Molecular self-assembly is a well-known technique to create highly functional nanostructures on surfaces. Self-assembly on two-dimensional materials is a developing field and has already resulted in the discovery of several rich and interesting phenomena. Here, we review this progress with an emphasis on the electronic properties of the adsorbates and the substrate in well-defined systems, as unveiled by scanning tunneling microscopy (STM). We cover three aspects of the self-assembly. The first one focuses on non-covalent self-assembly dealing with site-selectivity due to inherent moire pattern present on 2D materials deposited on substrates. Modification of intermolecular interactions and molecule-substrate interactions influences the assembly drastically and 2D materials can also be used as a platform to carry out covalent and metal-coordinated assembly. The second part deals with the electronic properties of molecules adsorbed on 2D materials. By virtue of being inert and possessing low density of states near the Fermi level, 2D materials decouple molecules electronically from the underlying metal substrate and allow high-resolution spectroscopy and imaging of molecular orbitals. The moire pattern on the 2D materials causes site-selective gating and charging of molecules in some cases. The last section covers the effects of self-assembled organic molecules on the electronic properties of graphene as revealed by spectroscopy and electrical transport measurements. Non-covalent functionalization of 2D materials has already been applied for their application as catalysts and sensors. With the current surge of activity on building van der Waals heterostructures from 2D materials, molecular self-assembly has the potential to add an extra level of flexibility and functionality for applications ranging from flexible electronics and OLEDs to novel electronic devices and spintronics.
Exfoliation and van der Waals heterostructure assembly of intercalated ferromagnet Cr1/3TaS2
铁磁范德华（vdW）材料是用于具有全二维材料异质结构的自旋电子器件的需求。在这里，我们证明了机械剥离的磁性原子嵌入过渡金属二硫属化物Cr 1/3 TaS 2从其散装晶体，以前这样的插层材料被认为是难以剥离。剥离的纳米厚的薄片的磁输运揭示了低于其居里温度TC ~ 110 K的铁磁有序性以及强的面内磁各向异性;这些与其本体性质相同。此外，范德瓦尔斯异质结构组装的Cr 1/3 TaS 2与另一个插入铁磁体Fe 1/4 TaS 2证明使用干转移方法。制造的异质结组成的Cr 1/3 TaS 2和Fe 1/4 TaS 2与天然Ta 2 O 5氧化物隧道势垒之间的隧道磁阻（TMR），揭示可能的自旋注入和检测这些剥离铁磁材料通过VDW结。
Polymer-free van der Waals assembly of 2D material heterostructures using muscovite crystals
Institute for Functional Intelligent Materials, National University of Singapore（新加坡国立大学功能智能材料研究所）；Department of Materials Science and Engineering, National University of Singapore（新加坡国立大学材料科学与工程系）
