We report the first coherent multidimensional spectroscopy study of a MoS2 film. A four-layer sample of MoS2 was synthesized on a silica substrate by a simplified sulfidation reaction and characterized by absorption and Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. State-selective coherent multidimensional spectroscopy (CMDS) on the as-prepared MoS2 film resolved the dynamics of a series of diagonal and cross-peak features involving the spin-orbit split A and B excitonic states and continuum states. The spectra are characterized by striped features that are similar to those observed in CMDS studies of quantum wells where the continuum states contribute strongly to the initial excitation of both the diagonal and cross-peak features, while the A and B excitonic states contributed strongly to the final output signal. The strong contribution from the continuum states to the initial excitation shows that the continuum states are coupled to the A and B excitonic states and that fast intraband relaxation is occurring on a sub-70 fs time scale. A comparison of the CMDS excitation signal and the absorption spectrum shows that the relative importance of the continuum states is determined primarily by their absorption strength. Diagonal and cross-peak features decay with a 680 fs time constant characteristic of exciton recombination and/or trapping. The short time dynamics are complicated by coherent and partially coherent pathways that become important when the excitation pulses are temporally overlapped. In this region, the coherent dynamics create diagonal features involving both the excitonic states and continuum states, while the partially coherent pathways contribute to cross-peak features.

The simple particle-in-a-sphere model of quantum dot excitons is the basis for understanding the excitonic peak positions, line widths, and relaxation dynamics in many spectroscopic experiments. Recent multiresonant coherent multidimensional spectroscopy (CMDS) with picosecond excitation pulses measured the two-dimensional spectra of PbSe quantum dots and successfully used this simple model of an inhomogeneous distribution of spherically confined exciton and biexciton states and rate constants to describe the dephasing and population relaxation dynamics. The long excitation pulses prevented resolution of faster dynamics. This work reports the development of multiresonant CMDS with femtosecond excitation pulses to resolve the spectra and dynamics associated with the 1S exciton line shape of PbSe quantum dots. The experiments use different combinations of excitation frequencies, excitation pulse time delays, and a monochromator to display and measure correlations between the spectral features and their dynamics. Line-narrowing of the inhomogeneous distribution occurs at short time delays where the excitation excites a subset of the quantum dots within the 1S line shape and the last pulse probes this subset. The line-narrowing disappears at longer delay times. Three pulse photon echo peak shifts (3PEPS) also occur when the line-narrowing is present, but the shifts disappear as the correlation between the first and last coherence frequencies disappears. Wigner plots reveal the spectral dynamics accompanying the peak shift and the disappearance of the line-narrowing. This work shows there is rapid relaxation dynamics occurring within the line profile of the quantum confined excitonic states that is not consistent with current understanding of the excitonic line broadening. The data suggest that the relaxation dynamics play a more dominant role in defining the excitonic line widths than the inhomogeneous broadening of the quantum dot size distribution. These observations are consistent with other spectroscopic experiments on CdSe and PbS quantum dots. The experiments also show the presence of a higher energy feature that lies outside the 1S line shape and undergoes very rapid relaxation.

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Three laser fields drive the population of AlH+ to a single hyperfine state.

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