Direct Visualization of Confinement and Many-Body Correlation Effects in 2D Spectroscopy of Quantum Dots

The size tunable color of colloidal semiconductor quantum dots (QDs) is probably the most elegant illustration of the quantum confinement effect. As explained by the simple "particle-in-a-box" model, the transition energies between the levels increase when the "box" becomes smaller. To investigate quantum confinement effects, typically a well-defined narrow size distribution of the nanoparticles is needed. In this contribution, how coherent electronic two-dimensional spectroscopy (2DES) can directly visualize the quantum size effect in a sample with broad size distribution of QDs is demonstrated. The method is based on two features of the 2DES - the ability to resolve inhomogeneous broadening and the capability to reveal correlations between the states. In QD samples, inhomogeneous spectral broadening is mainly caused by the size distribution and leads to elongated diagonal peaks of the spectra. Since the cross peaks correlate the energies of two states, they allow drawing conclusions about the size dependence of the corresponding states. It is also found that the biexciton binding energy changes between 3 and 8 meV with the QD size. Remarkably, the size dependence is non-monotonic with a clear minimum. Quantum confinement in quantum dots (QD) follows the "particle-in-a-box" model, where the transition energies increase as the size of the QD decreases. The application of coherent electronic multidimensional spectroscopy facilitates direct visualization of the confinement effect across a wide distribution of QDs in a single experiment. Moreover, the experiments provide access to size-dependent biexciton binding energy revealing surprising nonmonotonic behaviour. image