Charge transfer energy in iridates: a hard x-ray photoelectron spectroscopy study
D. Takegami, D. Kasinathan, K. K. Wolff, S. G. Altendorf, C. F. Chang, K. Hoefer, A. Melendez-Sans, Y. Utsumi, F. Meneghin, T. D. Ha, C. H. Yen, K. Chen, C. Y. … 展开作者
D. Takegami, D. Kasinathan, K. K. Wolff, S. G. Altendorf, C. F. Chang, K. Hoefer, A. Melendez-Sans, Y. Utsumi, F. Meneghin, T. D. Ha, C. H. Yen, K. Chen, C. Y. Kuo, Y. F. Liao, K. D. Tsuei, R. Morrow, S. Wurmehl, B. Büchner, B. E. Prasad, M. Jansen, A. C. Komarek, P. Hansmann, L. H. Tjeng
We have investigated the electronic structure of iridates in the double perovskite crystal structure containing either Ir$^{4+}$ or Ir$^{5+}$ using hard x-ray photoelectron spectroscopy. The experimental valence band spectra can be well reproduced using tight binding calculations including only the Ir $5d$, O $2p$ and O $2s$ orbitals with parameters based on the downfolding of the density-functional band structure results. We found that regardless of the A and B cations, the A$_2$BIrO$_6$ iridates have essentially zero O $2p$ to Ir $5d$ charge transfer energies. Hence, double perovskite iridates turn out to be extremely covalent systems with the consequence being that the magnetic exchange interactions become very long-ranged, thereby hampering the materialization of the long-sought Kitaev physics. Nevertheless, it still would be possible to realize a spin-liquid system using the iridates with a proper tuning of the various competing exchange interactions.
Building a full understanding of the complex magnetism in the rare-earth pyrochlore iridates, A2Ir2O7, is an ongoing issue in condensed matter physics. The possibility of two interpenetrating and interacting frustrated magnetic pyrochlore sublattices, connected with the strong spin-orbit coupling of the 5d Ir4+ ion, lends itself to a wide array of potential electronic and magnetic states. In this paper, we present longitudinal field and zero field muSR measurements of Er2Ir2O7. The muSR response of Er2Ir2O7 is dominated by the strong fluctuating fields of the Er3+ (J = 15/2) moments, showing a…
Crystal field splitting in Sr$_{n+1}$Ir$_n$O$_{3n+1}$ ($n$ = 1, 2) iridates probed by x-ray Raman spectroscopy
本文用硬X射线非共振喇曼光谱研究了铱酸盐Ruddlesden-Popper系列的前两个成员Sr $_{n+1}$ Ir $_n$ O $_{3n+1}$的电子结构。通过调整光子能量转移约530 eV，我们已经能够探索氧K近边结构与批量灵敏度。光谱的角度依赖性已被利用分配功能在528-535 eV的能量范围内的特定跃迁涉及的Ir 5d轨道。这使我们能够提取可靠的值，从晶体场的立方分量（10 Dq）产生的t2 g-eg分裂，除了分裂的eg轨道由于tetravel扭曲。得到Sr $_2$ IrO $_4$和Sr $_3$ Ir $_2$ O $_7$的电子能分别为（3.8，1.6）eV和（3.55，1.9）eV。
Comment on "Quantitative x-ray photoelectron spectroscopy: Quadrupole effects, shake up, Shirley background, and relative sensitivity factors from a database of true x-ray photoelectron spectra"
Eu2Ir2O7, a candidate Weyl semimetal, shows an insulator-to-metal transition as a function of Bi substitution at the Eu site. In this work, we investigate the (Eu_1-xBi_x)2Ir2O7 series via Hard X-ray Photoemission Spectroscopy (HAXPES), where substitution of larger Bi3+ for Eu3+ is reported to result in an anomalous lattice contraction (20 %) for low Bi doping (3.5 %). Using HAXPES, we confirm that all the cations retain their nominal valence state throughout the series. The asymmetric nature of Bi core-level spectra for compositions in the metallic region indicates that Bi contributes to the …
Spin correlated electronic state on the surface of a spin-orbit Mott system (Layered Iridates)
二维电子系统的新相是由新的表面或界面修饰的电子结构引起的，在材料科学中引起了极大的兴趣。我们利用光电子能谱表明，近表面的电子结构的体绝缘铱酸盐Sr $_3$ Ir $_2$ O $_7$位于附近的金属-莫特绝缘体过渡表现出弱的金属性表示有限的电子光谱重量在费米能级。表面电子表现出独特的自旋结构，由自旋轨道，库仑相互作用和表面量子磁性的相互作用，不同于拓扑绝缘体状态。我们的研究结果表明，一个新的准二维相互作用电子表面基态的实验实现，打开了大门，奇异的量子纠缠和输运现象的铱基氧化物器件。
The valence state of UTe$_2$ was studied by core-level photoelectron spectroscopy. The main peak position of the U $4f$ core-level spectrum of UTe$_2$ coincides with that of UB$_2$, which is an itinerant compound with a nearly $5f^3$ configuration. However, the main peak of UTe$_2$ is broader than that of UB$_2$, and satellite structures are observed in the higher binding energy side of the main peak, which are characteristics of mixed-valence uranium compounds. These results suggest that the U 5$f$ state in UTe$_2$ is in a mixed valence state with a dominant contribution from the itinerant $5…
