Sequential Carrier Transfer Can Accelerate Triplet Energy Transfer from Functionalized CdSe Nanocrystals.

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 kquench = 0.0096 ns-1 ligand-1 to 0.064 ns-1 ligand-1) 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 t > 300 ns, consistent with a dynamic quasi-equilibrium where photoexcitations can ultimately be extracted even when a carrier is initially trapped.

Elucidating the mechanism of dual-fluorescence in carbon dots.

Carbon dots have garnered significant attention owing to their versatile and highly tunable optical properties; however, the origins and the underlying mechanism remains a subject of debate especially for dual fluorescent systems. Here, we have prepared carbon dots from glutathione and formamide precursors via a one-pot solvothermal synthesis. Steady state and dynamic techniques indicate that these dual fluorescent dots possess distinct emissive carbon-core and a molecular states, which are responsible for the blue and red optical signatures, respectively. To further glean information into the fluorescence mechanism, electrochemical analysis was used to measure the bandgaps of the two fluorescent states, while femtosecond transient absorption spectroscopy evidenced the two-state model based on the observed heterogeneity and bimodal spectral distribution. Our findings provide novel and fundamental insights on the optical properties of dual fluorescent dots, which can translate to more effective and targeted application development particularly in bioimaging, multiplexed sensing and photocatalysis.

Binary Cu2-xS Templates Direct the Formation of Quaternary Cu2ZnSnS4 (Kesterite, Wurtzite) Nanocrystals.

Kesterite Cu2ZnSnS4 (k-CZTS) nanocrystals have received attention for their tunable optoelectronic properties, as well as the earth abundance of their constituent atoms. However, the phase-pure synthesis of these quaternary NCs is challenging due to their polymorphism, as well as the undesired formation of related binary and ternary impurities. A general synthetic route to tackle this complexity is to pass through intermediate template nanocrystals that direct subsequent cation exchange toward the desired quaternary crystalline phase, particularly those that are thermodynamically disfavored or otherwise synthetically challenging. Here, working within this model multinary system, we achieve control over the formation of three binary copper sulfide polymorphs, cubic digenite (Cu1.8S), hexagonal covellite (CuS), and monoclinic djurleite (Cu1.94S). Controlled experiments with Cu0 seeds show that selected binary phases can be favored by the identity and stoichiometry of the sulfur precursor alone under otherwise comparable reaction conditions. We then demonstrate that the nature of the Cu2-xS template dictates the final polymorph of the CZTS nanocrystal products. Through digenite, the cation exchange reaction readily yields the k-CZTS phase due to its highly similar anion sublattice. Covellite nanocrystals template the k-CZTS phase but via major structural rearrangement to digenite that requires elevated temperatures in the absence of a strong reducing agent. In contrast, we show that independently synthesized djurleite nanorods template the formation of the wurtzite polymorph (w-CZTS) but with prominent stacking faults in the final product. Applying this refined understanding to the standard one-pot syntheses of k- and w-CZTS nanocrystals, we identify that these reactions are each effectively templated by binary intermediates formed in situ, harnessing their properties to guide the overall synthesis of phase-pure quaternary materials. Our results provide tools for the careful development of tailored nanocrystal syntheses in complex polymorphic systems.