Resonant four-photon photoemission from SnSe2(001)

High-order nonlinear multiphoton absorption is usually inefficient, but can be enhanced by designing resonant excitations between occupied and unoccupied energy levels. We conducted angle-resolved multi-photon photoemission (mPPE) studies on the SnSe₂(001) surfaces excited by ultrashort laser pulses. By tuning photon energy and light polarization, we demonstrate the presence of a resonant four-photon photoemission (4PPE) process involving the occupied valence band (VB), the unoccupied second conduction band (CB2) and the unoccupied image-potential state (IPs) of SnSe₂. In this 4PPE process, VB electrons of SnSe₂ are resonantly excited into CB2 by adsorbing two photons, followed by the adsorption of another photon to populate the n = 1 IPs before being emitted out to the vacuum by adsorbing one more photon. This results in a double-resonant 4PPE process, which exhibits approximately a 40 times enhancement in photoemission yields compared to cases where one of the resonant pathways, CB2 → IPs, is inhibited by involving a virtual state instead of the IPs in the 4PPE. The double-resonant 4PPE process efficiently excite the bulk VB electrons outside the vacuum, like taking advantage of resonant “ladders” through two real empty electronic states of SnSe₂. Our results highlight the important applications of mPPE in probing the band-structure, particularly the unoccupied states, of recently emerging main group dichalcogenide semiconductors. Furthermore, the discovered resonant mPPE process contributes to the exploration of their promising optoelectronic applications.