Single organic molecules for photonic quantum technologies.

Isolating single molecules in the solid state has allowed fundamental experiments in basic and applied sciences. When cooled down to liquid helium temperature, certain molecules show transition lines that are tens of megahertz wide, limited by only the excited-state lifetime. The extreme flexibility in the synthesis of organic materials provides, at low costs, a wide palette of emission wavelengths and supporting matrices for such single chromophores. In the past few decades, their controlled coupling to photonic structures has led to an optimized interaction efficiency with light. Molecules can hence be operated as single-photon sources and as nonlinear elements with competitive performance in terms of coherence, scalability and compatibility with diverse integrated platforms. Moreover, they can be used as transducers for the optical read-out of fields and material properties, with the promise of single-quanta resolution in the sensing of charges and motion. We show that quantum emitters based on single molecules hold promise to play a key role in the development of quantum science and technologies.

On the origin of fluorescence emission in optically non-linear DCNP crystals.

We study absorption and emission spectra of optically nonlinear single crystals of 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DCNP) at 5 K. We argue that fluorescence has a complex origin, it is emitted from the excitonic band, with the bottom at ∼18,115 cm(-1), and from trap states, and the two main traps have depths of ∼875 and ∼2465 cm(-1). The excitonic origin of the emission is confirmed by the vibrational structure of fluorescence, closely resembling vibrations observed in the Raman scattering spectrum (recorded for DCNP crystals at 295 K) and by very short decay time of the excitonic emission, as a consequence of exciton migration and trapping at deep traps.

Nanoscale probing of charge transport in an organic field-effect transistor at cryogenic temperatures.

We studied charge transport in a field-effect transistor based on an anthracene crystal by single-molecule spectroscopy at cryogenic temperatures. When applying a control voltage to the gate, source and drain electrodes, we observe spectral drifts of the probe molecules' lines, which follow strongly non-exponential (stretched) kinetics, from seconds to tens of minutes. Applying a gate voltage alone, we find a dependence of the spectral shift as the logarithm of time. When an additional source-drain voltage is applied, the spectral shift follows a power law of time, similar to the elementary step of conduction in amorphous solids, postulated in the continuous-time random walk theory of Scher and Montroll.

Intermolecular intersystem crossing in single-molecule spectroscopy: Terrylene in anthracene crystal.

We present a spectroscopic study of terrylene in anthracene crystals at the ensemble and single-molecule levels. In this matrix, single-molecule fluorescence is reduced by three orders of magnitude. Correlation measurements allow us to identify a new relaxation channel, matrix-enhanced intersystem crossing. This process starts with a singlet-to-triplet energy transfer from guest to host, after which the triplet exciton is transferred back to the guest. The intermolecular intersystem crossing is expected whenever the lowest triplet state of the host is located between the lowest singlet S(1) and lowest triplet T(1) excited states of the guest. It must be considered when searching for new host-guest systems for single-molecule spectroscopy.