Absence of Ni²/Ni³ charge disproportionation and possible roles of O 2p holes in La₃Ni₂O₇₋δ revealed by hard x-ray photoemission spectroscopy
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Recently, the Ruddlesden-Popper bilayer nickelate $La_3Ni_2O_7$ has emerged as a superconductor with a transition temperature ($T_c$) of ~ 80 K above 14 GPa$^{[1-4]}$. Efforts to search for nickelate superconductors with higher $T_c$$^{[5,6]}$, to grow reproducible high-quality single crystals$^{[2,7-10]}$, and to eliminate reliance on demanding high gas pressure synthesis conditions$^{[11]}$, remain significant challenges. Here we report superconductivity up to 92 K under high pressure in single crystals of bilayer nickelates synthesized at ambient pressure using flux methods. High quality $La_2SmNi_2O_{7-δ}$ single crystals with dimensions up to 220 μm on edge were successfully grown. At ~ 15 GPa, these crystals exhibit superconductivity with an onset transition temperature ($T_c^{onset}$) of 68 K and zero-resistance temperature ($T_c^{zero}$) of 47 K. Increasing pressure further enhances both transition temperatures, reaching record values for nickelates: $T_{c,max}^{onset}$ = 92 K and $T_{c,max}^{zero}$ = 73 K @ 21 GPa. Notably, higher $T_c$ correlates with larger in-plane lattice distortion at ambient conditions for bilayer nickelates. Furthermore, we observed a structural transition from monoclinic $P2_1/a$ to tetragonal $I4/mmm$ at ~ 18 GPa, indicating that tetragonal structure is not a prerequisite for superconductivity to appear in this bilayer nickelate. This study provides an easy-to-access method for growing reproducible high-quality bilayer nickelate single crystals and offers new insights into achieving higher Tc superconductivity.
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本研究采用高压高温法生长四层Ruddlesden–Popper镍酸盐La5Ni4O13块体单晶，并复现五层La6Ni5O16的合成；随后以CaH2对La5Ni4O13单晶进行拓扑还原，得到方平面相La5Ni4O10。该还原相在常压下表现为块体超导体，起始转变温度Tc^onset约18 K，零场冷屏蔽分数超过60%，比热跃变证实发生块体配对转变；同时所有晶体中超导与密度波或金属—绝缘转变共存。上临界场各向异性γ≈2.4且在T→Tc时仍保持有限，表明超导具有三维特征且四层块之间存在显著耦合。作者据此提出，方平面镍酸盐R_{n+1}Ni_nO_{2n+2}可仅通过层数调控镍价态进入超导区，无需化学替代、外加压力或外延约束。
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本文利用极化分辨电子拉曼散射测量了高质量La₃Ni₂O₇单晶，在150 K以下的密度波转变中观察到显著的、对称性依赖的谱权重重新分布：B₁g通道呈现不对称峰，B₂g通道呈现对称宽峰，分别对应布里渊区X/Y点附近和对角线方向的电子激发。定量分析提取出两组SDW能隙值，B₁g通道能隙约为37.5–40.4 meV（2Δ/kBTc≈5.5–5.9），B₂g通道能隙约为23.0 meV（2Δ/kBTc≈3.4），表明前者属中等至强耦合，后者属弱耦合。这种动量选择的各向异性耦合强度无法用简单的弱耦合嵌套理论解释，揭示了非常规SDW源于各向异性电子关联。能隙的温度依赖性明显弱于平均场预期，且B₂g通道各向同性与B₁g通道弱各向异性也支持两种不同耦合机制的共存。该工作确立了La₃Ni₂O₇中SDW的电子特性，为理解压力下镍酸盐高温超导的涌现提供了微观基础。
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