Advances in the photon avalanche luminescence of inorganic lanthanide-doped nanomaterials.

Photon avalanche (PA)-where the absorption of a single photon initiates a 'chain reaction' of additional absorption and energy transfer events within a material-is a highly nonlinear optical process that results in upconverted light emission with an exceptionally steep dependence on the illumination intensity. Over 40 years following the first demonstration of photon avalanche emission in lanthanide-doped bulk crystals, PA emission has been achieved in nanometer-scale colloidal particles. The scaling of PA to nanomaterials has resulted in significant and rapid advances, such as luminescence imaging beyond the diffraction limit of light, optical thermometry and force sensing with (sub)micron spatial resolution, and all-optical data storage and processing.

Unlocking Single-Particle Multiparametric Sensing: Decoupling Temperature and Viscosity Readouts through Upconverting Polarized Spectroscopy.

Upconverting particles (UCPs), renowned for their capability to convert infrared to visible light, serve as invaluable imaging probes. Furthermore, their responsiveness to diverse external stimuli holds promise for leveraging UCPs as remote multiparametric sensors, capable of characterizing medium properties in a single assessment. However, the utility of UCPs in multiparametric sensing is impeded by crosstalk, wherein distinct external stimuli induce identical alterations in UCP luminescence, hindering accurate interpretation, and yielding erroneous outputs.

Understanding Yb-sensitized photon avalanche in Pr co-doped nanocrystals: modelling and optimization.

Among different upconversion processes where the emitted photon has higher energy than the one absorbed, photon avalanche (PA) is unique, because the luminescence intensity increases by 2-3 orders of magnitude in response to a tiny increase in excitation intensity. Since its discovery in 1979, PA has been observed in bulk materials but until recently, obtaining it at the nanoscale has been a significant challenge. In the present work, the PA phenomenon in β-NaYF colloidal nanocrystals co-doped with Pr and Yb ions was successfully observed at 482 nm (P → H) and 607 nm (P → H) under excitation at 852 nm.

Quantitative Comparison of the Light-to-Heat Conversion Efficiency in Nanomaterials Suitable for Photothermal Therapy.

Functional colloidal nanoparticles capable of converting between various energy types are finding an increasing number of applications. One of the relevant examples concerns light-to-heat-converting colloidal nanoparticles that may be useful for localized photothermal therapy of cancers. Unfortunately, quantitative comparison and ranking of nanoheaters are not straightforward as materials of different compositions and structures have different photophysical and chemical properties and may interact differently with the biological environment.

Laser Refrigeration by an Ytterbium-Doped NaYF Microspinner.

Thermal control of liquids with high (micrometric) spatial resolution is required for advanced research such as single molecule/cell studies (where temperature is a key factor) or for the development of advanced microfluidic devices (based on the creation of thermal gradients at the microscale). Local and remote heating of liquids is easily achieved by focusing a laser beam with wavelength adjusted to absorption bands of the liquid medium or of the embedded colloidal absorbers. The opposite effect, that is highly localized cooling, is much more difficult to achieve.

Enhancing FRET biosensing beyond 10 nm with photon avalanche nanoparticles.

Förster Resonance Energy Transfer (FRET) between donor (D) and acceptor (A) molecules is a phenomenon commonly exploited to study or visualize biological interactions at the molecular level. However, commonly used organic D and A molecules often suffer from photobleaching and spectral bleed-through, and their spectral properties hinder quantitative analysis. Lanthanide-doped upconverting nanoparticles (UCNPs) as alternative D species offer significant improvements in terms of photostability, spectral purity and background-free luminescence detection, but they bring new challenges related to multiple donor ions existing in a single large size UCNP and the need for nanoparticle biofunctionalization.

Single-Cell Biodetection by Upconverting Microspinners.

Near-infrared-light-mediated optical tweezing of individual upconverting particles has enabled all-optical single-cell studies, such as intracellular thermal sensing and minimally invasive cytoplasm investigations. Furthermore, the intrinsic optical birefringence of upconverting particles renders them light-driven luminescent spinners with a yet unexplored potential in biomedicine. In this work, the use of upconverting spinners is showcased for the accurate and specific detection of single-cell and single-bacteria attachment events, through real-time monitoring of the spinners rotation velocity of the spinner.

Near-infrared excited luminescence and imaging of HeLa cells by using Mn enhanced Tb and Yb cooperative upconversion in NaYF nanocrystals.

Advanced biodetection and bioimaging require fluorescent labels which exhibit many, easily distinguishable colors to identify or study numerous biotargets in a single sample. Although numerous different colors have been demonstrated with lanthanide doped nanoparticles, these colors usually originate from various ratios of overlapping multiple emission bands from activators, which severely limits the number of available labels. As a consequence, different lanthanide doped labels cannot be easily distinguished from each other ( Er from Ho) in a quantitative way, when such labels are co-localized during microscopy wide-field imaging.

Spectral properties of Tm doped NaYF up-converting nanoparticles under single and double photoexcitation wavelengths.

As soon as excited long-living levels of lanthanides become populated, numerous novel photoexcitation schemes may become available. It paves the way to numerous new possibilities or applications, such as up-conversion (UC) enhancement or intentional depletion towards stimulated emission depletion microscopy (STED). However, this type of studies requires the possibility of performing power dependent measurements upon both single and double photoexcitation.

Optical Forces at the Nanoscale: Size and Electrostatic Effects.

The reduced magnitude of the optical trapping forces exerted over sub-200 nm dielectric nanoparticles complicates their optical manipulation, hindering the development of techniques and studies based on it. Improvement of trapping capabilities for such tiny objects requires a deep understanding of the mechanisms beneath them. Traditionally, the optical forces acting on dielectric nanoparticles have been only correlated with their volume, and the size has been traditionally identified as a key parameter.

Shaping Luminescent Properties of Yb and Ho Co-Doped Upconverting Core-Shell β-NaYF Nanoparticles by Dopant Distribution and Spacing.

At the core of luminescence color and lifetime tuning of rare earth doped upconverting nanoparticles (UCNPs), is the understanding of the impact of the particle architecture for commonly used sensitizer (S) and activator (A) ions. In this respect, a series of core@shell NaYF UCNPs doped with Yb and Ho ions are presented here, where the same dopant concentrations are distributed in different particle architectures following the scheme: YbHo core and YbHo@…, …@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-shell NPs. As revealed by quantitative steady-state and time-resolved luminescence studies, the relative spatial distribution of the A and S ions in the UCNPs and their protection from surface quenching has a critical impact on their luminescence characteristics.

The impact of shell host (NaYF₄/CaF₂) and shell deposition methods on the up-conversion enhancement in Tb³⁺, Yb³⁺ codoped colloidal α-NaYF₄ core-shell nanoparticles.

Lanthanide doped, up-converting nanoparticles have found considerable interest as luminescent probes in the field of bio-detection. Although the nanoparticles (NPs) have already been successfully applied for fluorescent bio-imaging and bio-assays, the efficiency of the up-conversion process seems to be the bottle-neck in rigorous applications. In this work, we have shown enhancement of the up-conversion in colloidal α-NaYF₄:Yb(3+), Tb(3+) doped nanocrystals owing to passivation of their surface.