Ultrafast exciton decay in PbS quantum dots through simultaneous electron and hole recombination with a surface-localized ion pair

作者：Edme Kedy; Homan Stephanie Bettis; Nepomnyashchii Alexander B; Weiss Emily A^*

来源：Chemical Physics, 2016, 471: 46-53.

DOI：10.1016/j.chemphys.2015.09.012

• PbS quantum dot
• Simultaneous electron and hole transfer
• TCNQ

This paper describes the ultrafast decay of the band-edge exciton in PbS quantum dots (QDs) through simultaneous recombination of the excitonic hole and electron with the surface localized ion pair formed upon adsorption of tetracyanoquinodimethane (TCNQ). Each PbS QD (R = 1.8 nm) spontaneously reduces up to 17 TCNQ molecules upon adsorption of the TCNQ molecule to a sulfur on the QD surface. The photoluminescence of the PbS QDs is quenched in the presence of the reduced TCNQ species through ultrafast (<= 15-ps) non-radiative decay of the exciton; the rate constant for the decay process increases approximately linearly with the number of adsorbed, reduced TCNQ molecules. Near-infrared and mid-infrared transient absorption show that this decay occurs through simultaneous transfer of the excitonic electron and hole, and is assigned to a four-carrier, concerted charge recombination mechanism based on the observations that (i) the PL of the QDs recovers when spontaneously reduced TCNQ(1) desorbs from the QD surface upon addition of salt, and (ii) the PL of the QDs is preserved when another spontaneous oxidant, ferrocinium, which cannot participate in charge transfer in its reduced state, is substituted for TCNQ.

• 出版日期2016-6-1
• 单位西北大学