Paper

该研究通过动量分辨与偏振分辨共振非弹性X射线散射（RIXS）测量，系统比较了未掺杂超导无限层镍酸盐PrNiO₂与绝缘铜酸盐CaCuO₂的自旋和轨道激发特性。结果显示，PrNiO₂的面内磁交换积分（约46 meV）明显小于CaCuO₂（约82 meV），而面外交换积分相近（约6-7 meV），表明两种材料均支持三维反铁磁有序，且自旋-自旋关联的三维性类似。轨道激发（3d态内跃迁）在单离子模型下吻合良好，但Ni-dxy峰的能量显著低于Cu-dxy，且色散方向相反——镍酸盐中呈现最近邻轨道超交换耦合驱动的轨道激发传播，而铜酸盐则为次近邻耦合主导。尽管两者电荷转移能差异显著（镍酸盐更大），但自旋与轨道激发特性总体上高度相似，仅在Ni-dxy峰能量和色散上表现出关键区别，这归因于轨道超交换耦合机制的不同。该工作揭示了无限层镍酸盐与铜酸盐在磁性和轨道动力学上的核心共性，同时指出镍酸盐中自旋涨落能量更小、掺杂电荷在金属位点上的局域化更强。

该工作利用共振非弹性X射线散射（RIXS）系统研究了外延应变从约-2%至+1.9%的La₃Ni₂O₇（LNO）薄膜的电子和自旋激发。在呈现常压超导（起始转变温度>40 K）的压缩应变LNO/SrLaAlO₄薄膜中，观察到与块材LNO相似的dd激发和自旋动力学，但自旋激发带宽增大约10 meV，表明层间反铁磁交换作用Jz增强；而拉伸应变的LNO/SrTiO₃薄膜则表现出自旋激发和Ni 3dz²相关dd激发的显著抑制。这一演化反映了应变对Ni 3dz²-O 2pz杂化和层间距离的调控，进而影响层间磁耦合强度。结果表明，外延应变能有效调制双层镍酸盐的层间反铁磁超交换作用，且增强的Jz与常压超导的出现密切相关，支持层间磁交换作用促进层间配对的理论图像。

通过非弹性中子散射研究了稀土Pr和Nd掺杂的双层镍酸盐La₂LnNi₂O₇₋δ（Ln=La, Pr, Nd）粉末在常压下的自旋涨落。在未掺杂的La₃Ni₂O₇₋δ中观测到的45 meV平坦自旋涨落模式，在掺杂后分裂为43和48 meV两个模式，并在约60 meV处出现另一弱模式。其中La₂NdNi₂O₇₋δ的自旋涨落强度显著高于La₃Ni₂O₇₋δ和La₂PrNi₂O₇₋δ。这些结果与基于条纹型反铁磁海森堡模型的描述一致，表明稀土掺杂增强了层间磁耦合，层间交换耦合SJ⊥从约60 meV提升至69–73 meV，层内耦合保持较弱（≤3.5 meV）。这种增强可能解释了稀土掺杂后超导转变温度从80 K升至接近100 K的现象。该工作揭示了稀土掺杂对双层镍酸盐自旋动力学和超导配对的调控作用。

Spin-charge-orbital order in nickelate superconductors

High-pressure studies have revealed superconductivity in La4⁢Ni3⁢O10, sparking interest in its ambient-pressure properties and the underlying electronic correlations. Motivated by experimental observations of an incommensurate spin-density wave (SDW) at ambient pressure, we investigate the SDW characteristics and possible superconductivity in La4⁢Ni3⁢O10 using a multiorbital random-phase approximation (RPA). Starting with a 12-orbital tight-binding model derived from density functional theory (DFT) calculations, we include Hubbard interactions to explore the interplay between electronic correlations and magnetic instabilities. Our analysis reveals a stripe-like SDW with a wave vector 𝐐≈(±0.7⁢𝜋,0), suggesting a possible density wave instability in agreement with experiments. This configuration is driven by nesting between the 𝛼1 pocket, primarily contributed by the outer-layer Ni 𝑑𝑧2 orbitals, and the 𝛽1 pocket, contributed by both the 𝑑𝑧2 and 𝑑𝑥2−𝑦2 orbitals of the outer layer. It exhibits interlayer antiferromagnetic ordering between the top and bottom NiO layers, with the magnetic moment of the middle layer being nearly zero. We demonstrate that the Hund coupling 𝐽𝐻 is the primary driver of the observed SDW and determine the specific criterion: 𝐽𝐻>0.16⁢𝑈. Building upon our findings on the SDW mechanism, we further demonstrate that hole doping (𝛿=−0.4) enhances Fermi surface nesting, leading to the emergence of a superconducting state with a gap structure similar to that of the high-pressure phase.

本研究成功合成了高质量的长程有序杂化1313型La₃Ni₂O₇单晶（交替单层-三层结构），并对其物理性质进行了系统表征。在常压下，该材料呈现典型的半导体行为，并在170 K处出现明显的电阻率、磁化率和比热异常。¹³⁹La核磁共振谱明确证实该异常源于自旋密度波（SDW）相变。高压电输运测量表明，施加压力可以诱导金属化，但在高达65 GPa的压力下未观察到超导电性。这些发现将杂化1313型La₃Ni₂O₇确立为Ruddlesden-Popper镍酸盐家族中具有独特SDW转变的新成员，为研究杂化镍酸盐中晶体结构、电子序和超导电性之间的相互作用提供了新的平台。

采用密度泛函理论结合团簇动力学平均场方法，本文研究了双层Ruddlesden-Popper镍酸盐，发现其物理性质主要受由3z²−r²轨道单电子形成的层间“动力学单态”支配，这些单态与巡游的x²−y²平面轨道发生杂化。该杂化对静水压与面内压应变的响应截然不同：应变增强层间关联，导致轨道选择性单态配对莫特机制，而静水压主要提升面内巡游性。这一差异解释了块材与应变薄膜在角分辨光电子能谱和输运测量中的实验分歧。理论框架将此低能态视为动力学单态与巡游轨道的杂化体系，为后续理解超导电性提供了新思路。

Stabilizing and tuning superconductivity in La₃Ni₂O₇−δ films: Oxygen recycling protocol reveals hole-doping analogue

After several decades of studies of high-temperature superconductivity, there is no compelling theory for the mechanism yet; however, the spin fluctua…

The discovery of superconductivity with an onset temperature of ∼80 K in pressurized bilayer Ruddlesden-Popper La3Ni2O7-δ has attracted much attention. Despite intense research, determination of the exact oxygen content and understanding of the relationship between superconductivity and oxygen content remain a big challenge. Here, we report a systematical study on the structure and physical properties of La3Ni2O7-δ polycrystalline powders which were prepared using the sol-gel method at ambient pressure and then annealed under high oxygen pressure (pO2) or in ozone. The superconducting transition of La3Ni2O7-δ at ∼80 K under high pressure is suppressed for high pO2 and ozone annealed samples. We attribute this to the combination of the following two reasons: (i) damage of the bilayer structure, as revealed by powder X-ray diffraction, scanning transmission electron microscopy and pair distribution function measurements, and (ii) hole overdoping due to the increasing of oxygen content. Our results reveal that the bilayer structure in La3Ni2O7-δ is fragile and post-annealing under mild oxidization is suitable for maintaining the integrity of the bilayer structure and increasing oxygen content.