RESUMEN
Hybrid perovskites have emerged as a promising material candidate for exciton-polariton (polariton) optoelectronics. Thermodynamically, low-threshold Bose-Einstein condensation requires efficient scattering to the polariton energy dispersion minimum, and many applications demand precise control of polariton interactions. Thus far, the primary mechanisms by which polaritons relax in perovskites remains unclear. In this work, we perform temperature-dependent measurements of polaritons in low-dimensional perovskite wedged microcavities achieving a Rabi splitting of [Formula: see text] = 260 ± 5 meV. We change the Hopfield coefficients by moving the optical excitation along the cavity wedge and thus tune the strength of the primary polariton relaxation mechanisms in this material. We observe the polariton bottleneck regime and show that it can be overcome by harnessing the interplay between the different excitonic species whose corresponding dynamics are modified by strong coupling. This work provides an understanding of polariton relaxation in perovskites benefiting from efficient, material-specific relaxation pathways and intracavity pumping schemes from thermally brightened excitonic species.
RESUMEN
We demonstrate three general effective strategies to mitigate non-radiative losses in the superradiant emission from supramolecular assemblies. We focus on J-aggregates of 5,5',6,6'-tetrachloro-1,1'-diethyl-3,3'-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC) and elucidate the nature of their nonradiative processes. We show that self-annealing at room temperature, photo-brightening, and the purification of the dye monomers all lead to substantial increases in emission quantum yields (QYs) and a concomitant lengthening of the emission lifetime, with purification of the monomers having the largest effect. We use structural and optical measurements to support a microscopic model that emphasizes the deleterious effects of a small number of impurity and defect sites that serve as non-radiative recombination centers. This understanding has yielded a room temperature molecular fluorophore in solution with an unprecedented combination of fast emissive lifetime and high QY. We obtain superradiant emission from J-aggregates of TDBC in solution at room temperature with a QY of 82% coupled with an emissive lifetime of 174 ps. This combination of high QY and fast lifetime at room temperature makes supramolecular assemblies of purified TDBC a model system for the study of fundamental superradiance phenomena. High QY J-aggregates are uniquely suited for the development of applications that require high speed and high brightness fluorophores such as devices for high speed optical communication.
RESUMEN
Excitonic chromophore aggregates have wide-ranging applicability in fields such as imaging and energy harvesting; however their rational design requires adapting principles of self-assembly to the requirements of excited state coupling. Using the well-studied amphiphilic cyanine dye C8S3 as a template-known to assemble into tubular excitonic aggregates-we synthesize several redshifted variants and study their self-assembly and photophysics. The new pentamethine dyes retain their tubular self-assembly and demonstrate nearly identical bathochromic shifts and lineshapes well into near-infrared wavelengths. However, detailed photophysical analysis finds that the new aggregates show a significant decline in superradiance. Additionally, cryo-TEM reveals that these aggregates readily form short bundles of nanotubes that have nearly half the radii of their trimethine comparators. We employ computational screening to gain intuition on how the structural components of these new aggregates affect their excitonic states, finding that the narrower tubes are able to assemble into a larger number of arrangements, resulting in more disordered aggregates (i.e. less superradiant) with highly similar degrees of redshift.
RESUMEN
The continuous and concerted development of colloidal quantum dot light-emitting diodes over the past two decades has established them as a bedrock technology for the next generation of displays. However, a fundamental issue that limits the performance of these devices is the quenching of photoluminescence due to excess charges from conductive charge transport layers. Although device designs have leveraged various workarounds, doing so often comes at the cost of limiting efficient charge injection. Here we demonstrate that high-field terahertz (THz) pulses can dramatically brighten quenched QDs on metallic surfaces, an effect that persists for minutes after THz irradiation. This phenomenon is attributed to the ability of the THz field to remove excess charges, thereby reducing trion and nonradiative Auger recombination. Our findings show that THz technologies can be used to suppress and control such undesired nonradiative decay, potentially in a variety of luminescent materials for future device applications.
RESUMEN
Photoluminescence intermittency is a ubiquitous phenomenon, reducing the temporal emission intensity stability of single colloidal quantum dots (QDs) and the emission quantum yield of their ensembles. Despite efforts to achieve blinking reduction by chemical engineering of the QD architecture and its environment, blinking still poses barriers to the application of QDs, particularly in single-particle tracking in biology or in single-photon sources. Here, we demonstrate a deterministic all-optical suppression of QD blinking using a compound technique of visible and mid-infrared excitation. We show that moderate-field ultrafast mid-infrared pulses (5.5 µm, 150 fs) can switch the emission from a charged, low quantum yield grey trion state to the bright exciton state in CdSe/CdS core-shell QDs, resulting in a significant reduction of the QD intensity flicker. Quantum-tunnelling simulations suggest that the mid-infrared fields remove the excess charge from trions with reduced emission quantum yield to restore higher brightness exciton emission. Our approach can be integrated with existing single-particle tracking or super-resolution microscopy techniques without any modification to the sample and translates to other emitters presenting charging-induced photoluminescence intermittencies, such as single-photon emissive defects in diamond and two-dimensional materials.
RESUMEN
As luminescence applications of colloidal semiconductor nanocrystals push toward higher excitation flux conditions, there is an increased need to both understand and potentially control emission from multiexciton states. We develop a spectrally resolved correlation method to study the triply excited state that enables direct measurements of the recombination pathway for the triexciton, rather than relying on indirect extraction of rates. We demonstrate that, for core-shell CdSe-CdS nanocrystals, triexciton emission arises exclusively from the band-edge S-like state. Time-dependent density functional theory and extended particle-in-a-sphere calculations demonstrate that reduced carrier overlap induced by the core-shell heterostructure can account for the lack of emission observed from the P-like state. These results provide a potential avenue for the control of nanocrystal luminescence, where core-shell heterostructures can be leveraged to control carrier separation and therefore maintain emission color purity over a broader range of excitation fluxes.
