Understanding the
fundamental mechanisms ruling laser-induced coherent
charge transfer in hybrid organic/inorganic interfaces is of paramount
importance to exploit these systems in next-generation optoelectronic
applications. In a first-principles work based on real-time time-dependent
density-functional theory, we investigate the ultrafast charge-carrier
dynamics of a prototypical two-dimensional vertical nanojunction formed
by a MoSe2 monolayer with adsorbed pyrene molecules. The
response of the system to the incident pulse, set in resonance with
the frequency of the lowest-energy transition in the physisorbed moieties,
is clearly nonlinear. Under weak pulses, charge transfer occurs from
the molecules to the monolayer, while for intensities higher than
1000 GW/cm2, the direction of charge transfer is reverted,
with electrons being transferred from MoSe2 to pyrene.
This finding is explained by Pauli blocking: laser-induced (de)population
of (valence) conduction states saturates for intensities beyond 200
GW/cm2. Evidence of multiphoton absorption is also provided
by our results. A thorough analysis of electronic current density,
excitation energy, and number of excited electrons supports the proposed
rationale and suggests the possibility to create an inorganic/organic
coherent optical nanojunction for ultrafast electronics.