We present a thorough experimental study of the three-dimensional hyperhoneycomb Kitaev magnet $β$-Li$_2$IrO$_3$, using a combination of inelastic neutron scattering (INS), time-domain THz spectroscopy, and heat capacity measurements. The main results include a massive low-temperature reorganization of the INS spectral weight that evolves into a broad peak centered around 12 meV, and a distinctive peak in the THz data at 2.8(1) meV. A detailed comparison to powder-averaged spin-wave theory calculations reveals that the positions of these two features are controlled by the anisotropic $Γ$ coupl…
The three-dimensional (3D) electronic structure of the hidden order compound URu$_2$Si$_2$ in a paramagnetic phase was revealed using a 3D angle-resolved photoelectron spectroscopy where the electronic structure of the entire Brillouin zone is obtained by scanning both incident photon energy and detection angles of photoelectrons. The quasi-particle bands with enhanced contribution from the $\mathrm{U}~5f$ state were observed near $E_\mathrm{F}$, formed by the hybridization with the $\mathrm{Ru}~4d$ states. The energy dispersion of the quasi-particle band is significantly depend on $k_z$, indi…
Quantitative study of valence and configuration interaction parameters of the Kondo semiconductors CeM2Al10 (M = Ru, Os and Fe) by means of bulk-sensitive hard x-ray photoelectron spectroscopy
Evolution of structure, magnetism and electronic transport in doped pyrochlore iridate Y$_2$Ir$_{2-x}$Ru$_{x}$O$_7$
在铱氧化物中，自旋轨道耦合（SOC）和电子关联（$U$）之间的相互作用被认为是许多奇异现象的原因。我们研究了烧绿石铱酸盐Y $_2$ Ir $_{2-x}$ Ru $_{x}$ O $_7$的结构、磁性和电子性质的演变，其中Ru的取代旨在调节这种相互作用。Ru替代不引入任何结构相变，然而，我们确实观察到晶格参数随掺杂水平$x$的演变。X射线光电子能谱（XPS）研究表明，Ru取代了Ru $^{4+}$的电荷状态，取代了Ir的$^{4+}$。磁化强度数据揭示了磁性不可逆性的发生和磁矩的减少与Ru的逐步取代。这些材料显示出非平衡的低温磁状态所揭示的磁弛豫数据。有趣的是，我们发现磁弛豫速率随着Ru的取代而增加。电阻率在整个温度范围内均表现出绝缘特性，但随着Ru的替代，电阻率降低。所有材料的电子传导性质都遵循幂律行为。
A new method for the analysis of the scattering rates from angle-resolved photoelectron spectroscopy (ARPES) is presented and described in details. It takes into account experimental instrumental resolution and finite temperature effects. More accurate results are obtained in comparison with a standard, commonly used method. The application of the method is demonstrated for several examples commonly encountered in new quantum materials. Its usefulness is especially apparent in investigations of systems with strongly correlated electrons.
The electronic structure of La$_{1.48}$Nd$_{0.4}$Sr$_{0.12}$CuO$_4$ probed by high- and low-energy angle-resolved photoelectron spectroscopy: evolution with probing depth
Iridates with the 5$d^4$ electronic configuration have attracted recent interest due to reports of magnetically-ordered ground states despite longstanding expectations that their strong spin-orbit coupling would generate a $J = 0$ electronic ground state for each Ir$^{5+}$ ion. The major focus of prior research has been on the double perovskite iridates Ba$_2$YIrO$_6$ and Sr$_2$YIrO$_6$, where the nature of the ground states (i.e. ordered vs non-magnetic) is still controversial. Here we present neutron powder diffraction, high energy resolution fluorescence detected x-ray absorption spectrosco…
Electronic structures of CeRu$_2X_2$ ($X$ = Si, Ge) in the paramagnetic phase studied by soft X-ray ARPES and hard X-ray photoelectron spectroscopy
对重费米子系统CeRu $_2$ Si $_2$和处于顺磁相的$4f$局域铁磁体CeRu $_2$ Ge $_2$进行了软、硬X射线光电子能谱学（PES）研究.用软X射线$hν$依赖角分辨光电子能谱学（ARPES）研究了CeRu $_2$ Si $_2$的三维能带结构和费米面形状.通过对$4f$巡游模型和定域模型的能带结构计算，定性地解释了CeRu $_2$ Si $_2$和CeRu $_2$ Ge $_2$在费米面拓扑和非$4f$电子结构上的差异.用单杂质Anderson模型计算了CeRu $_2X_2$（$X$ = Si，Ge）中Ce的价态，Ce 3d硬X射线芯能级PES和Ce 3d X射线吸收谱显示出部分$_2$对CeRu $_2$ Si $_2$中传导电子的贡献具有较强的杂化和特征.
