This article is devoted to the spectroscopic characterization of ZnS-ZnO nanoscale heterostructures synthesized by the microwave-assisted solvothermal method. The synthesized samples were investigated by means of X-ray powder diffraction (XRPD), high energy resolution fluorescence detected X-ray absorption near-edge-structure (HERFD-XANES) spectroscopy, valence-to-core X-ray emission spectroscopy (VtC-XES) and high resolution transmission electron microscopy (HR-TEM) as well as energy dispersive X-ray spectroscopy (EDX). The average crystallite size estimated by the broadening of XRPD peaks increases from 2.7 nm to 3.7 nm in the temperature range from 100 °C to 150 °C. HR-TEM images show that nanoparticles are arranged in aggregates with the 60–200 nm size. Theoretical estimation shows that the systems synthesized at higher temperatures more prone to the agglomeration. The full profile Reitveld analysis of XRPD data reveals the formation of hexagonal zinc sulfide structure, whereas electron diffraction data reveal also the formation of cubic zinc sulfide and claim the polymorphous character of the system. High energy resolution Zn K-edge XANES data unambiguously demonstrate the presence of a certain amount of the zinc oxide which is likely to have an amorphous structure and could not be detected by XRPD. Qualitative analysis of XANES data allows deriving ZnS/ZnO ratio as a function of synthesis temperature. EDX analysis depicts homogeneous distribution of ZnS and amorphous ZnO phases across the conglomerates. A complementary element-selective valence to core X-ray emission spectroscopy evidences formation of two-component system and confirms estimations of ZnS/ZnO fractions obtained by linear combination fit of XANES data.

本文致力于通过微波辅助溶剂热法合成的ZnS-ZnO纳米级异质结构的光谱表征。通过X射线粉末衍射（XRPD），高能分辨率荧光检测X射线吸收近边缘结构（HERFD-XANES）光谱，价芯X射线发射光谱（VtC）对合成样品进行了研究-XES）和高分辨率透射电子显微镜（HR-TEM）以及能量色散X射线光谱仪（EDX）。在100°C至150°C的温度范围内，通过XRPD峰的增宽估计的平均微晶尺寸从2.7 nm增加到3.7 nm。HR-TEM图像显示纳米颗粒以60-200 nm的大小聚集在一起。理论估计表明，在较高温度下合成的系统更容易发生团聚。XRPD数据的完整轮廓Reitveld分析显示出六边形硫化锌结构的形成，而电子衍射数据也显示出立方硫化锌的形成，并声称该系统具有多态性。高能量分辨率Zn K-edge XANES数据明确表明存在一定量的氧化锌，该氧化锌可能具有无定形结构，无法通过XRPD检测到。XANES数据的定性分析可以得出ZnS / ZnO比值随合成温度的变化。EDX分析显示了整个集团中ZnS和非晶态ZnO相的均匀分布。