Two-dimensional (2D) semiconductors exhibit unique electronic and optical properties arising from the atomic-scale thickness and two-dimensional electronic structure. However, it is usually limited by an intrinsically flat morphology of 2D materials. Here, we report an effect of spontaneous folding of quasi-2D CdTe nanosheets stimulated by ligand exchange. We show that initially flat CdTe nanosheets with 100−200 nm lateral size and 5−6 ML thickness are uniformly rolled up when oleic acid is replaced by thiol-containing ligands. Detailed study shows nanosheet folding along the [110] direction forming multiwall scroll-like structures with the diameter being dependent on sheet thickness. A pronounced red shift of the exciton transitions of CdTe nanosheets is found due to thickness increase and strain appearance under thiol attachment. The folding mechanism is likely related to misfit strain at CdTe (001) basal planes as ultrathin CdS layer is formed. Possibility to precisely tune the nanostructure shape simply by ligand-induced strain can evolve into new synthetic strategies to control a spatial morphology of 2D materials.
Semiconductor nanoparticles of cadmium chalcogenides are known to exhibit pronounced thickness-dependent E0 series of exciton transitions at the Γ point of the Brillouin zone (BZ). In this work, we report an experimental evidence for high-energy series of exciton transitions, which originates from BZ points different from the Γ point, in the family of cadmium chalcogenide quasi-2D nanoplatelets (NPLs). Intensive UV absorption bands demonstrating a pronounced size effect are observed for CdTe, CdSe, and CdS NPLs in addition to the E0 exciton bands in the visible region. These new bands are attributed to transitions analogous to the E1, E1 + ∆1, and E2 series observed in bulk crystals. First-principles DFT calculations of the electronic structure and absorption spectra support this explanation and show that the main contribution to these optical transitions comes from X and M points of the 2D BZ, which originate from L and X points of the 3D BZ. At the same time, the E0 series of transitions at the Γ point is well described by the multiband effective-mass model. The observation of the UV exciton bands reveals tunable optical properties of cadmium chalcogenide NPLs in UV spectral region, which may be interesting for practical applications.
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