Raman and photoluminescence spectra of two-dimensional nanocrystallites of monolayer WS2 and WSe2

Defects strongly modify optical properties in pristine and nanostructured two-dimensional (2D) materials. The ion implantation technique can be used to gradually introduce defects in semiconductor to obtain nanocrystallites (NCs) with different domain sizes. Here, we present a detailed study on the Raman and photoluminescence spectra of 2D NCs of monolayer WS2 (IL WS2) and 1L WSe2 prepared by ion implantation. With increasing ion dosages, both E' and A(1)' modes of 1L WS2 exhibit a downshift in frequency and an asymmetrical broadening toward lower frequency, while the A(1)' mode in 1L WSe2 NCs exhibits an opposite behavior, showing asymmetrical broadening and peak shift toward higher frequency. This behavior is well understood by phonon quantum confinement of the out-of-plane optical branch whose frequency displays a minimum at Fin pristine 1L WSe2. After the ion implantation, phonons from the Brillouin zone boundary are revealed in the Raman spectra, and the corresponding assignments are identified by resonant Raman spectra at low temperature. The defects can act as trapping centers of free carriers, which result in a sharp decrease of photoluminescence (PL) emission from A exciton with increasing ion dosage. The PL peak from A-exciton in both 1L WS2 and 1L WSe2 NCs blueshifts with increasing the ion dosage due to the quantum confinement effect of smaller NC size. The ion-implantation results in a new emission peak of defect-bound neutral excitons below the A-exciton peak in both 1L WS2 and 1L WSe2 NCs. Its relative intensity to the A exciton increases with increasing the ion dosage and finally vanishes along with the A exciton. These results offer a route toward tailoring the optical properties of 2D materials by controlling the size of 2D NCs.