Optical signature of symmetry variations and spin-valley coupling in atomically thin tungsten dichalcogenides

TL;DR

This paper investigates the optical properties of tungsten dichalcogenide monolayers and multilayers, revealing strong spin-valley coupling and symmetry-dependent phenomena that could advance spintronics and valleytronics applications.

Contribution

It provides the first optical characterization of WS2 and WSe2 monolayers, demonstrating layer-dependent inversion symmetry effects and quantifying spin-valley coupling.

Findings

Second harmonic generation oscillates with layer number

Transition from indirect to direct band gap at monolayers

Spin-valley coupling of 0.4 eV observed

Abstract

Motivated by the triumph and limitation of graphene for electronic applications, atomically thin layers of group VI transition metal dichalcogenides are attracting extensive interest as a class of graphene-like semiconductors with a desired band-gap in the visible frequency range. The monolayers feature a valence band spin splitting with opposite sign in the two valleys located at corners of 1st Brillouin zone. This spin-valley coupling, particularly pronounced in tungsten dichalcogenides, can benefit potential spintronics and valleytronics with the important consequences of spin-valley interplay and the suppression of spin and valley relaxations. Here we report the first optical studies of WS2 and WSe2 monolayers and multilayers. The efficiency of second harmonic generation shows a dramatic even-odd oscillation with the number of layers, consistent with the presence (absence) of inversion symmetry in even-layer (odd-layer). Photoluminescence (PL) measurements show the crossover from an indirect band gap semiconductor at mutilayers to a direct-gap one at monolayers. The PL spectra and first-principle calculations consistently reveal a spin-valley coupling of 0.4 eV which suppresses interlayer hopping and manifests as a thickness independent splitting pattern at valence band edge near K points. This giant spin-valley coupling, together with the valley dependent physical properties, may lead to rich possibilities for manipulating spin and valley degrees of freedom in these atomically thin 2D materials.