通过吸附的氧气和水揭示磷化锌（Zn3P2）表面的早期氧化机理：第一性原理DFT-D3研究。,Physical Chemistry Chemical Physics

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通过吸附的氧气和水揭示磷化锌（Zn3P2）表面的早期氧化机理：第一性原理DFT-D3研究。
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2019-12-20 , DOI: 10.1039/c9cp03902c
Nelson Y Dzade ₁

Affiliation

磷化锌（Zn3P2）是一种新型的地球上富裕的光伏材料，其直接带隙为1.5 eV。在本文中，已通过以下方法详细研究了（001），（101）和（110）Zn3P2表面在氧气和水的存在下的初始氧化机理，这严重限制了有效的Zn3P2基光伏电池的制造。色散校正密度泛函理论（DFT-D3）计算。介绍并讨论了氧和水吸附的基本方面，包括初始吸附几何形状，吸附能，结构参数和电子性质。通过对Bader电荷，态的部分密度和差分电荷密度等值线轮廓的分析，提出了Zn3P2表面氧化初始步骤的化学图片和起源。给出的结果表明，尽管水与Zn3P2表面上的Zn离子相互作用较弱，但分子和离解氧物种与（001），（101）和（110）表面物种强烈相互作用。氧的吸附被证明具有相互作用的表面物质大量电荷转移的特征，从而使它们从Zn2 +氧化为Zn3 +形式的氧化态。已显示，预先吸附的氧会促进水的OH键解离，而吸附的氢氧化物（OH-）会从相互作用的表面位点吸引大量电荷。尽管保留了不同Zn3P2表面的半导体性质，但我们观察到明显的吸附诱导的电子结构变化，覆盖的表面显示出比裸露表面小的带隙。本研究证明了氧-水/固体界面对于了解在分子水平上存在氧气和水的情况下Zn3P2氧化机理的重要性。该研究还强调了需要通过原位官能化保护Zn3P2纳米颗粒在氧气和水分存在下免受可能的氧化的作用，其中Zn3P2纳米颗粒在合成后立即暴露于有机功能分子的蒸气中。

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Unravelling the early oxidation mechanism of zinc phosphide (Zn3P2) surfaces by adsorbed oxygen and water: a first-principles DFT-D3 investigation.

Zinc phosphide (Zn3P2) is a novel earth-abundant photovoltaic material with a direct band gap of 1.5 eV. Herein, the incipient oxidation mechanism of the (001), (101), and (110) Zn3P2 surfaces in the presence of oxygen and water, which severely limits the fabrication of efficient Zn3P2-based photovoltaics, has been investigated in detail by means of dispersion-corrected density functional theory (DFT-D3) calculations. The fundamental aspects of the oxygen and water adsorption, including the initial adsorption geometries, adsorption energies, structural parameters, and electronic properties, are presented and discussed. A chemical picture and origin of the initial steps of Zn3P2 surface oxidation are proposed through analyses of Bader charges, partial density of states, and differential charge density isosurface contours. The results presented show that while water interacts weakly with the Zn ions on the Zn3P2 surfaces, molecular and dissociative oxygen species interact strongly with the (001), (101), and (110) surface species. The adsorption of oxygen is demonstrated to be characterized by a significant charge transfer from the interacting surface species, causing them to be oxidized from Zn2+ to Zn3+ formal oxidation states. Preadsorbed oxygen species are shown to facilitate the O-H bond activation of water towards its dissociation, with the adsorbed hydroxide species (OH-) demonstrated to draw a significant amount of charges from the interacting surface sites. Despite the fact that the semiconducting nature of the different Zn3P2 surfaces is preserved, we observe noticeable adsorption induced changes in their electronic structures, with the covered surface exhibiting smaller band gaps than the naked surfaces. The present study demonstrates the importance of the oxygen-water/solid interface to understand the oxidation mechanism of Zn3P2 in the presence of oxygen and water at the molecular level. The study also highlights the need for Zn3P2 nanoparticles to be protected against possible oxidation in the presence of oxygen and moisture via in situ functionalization, wherein the Zn3P2 nanoparticles are exposed to a vapour of organic functional molecules immediately after synthesis.

更新日期：2019-12-20

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