RESUMEN
Large two-photon absorption (2PA) cross-section combined with high emission quantum efficiency and size-tunable bandgap energy has put colloidal semiconductor nanocrystals (NCs) on the vanguard of nonlinear optical materials. After nearly two decades of intense studies on the nonlinear optical response in quantum-confined semiconductors, this is still a vibrant field, as novel nanomaterials are being developed and new applications are being proposed. In this review, we examine the progress of 2PA research in NCs, highlighting the impact of quantum confinement on the magnitude and spectral characteristics of this nonlinear response in semiconductor materials. We show that for NCs with three-dimensional quantum confinement, the so-called quantum dots, 2PA cross-section grows linearly with the nanoparticle volume, following a universal volume scaling. We overview strategies used to gain further control over the nonlinear optical response in these structures by shape and heterostructure engineering and some applications that might take advantage of the series of unique properties of these nanostructures.
RESUMEN
Colloidal semiconductor nanomaterials present broadband, with large cross-section, two-photon absorption (2PA) spectra, which turn them into an important platform for applications that benefit from a high nonlinear optical response. Despite that, to date, the only means to control the magnitude of the 2PA cross-section is by changing the nanoparticle volume, as it follows a universal volume scale, independent of the material composition. As the emission spectrum is connected utterly to the nanomaterial dimensions, for a given material, the magnitude of the nonlinear optical response is also coupled to the emission spectra. Here, we demonstrate a means to decouple both effects by exploring the 2PA response of different types of heterostructures, tailoring the volume dependence of the 2PA cross-section due to the different dependence of the density of final states on the nanoparticle volume. By heterostructure engineering, one can obtain 1 order of magnitude enhancement of the 2PA cross-section with minimum emission spectra shift.
RESUMEN
Perovskite nanoplatelets possess extremely narrow absorption and emission line widths, which are crucial characteristics for many optical applications. However, their underlying intrinsic and extrinsic line-broadening mechanisms are poorly understood. Here, we apply multidimensional coherent spectroscopy to determine the homogeneous line broadening of colloidal perovskite nanoplatelet ensembles. We demonstrate a dependence of not only their intrinsic line widths but also of various broadening mechanisms on platelet geometry. We find that decreasing nanoplatelet thickness by a single monolayer results in a 2-fold reduction of the inhomogeneous line width and a 3-fold reduction of the intrinsic homogeneous line width to the sub-millielectronvolts regime. In addition, our measurements suggest homogeneously broadened exciton resonances in two-layer (but not necessarily three-layer) nanoplatelets at room-temperature.
RESUMEN
Advances in optoelectronics require materials with novel and engineered characteristics. A class of materials that has garnered tremendous interest is metal-halide perovskites, stimulated by meteoric increases in photovoltaic efficiencies of perovskite solar cells. In addition, recent advances have applied perovskite nanocrystals (NCs) in light-emitting devices. It was found recently that, for cesium lead-halide perovskite NCs, their unusually efficient light emission may be due to a unique excitonic fine structure composed of three bright triplet states that minimally interact with a proximal dark singlet state. To study this fine structure without isolating single NCs, we use multidimensional coherent spectroscopy at cryogenic temperatures to reveal coherences involving triplet states of a CsPbI3 NC ensemble. Picosecond time scale dephasing times are measured for both triplet and inter-triplet coherences, from which we infer a unique exciton fine structure level ordering composed of a dark state energetically positioned within the bright triplet manifold.
RESUMEN
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.
RESUMEN
The bandgaps of CsPbI3 perovskite nanocrystals are measured by absorption spectroscopy at cryogenic temperatures. Anomalous bandgap shifts are observed in CsPbI3 nanocubes and nanoplatelets, which are modeled accurately by bandgap renormalization due to lattice vibrational modes. We find that decreasing dimensionality of the CsPbI3 lattice in nanoplatelets greatly reduces electron-phonon coupling, and dominant out-of-plane quantum confinement results in a homogeneously broadened absorption line shape down to cryogenic temperatures. An absorption tail forms at low-temperatures in CsPbI3 nanocubes, which we attribute to shallow defect states positioned near the valence band edge.
RESUMEN
We investigate the operational instability of quantum dot (QD)-based light-emitting diodes (QLEDs). Spectroscopic analysis on the QD emissive layer within devices in chorus with the optoelectronic and electrical characteristics of devices discloses that the device efficiency of QLEDs under operation is indeed deteriorated by two main mechanisms. The first is the luminance efficiency drop of the QD emissive layer in the running devices owing to the accumulation of excess electrons in the QDs, which escalates the possibility of nonradiative Auger recombination processes in the QDs. The other is the electron leakage toward hole transport layers (HTLs) that accompanies irreversible physical damage to the HTL by creating nonradiative recombination centers. These processes are distinguishable in terms of the time scale and the reversibility, but both stem from a single origin, the discrepancy between electron versus hole injection rates into QDs. Based on experimental and calculation results, we propose mechanistic models for the operation of QLEDs in individual quantum dot levels and their degradation during operation and offer rational guidelines that promise the realization of high-performance QLEDs with proven operational stability.
RESUMEN
CuInS2 (CIS) quantum dots (QDs) have emerged as one of the most promising candidates for application in a number of new technologies, mostly due to their heavy-metal-free composition and their unique optical properties. Among those, the large Stokes shift and the long-lived excited state are the most striking ones. Although these properties are important, the physical mechanism that originates them is still under debate. Here, we use two-photon absorption spectroscopy and ultrafast dynamics studies to investigate the physical origin of those phenomena. From the two-photon absorption spectroscopy, we observe yet another unique property of CIS QDs, a two-photon absorption transition below the one-photon absorption band edge, which has never been observed before for any other semiconductor nanostructure. This originates from the inversion of the 1S and 1P hole level order at the top of the valence band and results in a blue-shift of the experimentally measured one photon absorption edge by nearly 100 to 200 meV. However, this shift is not large enough to account for the Stokes shift observed, 200-500 meV. Consequently, despite the existence of the below band gap optical transition, photoluminescence in CIS QDs must originate from trap sites. These conclusions are reinforced by the multiexciton dynamics studies. From those, we demonstrate that biexciton Auger recombination behaves similarly to negative trion dynamics on these nanomaterials, which suggests that the trap state is an electron donating site.
RESUMEN
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.
RESUMEN
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.
