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Two-quantum variants of two-dimensional electronic spectroscopy (2DES) have previously been used to characterize multi-exciton interactions in molecules and semiconductor nanostructures though many implementations are limited by phasing procedures or non-resonant signals. We implement 2DES using phase-cycling to simultaneously measure one-quantum and two-quantum spectra in colloidal CdSe quantum dots. In the pump–probe geometry, fully absorptive spectra are automatically acquired by measuring the sum of the rephasing and nonrephasing signals. Fifth-order two-quantum spectroscopy allows for direct access to multi-exciton states that may be obscured in excited state absorption signals due to population relaxation or third-order two-quantum spectra due to the non-resonant response.

The microscopic origin and timescale of the fluctuations of the energies of electronic states has a significant impact on the properties of interest of electronic materials, with implication in fields ranging from photovoltaic devices to quantum information processing. Spectroscopic investigations of coherent dynamics provide a direct measurement of electronic fluctuations. Modern multidimensional spectroscopy techniques allow the mapping of coherent processes along multiple time or frequency axes and thus allow unprecedented discrimination between different sources of electronic dephasing. Exploiting modern abilities in coherence mapping in both amplitude and phase, we unravel dissipative processes of electronic coherences in the model system of CdSe quantum dots (QDs). The method allows the assignment of the nature of the observed coherence as vibrational or electronic. The expected coherence maps are obtained for the coherent longitudinal optical (LO) phonon, which serves as an internal standard and confirms the sensitivity of the technique. Fast dephasing is observed between the first two exciton states, despite their shared electron state and common environment. This result is contrary to predictions of the standard effective mass model for these materials, in which the exciton levels are strongly correlated through a common size dependence. In contrast, the experiment is in agreement with ab initio molecular dynamics of a single QD. Electronic dephasing in these materials is thus dominated by the realistic electronic structure arising from fluctuations at the atomic level rather than static size distribution. The analysis of electronic dephasing thereby uniquely enables the study of electronic fluctuations in complex materials.

Strong confinement in semiconductor quantum dots enables them to host multiple electron–hole pairs or excitons. The excitons in these materials are forced to interact, resulting in quantum-confined multiexcitons (MXs). The MXs are integral to the physics of the electronic properties of these materials and impact their key properties for applications such as gain and light emission. Despite their importance, the electronic structure of MX has yet to be fully characterized. MXs have a complex electronic structure arising from quantum many-body effects, which is challenging for both experiments and theory. Here, we report on the investigation of the electronic structure of MX in colloidal CdSe QDs using time-resolved photoluminescence, state-resolved pump–probe, and two-dimensional spectroscopies. The use of varying excitation energy and intensities enables the observation of many signals from biexcitons and triexcitons. The experiments enable the study of MX structures and dynamics on time scales spanning 6 orders of magnitude and directly reveal dynamics in the biexciton manifold. These results outline the limits of the simple concept of binding energy. The methods of investigations should be applicable to reveal complex many-body physics in other nanomaterials and low-dimensional materials of interest.

The electronic structure of multiexcitons significantly impacts the performance of nanostructures in lasing and light-emitting applications. However, these multiexcitons remain poorly understood due to their complexity arising from many-body physics. Standard transient-absorption and photoluminescence spectroscopies are unable to unambiguously distinguish effects of sample inhomogeneity from exciton-biexciton interactions. Here, we exploit the energy and time resolution of two-dimensional electronic spectroscopy to access the electronic structure of the band-edge biexciton in colloidal CdSe quantum dots. By removing effects of inhomogeneities, we show that the band-edge biexciton structure must consist of a discrete manifold of electronic states. Furthermore, the biexciton states within the manifold feature distinctive binding energies. Our findings have direct implications for optical gain thresholds and efficiency droop in light-emitting devices and provide experimental measures of many-body physics in nanostructures.

Coherent Multi-dimensional Spectroscopy is ideally suited to investigate many-body effects in semiconductor nanostructures. Here we employ 2D optical spectroscopy on the model system of CdSe quantum dots to reveal the structure of the bandedge biexciton.

We present a detailed analysis of a setup capable of arbitrary amplitude, phase, and polarization shaping of broadband visible femtosecond pulses at 1 kHz via a pair of actively phase stabilized acousto-optic programmable dispersive filters arranged in a Mach-Zehnder interferometer geometry. The setup features phase stability values around λ/225 at 580 nm as well as degrees of polarization of at least 0.9 for any polarization state. Both numbers are important metrics to evaluate a setup's potential for applications based on polarization-shaped femtosecond pulses, such as fully coherent multi-dimensional electronic spectroscopy.