Brune Veronika, Hegemann Corinna, Mathur Sanjay
Institute of Inorganic Chemistry , University of Cologne , Greinstraße 6 , D-50939 Cologne , Germany.
Inorg Chem. 2019 Aug 5;58(15):9922-9934. doi: 10.1021/acs.inorgchem.9b01084. Epub 2019 Jul 16.
New synthetic access to two-dimensional transition metal dichalcogenides (TMDCs) is highly desired to exploit their extraordinary semiconducting and optoelectronic properties for practical applications. We introduce here an entirely novel class of molecular precursors, [M(XEtN(Me)EtX)] (M = Mo, W, X = S, Se), enabling chemical vapor deposition of TMDC thin films. Molybdenum and tungsten complexes of dianionic tridentate pincer-type ligands (HXEt)NR (R = methyl, -butyl, phenyl) produced air-stable monomeric dichalcogenide complexes, [W(SEtN(Me)EtS)] and [Mo(SEtN(Me)EtS)], displaying W and Mo centers in an octahedral environment of 4 S and 2 N donor atoms. Owing to their remarkable volatility and clean thermal decomposition, both Mo and W complexes, when used in the chemical vapor deposition (CVD) process, produced crystalline MoS and WS thin films. X-ray diffraction analysis and atomic-scale imaging confirmed the phase purity and 2D structural characteristics of MoS and WS films. The new set of ligands presented in this work open ups convenient access to a scalable and precursor-based synthesis of 2D transition metal dichalcogenides.
人们迫切希望通过新的合成方法来制备二维过渡金属二硫属化物(TMDCs),以便将其卓越的半导体和光电特性应用于实际。在此,我们介绍了一类全新的分子前驱体,即[M(XEtN(Me)EtX)](M = 钼、钨,X = 硫、硒),它能够实现TMDC薄膜的化学气相沉积。具有双阴离子三齿钳型配体(HXEt)NR(R = 甲基、丁基、苯基)的钼和钨配合物生成了空气稳定的单体二硫属化物配合物,如[W(SEtN(Me)EtS)]和[Mo(SEtN(Me)EtS)],其中钨和钼中心处于由4个硫和2个氮供体原子构成的八面体环境中。由于其显著的挥发性和清洁的热分解特性,钼和钨的配合物在化学气相沉积(CVD)过程中均能生成结晶态的MoS和WS薄膜。X射线衍射分析和原子尺度成像证实了MoS和WS薄膜的相纯度及二维结构特征。本文中提出的这组新配体为二维过渡金属二硫属化物的可扩展且基于前驱体的合成提供了便利途径。
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