Untangling the intertwined: metallic to semiconducting phase transition of colloidal MoS2 nanoplatelets and nanosheets

Abstract

2D semiconducting transition metal dichalcogenides (TMDCs) are highly promising materials for future spin- and valleytronic applications and exhibit an ultrafast response to external (optical) stimuli which is essential for optoelectronics. Colloidal nanochemistry on the other hand is an emerging alternative for the synthesis of 2D TMDC nanosheet (NS) ensembles, allowing for the control of the reaction via tunable precursor and ligand chemistry. Up to now, wet-chemical colloidal syntheses yielded intertwined/agglomerated NSs with a large lateral size. Here, we show a synthesis method for 2D mono- and bilayer MoS₂ nanoplatelets with a particularly small lateral size (NPLs, 7.4 nm ± 2.2 nm) and MoS₂ NSs (22 nm ± 9 nm) as a reference by adjusting the molybdenum precursor concentration in the reaction. We find that in colloidal 2D MoS₂ syntheses initially a mixture of the stable semiconducting and the metastable metallic crystal phase is formed. 2D MoS₂ NPLs and NSs then both undergo a full transformation to the semiconducting crystal phase by the end of the reaction, which we quantify by X-ray photoelectron spectroscopy. Phase pure semiconducting MoS₂ NPLs with a lateral size approaching the MoS₂ exciton Bohr radius exhibit strong additional lateral confinement, leading to a drastically shortened decay of the A and B exciton which is characterized by ultrafast transient absorption spectroscopy. Our findings represent an important step for utilizing colloidal TMDCs, for example small MoS₂ NPLs represent an excellent starting point for the growth of heterostructures for future colloidal photonics.