掺锂氧化镍中的空穴态：Zhang-Rice 光谱重量的掺杂依赖性

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-10-21 DOI:10.1039/d4cp03373f

Suman Mandal, Krishnakumar S. R. Menon

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引用次数: 0

摘要

我们报告了在 LixNi1-xO （0 ≤ x ≤ 0.24）中掺入空穴后，在 O K 边 X 射线吸收 (XA) 光谱上观察到的结构演变和光谱权重的动态转移。我们发现，掺杂镍氧化物的单胞以一种特定的方式演化到中间掺杂水平（x=0.12），然后遵循不同的趋势。我们确定并量化了 O K 边缘低能谱重量（LESW）的双峰结构（一个是局部的，另一个是更分散的）。归一化 LESW 随有效掺杂浓度 (∼ x/(1 - 2x))线性增加，在 x=0.12 时斜率发生变化，这与观察到的结构演变相关。Ni L3 边 XA 光谱形状的掺杂依赖性与 O K 边 LESW 的局部峰值密切相关。我们的观察结果有力地支持了 Zhang-Rice (ZR) 图像，证实了 NiO 中的掺杂空穴主要具有 ZR 特性。此外，我们还发现，铁的共掺杂会破坏 ZR 光谱权重，并使光谱形状恢复到 NiO 的光谱形状。

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Hole-states in Li doped NiO: Doping dependence of Zhang-Rice spectral weight

We report on structural evolution and a dynamical transfer of spectral weight as observed at O K-edge x-ray absorption (XA) spectra up on hole doping in LixNi1−xO (0 ≤ x ≤ 0.24). We find that, the unit cell of doped NiO evolves in a specific way up to an intermediate doping level (x=0.12) and then follows a different trend. A double peak structure (one is localized and other one being more delocalized) of low energy spectral weight (LESW) at O K-edge is identified and quantified. Normalized LESW is found to increase linearly with an effective doping concentration (∼ x/(1 − 2x)) with a change in slope at x=0.12, which is correlated to the observed structural evolution. Doping dependence of Ni L3-edge XA spectral shape closely follows the localized peak of LESW at O K-edge. Our observations strongly support the Zhang-Rice (ZR) picture, confirming doped holes in NiO are of primarily ZR character. Further, we find that Fe co-doping destroys ZR spectral weight and recovers the spectral shapes to that of NiO.

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.