Ultralow-threshold, continuous-wave upconverting lasing from subwavelength plasmons.

Miniaturized lasers are an emerging platform for generating coherent light for quantum photonics, in vivo cellular imaging, solid-state lighting and fast three-dimensional sensing in smartphones1-3. Continuous-wave lasing at room temperature is critical for integration with opto-electronic devices and optimal modulation of optical interactions4,5. Plasmonic nanocavities integrated with gain can generate coherent light at subwavelength scales6-9, beyond the diffraction limit that constrains mode volumes in dielectric cavities such as semiconducting nanowires10,11. However, insufficient gain with respect to losses and thermal instabilities in nanocavities has limited all nanoscale lasers to pulsed pump sources and/or low-temperature operation6-9,12-15. Here, we show continuous-wave upconverting lasing at room temperature with record-low thresholds and high photostability from subwavelength plasmons. We achieve selective, single-mode lasing from Yb3+/Er3+-co-doped upconverting nanoparticles conformally coated on Ag nanopillar arrays that support a single, sharp lattice plasmon cavity mode and greater than wavelength λ/20 field confinement in the vertical dimension. The intense electromagnetic near-fields localized in the vicinity of the nanopillars result in a threshold of 70 W cm-2, orders of magnitude lower than other small lasers. Our plasmon-nanoarray upconverting lasers provide directional, ultra-stable output at visible frequencies under near-infrared pumping, even after six hours of constant operation, which offers prospects in previously unrealizable applications of coherent nanoscale light

Giant nonlinear optical responses from photon avalanching nanoparticles

Avalanche phenomena leverage steeply nonlinear dynamics to generate disproportionately high responses from small perturbations and are found in a multitude of events and materials, enabling technologies including optical phase-conjugate imaging, infrared quantum counting, and efficient upconverted lasing. However, the photon avalanching (PA) mechanism underlying these optical innovations has been observed only in bulk materials and aggregates, and typically at cryogenic temperatures, limiting its utility and impact. Here, we report the realization of PA at room temperature in single nanostructures--small, Tm-doped upconverting nanocrystals--and demonstrate their use in superresolution imaging at near-infrared (NIR) wavelengths within spectral windows of maximal biological transparency. Avalanching nanoparticles (ANPs) can be pumped by continuous-wave or pulsed lasers and exhibit all of the defining features of PA. These hallmarks include excitation power thresholds, long rise time at threshold, and a dominant excited-state absorption that is >13,000x larger than ground-state absorption. Beyond the avalanching threshold, ANP emission scales nonlinearly with the 26th power of pump intensity. This enables the realization of photon-avalanche single-beam superresolution imaging (PASSI), achieving sub-70 nm spatial resolution using only simple scanning confocal microscopy and before any computational analysis. Pairing their steep nonlinearity with existing superresolution techniques and computational methods, ANPs allow for imaging with higher resolution and at ca. 100-fold lower excitation intensities than is possible with other probes. The low PA threshold and exceptional photostability of ANPs also suggest their utility in a diverse array of applications including sub-wavelength bioimaging, IR detection, temperature and pressure transduction, neuromorphic computing, and quantum optics.Comment: 14 pages, 4 figure

Indefinite and Bidirectional Near Infrared Nanocrystal Photoswitching

Materials whose luminescence can be switched by optical stimulation drive technologies ranging from superresolution imaging1-4, nanophotonics5, and optical data storage6-8, to targeted pharmacology, optogenetics, and chemical reactivity9. These photoswitchable probes, including organic fluorophores and proteins, are prone to photodegradation, and often require phototoxic doses of ultraviolet (UV) or visible light. Colloidal inorganic nanoparticles have significant stability advantages over existing photoswitchable materials, but the ability to switch emission bidirectionally, particularly with NIR light, has not been reported with nanoparticles. Here, we present 2-way, near-infrared (NIR) photoswitching of avalanching nanoparticles (ANPs), showing full optical control of upconverted emission using phototriggers in the NIR-I and NIR-II spectral regions useful for subsurface imaging. Employing single-step photodarkening10-13 and photobrightening12,14-18, we demonstrate indefinite photoswitching of individual nanoparticles (>1000 cycles over 7 h) in ambient or aqueous conditions without measurable photodegradation. Critical steps of the photoswitching mechanism are elucidated by modeling and by measuring the photon avalanche properties of single ANPs in both bright and dark states. Unlimited, reversible photoswitching of ANPs enables indefinitely rewritable 2D and 3D multi-level optical patterning of ANPs, as well as optical nanoscopy with sub-{\AA} localization superresolution that allows us to distinguish individual ANPs within tightly packed clusters.Comment: 15 pages, 5 figure

Broadband Near-Infrared to Visible Upconversion in Quantum Dot–Quantum Well Heterostructures

Upconversion is a nonlinear process in which two, or more, long wavelength photons are converted to a shorter wavelength photon. It holds great promise for bioimaging, enabling spatially resolved imaging in a scattering specimen and for photovoltaic devices as a means to surpass the Shockley–Queisser efficiency limit. Here, we present dual near-infrared and visible emitting PbSe/CdSe/CdS nanocrystals able to upconvert a broad range of NIR wavelengths to visible emission at room temperature. The synthesis is a three-step process, which enables versatility and tunability of both the visible emission color and the NIR absorption edge. Using this method, one can achieve a range of desired upconverted emission peak positions with a suitable NIR band gap

Probing the Interaction of Quantum Dots with Chiral Capping Molecules Using Circular Dichroism Spectroscopy

Circular dichroism (CD) induced at exciton transitions by chiral ligands attached to single component and core/shell colloidal quantum dots (QDs) was used to study the interactions between QDs and their capping ligands. Analysis of the CD line shapes of CdSe and CdS QDs capped with l-cysteine reveals that all of the features in the complex spectra can be assigned to the different excitonic transitions. It is shown that each transition is accompanied by a derivative line shape in the CD response, indicating that the chiral ligand can split the exciton level into two new sublevels, with opposite angular momentum, even in the absence of an external magnetic field. The role of electrons and holes in this effect could be separated by experiments on various types of core/shell QDs, and it was concluded that the induced CD is likely related to interactions of the highest occupied molecular orbitals of the ligands with the holes. Hence, CD was useful for the analysis of hole level–ligand interactions in quantum semiconductor heterostructures, with promising outlook toward better general understanding the properties of the surface of such systems

Apparent self-heating of individual upconverting nanoparticle thermometers.

Individual luminescent nanoparticles enable thermometry with sub-diffraction limited spatial resolution, but potential self-heating effects from high single-particle excitation intensities remain largely uninvestigated because thermal models predict negligible self-heating. Here, we report that the common "ratiometric" thermometry signal of individual NaYF4:Yb3+,Er3+ nanoparticles unexpectedly increases with excitation intensity, implying a temperature rise over 50 K if interpreted as thermal. Luminescence lifetime thermometry, which we demonstrate for the first time using individual NaYF4:Yb3+,Er3+ nanoparticles, indicates a similar temperature rise. To resolve this apparent contradiction between model and experiment, we systematically vary the nanoparticle's thermal environment: the substrate thermal conductivity, nanoparticle-substrate contact resistance, and nanoparticle size. The apparent self-heating remains unchanged, demonstrating that this effect is an artifact, not a real temperature rise. Using rate equation modeling, we show that this artifact results from increased radiative and non-radiative relaxation from higher-lying Er3+ energy levels. This study has important implications for single-particle thermometry