和常压La掺杂样品均不同,符合重掺杂局域磁绝缘态。相比之下,(Sr$_{0.77}$La$_{0.23}$)$_3$Ir$_2$O$_7$表现出类金属电子行为、减弱的磁序和增强的载流子离域化,尽管在低温下仍存在无序驱动的局域化。这些结果表明,高压合成显著扩展了双层铱酸盐的可达掺杂范围,并揭示了常规合成路线无法获得的电子和磁态。
La-doped bilayer iridates provide an important platform for studying the evolution of the spin-orbit-assisted Mott state under electron doping, but the La solubility achieved by conventional ambient-pressure synthesis is limited. Here, we report the synthesis and physical properties of nominally La-doped (Sr$_{1-x}$La$_x$)$_3$Ir$_2$O$_7$ (x = 0.05, 0.10, 0.15, and 0.20) prepared using high-pressure high-temperature techniques. Single-crystal X-ray diffraction refinements, supported by scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX), reveal significantly enhanced La incorporation, with nominal x = 0.05 and 0.15 corresponding to actual compositions of approximately (Sr$_{0.89}$La$_{0.11}$)$_3$Ir$_2$O$_7$ and (Sr$_{0.77}$La$_{0.23}$)$_3$Ir$_2$O$_7$, respectively. At nominal x = 0.20, the bilayer phase is no longer stabilized and instead transforms into cubic perovskite Sr$_{1-x}$La$_x$IrO$_3$. (Sr$_{0.89}$La$_{0.11}$)$_3$Ir$_2$O$_7$ exhibits a ferromagnetic-like transition near 186 K accompanied by magnetic hysteresis and subtle lattice anomalies indicative of spin-lattice coupling. Despite its high electron-doping level, the compound remains strongly insulating, consistent with a heavily doped localized magnetic insulating state distinct from both parent Sr$_3$Ir$_2$O$_7$ and ambient-pressure La-doped samples. In contrast, (Sr$_{0.77}$La$_{0.23}$)$_3$Ir$_2$O$_7$ displays metal-like electronic behavior, weakened magnetic order, and enhanced carrier delocalization, although disorder-driven localization persists at low temperatures. These results demonstrate that high-pressure synthesis substantially extends the accessible doping range of bilayer iridates and reveals electronic and magnetic states inaccessible through conventional synthesis routes.