Point spread function (PSF) engineering of the emitter can code higher spatial frequency information of an image to break diffraction limit but suffer from the complexed optical systems. Here we present a robust strategy to simultaneously achieve diverse PSFs from upconversion nanoparticles under a single doughnut-shape scanning beam. By saturating the four-photon state, the high-frequency information can be extracted through the doughnut emission PSF. In contrast, the complementary lower frequency information can be carried out by the Gaussian-like emission PSF, as a result of over-saturated at the two-photon state. With the Fourier domain heterochromatic fusion, we verify the capability of the synthesised PSF to cover both low and high-frequency information, yielding the overall enhanced image quality. We show a spatial resolution of 40 nm, 1/24th of the excitation wavelength. This work suggests a new scope for developing nonlinear multi-colour emitting probes to improve image quality and noise control in nanoscopy.
It is well known that Raman scattering and fluorescence can be enhanced by the presence of metallic nanoparticles. Here, we derive simple equations to analyse the influence of metallic nanoparticles on upconversion processes such as non-radiative energy transfer or excited state absorption. We compare the resulting expressions with the more familiar Raman and fluorescence cases, and find significant differences. We use numerical simulations to calculate the upconverted signal enhancement achievable by means of metallic spheres of different radii, and find particles of 100-400nm radius at infra…
We investigate plasmon resonances in gold nanoparticles to enhance the quantum yield of upconverting materials. For this purpose, we use a rate equation model that describes the upconversion of trivalent erbium based upconverters. Changes of the optical field acting on the upconverter and the changes to the transition probabilities of the upconverter in the proximity of a gold nanoparticle are calculated using Mie theory and exact electrodynamic theory respectively. With this data, the influence on the luminescence of the upconverter is determined using the rate equation model. The results sho…
We report on the in situ formation of 2D and 3D self assembled superlattices of upconverting nanoparticles. These as synthesized self assembled nanophosphors can emit sharp and intence luminescence and fluorescence using tunable wavelength femtosecond laser interaction and NIR 980 nm CW laser source, respectively. The relative up conversion luminescence intensities and the number of absorbed photons per photon emitted under the fs laser excitation power corresponds to each of the luminescence have been evaluated. The internal and external quantum yield of the self-assembled nanoparticles have …
Single-beam super-resolution microscopy, also known as superlinear microscopy, exploits the nonlinear response of fluorescent probes in confocal microscopy. The technique requires no complex purpose-built system, light field modulation, or beam shaping. Here, we present a strategy to enhance spatial resolution of superlinear microscopy by modulating excitation intensity during image acquisition. This modulation induces dynamic optical nonlinearity in upconversion nanoparticles (UCNPs), resulting in variations of higher spatial-frequency information in the obtained images. The high-order inform…
Upconversion nanoparticles (UCNPs) exhibit unique optical properties such as photo-emission stability, large anti-Stokes shift, and long excited-state lifetimes, allowing significant advances in a broad range of applications from biomedical sensing to super-resolution microscopy. In recent years, progress on nanoparticle synthesis led to the development of many strategies for enhancing their upconversion luminescence, focused in particular on heavy doping of lanthanide ions and core-shell structures. In this article, we investigate the non-linear emission properties of fully Yb-based core-shel…
We propose a novel scheme of photon upconversion based on harnessing the energy of plasmonic hot carriers. Low-energy photons excite hot electrons and hot holes in a plasmonic nanoparticle, which are then injected into an adjacent semiconductor quantum well where they radiatively recombine to emit a photon of higher energy. We theoretically study the proposed upconversion scheme using Fermi-liquid theory and determine the upconversion quantum efficiency to be as high as 25% in 5 nm silver nanocubes. This upconversion scheme is linear in its operation, does not require coherent illumination, of…
The emerging optical multiplexing within nanoscale shows super-capacity in encoding information by using the time-domain fingerprints from uniform nanoparticles. However, the optical diffraction limit compromises the decoding throughput and accuracy of the nanoparticles during wide-field imaging. This, in turn, challenges the quality of nanoparticles to afford the modulated excitation condition, and further to retain the multiplexed optical fingerprints for super-resolution multiplexing. Here we report a tailor-made time-domain super-resolution method with the lifetime-engineered upconversion …
