Sequential Carrier Transfer Can Accelerate Triplet Energy Transfer from Functionalized CdSe Nanocrystals Article Swipe
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· 2023
· Open Access
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· DOI: https://doi.org/10.1021/acs.jpclett.2c03443
· OA: W4320483288
Nanocrystal (NC)-sensitized triplet-fusion upconversion is a rising strategy to convert long-wavelength, incoherent light into higher-energy output photons. Here, we chart the photophysics of tailor-functionalized CdSe NCs to understand energy transfer to surface-anchored transmitter ligands, which can proceed via correlated exciton transfer or sequential carrier hops. Varying NC size, we observe a pronounced acceleration of energy transfer (from <i>k</i><sub>quench</sub> = 0.0096 ns<sup>-1</sup> ligand<sup>-1</sup> to 0.064 ns<sup>-1</sup> ligand<sup>-1</sup>) when the barrier to hole-first sequential transfer is lowered from 100 ± 25 meV to 50 ± 25 meV. This acceleration is 5.1× the expected effect of increased carrier wave function leakage, so we conclude that sequential transfer becomes kinetically dominant under the latter conditions. Last, transient photoluminescence shows that NC band-edge and trap states are comparably quenched by functionalization (up to ∼98% for sequential transfer) and exhibit matched dynamics for <i>t</i> > 300 ns, consistent with a dynamic quasi-equilibrium where photoexcitations can ultimately be extracted even when a carrier is initially trapped.
