Quantum coherent dynamics of excitons and valley pseudospins in atomically thin semiconductors




Hao, Kai, Ph. D.

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Monolayer transition metal dichalcogenides (TMDCs) are new emerging van der Waals materials. Several TMDC materials go through with a transition from indirect to direct gap semiconductors when reduced to monolayer thickness limit with emission in the visible to near-infrared range, making them attractive materials for optoelectronic applications. Their near-gap optical properties are dominant by excitons (bound electron-hole pairs), charged excitons (known as trions) or higher order bound states (e.g., neutral and charged biexcitons). In this dissertation, we explored the quantum coherent dynamics of exciton, trions and their associated valley index using a powerful ultrafast spectroscopy tool known as the two-dimensional coherent spectroscopy (2DCS). We investigated the underlying mechanisms that determined the valley coherence associated with excitons and trions. In monolayer TMDCs, there are two inequivalent K and K’ points in momentum space, where the band extrema are located and the excitons are formed. The excitonic states in the two valleys are selectively coupled to light with opposite helicity. This valley contrasting optical selection rules allow one to address and manipulate the valley index readily, a unique property and advantage of TMDC materials for valleytronic applications. The valley coherence can be quantitatively evaluated in polarization resolved zero-quantum 2D spectra. We found that the exciton valley coherence is limited by the electron-hole exchange interaction in the system. In contrast, for the charged exciton (trion) states, where the inter-valley scattering is suppressed, it is the intra-valley pure dephasing limits the inter-valley coherence time. These results provide the insight of valley coherence dynamics in monolayer TMDCs and suggest possible approaches to improve the valley coherence time. Next, we investigate the coherence coupling between excitons and trions created in one valley. The trions are charged quasiparticles which contribute to the charge transport directly. Thus, the coupling between exciton and trion states can significantly influent the interpretation of transport measurements. We demonstrate that these two types of quasiparticles are coherently coupled to each other by the observation of the quantum beating of the cross-diagonal peaks in one-quantum 2D spectra. The coherence time between them can be extracted by monitoring the amplitude decay of the beating signal. We found that the coherent coupling dephasing rate between the exciton and trion equals to the sum of the exciton and trion dephasing rate, indicating uncorrelated dephasing process for excitons and trions. At longer time scale, the phonon-assisted energy transfer couples the two states incoherently. Finally, we studied the higher order correlated states in monolayer TMDCs. We used polarization resolved 2DCS to reveal bounded inter-valley neutral biexcitons and charged biexcitons as new peaks which spectrally shifted in 2D spectra. The binding energies of these biexcitons are ∼20 and ∼5 meV respectively. Unlike linear optical spectroscopy studies, the 2D spectra separate the different quantum pathways. Hence, these spectra provide unambiguous evidence of the biexciton states. The extracted binding energy of the biexciton states agrees with theoretical calculation and resolves controversies in the literature. Biexciton formation is important for applications such as lasers and generations of entangled photon pairs.



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