We use x-ray spectroscopy at Ir L$_3$/L$_2$ absorption edge to study powder samples of the intercalated honeycomb magnet Ag$_3$LiIr$_2$O$_6$. Based on x-ray absorption and resonant inelastic x-ray scattering measurements, and exact diagonalization calculations including next-neighbour Ir-Ir electron hoping integrals, we argue that the intercalation of Ag atoms results in a nearly itinerant electronic structure with enhanced Ir-O hybridization. As a result of the departure from the local relativistic $j_{\rm eff}\! = \!1/2$ state, we find that the relative orbital contribution to the magnetic m…
The treatment of electronic correlations in open-shell systems is among the most challenging problems of condensed matter theory. Current approximations are only partly successful. Ligand field multiplet theory (LFMT) has been widely successful in describing intra-atomic correlation effects in x-ray spectra, but typically ignores itinerant states. The cumulant expansion for the one electron Greens function has been successful in describing shake-up effects but ignores atomic multiplets. More complete methods, such as dynamic mean-field theory can be computationally problematic. Here we show th…
Evolution of structure and magnetism across the metal-insulator transition in the pyrochlore iridate $($Nd$_{1-x}$Ca$_x)_2$Ir$_2$O$_7$
我们报告的演化的热金属绝缘体转变的多晶样品的Nd $_2$ Ir $_2$ O $_7$空穴掺杂后，通过取代Nd $^{3+}$的Ca $^{2+}$。Ca取代介导的填充控制莫特样过渡，最小的可分辨的结构变化，而不改变网站的对称性。局部结构证实，Ca取代不会导致局部化学相分离，吸收光谱确定，Ir阳离子保持自旋轨道纠缠的电子配置。的金属-绝缘体的转变与反铁磁有序的Ir亚晶格上的所有测量的样品相一致，都降低了起始温度与Ca含量。弱低温上升的磁化率和电阻率的样品与高钙含量表明，钕亚晶格反铁磁性继续耦合到金属制度的载体。
Na2IrO3 (NIO) is known to be a spin-orbit (SO) driven j=1/2 pseudo-spin Mott-Hubbard (M-H) insulator. However, the microscopic origin of the pseudo-spin state and the role of local structural distortions have not been clearly understood. Using a combination of theoretical calculations and x-ray spectroscopy, we show that the energetics in the vicinity of Fermi level (EF) is governed by SO interactions, electron correlation and local octahedral distortions. Contrary to the earlier understanding, here we show that the j=3/2 and 1/2 pseudo-spin states have admixture of both t2g and eg characters …
Imaging the evolution of metallic states in a spin-orbit interaction driven correlated iridate
Ruddlesden-Popper（RP）系列的虹彩酸盐（Srn+1 IrnO 3 n +1）最近受到了广泛关注，这是由于自旋-轨道（SO）驱动的能带分裂和库仑相互作用的协同作用所产生的涌现物理的预期[1-3]。然而，关于相关性在电荷间隙形成中的作用的持续争论以及缺乏对掺杂对低能电子结构的影响的理解阻碍了实现许多预测状态的实验进展[4-8]，包括可能的高Tc超导性[7，9]。使用扫描隧道光谱，我们映射出的n=2 RP成员，Sr 3 Ir 2 O 7（Ir 327）的空间分辨态密度。我们发现，Ir 327的母体化合物，认为只存在作为一个弱相关的带绝缘体，实际上具有大量的~ 130 meV的电荷激发间隙驱动的结构，SO耦合和相关性之间的相互作用。在区分内的非均匀纹理电子结构的固有电子字符的一个关键组成部分是我们的识别的签名失踪的顶端氧缺陷，这在许多层状氧化物中发挥了关键作用。我们的测量结合从计算的见解揭示了顶端氧空位转移光谱重量从较高的能量的间隙能量，从而揭示了一个路径，以获得金属的电子状态从父母绝缘状态的虹膜。
Spin-orbit coupling in heavy 5$d$ metal oxides, in particular, iridates have received tremendous interest in recent years due to the realization of exotic electronic and magnetic phases. Here, we report the synthesis, structural, magnetic, thermodynamic, and optical properties of the ternary iridate Pr$_3$IrO$_7$. Single crystals of Pr$_3$IrO$_7$ have been grown by the KF flux method. Structural analysis shows that Pr$_3$IrO$_7$ crystallizes in an orthorhombic phase with $Cmcm$ symmetry. The electron energy loss spectroscopy study indicates that Pr is in a 3+ valence state, which implies a 5+ …
We present a simplified web-based application for simulating x-ray and photoelectron spectra of transition metals, built around the notion that web-based applications lower the bar for novice users. The application provides a simple interface to simulate x-ray absorption spectroscopy, resonant inelastic x-ray scattering, and angle-resolved photoemission spectroscopy, incorporating the effects of local electronic interactions, which give rise to multiplets, spin-orbit coupling, crystal field effects, and ligand hybridization/charge transfer. Results can be obtained that highlight the key role o…
