Spatial-Arrangement-Assisted Emission Energy Fine Tuning of CdSe Quantum Dots (QDs) in QD-Block Copolymer Complexes

Quantum dots (QDs) exhibit size-dependent optical properties, where both the absorption and fluorescence energy levels vary with QD size. However, this dependence results in a discontinuity of intrinsically accessible energy levels for the bandgap, posing challenges in achieving precise energy tuning within a specific range. Herein, we demonstrate emission energy control of QDs with identical absorption energy levels by manipulating the spatial arrangement of QDs within QD-polymer complexes through hydrophobic interactions. The phase behavior of the QD-polymer complexes was modulated by adjusting the mass fraction of hydrophilic and hydrophobic blocks in the block copolymer, utilizing two types of amphiphilic block copolymers and varying temperatures. The QDs were spontaneously trapped within the hydrophobic region of the polymer template in water, resulting in spherical, cylindrical, and vesicle structures of QD-polymer complexes, corresponding to spherical, cylindrical, and layered assemblies of QDs, respectively. Depending on the QDs' location within the QD-polymer complex, the surface area in contact with water varied, leading to different degrees of oxidation and, consequently, a change in the fluorescence energy level of QDs. This study introduces a novel method to fine tune the emission energy (<15 eV) of QDs by adjusting the polymer form factor without complicated procedures.