RESUMO
Hydrophobic lead sulfide quantum dots (PbS/OA) synthesized in the presence of oleic acid were transferred from nonpolar organic solvents to polar solvents such as alcohols and water by a simple ligand exchange with poly(acrylic acid) (PAA). Ligand exchange took place rapidly at room temperature When a colloidal solution of PbS/OA in tetrahydrofuran (THF) was treated with excess PAA, the PbS/PAA nanocrystals that formed were insoluble in hexane and toluene but could be dissolved in methanol or water, where they formed colloidal solutions that were stable for months. Ligand exchange was accompanied by a small blue shift in the band-edge absorption, consistent with a small reduction in particle size. While there was a decrease in quantum yield associated with ligand exchange and transfer to polar solvents, as is commonly found for colloidal quantum dots, the quantum yields determined were impressively high: PbS/OA in toluene (82%) and in THF (58%); PbS/PAA in THF (42%) and in water (24%). The quantum yields for the PbS/PAA solutions decreased over time as the solutions were allowed to age in the presence of air.
Assuntos
Resinas Acrílicas/química , Chumbo/química , Nanopartículas Metálicas/química , Compostos Orgânicos/química , Solventes/química , Sulfetos/química , Água/química , Ligantes , Nanopartículas Metálicas/ultraestrutura , Microscopia Eletrônica de Transmissão , Pontos Quânticos , Espectrometria de Fluorescência , Propriedades de SuperfícieRESUMO
Size-dependent optical properties of semiconductor nanocrystals are of great interest because of the myriad of phenomena stemming from them. The preparation of more complex colloidal shapes will facilitate the systematic study of shape-dependent phenomena. It is shown that a strategy to obtain systematically more complex nanocrystal structures is to exert a sequence of shape-directing steps during the colloidal growth. Using experiments based on multiple reagent injections we show how changes in the type of surfactant introduced during growth of CdSe nanocrystals promotes shape evolution. On this basis, we propose a means to achieve a further generation of shape design in nanometer-sized colloids by using a series of growth steps, each one building from the previous conditions of shape as well as surface-specific reactivity. To understand the shape formation and stability in nanocrystalline colloids, and particularly the importance of surface ligands, we introduce an analogy with the thermodynamics of droplets.
Assuntos
Coloides/química , Cristalização/métodos , Modelos Químicos , Modelos Moleculares , Nanotecnologia/métodos , Pontos Quânticos , Simulação por Computador , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
The dynamics of exciton spin relaxation in CdSe nanorods of various sizes and shapes are measured by an ultrafast transient polarization grating technique. The measurement of the third-order transient grating (3-TG) signal utilizing linear cross-polarized pump pulses enables us to monitor the history of spin relaxation among the bright exciton states with a total angular momentum of F = +/-1. From the measured exciton spin relaxation dynamics, it is found that the effective mechanism of exciton spin relaxation is sensitive to the size of the nanorod. Most of the measured cross-polarized 3-TG signals show single-exponential spin relaxation dynamics, while biexponential spin relaxation dynamics are observed in the nanorod of the largest diameter. This analysis suggests that a direct exciton spin flip process between the bright exciton states with F = +/-1 is the dominant spin relaxation mechanism in small nanocrystals, and an indirect spin flip via the dark states with F = +/-2 contributes as the size of the nanocrystal increases. This idea is examined by simulations of 3-TG signals with a kinetic model for exciton spin relaxation considering the states in the exciton fine structure. Also, it is revealed that the rate of exciton spin relaxation has a strong correlation with the diameter, d, of the nanorod, scaled by the power law of 1/d4, rather than other shape parameters such as length, volume, or aspect ratio.
Assuntos
Compostos de Cádmio/química , Nanoestruturas/química , Compostos de Selênio/química , Tamanho da Partícula , Pontos Quânticos , Sensibilidade e Especificidade , Análise Espectral , Marcadores de Spin , Fatores de TempoRESUMO
The rate of exciton spin relaxation (flips) between the bright exciton states (F = +/-1) of CdSe nanocrystals is reported as a function of shape, for dots and nanorods. The spin relaxation is measured using an ultrafast transient grating method with a crossed linearly polarization sequence. It is found that the spin relaxation rate depends on the radius, not length, of the nanocrystals. That observation is explained by deriving an expression for the electronic coupling matrix element that mixes the bright exciton states.
Assuntos
Compostos de Cádmio/química , Modelos Químicos , Modelos Moleculares , Nanoestruturas/química , Pontos Quânticos , Sulfetos/química , Compostos de Cádmio/efeitos da radiação , Simulação por Computador , Cristalização/métodos , Luz , Conformação Molecular , Nanoestruturas/efeitos da radiação , Marcadores de Spin , Sulfetos/efeitos da radiaçãoRESUMO
The thermolysis reaction of a dual precursor system, comprising one that promotes a controlled nucleation event to produce a rod-shaped nanocrystal template, and the other introduced through a subsequent series of injections that maintain the reaction under kinetic drive, is shown to provide a means of controlling growth of CdSe nanorods with a pre-determined aspect ratio.
