Two dimensional layered transition metal dichalcogenides (TMDs) have attracted much attention for future electronics and optoelectronics due to their unique semiconducting features [1]. Nonetheless their properties are strongly influenced by the structural and chemical atomic arrangement in these atomically thin layers. The control and understanding of the atomic structure of synthesized TMD monolayers are thus crucial to exploit the potential properties predicted and/or to be newly discovered. In addition, compared to graphene which is a mono-atomic planar structure, the structural and chemical configuration of the TMD materials can have a lot of variations and it can be a way to tune their semi-conducting features. For instance, a ternary mixture such as Mo_xW_1-xS₂ and vertical/horizontal heterostructures between TMD structures with different chemical components or with other layered structures such as graphene and boron nitride can open the possibility of unique architectures [2]. In particular, vertical heterostructures are promising building blocks for novel semiconducting future materials because these layers have no surface dangling bond and vertically stacked layers are connected with van der Waals (vdW) forces. This allows to create atomically sharp interface with a desired structure design down to single atomic layered scale. Today a lot of efforts have been made to fabricate vdW heterostructures [3].

       In this work, vdW vertical heterostructures of MoSe₂ and graphene are studied using a transmission electron microscopy (TEM). The vdW stacks are fabricated by two step growth process. First graphene is grown by conventional CVD technique on Pt substrate, then followed by MoSe₂ growth via vdW epitaxy by Molecular beam epitaxy (MBE) technique in another reactor. The direct growth approach presents various interests compared to the manual stacking, such as clean interface and large surface production. In addition, using as grown CVD graphene, the obtained stack layers can be easily transferred on appropriate substrates. The synthesized MoSe₂/graphene layers are studied from micron down to atomic scale by several TEM techniques mainly using Low Voltage Aberration Corrected (LVAC) TEM in order to understand the growth mechanism of the vdW epitaxy by MBE and the correlation between grown MoSe₂ layer and graphene substrate. Using (S)TEM techniques, abundant information on synthesized structures can be provided. Local number of layers can be determined by several STEM techniques such as STEM HAADF imaging (Figure 1) and PACBED (Partially averaged convergent beam electron diffraction) [4]. Domains in graphene and MoSe₂ layers were independently recognized together with their local orientation using diffraction information, which allowed to study the local structural relationship between MoSe₂ and graphene substrate. Figure 2 shows a TEM image of stack layer and the orientation of MoSe₂ and graphene is determined by Fourier transform shown in the inset. MoSe₂ layers are often grown oriented to graphene with small range of misorientation 0 to 5°. The edge of MoSe₂ monolayer are observed along the zig-zag line of graphene in the case of non-continuous MoSe₂ monolayers. In addition, typical line defects are observed in a continuous domain (Figure 3a). This line defect consists of a symmetrical mirror structures (Figure 3b and 3c) [5], considered to be related to the stoichiometry control during the growth. Local chemical quantitative analysis by energy dispersive X-ray spectroscopy (EDX) was also applied on MoSe_x in order to exploit the sensitivity of the measurements, which will be a powerful method applicable at multi scale to predict various defect structures influencing their stoichiometry. Finally the MoSe₂ layers grown on CVD graphene with different experimental conditions were characterized using TEM and STEM based techniques. The influence of process parameters on the atomic configuration such as line defects are studied and the crystal mosaicity in MoSe₂ monolayer related to graphene substrate will be discussed by local structural analysis with a theoretical support.

References

[1] Splendiani et al., Nano Lett. 10 (2010) p1271

[2] A. Geim et al., Nature 499 (2013) p419

[3] N. Massicotte, Nature Nanotechnology 11 (2016) p42

[4] Thesis of Y. Martin ; University Joseph Fourier, Grenoble France, 2014

[5] Lehtinen et al., ACS Nano 9 (2015) p3724

Figures:

Figure1. HAADF STEM image of few-layer MoSe2/graphene stack layer. Contrast reflects local number of layer of MoSe2 grown on graphene.

Figure2. Atomic resolution TEM image of monolayer MoSe2 grown on monolayer graphene. Fourier transform in inset shows orientations of graphene and MoSe2 layers. Red square is zoomed in inset.

Figure 3. (a) TEM image under particular defocus, showing line defects formed in a MoSe2 domain, (b) atomic structure of line defects observed in MoSe2 monolayer and red square is zoomed in (c) showing symmetrical mirror structures connected shearing Se atoms (red points).

« Back to The 16th European Microscopy Congress 2016

EMC Abstracts - https://emc-proceedings.com/abstract/van-der-waals-heterostructures-of-mose2-and-graphene-studied-by-transmission-electron-microscopy/