Energy relaxation pathways between light-matter states revealed by coherent two-dimensional spectroscopy

Coupling matter excitations to electromagnetic modes inside nano-scale optical resonators leads to the formation of hybrid light-matter states, so-called polaritons, allowing the controlled manipulation of material properties. Here, we investigate the photo-induced dynamics of a prototypical strongly-coupled molecular exciton-microcavity system using broadband two-dimensional Fourier transform spectroscopy and unravel the mechanistic details of its ultrafast photo-induced dynamics. We find evidence for a direct energy relaxation pathway from the upper to the lower polariton state that initially bypasses the excitonic manifold of states, which is often assumed to act as an intermediate energy reservoir, under certain experimental conditions. This observation provides new insight into polariton photophysics and could potentially aid the development of applications that rely on controlling the energy relaxation mechanism, such as in solar energy harvesting, manipulating chemical reactivity, the creation of Bose-Einstein condensates and quantum computing. Recent spectroscopic studies have elucidated light-matter interactions in exciton-polaritons at room temperature, yet their precise excited-state dynamics remain unclear. Here, broadband 2D Fourier transform spectroscopy reveals the relaxation between polaritonic states and the role of dark states.

Bose-Einstein condensation of microcavity polaritons

Davide Sarchi

This thesis presents a theoretical description of the phase transition, with formation of long-range spatial coherence, occurring in a gas of exciton-polaritons in a semiconductor microcavity structure. The results and predictions of the theories developed in this thesis suggest that this phase transition, recently observed in experiments, can be interpreted as the Bose-Einstein Condensation (BEC) of microcavity polaritons. Our theoretical framework is conceived as a generalization to the microcavity polariton system of the standard theories describing the BEC of a weakly interacting Bose gas. These latter are reviewed in Chapter 2, where an introduction to the physics of polaritons is also given. The polariton system is peculiar, basically due to three main features, i.e. the composite nature of polaritons, which are a linear superposition of photon and exciton states, their intrinsic 2-D nature, and the presence of two-body interactions, arising both from the mutual interaction between excitons and from the saturation of the exciton oscillator strength. Therefore it is not clear whether the observed phase transition can be properly described in terms of BEC of a trapped gas. To clarify this point, one has to describe self-consistently the linear exciton-photon coupling giving rise to polariton quasiparticles, and the exciton-nonlinearities. This is made in Chapter 3, where a bosonic theory is developed by generalizing the Hartree-Fock-Popov description of BEC to the case of two coupled Bose fields at thermal equilibrium. Hence, we derive the classical equations describing the condensate wave function and the Dyson-Beliaev equations for the field of collective excitations. In this way, for each value of the temperature and of the total polariton density, a self-consistent solution can be obtained, fixing the populations of the condensate and of the excited states. In particular, the theory allows to describe simultaneously the properties of the polariton, the exciton and the photon fields, this latter being directly investigated in the typical optical measurements. The predicted phase diagram, the energy shifts, the population energy distribution and the behavior of the resulting first order spatial correlation function agree with the recent experimental findings [Kasprzak 06, Balili 07]. These results thus support the idea that the observed experimental signatures are a clear evidence of polariton BEC. However, from a quantitative pint of view, the measured coherence amount in the condensed regime is significantly lower than the predicted one. This discrepancy could be due to deviations from the weakly interacting Bose gas picture and/or to deviations from the thermal equilibrium regime. In particular, these latter are expected to be strong in current experiments, because polaritons have a short radiative lifetime, while the rate of the energy-relaxation mechanisms is very slow. To investigate how the deviations from equilibrium could affect the condensate fraction and the formation of off-diagonal long-range correlations, in Chapter 4, we develop a kinetic theory of the polariton condensation, accounting for both the relaxation mechanisms and for the field dynamics of fluctuations. Within the Hartree-Fock-Bogoliubov limit, we derive a set of coupled equations of motion for the one-particle populations and for the two particle correlations describing quantum fluctuations. We account for the relaxation processes due both to the polariton-phonon coupling and to the exciton-exciton scattering. The actual spectrum of the system is evaluated within the Popov limit, during the relaxation kinetics. Within this model, we solve self-consistently the populations kinetics and the dynamics of the excitation field, for typical experimental conditions. In particular, we show that the role of quantum fluctuations is amplified by non-equilibrium, resulting in a significant condensate depletion. This behavior could explain the partial suppression of off-diagonal long-range coherence reported in experiments [Kasprzak 06, Balili 07]. We complete the analysis, by studying how the deviations from equilibrium depend on the system parameters. Our results show that the polariton lifetime plays a crucial role. In particular, we expect that the increase of the polariton lifetime above 10 ps would lead to thermal-equilibrium polariton BEC in realistic samples. In Chapter 5, devoted to the conclusions, we discuss which issues of BEC could be clarified, by achieving polariton BEC at thermal-equilibrium, and which extensions of the present work would be most promising in this respect.

