Abstract Zn1-xMnxAl2O4 (x = 0, 0.10, 0.20, 0.30 and 0.40) nanoparticles were synthesized by hydrothermal method, and the effects of Mn doping on the microstructure, morphology, binding energy and optical property of the samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDX), x-ray photoemission spectroscopy (XPS), ultraviolet–visible (UV–Vis) spectroscopy, photoluminescence spectra (PL) and fourier transform infrared spectroscopy (FT-IR). And the energy band structure of various defects in ZnAl2O4 structure were calculated by means of the first-principles calculations. The experimental results show that Zn1-xMnxAl2O4 nanoparticles possess cubic spinel structure without other impurity phases. The morphology of the samples exhibits irregular spherical or ellipsoid particles with uniform particle size. EDX Mapping display that Zn, Al, O and Mn elements are uniformly distributed without any enrichment phenomenon throughout the sample. Mn ions successfully used as doping agent replaced Zn2+ and entered ZnAl2O4 matrix. Combined with the calculated results of the first principle calculations, the substitution of Mn introduced new energy levels, which level make the intensity of PL spectra decrease and occur quenching phenomenon. XPS spectra demonstrate that the doped Mn ions mainly occupy the tetrahedral sites. UV–vis spectra indicate with the increase of Mn ion concentration, the band gap of the doped sample decrease with the increase of Mn content and exhibit red shift. FT-IR show that all Mn2+ ions substituted for Zn2+ ions without changing ZnAl2O4 spinel structure.

中文翻译：

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尖晶石结构Mn掺杂ZnAl2O4纳米粒子的光学性质及理论研究

摘要 采用水热法合成了 Zn1-xMnxAl2O4 (x = 0, 0.10, 0.20, 0.30 和 0.40) 纳米粒子，并通过 X 射线表征了 Mn 掺杂对样品微观结构、形貌、结合能和光学性能的影响衍射 (XRD)、场发射扫描电子显微镜 (FE-SEM)、高分辨率透射电子显微镜 (HRTEM)、能量色散 X 射线光谱 (EDX)、X 射线光电子能谱 (XPS)、紫外-可见光 ( UV-Vis) 光谱、光致发光光谱 (PL) 和傅立叶变换红外光谱 (FT-IR)。并通过第一性原理计算计算了ZnAl2O4结构中各种缺陷的能带结构。实验结果表明，Zn1-xMnxAl2O4纳米颗粒具有立方尖晶石结构，不含其他杂质相。样品的形貌表现为粒径均匀的不规则球形或椭球形颗粒。EDX Mapping 显示 Zn、Al、O 和 Mn 元素均匀分布在整个样品中，没有任何富集现象。Mn 离子成功地用作掺杂剂，取代了 Zn2+ 并进入了 ZnAl2O4 基体。结合第一性原理计算的计算结果，Mn的取代引入了新的能级，该能级使PL光谱强度降低并发生猝灭现象。XPS 谱表明掺杂的 Mn 离子主要占据四面体位点。UV-vis光谱表明，随着Mn离子浓度的增加，掺杂样品的带隙随着Mn含量的增加而减小并表现出红移。