We study the structural and electronic properties of p‐type layered oxypnictides (LaO)ZnPn (Pn = P, As, Sb), calculated by first principles. Pn substitution from P to Sb increases D_2d‐type local symmetry distortions at ZnPn₄ and OLa₄ tetrahedra. (LaO)ZnP and (LaO)ZnAs exhibit direct band gaps (Γ → Γ) of 0.621 eV and 0.528 eV, respectively, while (LaO)ZnSb exhibits an indirect band gap (Γ → 0.2Λ) of 0.029 eV. The band gaps come from valence Pn p _x/p _y and conduction Zn 4s states. Moreover, the substitution increases split‐off energy at Z and Γ points. We find localized valence degeneracy‐lifted Zn 3d states because of the possible second‐order Jahn‐Teller effect, which induces the local symmetry distortions. The localized Zn 3d states are followed by minor bonding s‐p hybridization of Zn and Pn. Above them, we show major bonding s‐p hybridization; O 2p states in electron‐blocking [LaO]⁺ layers, which are essential for thermoelectricity; and nonbonding Pn p states near Fermi level. In the conduction band, antibonding s‐p hybridization is found. Our result shows new insights and findings of structural and electronic properties, which explain previous experimental results, as the focus of this study is related to inorganic chemistry. This study is important for future functional device applications.

中文翻译：

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在层状氧化氧（LaO）ZnPn（Pn = P，As，Sb）中通过光子取代来研究结构和电子性质

我们研究了通过第一性原理计算出的p型层状氧氧化（LaO）Zn Pn（Pn = P，As，Sb）的结构和电子性质。从P到Sb的Pn取代增加了Zn Pn ₄和OLa ₄四面体的D _{2 d}型局部对称畸变。（LaO）ZnP和（LaO）ZnA分别表现出0.621 eV和0.528 eV的直接带隙（Γ→Γ），而（LaO）ZnSb表现出0.029 eV的间接带隙（Γ→0.2Λ）。带隙来自化合价Pn p _x / p _y 和导电Zn 4s态。此外，代换会增加Z和Γ点处的分离能。由于可能的二阶Jahn-Teller效应，我们发现局部价简并性提升的Zn 3d状态，这会引起局部对称畸变。局限的Zn 3d态之后是Zn和Pn的次键s-p杂化。在它们上方，我们显示了主要的键合s-p杂交；电子阻挡[LaO] ⁺层中的O 2p态，这对于热电至关重要。和非键合Pnp表示费米能级附近。在导带中，发现了抗键s-p杂交。我们的结果显示了结构和电子特性的新见解和发现，这可以解释先前的实验结果，因为本研究的重点与无机化学有关。这项研究对于将来的功能设备应用非常重要。