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In triplet-triplet annihilation based upconversion, high-energy photons are generated through the annihilation of fluorophore triplets, populated via energy transfer from a light-harvesting sensitizer. However, the absorption band of common sensitizers is narrow, limiting the fraction of recoverable photons. We overcome this issue using a third chromophore as an additional light-harvester in the transparency window between the upconverted luminescence and the sensitizer absorption. The third component transfers the extra-collected energy to sensitizers, realizing a cascade-sensitized upconversion that shows a 20% increment of the high-energy photon output and a conversion yield of 10% at solar irradiance.

Sensitized triplet–triplet annihilation based photon up-conversion (TTA-UC) greatly improves the scope and applicability of fluorescence bioimaging by enabling anti-Stokes detection at low powers, thus eliminating the background autofluorescence and limiting the potential damage of the living tissues. Here the authors present a facile, one-step protocol to prepare dual dye-doped, TTA-UC active nanomicelles starting from the commercially available surfactant Kolliphor EL, a component of several FDA approved preparations. These nanosized micelles show an unprecedented up-conversion yield of 6.5% under 0.1 W cm−2 excitation intensity in an aqueous, nondeaerated dispersion. The supramolecular architecture obtained preserves the embedded dyes from oxygen quenching, allowing satisfactory anti-Stokes fluorescence imaging of 3T3 cells. This is the first example of efficient multicomponent up-converters prepared using highly biocompatible materials approved by the international authority, paving the way for the development of new complex and multifunctional materials for advanced theranostics.

The conversion of low-energy light into photons of higher energy based on sensitized triplet-triplet annihilation (sTTA) upconversion is emerging as the most promising wavelength-shifting methodology because it operates efficiently at excitation powers as low as the solar irradiance. However, the production of solid-state upconverters suited for direct integration in devices is still an ongoing challenge owing to the difficulties concerning the organization of two complementary moieties, the triplet sensitizer, and the annihilator, which must interact efficiently. This problem is solved by fabricating porous fluorescent nanoparticles wherein the emitters are integrated into robust covalent architectures. These emitting porous aromatic framework (ePAF) nanoparticles allow intimate interaction with the included metallo-porphyrin as triplet sensitizers. Remarkably, the high concentration of framed chromophores ensures hopping-mediated triplet diffusion required for TTA, yet the low density of the framework promotes their high optical features without quenching effects, typical of the solid state. A green-to-blue photon upconversion yield as high as 15% is achieved: a record performance among annihilators in a condensed phase. Furthermore, the engineered ePAF architecture containing covalently linked sensitizers produces full-fledge solid-state bicomponent particles that behave as autonomous nanodevices.

The technological application of sensitized upconversion based on triplet-triplet annihilation (TTA) requires the transition from systems operating in liquid solutions to solid-state materials. Here, we demonstrate that the high upconversion efficiency reported in hyper-cross-linked nanoparticles does not originate from residual mobility of the embedded dyes as it happens in soft hosts. The hyper-reticulation from one side blocks the dyes in fixed positions, but on the other one, it suppresses the nonradiative spontaneous decay of the triplet excitons, reducing intramolecular relaxations. TTA is thus enabled by an unprecedented extension of the triplet lifetime, which grants long excitons diffusion lengths by hopping among the dye framework and gives rise to high upconversion yield without any molecular displacement. This finding paves the way for the design of a new class of upconverting materials, which in principle can operate at excitation intensities even lower than those requested in liquid or in rubber hosts.

Long-life excimer-like structures Metal quantum clusters have ideal properties for medical applications such as imaging. The challenge is to prolong their transient properties for the fabrication of useful devices. Santiago-Gonzalez et al. arranged gold clusters in a supramolecular lattice held together by hydrogen bonding and showed that this material can be used for imaging of fibroblast cells. In the superstructure, the gold molecules can come together in the excited state as excimers and then dissociate to emit radiation. Because they are within a lattice, this behavior shows long-term stability. Furthermore, the lattice superstructure scavenges reactive oxygen species and reduces cell damage. Science , this issue p. 571

Intracellular pH is a key parameter in many biological mechanisms and cell metabolism and is used to detect and monitor cancer formation and brain or heart diseases. pH-sensing is typically performed by fluorescence microscopy using pH-responsive dyes. Accuracy is limited by the need for quantifying the absolute emission intensity in living biological samples. An alternative with a higher sensitivity and precision uses probes with a ratiometric response arising from the different pH-sensitivity of two emission channels of a single emitter. Current ratiometric probes are complex constructs suffering from instability and cross-readout due to their broad emission spectra. Here, we overcome such limitations using a single-particle ratiometric pH probe based on dot-in-bulk CdSe/CdS nanocrystals (NCs). These nanostructures feature two fully-separated narrow emissions with different pH sensitivity arising from radiative recombination of core- and shell-localized excitons. The core emission is nearly independent of the pH, whereas the shell luminescence increases in the 3–11 pH range, resulting in a cross-readout-free ratiometric response as strong as 600%. In vitro microscopy demonstrates that the ratiometric response in biologic media resembles the precalibralation curve obtained through far-field titration experiments. The NCs show good biocompatibility, enabling us to monitor in real-time the pH in living cells.

Lead halide perovskite nanocrystals (NCs) are emerging as optically active materials for solution-processed optoelectronic devices. Despite the technological relevance of tracing rational guidelines for optimizing their performances and stability beyond their intrinsic resilience to structural imperfections, no in-depth study of the role of selective carrier trapping and environmental conditions on their exciton dynamics has been reported to date. Here we conduct spectro-electrochemical (SEC) experiments, side-by-side to oxygen sensing measurements on CsPbBr3 NCs for the first time. We show that the application of EC potentials controls the emission intensity by altering the occupancy of defect states without degrading the NCs. Reductive potentials lead to strong (60%) emission quenching by trapping of photogenerated holes, whereas the concomitant suppression of electron trapping is nearly inconsequential to the emission efficiency. Consistently, oxidizing conditions result in minor (5%) brightening due to suppressed hole trapping, confirming that electron traps play a minor role in nonradiative decay. This behavior is rationalized through a model that links the occupancy of trap sites with the position of the NC Fermi level controlled by the EC potential. Photoluminescence measurements in controlled atmosphere reveal strong quenching by collisional interactions with O2, which is in contrast to the photobrightening effect observed in films and single crystals. This indicates that O2 acts as a scavenger of photoexcited electrons without mediation by structural defects and, together with the asymmetrical SEC response, suggests that electron-rich defects are likely less abundant in nanostructured perovskites than in the bulk, leading to an emission response dominated by direct interaction with the environment.

We investigate light-matter interactions in periodic silicon microcrystals fabricated combining top-down and bottom-up strategies. The morphology of the microcrystals, their periodic arrangement, and their high refractive index allow the exploration of photonic effects in microstructured architectures. We observe a notable decrease in reflectivity above the silicon bandgap from the ultraviolet to the near-infrared. Finite-difference time-domain simulations show that this phenomenon is accompanied by a ∼2-fold absorption enhancement with respect to a flat sample. Finally, we demonstrate that ordered silicon microstructures enable a fine tuning of the light absorption by changing experimentally accessible knobs as pattern and growth parameters. This work will facilitate the implementation of optoelectronic devices based on high-density microcrystals arrays with optimized light-matter interactions.