Transmission electron imaging and diffraction characterisation of 2D nanomaterials

Abstract

Following the discovery of graphene, 2D nanostructures have been noted for their potential in a range of high-impact applications, such as sensing, catalysis, and composite reinforcement. Liquid-phase exfoliation and chemical vapour deposition have been demonstrated and indicate the feasibility of mass-scale production. With the advent of mass-produced 2D nanostructures a key focus of research is to characterise these materials. This thesis is concerned with imaging and structural properties of the 2D nanomaterials, hexagonal boron nitride (h-BN), molybdenum disulfide (MoS2), tungsten disulfide (WS2), titanium disulfide (TiS2) and hexabenzocoronene (HBC), produced via liquid phase exfoliation. HBC strictly speaking is not 2D nanomaterial, however, it can be viewed as transition molecule from benzene to graphene. The data used for characterisation is based primarily on electron diffraction and, in particular, aberration corrected annular dark field (ADF) scanning transmission electron microscopy (STEM). The incoherent nature of ADF STEM provides direct atomic imaging without the contrast reversals upon focus changes seen in conventional high-resolution transmission electron microscopy (HRTEM). The main structural feature investigated in this thesis was the stacking sequences in few-layers h-BN, MoS2, WS2 and TiS2. Simple stacking (AAA) can be distinguished from Bernal (ABA) and rhombohedral (ABC) on the basis of intensity ratio, I{10̅10}/I{11̅20} , in diffraction patterns and indirectly in HRTEM images. Nonetheless acquisition of the diffraction patterns suitable for analysis can be challenging due to the sample issues. Non-bulk stacking sequences were reliably confirmed for all above 2D nanomaterials on the basis of atomically resolved ADF STEM. 20 h-BN, 28 MoS2, 5 WS2 and 6 TiS2 nanoflakes were imaged and analysed. Amongst them 2 h-BN, 9 MoS2, 4 WS2 and 1 TiS2 nanoflakes displayed non-bulk stacking. Hence, it appears that 2D WS2 has the greatest affinity for non-bulk stacking. Finally, an interesting structural transformation was observed in HBC molecules. Under the influence of electron beam HBC agglomerates were transformed into crystalline phase with 90o symmetryThis thesis is not currently available in ORA