Shell thickness effects on quantum dot brightness and energy transfer.

Heterostructured core/shell quantum dots (QDs) are prized in biomedical imaging and biosensing applications because of their bright, photostable emission and effectiveness as Förster resonance energy transfer (FRET) donors. However, as nanomaterials chemistry has progressed beyond traditional QDs to incorporate new compositions, ultra-thick shells, and alloyed structures, few of these materials have had their optical properties systematically characterized for effective application. For example, thick-shelled QDs, also known as 'giant' QDs (gQDs) are useful in single-particle tracking microscopy because of their reduced blinking, but we know only that CdSe/CdS gQDs are qualitatively brighter than thin-shelled CdSe/CdS in aqueous media. In this study, we quantify the impact of shell thickness on the nanoparticle molar extinction coefficient, quantum yield, brightness, and effectiveness as a FRET donor for CdSe/xCdS core/shell and CdSe/xCdS/ZnS core/shell/shell QDs, with variable thicknesses of the CdS shell (x). Molar extinction coefficients up to three orders of magnitude higher than conventional dyes and forty-fold greater than traditional QDs are reported. When thick CdS shells are combined with ZnS capping, quantum yields following thiol ligand exchange reach nearly 40%-5-10× higher than either the commercially available QDs or gQDs without ZnS caps treated the same way. These results clearly show that thick CdS shells and ZnS capping shells work in concert to provide the brightest possible CdSe-based QDs for bioimaging applications. We demonstrate that thicker shelled gQDs are over 50-fold brighter than their thin-shelled counterparts because of significant increases in their absorption cross-sections and higher quantum yield in aqueous milieu. Consistent with the point-dipole approximation commonly used for QD-FRET, these data show that thick shells contribute to the donor-acceptor distance, reducing FRET efficiency. Despite the reduction in FRET efficiency, even the thickest-shell gQDs exhibited energy transfer. Through this systematic study, we elucidate the tradeoffs between signal output, which is much higher for the gQDs, and FRET efficiency, which decreases with shell thickness. This study serves as a guide to nanobiotechnologists striving to use gQDs in imaging and sensing devices.