Chica Daniel G, Iyer Abishek K, Cheng Matthew, Ryan Kevin M, Krantz Patrick, Laing Craig, Dos Reis Roberto, Chandrasekhar Venkat, Dravid Vinayak P, Kanatzidis Mercouri G
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
Department of Material Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States.
Inorg Chem. 2021 Mar 15;60(6):3502-3513. doi: 10.1021/acs.inorgchem.0c03577. Epub 2021 Feb 26.
We report a reactive flux technique using the common reagent PS and metal precursors developed to circumvent the synthetic bottleneck for producing high-quality single- and mixed-metal two-dimensional (2D) thiophosphate materials. For the monometallic compound, MPS (M = Ni, Fe, and Mn), phase-pure materials were quickly synthesized and annealed at 650 °C for 1 h. Crystals of dimensions of several millimeters were grown for some of the metal thiophosphates using optimized heating profiles. The homogeneity of the bimetallic thiophosphates MM'PS (M, M' = Ni, Fe, and Mn) was elucidated using energy-dispersive X-ray spectroscopy and Rietveld refinement. The quality of the selected materials was characterized by transmission electron microscopy and atomic force microscopy measurements. We report two novel bimetallic thiophosphates, MnCoPS and FeCoPS. The NiPS and MnNiPS flux reactions were monitored in situ using variable-temperature powder X-ray diffraction to understand the formation reaction pathways. The phases were directly formed in a single step at approximately 375 °C. The work functions of the semiconducting materials were determined and ranged from 5.28 to 5.72 eV.
我们报道了一种反应通量技术，该技术使用常见试剂PS和金属前驱体，旨在突破高质量单金属和混合金属二维硫代磷酸盐材料生产中的合成瓶颈。对于单金属化合物MPS（M = Ni、Fe和Mn），可快速合成纯相材料，并在650°C下退火1小时。利用优化的加热曲线，生长出了尺寸达几毫米的某些金属硫代磷酸盐晶体。通过能量色散X射线光谱和Rietveld精修对双金属硫代磷酸盐MM'PS（M、M' = Ni、Fe和Mn）的均匀性进行了阐明。所选材料的质量通过透射电子显微镜和原子力显微镜测量进行了表征。我们报道了两种新型双金属硫代磷酸盐，即MnCoPS和FeCoPS。使用变温粉末X射线衍射对NiPS和MnNiPS通量反应进行原位监测，以了解其形成反应路径。这些相在约375°C下一步直接形成。测定了这些半导体材料的功函数，范围为5.28至5.72电子伏特。
