Phonon-assisted up-conversion photoluminescence can boost energy of an emission photon to be higher than that of the excitation photon by absorbing vibration energy (or phonons) of the emitter. Here, up-conversion photoluminescence power-conversion efficiency (power ratio between the emission and excitation photons) for CdSe/CdS core/shell quantum dots is observed to be beyond unity. Instead of commonly known defect-assisted up-conversion photoluminescence for colloidal quantum dots, temperature-dependent measurements and single-dot spectroscopy reveal the up-conversion photoluminescence and conventional down-conversion photoluminescence share the same electron-phonon coupled electronic states. Ultrafast spectroscopy results imply the thermalized excitons for up-conversion photoluminescence form within 200 fs, which is 100,000 times faster than the radiative recombination rate of the exciton. Results suggest that colloidal quantum dots can be exploited as efficient, stable, and cost-effective emitters for up-conversion photoluminescence in various applications.

Localization of exciton wavefunctions away from the inorganic–organic interface is proposed for synthesizing colloidal spheroidal quantum dots (QDs) with an ultranarrow photoluminescence (PL) peak width. This strategy is demonstrated by synthesizing uniform-alloy Cd x Zn1–x Se and Cd x Zn1–x Se/ZnSe/ZnS core/shell QDs. For blue-emitting QDs, the ensemble PL full width at half-maximum (fwhm) reaches 10.2 nm and the corresponding single-dot PL fwhm is 5.2 nm. The ensemble and single-dot PL fwhm values for green-emitting QDs are 16.3 and 9.7 nm, respectively. These record-low PL fwhm values for spheroidal QDs are close to the requirements for ideal displays. To control the composition homogeneity, the synthetic scheme is separated into four consecutive steps, namely, nucleation of monodisperse CdSe core QDs, epitaxial growth of thickness-controlled CdSe/ZnSe core/shell QDs with a low degree of spontaneous alloying, Cu-catalyzed alloying for uniform-alloy QDs, and additional epitaxy of outer ZnSe and ZnS shells onto uniform-alloy Cd x Zn1–x Se QDs. Among all metal ions tested, copper ions are identified to be the best catalysts for forming uniform-alloy Cd x Zn1–x Se QDs, which can enter a QD rapidly to initiate alloying and effectively exit a QD after the alloying process under the experimentally feasible conditions.

Bright anti-Stokes fluorescence (ASF) in the first near-infrared spectral region (NIR-I, 800 nm–900 nm) under the excitation of a 915 nm continuous wave (CW) laser, is observed in Indocyanine Green (ICG), a dye approved by the Food and Drug Administration for clinical use. The dependence of fluorescence intensity on excitation light power and temperature, together with fluorescence lifetime measurement, establish this ASF to be originated from absorption from a thermally excited vibrational level (hot-band absorption), as shown in our experiments, which is stronger than the upconversion fluorescence from widely-used rare-earth ion doped nanoparticles. To test the utility of this ASF NIR-I probe for advanced bioimaging, we successively apply it for biothermal sensing, cerebral blood vessel tomography and blood stream velocimetry. Moreover, in combination with L1057 nanoparticles, which absorb the ASF of ICG and emit beyond 1100 nm, these two probes generate multi-mode images in two fluorescent channels under the excitation of a single 915 nm CW laser. One channel is used to monitor two overlapping organs, urinary system & blood vessel of a live mouse, while the other shows urinary system only. Using in intraoperative real-time monitoring, such multi-mode imaging method can be beneficial for visual guiding in anatomy of the urinary system to avoid any accidental injury to the surrounding blood vessels during surgery.

Using CdSe/ZnSe core–shell quantum dots (QDs) as a model, we systematically investigate the photochemical properties of QDs with the ZnSe shells under an ambient environment, which show almost opposite responses to either oxygen or water in comparison with CdSe/CdS core/shell QDs. While the ZnSe shells provide an efficient potential barrier for photoinduced electron transfer from the core to the surface-adsorbed oxygen, they also act as a stepping stone for hot-electron transfer directly from the ZnSe shells to oxygen. The latter process is so effective and competes favorably with ultrafast relaxation of hot electrons from the ZnSe shells to the core QDs, which can completely quench the photoluminescence (PL) with saturated adsorption of oxygen (1 bar) and initiate oxidation of the surface anion sites. Water can slowly eliminate the excess hole to neutralize the positively charged QDs, partially canceling the photochemical effects of oxygen. Alkylphosphinesthrough two distinctive reaction pathways with oxygenstop the photochemical effects of oxygen and completely recover PL. With limited thickness (around two monolayers), the ZnS outer shells substantially slow down photochemical effects on CdSe/ZnSe/ZnS core/shell/shell QDs but cannot fully stop PL quenching by oxygen.

Hot-band absorption (HBA)-induced anti-Stokes fluorescence (ASF) with longer-wavelength excitation is one effective pathway to deep penetration and low autofluorescence in intravital fluorescence imaging, raising demands for fluorophores with broad spectra, high absorption, and strong emission. However, typical fluorescent dyes display some emission quenching when their concentration is increased in order to obtain brighter fluorescence. In this work, the HBA-induced ASF of aggregation-induced emission (AIE) dots is reported. BPN-BBTD dots were synthesized and confirmed with a fluorescence enhancement and a considerable ASF intensity. In addition, the mechanism of ASF and the HBA process of BPN-BBTD dots were carefully validated and discussed. To obtain the full advantages of the long-wavelength excitation and the short fluorescence lifetime in deep-tissue bioimaging, a large-depth ASF confocal microscopic imaging of in vivo cerebral vasculature was conducted under the excitation of a 980 nm continuous wave laser after intravenous injection of BPN-BBTD dots. Meanwhile, the 3D structure of the cerebrovascular network was successfully reconstructed.