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Two-dimensional electronic spectroscopy (2DES) has recently been gaining popularity as an alternative to the more common transient absorption spectroscopy due to the combination of high frequency and time resolution of 2DES. In order to advance the reliable analysis of population dynamics and to optimize the time resolution of the method, one has to understand the numerous field matter interactions that take place at an early and negative time. These interactions have historically been discussed in one-dimensional spectroscopy as coherent artifacts and have been assigned to both resonant and non-resonant system responses during or before the pulse overlap. These coherent artifacts have also been described in 2DES but remain less well-understood due to the complexity of 2DES and the relative novelty of the method. Here, we present 2DES results in two model nanocrystal samples, CdSe and CsPbI3. We demonstrate non-resonant signals due to solvent response during the pulse overlap and resonant signals, which we assign to perturbed free induction decay (PFID), both before and during the pulse overlap. The simulations of the 2DES response functions at early and negative time delays reinforce the assignment of the negative time delay signals to PFID. Modeling reveals that the PFID signals will severely distort the initial picture of the resonant population dynamics. By including these effects in models of 2DES spectra, one is able to push forward the extraction of early time dynamics in 2DES.

Despite the impressive abilities of coherent multi-dimensional spectroscopy (CMDS), its’ implementation is limited due to the complexity of continuum generation and required phase stability between the pump pulse pair. In light of this, we have implemented a system producing sub-10 fs pulses with tunable central wavelength. Using a commercial OPA to drive a hollow-core fiber, the system is extremely simple. Output pulse energies lie in the 40-80 μJ range, more than sufficient for transmission through the pulse shaping optics and beam splitters necessary for CMDS. Power fluctuations are minimal, mode quality is excellent, and spectral phase is well behaved at the output. To demonstrate the strength of this source, we measure the two-dimensional spectrum of CdSe quantum dots over a range of population times and find clean signals and clear phonon vibrations. This combination of OPA and hollow-core fiber provides a substantial extension to the capabilities of CMDS.

A novel microfluidic optical cell is presented that enables simultaneous measurement of both light absorbance and fluorescence on microlitre volumes of fluid. The chip design is based on an inlaid fabrication technique using clear and opaque poly(methyl methacrylate) or PMMA to create a 20.2 mm long optical cell. The inlaid approach allows fluid interrogation with minimal interference from external light over centimeter long path lengths. The performance of the optical cell is evaluated using a stable fluorescent dye: rhodamine B. Excellent linear relationships (R2 &gt, 0.99) are found for both absorbance and fluorescence over a 0.1–10 µM concentration range. Furthermore, the molar attenuation spectrum is accurately measured over the range 460–550 nm. The approach presented here is applicable to numerous colorimetric- or fluorescence-based assays and presents an important step in the development of multipurpose lab-on-chip sensors.

Lead-halide perovskites have attracted tremendous attention, initially for their performance in thin film photovoltaics, and more recently for a variety of remarkable optical properties. Defect tolerance through polaron formation within the ionic lattice is a key aspect of these materials. Polaron formation arises from the dynamical coupling of atomic fluctuations to electronic states. Measuring the properties of these fluctuations is therefore essential in light of potential optoelectronic applications. Here we apply two-dimensional electronic spectroscopy (2DES) to probe the timescale and amplitude of the electronic gap correlations in CsPbI3 perovskite nanocrystals via homogeneous lineshape dynamics. The 2DES data reveal irreversible, diffusive dynamics that are qualitatively inconsistent with the coherent dynamics in covalent solids such as CdSe quantum dots. In contrast, these dynamics are consistent with liquid-like structural dynamics on the 100 femtosecond timescale. These dynamics are assigned to the optical signature of polaron formation, the conceptual solid-state analogue of solvation. Lead-halide perovskites have promising optoelectronic properties, determined by interplay of electronic and structural properties. Here the authors probe CsPbI3 nanocrystals by two-dimensional electronic spectroscopy, showing liquid-like structural dynamics signature of polaron formation.

Semiconductor nanocrystals are being developed with increasingly complex shapes and geometries, often featuring complex shell structures. One aims to characterize these structures by different probes, beyond electronic spectroscopies. Vibrational spectroscopy is a useful tool to probe the phononic structure, but the commonly used frequency-domain methods can be plagued by artifacts due to charge-trapping dynamics. To circumvent these issues, coherent phonons may be measured in the time domain via excitonic state-resolved pump/probe spectroscopy. These measurements reveal several new observations on phononic processes, focusing on model systems of radially graded alloys of core/shell nanocrystals: CdSeCdXZn1–XS. The main new observation is frequency changes to the longitudinal optical phonon at high energy due to electronic mixing. This new, softened phonon mode appears via previously unobserved biexcitonic signals. The state-resolved measurements reveal insights into how the shelling process controls exci...

These authors show that perovskites support a new state of quantum confined excitonic polarons.

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.

Excitonic-state-resolved pump/probe spectroscopy is performed on semiconductor dot-in-rod nanocrystals. Using excitonic-state-resolved pumping we are able to resolve effects of the rod upon exciton...

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.

We report on the performance of Ar-filled hollow-core fibers (HCFs) capillary driven by long pulses ( > 100 fs) of moderate energy ( < 600 μ J) for coherent multidimensional spectroscopy in the visible range. The source is characterized by high overall transmission and excellent spatial mode. Broadening is achieved by self-phase modulation. Notably, the uncompressed visible output is shorter than the input pulse. This peculiar observation is explained by the structure of self-phase modulated pulses, coupled with spectral filtering. By virtue of its simplicity, low requirements, spectral stability, and the excellent properties of its spatial output, HCFs can provide an interesting alternative to achieve broadband visible pulses for broadband optical excitation and multidimensional spectroscopy applications.