Speckle patterns have been widely confirmed that can be utilized to reconstruct the wavelength information. In order to achieve higher resolution, a varies of optical diffusing waveguides have been investigated with a focus on their wavelength sensitivity. However, it has been a challenge to reach the balance among cost, volumes, resolution, and stability. In this work, we designed a compact cylindrical random scattering waveguide (CRSW) as the light diffuser only by mixing TiO2 particles and ultra-violate adhesive. The speckle patterns are generated by the light multiple scattering in the CRS…
Upconversion of infrared photons is a promising possibility to enhance solar cell efficiency by producing electricity from otherwise unused sub-band-gap photons. We present a rate equation model, and the relevant processes, in order to describe upconversion of near-infrared photons. The model considers stimulated and spontaneous processes, multi-phonon relaxation and energy transfer between neighboring ions. The input parameters for the model are experimentally determined for the material system β-NaEr0.2Y0.8F4. The determination of the transition probabilities, also known as the Einstein coef…
We demonstrate effective background-free continuous wave nonlinear optical excitation of molecules that are sandwiched between asymmetrically constructed plasmonic gold nanoparticle clusters. We observe that near infrared photons are converted to visible photons through efficient plasmonic second harmonic generation. Our theoretical model and simulations demonstrate that Fano resonances may be responsible for being able to observe nonlinear conversion using a continuous wave light source. We show that nonlinearity enhancement of plasmonic nanostructures via coupled quantum mechanical oscillato…
Lanthanide-based upconversion nanoparticles (UCNPs) generally require high power laser excitation. Here we report wide-field upconversion microscopy at single-nanoparticle sensitivity using incoherent excitation of a 970-nm light-emitting diode (LED). We show that due to its broad emission spectrum, LED excitation is about 3 times less effective for UCNPs and generates high background compared to laser illumination. To counter this, we use time-gated luminescence detection to eliminate the residual background from the LED source, so that individual UCNPs with high sensitizer (Yb3+) doping and …
A novel concept of a \textit{mesocavity}, based on a simple yet counter-intuitive idea of covering metal nanoparticles with unusually thick ($\gtrsim 100$ nm) high-index dielectric shells, is demonstrated in technologically relevant and largely sought-after case of an upconversion (UC) enhancement. For readily available combinations of materials and geometrical parameters of metal-dielectric core-shell mesocavity, record high values of UC enhancement of $\gtrsim 10^6$ can be achieved on the cavity surface. For emitter inside the high-index dielectric shell with refractive index $n=2.7$, the Lo…
Video-rate super-resolution imaging through biological tissue can visualize and track biomolecule interplays and transportations inside cellular organisms. Structured illumination microscopy allows for wide-field super resolution observation of biological samples but is limited by the strong absorption and scattering of light by biological tissues, which degrades its imaging resolution. Here we report a photon upconversion scheme using lanthanide-doped nanoparticles for wide-field super-resolution imaging through the biological transparent window, featured by near-infrared and low-irradiance n…
The control in optical uniformity of single nanoparticles and tuning their diversity in orthogonal dimensions, dot to dot, holds the key to unlock nanoscience and applications. Here we report that the time-domain emissive profile from single upconversion nanoparticle, including the rising, decay and peak moment of the excited state population (T2 profile), can be arbitrarily tuned by upconversion schemes, including interfacial energy migration, concentration dependency, energy transfer, and isolation of surface quenchers. This allows us to significantly increase the coding capacity at the nano…
Band-Selective LDOS Engineering of Yb/Er Upconversion: an Electromagnetic-Kinetic Diagnostic Framework
National University of Singapore（新加坡国立大学）；Univ. Bordeaux, CNRS, CRPP, UMR 5031（波尔多大学，法国国家科学研究中心，聚合物与材料研究所）；Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)（巴塞罗那材料科学研究所）
In optical anti-counterfeiting, several distinct optically variable devices (OVDs) are often concurrently employed to compensate for the insufficient security level of constituent OVDs. Alternatively, metasurfaces that exhibit multiple optical responses effectively combine multiple OVDs into one, thus significantly enhancing their security and hindering fraudulent replication. This work demonstrates the simultaneous control of three separate optical responses, i.e., phase, amplitude, and luminescence, using anisotropic gap-plasmon metasurfaces. Due to the incorporated geometric anisotropy, the…
