ABSTRACT
In recent years, perovskite nanocrystal superlattices have been reported with collective optical phenomena, offering a promising platform for both fundamental science studies and device engineering. In this same avenue, superlattices of perovskite nanoplates can be easily prepared on different substrates, and they too present an ensemble optical response. However, the self-assembly and optical properties of these aggregates in solvents have not been reported to date. Here, we report on the conditions for this self-assembly to occur and show a simple strategy to induce the formation of these nanoplate stacks in suspension in different organic solvents. We combined wide- and small-angle X-ray scattering and scanning transmission electron microscopy to evaluate CsPbBr3 and CsPbI3 perovskite nanoplates with different thickness distributions. We observed the formation of these stacks by changing the concentration of nanoplates and the viscosity of the colloidal suspensions, without the need for antisolvent addition. We found that, in hexane, the concentration for the formation of the stacks is rather high and approximately 80 mg mL-1. In contrast, in decane, dodecane, and hexadecane, we observe a much easier self-assembly of the nanoplates, presenting a clear correlation between the degree of aggregation and viscosity. We, then, discuss the impact of the self-assembly of perovskite nanoplates on Förster resonant energy transfer. Our predictions suggest an energy transfer efficiency higher than 50% for all the donor-acceptor systems evaluated. In particular, we demonstrate how the aggregation of these particles in hexadecane induces FRET for CsPbBr3 nanowires. For the n = 2 nanowires (donor) to the n = 3 nanowires (acceptor), the FRET rate was found to be 4.1 ns-1, with an efficiency of 56%, in agreement with our own predictions.
ABSTRACT
CsPbX3 perovskite nanoplates (PNPLs) were formed in a synthesis driven by SnX4 (X=Cl, Br, I) salts. The role played by these hard Lewis acids in directing PNPL formation is addressed. Sn4+ disturbs the acid-base equilibrium of the system, increasing the protonation rate of oleylamine and inducing anisotropic growth of nanocrystals. Sn4+ cations influence the reaction dynamics owing to complexation with oleylamine molecules. By monitoring the photoluminescence excitation and photoluminescence (PL) spectra of the PNPLs grown at different temperatures, the influence of the thickness on their optical properties is mapped. Time-resolved and spectrally resolved PL for colloidal dispersions with different optical densities reveals that the dependence of the overall PL lifetime on the emission wavelength do not originate from energy transfer between PNPLs but from the contribution of PNPLs with distinct thickness, indicating that thicker PNPLs exhibit longer PL lifetimes.
ABSTRACT
Perovskite quantum dots (PQDs) emerged as a promising class of material for applications in lighting devices, including light emitting diodes and lasers. In this work, we explore nonlinear absorption properties of PQDs showing the spectral signatures and the size dependence of their two-photon absorption (2PA) cross-section, which can reach values higher than 106 GM. The large 2PA cross section allows for low threshold two-photon induced amplified spontaneous emission (ASE), which can be as low as 1.6 mJ/cm2. We also show that the ASE properties are strongly dependent on the nanomaterial size, and that the ASE threshold, in terms of the average number of excitons, decreases for smaller PQDs. Investigating the PQDs biexciton binding energy, we observe strong correlation between the increasing on the biexciton binding energy and the decreasing on the ASE threshold, suggesting that ASE in PQDs is a biexciton-assisted process.
ABSTRACT
Cesium lead halide perovskite quantum dots (PQDs) have emerged as a promising new platform for lighting applications. However, to date, light emitting diodes (LED) based on these materials exhibit limited efficiencies. One hypothesized limiting factor is fast nonradiative multiexciton Auger recombination. Using ultrafast spectroscopic techniques, we investigate multicarrier interaction and recombination mechanisms in cesium lead halide PQDs. By mapping the dependence of the biexciton Auger lifetime and the biexciton binding energy on nanomaterial size and composition, we find unusually strong Coulomb interactions among multiexcitons in PQDs. This results in weakly emissive biexcitons and trions, and accounts for low light emission efficiencies. We observe that, for strong confinement, the biexciton lifetime depends linearly on the PQD volume. This dependence becomes sublinear in the weak confinement regime as the PQD size increases beyond the Bohr radius. We demonstrate that Auger recombination is faster in PQDs compared to CdSe nanoparticles having the same volume, suggesting a stronger Coulombic interaction in the PQDs. We confirm this by demonstrating an increased biexciton binding energy, which reaches a maximum of about 100 meV, fully three times larger than in CdSe quantum dots. The biexciton shift can lead to low-threshold optical gain in these materials. These findings also suggest that materials engineering to reduce Coulombic interaction in cesium lead halide PQDs could improve prospects for high efficiency optoelectronic devices. Core-shell structures, in particular type-II nanostructures, which are known to reduce the bandedge Coulomb interaction in CdSe/CdS, could beneficially be applied to PQDs with the goal of increasing their potential in lighting applications.