Increase of Third-Order Nonlinear Optical Activity of PbS Quantum Dots in Zeolite Y by Increasing Cation Size
2012-02-08T00:00:00Z (GMT) by
The third-order nonlinear optical (3NLO) activity of PbS quantum dots (QDs) encapsulated in zeolite Y has been expected to depend sensitively on the countercation of the zeolite host. However, ion exchange of the pristine countercation, H<sup>+</sup>, with other cations has not been possible because the framework decomposes and the QDs aggregate immediately when the PbS QD-incorporating zeolite Y with H<sup>+</sup> as the countercation is exposed to the atmosphere. We now report that when H<sup>+</sup> is transformed to NH<sub>4</sub><sup>+</sup>, the framework of PbS QD-containing zeolite Y does not undergo decomposition and the PbS QDs do not undergo aggregation to form larger QDs during the aqueous ion exchange of NH<sub>4</sub><sup>+</sup> with alkali-metal ions (M<sub>A</sub><sup>+</sup> = Li, Na<sup>+</sup>, K<sup>+</sup>, Rb<sup>+</sup>). The 3NLO activity of the M<sub>A</sub><sup>+</sup>-exchanged PbS QD-incorporating zeolite Y film increases with increasing size of M<sub>A</sub><sup>+</sup>. The stabilization of the surface-bound exciton by the electron-rich framework oxide and electron-poor cation is proposed to be responsible for the increase. This is the first example of a method for systematically increasing the 3NLO activity of QDs dispersed in a dielectric matrix by systematically changing its properties. These results will serve as a guideline for future research and also promote applications of QD-incorporating zeolites in various fields.
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