Large-Area Near-Infrared Emission Enhancement on Single Upconversion Nanoparticles by Metal Nanohole Array.

Single lanthanide (Ln) ion doped upconversion nanoparticles (UCNPs) exhibit great potential for biomolecule sensing and counting. Plasmonic structures can improve the emission efficiency of single UCNPs by modulating the energy transferring process. Yet, achieving robust and large-area single UCNP emission modulation remains a challenge, which obstructs investigation and application of single UCNPs. Here, we present a strategy using metal nanohole arrays (NHAs) to achieve energy-transfer modulation on single UCNPs simultaneously within large-area plasmonic structures. By coupling surface plasmon polaritons (SPPs) with higher-intermediate state (1D2 → 3F3, 1D2 → 3H4) transitions, we achieved a remarkable up to 10-fold enhancement in 800 nm emission, surpassing the conventional approach of coupling SPPs with an intermediate ground state (3H4 → 3H6). We numerically simulate the electrical field distribution and reveal that luminescent enhancement is robust and insensitive to the exact location of particles. It is anticipated that the strategy provides a platform for widely exploring applications in single-particle quantitative biosensing.

Three-dimensional, dual-color nanoscopy enabled by migrating photon avalanches with one single low-power CW beam.

The development of super-resolution fluorescence microscopy is very essential for understanding the physical and biological fundamentals at nanometer scale. However, to date most super-resolution modalities require either complicated/costly purpose-built systems such as multiple-beam architectures or complex post-processing procedures with intrinsic artifacts. Achieving three-dimensional (3D) or multi-channel sub-diffraction microscopic imaging using a simple method remains a challenging and struggling task. Herein, we proposed 3D highly-nonlinear super-resolution microscopy using a single-beam excitation strategy, and the microscopy principle was modelled and studied based on the ultrahigh nonlinearity enabled by photon avalanches. According to the simulation, the point spread function of highly nonlinear microscopy is switchable among different modes and can shrink three-dimensionally to sub-diffraction scale at the photon avalanche mode. Experimentally, we demonstrated 3D optical nanoscopy assisted with huge optical nonlinearities in a simple laser scanning configuration, achieving a lateral resolution down to 58 nm (λ/14) and an axial resolution down to 185 nm (λ/5) with one single beam of low-power, continuous-wave, near-infrared laser. We further extended the photon avalanche effect to many other emitters to develop multi-color photon avalanching nanoprobes based on migrating photon avalanche mechanism, which enables us to implement single-beam dual-color sub-diffraction super-resolution microscopic imaging.

Achieving low-power single-wavelength-pair nanoscopy with NIR-II continuous-wave laser for multi-chromatic probes.

Stimulated emission depletion (STED) microscopy is a powerful diffraction-unlimited technique for fluorescence imaging. Despite its rapid evolution, STED fundamentally suffers from high-intensity light illumination, sophisticated probe-defined laser schemes, and limited photon budget of the probes. Here, we demonstrate a versatile strategy, stimulated-emission induced excitation depletion (STExD), to deplete the emission of multi-chromatic probes using a single pair of low-power, near-infrared (NIR), continuous-wave (CW) lasers with fixed wavelengths. With the effect of cascade amplified depletion in lanthanide upconversion systems, we achieve emission inhibition for a wide range of emitters (e.g., Nd3+, Yb3+, Er3+, Ho3+, Pr3+, Eu3+, Tm3+, Gd3+, and Tb3+) by manipulating their common sensitizer, i.e., Nd3+ ions, using a 1064-nm laser. With NaYF4:Nd nanoparticles, we demonstrate an ultrahigh depletion efficiency of 99.3 ± 0.3% for the 450 nm emission with a low saturation intensity of 23.8 ± 0.4 kW cm-2. We further demonstrate nanoscopic imaging with a series of multi-chromatic nanoprobes with a lateral resolution down to 34 nm, two-color STExD imaging, and subcellular imaging of the immunolabelled actin filaments. The strategy expounded here promotes single wavelength-pair nanoscopy for multi-chromatic probes and for multi-color imaging under low-intensity-level NIR-II CW laser depletion.

Migrating photon avalanche in different emitters at the nanoscale enables 46th-order optical nonlinearity.

A photon avalanche (PA) effect that occurs in lanthanide-doped solids gives rise to a giant nonlinear response in the luminescence intensity to the excitation light intensity. As a result, much weaker lasers are needed to evoke such PAs than for other nonlinear optical processes. Photon avalanches are mostly restricted to bulk materials and conventionally rely on sophisticated excitation schemes, specific for each individual system. Here we show a universal strategy, based on a migrating photon avalanche (MPA) mechanism, to generate huge optical nonlinearities from various lanthanide emitters located in multilayer core/shell nanostructrues. The core of the MPA nanoparticle, composed of Yb3+ and Pr3+ ions, activates avalanche looping cycles, where PAs are synchronously achieved for both Yb3+ and Pr3+ ions under 852 nm laser excitation. These nanocrystals exhibit a 26th-order nonlinearity and a clear pumping threshold of 60 kW cm-2. In addition, we demonstrate that the avalanching Yb3+ ions can migrate their optical nonlinear response to other emitters (for example, Ho3+ and Tm3+) located in the outer shell layer, resulting in an even higher-order nonlinearity (up to the 46th for Tm3+) due to further cascading multiplicative effects. Our strategy therefore provides a facile route to achieve giant optical nonlinearity in different emitters. Finally, we also demonstrate applicability of MPA emitters to bioimaging, achieving a lateral resolution of ~62 nm using one low-power 852 nm continuous-wave laser beam.