Giant Fine Structure Splitting of the Bright Exciton in a Bulk MAPbBr3 Single Crystal.

Exciton fine structure splitting in semiconductors reflects the underlying symmetry of the crystal and quantum confinement. Because the latter factor strongly enhances the exchange interaction, most work has focused on nanostructures. Here, we report on the first observation of the bright exciton fine structure splitting in a bulk semiconductor crystal, where the impact of quantum confinement can be specifically excluded, giving access to the intrinsic properties of the material. Detailed investigation of the exciton photoluminescence and reflection spectra of a bulk methylammonium lead tribromide single crystal reveals a zero magnetic field splitting as large as ∼200 µeV. This result provides an important starting point for the discussion of the origin of the large bright exciton fine structure splitting observed in perovskite nanocrystals.

Exciton Fine Structure of CsPbCl3 Nanocrystals: An Interplay of Electron-Hole Exchange Interaction, Crystal Structure, Shape Anisotropy, and Dielectric Mismatch.

In the semiconducting perovskite materials family, the cesium-lead-chloride compound (CsPbCl3) supports robust excitons characterized by a blue-shifted transition and the largest binding energy, thus presenting a high potential to achieve demanding solid-state room-temperature photonic or quantum devices. Here we study the fundamental emission properties of cubic-shaped colloidal CsPbCl3 nanocrystals (NCs), examining in particular individual NC responses using micro-photoluminescence in order to unveil the exciton fine structure (EFS) features. Within this work, NCs with average dimensions ⟨Lα⟩ ≈ 8 nm (α = x, y, z) are studied with a level of dispersity in their dimensions that allows disentangling the effects of size and shape anisotropy in the analysis. We find that most of the NCs exhibit an optical response under the form of a doublet with crossed polarized peaks and an average inter-bright-state splitting, ΔBB ≈ 1.53 meV, but triplets are also observed though being a minority. The origin of the EFS patterns is discussed in the frame of the electron-hole exchange model by taking into account the dielectric mismatch at the NC interface. The different features (large dispersity in the ΔBB values and occasional occurrence of triplets) are reconciled by incorporating a moderate degree of shape anisotropy, observed in the structural characterization, by preserving the relatively high degree of the NC lattice symmetry. The energy distance between the optically inactive state and the bright manifold, ΔBD, is also extracted from time-resolved photoluminescence measurements (ΔBD ≈ 10.7 meV), in good agreement with our theoretical predictions.

Dielectric Confinement and Exciton Fine Structure in Lead Halide Perovskite Nanoplatelets.

Owing to their flexible chemical synthesis and the ability to shape nanostructures, lead halide perovskites have emerged as high potential materials for optoelectronic devices. Here, we investigate the excitonic band edge states and their energies levels in colloidal inorganic lead halide nanoplatelets, particularly the influence of dielectric effects, in a thin quasi-2D system. We use a model including band offset and dielectric confinements in the presence of Coulomb interaction. Short- and long-range contributions, modified by dielectric effects, are also derived, leading to a full modelization of the exciton fine structure, in cubic, tetragonal and orthorhombic phases. The fine splitting structure, including dark and bright excitonic states, is discussed and compared to recent experimental results, showing the importance of both confinement and dielectric contributions.

Anisotropic shape of CsPbBr3 colloidal nanocrystals: from 1D to 2D confinement effects.

We synthesized strongly anisotropic CsPbBr3 nanocrystals with very narrow emission and absorption lines associated to confinement effects along one or two dimensions, called respectively nanoplatelets (NPLs) and nanosticks (NSTs). Transmission Electron Microscopy (TEM) images, absorption and photoluminescence (PL) spectra taken at low temperature are very precise tools to determine which kind of confinement has to be considered and to deduce the shape, the size and the thickness of nanocrystals under focus. We show that the energy of the band-edge absorption and PL peaks versus the inverse of the square of the NPL thickness has a linear behaviour from 11 monolayers (MLs) i.e. a thickness of 6.38 nm, until 4 MLs (2.32 nm) showing that self-energy correction compensates the increase of the exciton binding energy in thin NPLs as already observed in Cadmium chalcogenides-based NPLs. We also show that slight changes in the morphology of NSTs leads to a very drastic modification of their absorption spectra. Time-resolved PL of NSTs has a non-monotonous behaviour with temperature. At 5 K, a quasi-single exponential with a lifetime of 80 ps is obtained; at intermediate temperature, the decay is bi-exponential and at 150 K, a quasi-single exponential decay is recovered (≈0.4 ns). For NSTs, the exciton interaction with LO phonons governs the broadening of the absorption and PL peaks at room temperature and is stronger than in chalcogenides quantum dots and NPLs.