Theory of Plasmonic Hot-Carrier Generation and Relaxation.
Theory of Plasmonic Hot-Carrier Generation and Relaxation.
复制标题
等离子体热载流子产生和弛豫理论。
DOI：
10.1021/acs.jpca.1c05837
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Yu Zhang
中科院分区：
文献类型：
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作者：
Yu Zhang
（局部）表面等离子体衰变产生的热载流子（HC）由于其在物理、化学、材料和能源科学中的广阔应用前景而引起了广泛关注。然而，等离子体HC产生、弛豫和捕获的详细机制研究较少。在这项工作中，我们开发并应用了量子力学模型和耦合主方程方法来研究等离激元衰变产生的碳氢化合物及其随后的弛豫过程，并平等对待不同的机制。首先，开发了用于 HC 生成的量子力学模型。讨论了它与现有半经典模型和瞬态密度泛函理论 (TDDFT) 的联系。其次，在电子-电子和电子-声子相互作用的情况下研究了碳氢化合物的弛豫和寿命。引入类似 GW 的近似来解释电子-电子散射。对尺寸高达 1.6 nm 的 Jellium 纳米颗粒的数值模拟表明，电子-电子散射和电子-声子散射在弛豫动力学的不同时间尺度中占主导地位。我们还推广了该模型来研究将 HC 提取到附着分子上。研究发现，提取碳氢化合物用于其他应用的量子产率取决于尺寸。一般来说，较小尺寸的纳米粒子可以提高量子产率，这与最近的实验测量结果一致。尽管我们用 Jellium 模型证明了这种新发展的理论形式主义，但该理论适用于任何其他原子论模型。
Hot-carrier (HC) generation from (localized) surface plasmon decay has recently attracted much attention due to its promising applications in physical, chemical, materials, and energy science. However, the detailed mechanisms of plasmonic HC generation, relaxation, and trapping are less studied. In this work, we developed and applied a quantum-mechanical model and coupled master equation method to study the generation of HCs from plasmon decay and their following relaxation processes with different mechanisms treated on equal footing. First, a quantum-mechanical model for HC generation is developed. Its connection to existing semiclassical models and time-dependent density functional theory (TDDFT) is discussed. Second, the relaxation and lifetimes of HCs are investigated in the presence of electron-electron and electron-phonon interactions. A GW-like approximation is introduced to account for the electron-electron scattering. The numerical simulations on the Jellium nanoparticles with a size up to 1.6 nm demonstrate the electron-electron scattering and electron-phonon scattering dominate different time scale in the relaxation dynamics. We also generalize the model to study the extraction of HCs to attached molecules. The quantum yield of extracting HCs for other applications is found to be size-dependent. In general, the smaller size of NP improves the quantum yield, which is in agreement with recent experimental measurements. Even though we demonstrate this newly developed theoretical formalism with Jellium model, the theory applies to any other atomistic models.