EPFL2007

Investigations of the non-adiabatic photophysics of Cu(I)-phenanthroline complexes

Gloria Capano

Cu(I)-phenanthrolines are an important class of metal-organic molecules that exhibits much promise for solar energy harvesting and solar-driven catalysis applications. Although many experimental studies have been performed calling for high-level simulations to elucidate their photophysics, a complete picture is still missing. This is the goal of the present thesis. On the ultrafast (femtosecond) timescale we studied the non-adiabatic relaxation of a prototypical Cu(I)-phenanthroline, [Cu(dmp)2]+, by performing excited state simulations using two approaches: quantum dynamics and trajectory surface hopping. These simulations help to identify several mechanisms, internal conversion, pseudo Jahn-Teller distortion, intersystem crossing, occurring in the subpicosecond time scale. Surprisingly, we have found that intersystem crossing does not take place between the lowest singlet and triplet excited states, as previously proposed, but between the lowest singlet and higher triplet states. Moreover, we observed the initial stages (< 100 fs) of the solvent reorganization due to the electronic density changes in the excited state. This leads to an energy stabilization of the excited states that is associated with an increase of the non-radiative decay rate. The quantum dynamics simulations allowed us to provide indications for performing additional spectroscopy measurements by using the recently developed X-ray Free Electron Lasers (X-FELs). This technology can monitor both electronic and structural changes with an unprecedented time resolution of tens of femtoseconds and, therefore, is capable of revealing the aforementioned processes. In addition, we questioned the feasibility of such experiments and calculated the signal strengths for XAS and XES transient spectra. Finally, we analyzed the luminescence quenching, which has been observed for all Cu(I)-phenanthroline complexes when they are dissolved in strongly donating solvents. By performing Molecular Dynamics calculations we showed that, in contrast with the previously accepted model based on the formation of an exciplex (a species formed by two molecules, one in the excited state and one in the ground state), no stable exciplex is formed and that quenching is due to electrostatic solute-solvent interactions. In addition, we investigated how the geometry configuration can affect the luminescence lifetime in these molecules. We found a correlation between rigidity of the copper complex - inhibition of the pseudo Jahn-Teller distortion - and lifetime of the emission. The more the metal complex retains the ground state structure (large substituents), the longer its lifetime. This effect is attributed to a higher energy gap (excited state minus ground state energy) due to the reduction of relaxation. Our research reveals important insights into the relaxation mechanism and the complex interplay between geometry and electronic structure in Cu(I)-phenanthroline. These results can be exploited for guiding the synthesis of complexes with the desired physical properties.

EPFL2016

Direct Observation of Shallow Trap States in Thermal Equilibrium with Band‐Edge Excitons in Strongly Confined CsPbBr 3 Perovskite Nanoplatelets

Andrés Burgos Caminal, Brener Rodrigo De Carvalho Vale, Jacques-Edouard Moser, Etienne Christophe Socie

Lead halide perovskites exhibit great potential for light-emitting devices. Enhanced photoluminescence (PL) is obtained in perovskite materials of reduced dimensionalities due to the large exciton binding energy. However, as the nanocrystal size is reduced, the surface-to-volume ratio increases, leading to an abundance of surface defects. Here, a fast PL decay, 3–10 ps, is observed in quasi-1D CsPbBr3 perovskite nanoplatelets using broadband fluorescence upconversion spectroscopy. This decay is attributed to revers- ible trapping of band-edge excitons into dark states that lie close to the band edge. A simplified model is proposed to further confirm the presence of shallow traps and to fit the data obtained by ultrafast spectroscopy for mul- tiple samples. Finally, the presence of deep trap states in aged nanoplatelets is revealed, likely arising from desorption of the organic capping ligands from the surface. Exciton trapping into these states is slower, 20–30 ps, but leads to a decrease in the photoluminescence quantum yield. These results may not only explain the extended luminescence lifetimes that have been reported for perovskite nanocrystals but also demonstrate the potential of combining ultrafast transient absorption and fluorescence up-conversion to obtain a full description of the spectroscopic properties of the material.